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 Contents
S.no. Chapter Name Page no.
Questions Solutions
1. Some Basic Concepts of Chemistry 1 – 3 103-106

2. Structure of Atom 4 – 7 107-110

3. Classification of Elements and Periodicity

in Properties 8 – 10 111-112

4. Chemical Bonding and Molecular Structure 11 – 14 113-117

5. States of Matter 15 – 17 118-121

6. Thermodynamics 18 – 21 122-125

7. Equilibrium 22 – 25 126-130

8. Redox Reactions 26 – 27 131-132

9. Hydrogen 28 – 29 133-134

10. The s-Block Elements 30 – 32 135-136

11. The p-Block Elements (Group-13 and 14) 33 – 35 137-138

12. Organic Chemistry — Some Basic Principles

& Techniques 36 – 40 139-143

13. Hydrocarbons 41 – 45 144-147

14. Environmental Chemistry 46 – 47 148

15. The Solid State 48 – 50 149-152

16. Solutions 51 – 54 153-158

17. Electrochemistry 55 – 58 159-164

18. Chemical Kinetics 59 – 62 165-170

19. Surface Chemistry 63 – 66 171-74

20. General Principles and Processes of Isolation

of Elements  67 – 68 175

21. The p-Block Elements (Group 15, 16, 17 & 18) 69 – 70 176-177

22. The d-and f-Block Elements 71 – 72 178-179

23. Co-ordination Compounds 73 – 75 180-182

24. Haloalkanes and Haloarenes 76 – 78 183-185

25. Alcohols, Phenols and Ethers 79 – 82 186-188

26. Aldehydes, Ketones and Carboxylic Acids 83 – 86 189-192

27. Amines 87 – 90 193-195

28. Biomolecules 91 – 94 196-198

29. Polymers 95 – 97 199-200

30. Chemistry in Everyday Life 98 – 99 201

31. Analytical Chemistry 100 – 102 202-204

 SOME BASIC CONCEPTS
OF CHEMISTRY
MCQs with One Correct Answer
1. Which of the following statements is correct
about the reaction given below ?
4Fe(s) + 3O 2 (g) ¾¾ ® 2Fe 2 O 3 (g)
(a) Total mass of iron and oxygen in reactants =
total mass of iron and oxygen in product
therefore, it follows law of conservation of mass.
(b) Total mass of reactants = total mass of
product; therefore, law of multiple
proportions is followed.
(c) Amount of Fe2O3 can be increased by
reducing the amount of any one of the
reactants (iron or oxygen).
(d) Amount of Fe2O3 produced will decrease if
the amount of any one of the reactants (iron
or oxygen) is taken in excess.
2. Which of the following statements indicates that
law of multiple proportion is being followed.
(a) Sample of carbon dioxide taken from any
source will always have carbon and oxygen
in the ratio 1 : 2.
(b) Carbon forms two oxides namely CO2 and
CO, where masses of oxygen which
combine with fixed mass of carbon are in
the simple ratio 2 : 1.
1
(c) When magnesium burns in oxygen, the
amount of magnesium taken for the reaction
is equal to the amount of magnesium in
magnesium oxide formed.
(d) At constant temperature and pressure, 200
mL of hydrogen will combine with 100 mL
oxygen to produce 200 mL of water vapour.
3. The number of water molecules in 250 mL of
water is closest to [Given, density of water is 1.0
g mL–1; Avogadro’s number = 6.023 × 1023]
(a) 83.6 × 1023 (b) 13.9 × 1023
(c) 1.5 × 1023 (d) 33.6 × 1023
4. A metal oxide has the formula Z2O3. It can be
reduced by hydrogen to give free metal and water.
0.1596 g of the metal oxide requires 6 mg of
hydrogen for complete reduction. The atomic
weight of the metal is
(a) 27.9 (b) 159.6 (c) 79.8 (d) 55.8
5. 4 g of a hydrated crystal of formula A.xH2O has
0.8 g of water. If the molar mass of the anhydrous
crystal (A) is 144 g mol–1, The value of x is
(a) 4 (b) 1 (c) 2 (d) 3
6. A solution of 20.2 g of 1,2-dibromopropane in
MeOH upon heating with excess Zn produces
3.58 g of an unsaturated compound X. The yield
(%) of X is closest to [Atomic weight of Br is 80]
(a) 18 (b) 85 (c) 89 (d) 30
 2 CHEMISTRY

7. 5.0 g of a certain element X forms 10.0 g of its 16. 3.0 g of oxalic acid [(CO2H)2.2H2O] is dissolved
oxide having the formula X4O6. The atomic mass in a solvent to prepare a 250 mL solution. The
of X is density of the solution is 1.9 g/mL. The molality
(a) 12.0 amu (b) 24.0 amu and normality of the solution, respectively, are
(c) 30.0 amu (d) 32.0 amu closest to
8. The maximum number of molecules are present (a) 0.10 and 0.38
in (b) 0.10 and 0.19
(a) 15 L of H2 gas at STP (c) 0.05 and 0.19
(b) 5 L of N2 gas at STP (d) 0.05 and 0.09
(c) 0.5 g of H2 gas 17. How many moles of P4O6 and P4O10 will be
(d) 10 g of O2 gas produced by the combustion of 12.4 g of
9. Number of moles of MnO-4 required to oxidize phosphorous (atomic mass 31) in 12.8 g of
one mole of ferrous oxalate completely in acidic oxygen, leaving no P4 or O2?
medium will be (a) 0.1 and 0.3 mol
(a) 0.6 moles (b) 0.4 moles (b) 0.15 mol and 0.25 mol
(c) 7.5 moles (d) 0.2 moles (c) 0.05 mol each
10. A metallic chloride contain 47.22% metal. (d) 0.1 mol each
Calculate the equivalent weight of metal. 18. 5 g sample contain only Na2CO3 and Na2SO4.
(a) 39.68 (b) 31.76 (c) 36.35 (d) 33.46 This sample is dissolved and the volume made
11. The number of moles of water present in a up to 250 mL. 25 mL of this solution neutralizes
spherical water droplet of radius 1.0 cm is 20 mL of 0.1 M H2SO4. Calculate the % of Na2SO4
[Given: density of water in the droplet = 1.0 g in the sample.
cm–3] (a) 42.4 (b) 57.6 (c) 36.2 (d) 0.576
19. 1 mole of equimolar mixture of ferric oxalate and
p 2p 2p
(a) (b) (c) 24p (d) ferrous oxalate requires x mole of KMnO4 in
18 27 9 acidic medium for complete oxidation. x is:
12. If potassium chlorate is 80% pure, then 48 g of (a) 0.5 mole (b) 0.9 mole
oxygen would be produced from (atomic mass (c) 1.2 mole (d) 4.5 mole
of K =39) 20. Two solutions of a substance (non electrolyte)
(a) 153.12 g of KClO3 (b) 122.5 g of KClO3 are mixed in the following manner. 480 mL of 1.5
(c) 245 g of KClO3 (d) 98 g of KClO3 M first solution + 520 mL of 1.2 M second
13. 10 g CaCO3 were dissolved in 250 mL of 100 M solution. What is the molarity of the final mixture?
HCl or the solution was boiled. What volume of (a) 2.70 M (b) 1.344 M
2M KOH would be required to equivalence point (c) 1.50 M (d) 1.20 M
after boiling? Assume no change in volume
during boiling. Numeric Value Answer
(a) 50 mL (b) 25 mL (c) 75 mL (d) 60 mL 21. A mixture of HCOOH and H2C2O4 is heated
14. The density of 3M solution of sodium chloride with concentrated H2SO4. The gas produced is
is 1.252 g mL–1. The molality of the solution will collected and on treating with KOH solution,
be : the volume of gas decreases by one-sixth.
(molar mass, NaCl = 58.5 g mol–1) Calculate the molar ratio of the two acids
(a) 260 m (b) 2.18 m (c) 2.79 m (d) 3.00m (HCOOH : H2C2O4) in the original mixture.
15. 2 g of a mixture of CO and CO2 on reaction with 22. One gram of a metallic chloride was found to
excess I2O5 produced 2.54 g of I2. What would contain 0.835 g of chlorine. Its vapour density is
be the mass % of CO2 in the original mixture? 85.5. If its molecular formula is MxCly, then what
(a) 60 (b) 30 (c) 70 (d) 35 is value of (x + y)?
Some Basic Concepts of Chemistry
23. 0.7875 g of crystalline barium hydroxide is
dissolved in water. For the neutralization of this
solution 20 mL of N/4 HNO3 is required. How
many moles of water of crystallization are present
in one mole of this base? (Given : Atomic mass
Ba = 137, O = 16, N = 14, H = 1)
24. A mixture contains 1.0 mole each of NaOH, Na2CO3
and NaHCO3. When half of mixture is titrated with
HCl, it required x mole of HCl in presence of
phenolphthalein. In another experiment, half of
mixture required y mole of same HCl in presence of
methyl orange. Find the value of (x + y).
25. A 0.276 g impure sample of copper ore is dissolved
and Cu2+ is titrated with KI solution. I2 liberated
required 40 mL of 0.1M Na2S2O3 solution for
titration. What is the % of impurities in the ore?
3
26. Density of a sulphuric acid solution is 1.225g/
mL. and it is 40% H2SO4 by weight. Determine
molarity of this solution.
27. A 16.24 mL sample of vinegar of density 1.06 g/
mL required 48.24 mL of 0.36 N solution of a
standard alkali. Determine percentage weight of
acetic acid in vinegar.
28. How much volume of sulphur dioxide at STP will
be obtained by completely burning 10 g of pure
sulphur?
29. How much volume of 4.0 M HNO3 is required to
prepare 60 mL of 0.2 M HNO3 from a stock
solution of 4.0 M HNO3?
30. The minimum number of moles of O2 required
for complete combustion of 1 mole of propane
and 2 moles of butane is ______.

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

STRUCTURE OF ATOM
2

MCQs with One Correct Answer æ Z2 ö

1. The potential energy of electron present in 4. Based on equation E = – 2.178 × 10-18 J ç ÷
ç n2 ÷ ,
è ø
ground state of Li2+ ion is represented by :
certain conclusions are written. Which of them
+3e 2 - 3e is not correct ?
(a) (b) 4 pe 0 r (a) Larger the value of n, the larger is the orbit
4 pe 0 r
radius.
-3e 2 -3e 2 (b) Equation can be used to calculate the change
(c) (d) in energy when the electron changes orbit.
4pe0 r 2 4 pe 0 r
(c) For n = 1, the electron has a more negative
2. Let mp be the mass of a proton, mn that of a energy than it does for n = 6 which mean
neutron, M1 that of a 20 nucleus and M2 that the electron is more loosely bound in
10 Ne
the smallest allowed orbit.
that of a 40 nucleus. Then (d) The negative sign in equation simply means
20 Ca
that the energy or electron bound to the
(a) M2 = 2M1
nucleus is lower than it would be if the electrons
(b) M1<10(mp + mn)
were at the infinite distance from the nucleus.
(c) M2 > 2M1
5. An electron in the ground state of hydrogen
(d) M1 = M2
3. Which of the following pairs of nucleides are was excited to a higher energy level using
isodiaphers ? monochromatic radiations of wave length (l) 975
Å. The longest wave length that appears in the
(a) 13 and 16 (b) 1 and 12 H
6 C 8 O 1H resulting spectrum is due to transition from:
3 55 65 (a) n 4 ¾¾ ® n1 (b) n 4 ¾¾ ® n3
(c) 1H and 42 He (d) 25 Mn and 30 Zn
(c) n 5 ¾¾
® n4 (d) n 5 ¾¾
® n1
Structure of Atom 5
6. If m and e are the mass and charge of the
8. Among the following, the incorrect statement is
revolving electron in the orbit of radius r for
(a) No two electrons in an atom can have the
hydrogen atom, the total energy of the revolving
same set of four quantum numbers
electron will be:
(b) The maximum number of electrons in the
1 e2 e2 shell with principal quantum number, n is
(a) (b) - equal to n2 + 2
2 r r
(c) Electrons in an orbital must, have opposite
me2 1 e2 spin
(c) (d) -
r 2 r (d) In the ground state, atomic orbitals are filled
7. The correct representation of wavelength in the order of their increasing energies
intensity relationship of an ideal black body 9. What transition in He+ ion shall have the same
radiation at two different temperatures T1 and T2 is wave number as the first line in Balmer series of
H atom?
(a) 7 ® 5 (b) 6 ® 4
T2 T2 >T1 (c) 5 ® 3 (d) 4 ® 2
10. The velocity of an electron in excited state of H-
Intensity

(a) atom is 1.093 ´ 106 m/s. What is the circumference

T1 of this orbit?
(a) 3.32 ´ 10–10 m (b) 6.64 ´ 10–10 m
Wavelength (c) 13.30 ´ 10 m (d) 13.28 ´ 10–8 m
–10

11. The angular momentum of an electron in a

Bohr’s orbit of He+ is 3.1652 × 10–34 kg-m2/sec.
T2 >T1 What is the wave number in terms of Rydberg
T2
constant (R) of the spectral line emitted when
Intensity

an electron falls from this level to the first excited

(b) T1
state. [Use h = 6.626 ´ 10–34 J × s]
5R
(a) 3R (b)
Wavelength 9

3R 8R
(c) (d)
4 9
T1 T 2 >T 1 12. A electron in a hydrogen atom in its ground
Intensity

state absorbs 1.5 times as much energy as the

(c) minimum required for it to escape from the atom.
T2
What is the velocity of the emitted electron?
(a) 1.54 ´ 106 m/s
Wavelength (b) 1.54 ´ 108 m/s
(c) 1.54 ´ 103 m/s
(d) 1.54 ´ 104 m/s
T1 T2 > T1 13. For a multi-electron atom, the highest energy
level among the following is
Intensity

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

14. For Balmer series in the spectrum of atomic

hydrogen, the wave number of each line is given
(c)
æ 1 1 ö
by v = R H ç – 2 ÷ where RH is a constant
2
è n1 n2 ø
and n 1 and n 2 are integers. Which of the
following statement(s) is (are) correct?
I. As wavelength decreases, the lines in the (d)
series converge.
II. The integer n 1 is equal to 2.
III. The ionization energy of hydrogen can be
calculated from the wave number of these
lines. 18. The electrons, identified by quantum numbers n
IV. The line of longest wavelength corresponds and l,
to n2 = 3. (I) n = 3, l = 2 (II) n = 5, l = 0
(a) I, II and III (III) n = 4, l = 1 (IV) n = 4, l = 2
(b) II, III and IV only (V) n = 4, l = 0 can be placed in order of
(c) I, II and IV increasing energy, as
(d) II and IV only (a) I < V < III < IV < II (b) I < V < III, II, IV
15. Calculate the minimum and maximum number of (c) V < I < III < II < IV (d) V < I < II < III < IV
electrons which may have magnetic quantum 18. The energies E1 and E2 of two radiations are 25
number, m = +1 and spin quantum number, eV and 50 eV, respectively. The relation between
1 their wavelengths i.e., l1 and l2 will be :
s= - in chromium (Cr): (a) l1 = l2 (b) l1 = 2l2
2
(a) 0, 1 (b) 1, 2 1
(c) 4, 6 (d) 2, 3 (c) l1 = 4l2 (d) l1 = l2
2
16. The correct order of energy of 2s-orbitals in H,
19. Among the following, the correct statement
Li, Na and K, is
about cathode ray discharge tube is
(a) K < Na < Li < H
(a) the electrical discharge can only be
(b) Na < Li < K < H
observed at high pressure and at low
(c) Na < K < H < Li voltages.
(d) H < Na < Li < K (b) in the absence of external electrical or magnetic
17. Which of the following radial distribution graphs field, cathode rays travel in straight lines.
correspond to l = 2 for the H atom ? (c) the characteristics of cathode rays depend
upon the material of electrodes.
(d) the characteristics of cathode rays depend
(a) upon the gas present in the cathode ray
tube.
20. A 600 W mercury lamp emits monochromatic
radiation of wavelength 331.3 nm. How many
photons are emitted from the lamp per second?
(b) h = 6.62 × 10–34 Js velocity of light = 3 × 108 ms–1
(a) 1.0 × 1019 (b) 1.0 × 1023
(c) 1.0 × 10 21 (d) 2.0 × 1023
Structure of Atom 7

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

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

CLASSIFICATION OF 3
ELEMENTS & PERIODICITY
IN PROPERTIES

MCQs with One Correct Answer (c) halogens

(d) noble gases
1. Which form coloured salts?
5. Eka-aluminium and Eka-silicon are known as
(a) Non-metals
(a) gallium and germanium
(b) Metals
(b) aluminium and silicon
(c) p-block elements
(c) iron and sulphur
(d) Transitional elements
(d) manganese and magnesium
2. The ionic radii of Na+, F–, O2–, N3– follow the
6. What is the atomic number of the next halogen
order
if discovered?
(a) O2– > F– > Na+ > N3–
(a) 85 (b) 117
(b) N3– > Na+ > F– > O2–
(c) 167 (d) 104
(c) N3– > O2– > F– > Na+ 7. The electronic configuration of an element is
(d) Na+ > F– > O2– > N3–
1s 2 2s 2 2 p 6 3s 2 3 p 3 . The atomic number and
3. The electronic configuration of four elements
the group number of the element ‘X’ which is
are given below. Which elements does not be-
just below the above element in the periodic
long to the same family as others?
table are respectively
(a) [Xe]4 f 14 5d 10 ls 2 (b) [Kr]4d10 5s 2 (a) 23 and 5 (b) 23 and 15
(c) [Ne]3s23p5 (d) [Ar] 3d10 4s2 (c) 33 and 15 (d) 33 and 5
4. The elements with atomic numbers 9, 17, 35, 53 8. Which one of the following ions has the highest
and 85 belong to value of ionic radius ?
(a) alkali metals (a) O2– (b) B3+
(c) Li + (d) F–
(b) alkaline earth metals
Classification of Elements & Periodicity in Properties 9

9. The first ionisation potential in electron volts 15. The electron affinity for the inert gases is
of nitrogen and oxygen atoms are respectively (a) zero (b) high
given by (c) negative (d) positive
(a) 14.6, 13.6 (b) 13.6, 14.6 16. The correct order of acidic strength :
(c) 13.6, 13.6 (d) 14.6, 14.6 (a) Cl 2 O 7 > SO 2 > P4 O10
10. In which of the following process highest
energy is absorbed? (b) K 2O > CaO > MgO
(a) Cu ® Cu + (b) Br ® Br - (c) CO 2 > N 2 O 5 > SO 3
(c) I ® I- (d) Li ® Li + (d) Na 2 O > MgO > Al 2 O 3
11. Which ionisation potential (IP) in the following 17. The formation of the oxide ion O2–(g) requires
equations involves the greatest amount of first an exothermic and then an endothermic step
energy? as shown below :
(a) Na ® Na + + e -
O( g ) + e - = O - ( g ) DHº = -142 kJmol -1
(b) K+ ® K 2+ + e-
(c) C 2+
® C 3+ + e- O - ( g ) + e - = O 2 - ( g ) DHº = 844 kJmol -1

(d) Ca + ® Ca 2 + + e - This is because

(a) O– ion will tend to resist the addition of
12. Which of the following order is wrong?
another electron
(a) NH3 < PH3 < AsH3 – Acidic
(b) Oxygen has high electron affinity
(b) Li < Be < B < C – First IP
(c) Oxygen is more electronegative
(c) Al2O3 < MgO < Na2O < K2O – Basic
(d) O– ion has comparatively larger size than
(d) Li+ < Na+ < K+ < Cs+ – Ionic radius
oxygen atom
13. The incorrect statement among the following
18. Amphoteric-oxide combinations are in
is
(a) ZnO, K2O, SO3
(a) The first ionization potential of Al is less
(b) ZnO, P2O5, Cl2O7
than the first ionization potential of Mg
(c) SnO2, Al2O3, ZnO
(b) The second ionization potential of Mg is
(d) PbO2, SnO2, SO3
greater th an the second ionization
19. Electronic configurations of four elements A, B,
potential of Na
C and D are given below :
(c) The first ionization potential of Na is less
(i) 1s2 2s2 2p6
than the first ionization potential of Mg
(ii) 1s2 2s2 2p4
(d) The third ionization potential of Mg is
(iii) 1s2 2s2 2p6 3s1
greater than the third ionization potential
(iv) 1s2 2s2 2p5
of Al.
Which of the following is the correct order of
14. The ease of loss of electron from Ne and Na+
increasing tendency to gain electron ?
ion (both isoelectronic) are
(a) (i) < (iii) < (ii) < (iv)
(a) 4562 kJ mol–1, 2081 kJ mol–1
(b) (i) < (ii) < (iii) < (iv)
(b) 2081 kJ mol–1, 4562 kJ mol–1
(c) (iv) < (ii) < (iii) < (i)
(c) 2081 kJ mol–1 each
(d) (iv) < (i) < (ii) < (iii)
(d) 4562 kJ mol–1 each
 10 CHEMISTRY

20. The basic character of MgO, BaO, Na2O and 22. The first ionisation potential of Cu, Ag and Au
are 731, 745 and 890 KJ/mol (not in the same
FeO follow the order
order). What is the numerical value of I.E. for Ag?
(a) MgO < FeO < BaO < Na 2O 23. How many completely filled periods are there in
the long form of the periodic table ?
(b) FeO < MgO < Na 2O < BaO
24. What is the number of elements in the third period
(c) FeO < MgO < BaO < Na 2O of the periodic table except metalloids?
25. How many pairs are, in which first species has
(d) Na 2 O < MgO < FeO < BaO lower ionisation energy than second species:
(i) N and O (ii) Br and K
Numeric Value Answer (iii) Be and B (iv) I and I–
21. In the IUPAC nomenclature of elements, what (iv) Li and Li+ (v) O and S
is atomic number for the element ‘Unh’? (vii) Ba and Sr

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

MCQs with One Correct Answer (b) in NH3 as well as NF3 the atomic dipole and
bond dipole are in opposite directions
1. For AB bond if percent ionic character is plotted
(c) in NH3 the atomic dipole and bond dipole
against electronegativity difference (XA – XB),
are in the opposite directions whereas in
the shape of the curve would look like
NF3 these are in the same direction
C (d) in NH3 as well as in NF 3 the atomic
100
Percent ionic character

B
dipole and bond dipole are in the same
A D
direction
50 3. Among the following, the species with identical
bond order are
0 (a) CO and O2– 2
1 2 3 (b) O2– and CO
(XA – XB)
(c) O2–
2 and B2
The correct curve is
(d) CO and N+2
(a) (A) (b) (B)
4. Which of the following statements is/are true
(c) (C) (d) (D)
2. The electronegativity difference between N and 1. PH 5 and BiCl5 do not exist
F is greater than that between N and H yet the 2. p p – d p bond is present in SO2
dipole moment of NH3 (1.5 D) is larger than that
3. I3+ has bent geometry
of NF3 (0.2D). This is because
(a) in NH3 the atomic dipole and bond dipole 4. SeF4 and CH4 have same shape
are in the same direction whereas in NF3 (a) 1, 2, 3 (b) 1, 3
these are in opposite directions (c) 1, 3, 4 (d) 1, 2, 4
 12 CHEMISTRY

5. The number of sigma (s) and pi (p) bonds present 11. In which of the following species, d-orbitals
in 1,3,5,7 octatetraene respectively are having xz and yz two nodal planes involved in
(a) 14 and 3 (b) 17 and 4 hybridization of central atom?
(c) 16 and 5 (d) 15 and 4 (a) IO2F–2
6. The hybridizations of N, C and O shown in the (b) ClF–4
following compound (c) IF7
R (d) None of these
N==C==O 12. The type of bonds present in sulphuric
respectively, are anhydride is,
(a) 3s and three pp – dp
(a) sp2, sp, sp2 (b) sp2, sp2, sp2
(b) 3s, one pp – pp and two pp – dp
(c) sp2, sp, sp (d) sp, sp, sp2
(c) 2s and three pp – dp
7. The bond dissociation energy of B – F in BF3 is (d) 2s and two pp – dp
646 kJ mol–1 whereas that of C – F in CF4 is 515
13. The correct statement with regard to H+2 and
kJ mol–1. The correct reason for higher B – F
bond dissociation energy as compared to that
H-2 is
of C – F is
(a) stronger s bond between B and F in BF3 as (a) Both H+2 and H-2 do not exist
compared to that between C and F in CF4.
(b) significant pp – pp interaction between B (b) H-2 is more stable than H+2
and F in BF3 whereas there is no possibility
(c) H+2 is more stable than H-2
of such interaction between C and F in CF4.
(c) lower degree of pp – pp interaction between B (d) Both H+2 and H-2 are equally stable
and F in BF3 than that between C and F in CF4.
14. The correct order of bond energies in NO, NO+
(d) smaller size of B– atom as compared to that
and NO– is:
of C– atom.
8. The most polarizable ion among the following is (a) NO - > NO > NO +
(a) F– (b) I– (b) NO > NO - > NO +
(c) Na + (d) Cl–
9. Minimum F - S - F bond angle present in : (c) NO + > NO > NO -
(a) SSF2 (b) SF6 (d) NO + > NO - > NO
(c) SF2 (d) F3SSF 15. Which of the following represents the correct
10. Which of the following statement is correct order of Cl–O bond lengths in
about I3+ and I3- molecular ions? ClO – , ClO 2– , ClO3– , ClO 4– ?
(a) ClO 4–= ClO 3–= ClO 2–= ClO –
(a) Number of lone pairs at central atoms are
same in both molecular ions (b) ClO – < ClO 2– < ClO3– < ClO 4–
(b) Hybridization of central atoms in both ions
(c) ClO4– < ClO3– < ClO2– < ClO –
are same
(c) Both are polar species (d) ClO3– < ClO4– < ClO2– < ClO –
(d) Both are planar species
Chemical Bonding and Molecular Structure 13

16. Which one of the following molecule will have Numeric Value Answer
all equal X—F bond length? (where X = Central
21. Consider the following molecule
atom)
(a) SOCl2F2 (b) SeF4
O O O
(c) PBr2F3 (d) IF7 S S
17. Select the incorrect statement about N2F4 and O O
O O
N2H4 : S
(I) In N 2F4, d-orbitals are contracted by O O
electronegative fluorine atoms, but d-
orbital contraction is not possible by H- Calculate the value of p ÷ q, here p and q are
atom in N2H4 total number of dp–pp bonds and total number
(II) The N-N bond energy in N2F4 is more than of sp3 hybridised atoms respectively in given
N-N bond energy in N2H4 molecule.
(III) The N-N bond length in N2F4 is more than 22. Calculate the value of “x + y – z” here x, y and z
that of in N2H4 are total number of non-bonded electron pair(s),
(IV) The N-N bond length in N2F4 is less than pie(p) bond(s) and sigma (s) bonds in hydrogen
that of in N2H4 phosphite ion respectively.
(a) I, II and III 23. Total number of species which used all three p-
(b) I and III orbitals in hybridisation of central atoms and
(c) II and IV should be non-polar also are
(d) II and III XeO2F2, SnCl2, IF5, I3+ , XeO4, SO2, XeF7+ , SeF4
18. The correct order of ‘S—O’ bond length is
24. Consider the following orbitals 3s, 2px, 4dxy, 4dz2 ,
(a) SO 32 - > SO24 - > SO3 > SO2
3d , 3py, 4s, 4pz and find total number of
x2 - y2
(b) SO 32 - > SO24 - > SO2 > SO3
orbital(s) having even number of nodal plane.
(c) SO 24 - > SO24 - > SO2 > SO3 25. For the following molecules :
(d) SO 24 - > SO24 - > SO3 > SO2 PCl5, BrF3, ICl-2 , XeF5- , NO3- , XeO2F2, PCl+4 , CH3+
19. Among the following transformations, the
hybridization of the central atom remains a+b
Calculate the value of
unchanged in c
(a) CO2 ® HCOOH a = Number of species having sp 3
(b) BF3 ® BF4- d-hybridisation
+
(c) NH3 ® NH4 b = Number of species which are planar
(d) PCl3 ® PCl5 c = Number of species which are non-planar
20. In which species, X—O bond order is 1.5 and 26. Find total number of orbital which can overlap
contains pp – dp bond(s). colaterally, (if inter nuclear axis is z) s, px, py, pz,
(a) IO2F–2 (b) HCOO– dxy, dyz, dxz, d z 2, dx 2 - y 2
(c) SO2– 3 (d) XeO2F2
 14 CHEMISTRY

30. Consider the following values for an ionic

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

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

MCQs with One Correct Answer 4. X mL of H2 gas effuses through a hole in a

container in 5 seconds. The time taken for the
1. 600 c.c. of a gas at a pressure of 750 mm of Hg is
effusion of the same volume of the gas specified
compressed to 500 c.c. Taking the temperature
below under identical conditions is :
to remain constant, the increase in pressure, is
(a) 10 seconds : He
(a) 150 mm of Hg
(b) 20 seconds : O2
(b) 250 mm of Hg
(c) 25 seconds : CO
(c) 350 mm of Hg
(d) 55 seconds : CO2
(d) 450 mm of Hg
5. A container contains 1 mole of a gas at 1 atm
2. 16 g of oxygen and 3 g of hydrogen are mixed and
pressure and 27 °C, while its volume is 24.6 litres.
kept at 760 mm of Hg pressure and 0°C. The total
If its pressure is 10 atm and temperature 327 °C,
volume occupied by the mixture will be nearly
then new volume is
(a) 22.4 litres
(a) 2.56 litres (b) 3.15 litres
(b) 33.6 litres
(c) 4.92 litres (d) 5.44 litres
(c) 448 litres
6. 14 g of N2 and 36 g of ozone are at the same
(d) 44800 mL
pressure and temperature. Their volumes will be
3. Equal weights of methane and hydrogen are
related as
mixed in an empty container at 25ºC. The fraction
of the total pressure exerted by hydrogen is : (a) 2VN = 3VO3
2
1 8
(a) (b) (b) 3VN = 2VO3
2 9 2

(c) 3VN = 4VO3

1 16 2
(c) (d)
9 17 (d) 4VN = 3VO3
2
 16 CHEMISTRY

7. The pressure (P) and volume (V) isotherm of a 12. A container of volume 2.24 L can withstand a
van der Waals’ gas, at the temperature at which maximum pressure of 2 atm at 298 K before
it undergoes gas to liquid transition, is correctly exploding. The maximum amount of nitrogen (in g)
represented by that can be safely put in this container at this
temperature is closest to
(a) 2.8 (b) 5.6
(c) 1.4 (d) 4.2
(a) P (b) P 13. At 300 K, the density of a certain gaseous molecule
at 2 bar is double to that of dinitrogen (N2) at 4
V V bar. The molar mass of gaseous molecule is :
(a) 28 g mol–1 (b) 56 g mol–1
(c) 112 g mol–1 (d) 224 g mol–1
14. Calculate the total pressure in a 10.0 L cylinder
P P which contains 0.4 g helium, 1.6 g oxygen and
(c) (d) 1.4 g nitrogen at 27 °C.
(a) 0.492 atm (b) 49.2 atm
V V
(c) 4.52 atm (d) 0.0492 atm
8. One mole of gas A and three moles of a gas B are 15. I, II, and III are three isotherms, respectively, at
placed in flask of volume 100 litres at 27°C. T1, T2 and T3. Temperature will be in order
Calculate the total partial pressure of the gases
in the mixture.
(a) 1.0 atm. (b) 0.9 atm
P
(c) 0.985 atm (d) 10.850 atm.
9. Oxygen is present in 1 litre flask at a pressure of
I
7.6 × 10–10 mm of Hg. Calculate the number of II
oxygen molecules in the flask at 0ºC. III
(a) 2.8 ×108 (b) 2.7 × 1010
V3 V2 V1
(c) 0.27×1010 (d) 3.0 ×109
10. A spherical balloon of 21 cm diameter is to be (a) T1 = T2 = T3 (b) T1 < T2 < T3
filled up with hydrogen at N.T.P. from a cylinder (c) T1 > T2 > T3 (d) T1 > T2 = T3
containing the gas at 20 atmospheres at 27ºC. If 16. The root mean square speeds at STP for the
the cylinder can hold 2.82 litres of water, calculate gases H2, N2, O2 and HBr are in the order :
the number of balloons that can be filled up. (a) H2< N2< O2 < HBr
(a) 9 (b) 8 (b) HBr < O2 < N2 < H2
(c) 12 (d) 10 (c) H2 < N2 = O2< HBr
11. A given volume of ozonised oxygen (containing (d) HBr < O2 < H2 < N2.
60% oxygen by volume) required 220 sec to 17. Two flasks A and B of equal volumes maintained
effuse while an equal volume of oxygen took at temperatures 300K and 600K contain equal
200 sec only under identical conditions. If mass of H2 and CH4 respectively. The ratio of
density of O2 is 1.6 g/L then find density of O3. total translational kinetic energy of gas in flask
(a) 1.936 g/L (b) 2.16 g/L A to that in flask B is
(c) 3.28 g/L (d) 2.24 g/L (a) unity (b) 2
(c) 4 (c) 0.25
States of Matter 17

18. The root mean square speed of hydrogen in 23. At 400 K, the root mean square (rms) speed of a
5 times than that of nitrogen. If T is the gas X (molecular weight = 40) is equal to the
temperature of the gas, then : most probable speed of gas Y at 60 K. The
.
(a) TH = TN 2 (b) TH 2 > TN2 molecular weight of the gas Y is
2
24. One mole of a gas changed from its initial state
(c) TH 2 < TN2 (d) TH 2 = 7TN 2
(15L, 2 atm) to final state (4L, 10 atm) reversibly.
19. For one mole of a van der Waals gas, the If this change can be represented by a straight
æ PV ö line in P – V curve maximum temperature
compressibility factor Z ç = at a fixed
è RT ÷ø (approximate), the gas attained is x × 102K. Then
volume will certainly decrease if [Given: “a”, “b” find the value of x.
are standard parameters for van der Waals gas] 25. A flask containing air at 107°C and 722 mm of
(a) “b” increases and “a” decreases at constant Hg is cooled to 100 K and 760 mm of Hg. If
temperature density in the initial condition 1 g/cm3, then what
(b) “b” decreases and “a” increases at constant is the final density (g/cm3)?
temperature 26. If an ideal gas at 100 K is heated to 109 K in a
(c) temperature increases at constant “a” and rigid container, the pressure increases by X%.
“b” values What is the value of X?
(d) “b” increases at constant “‘a” and temperature 27. A flask has 10 gas particles, out of which four
20. A mixture of Ne and Ar kept in a closed vessel at particles are moving at 7 ms–1 and the remaining
250 K has a total K.E. = 3kJ. The total mass of are moving at the same speed of ‘X’ ms–1. If the
Ne and Ar is 30 g. Find mass % of Ne in gaseous r.m.s. of the gas is 5 ms–1, what is the value of X?
mixture at 250 K. 28. At 300 K, the average kinetic energy of a
(a) 61.63 (b) 38.37 deuterium molecule is n times than that of a
(c) 50% (d) 28.3 hydrogen molecule. Find the value of n.
Numeric Value Answer 29. The root mean square speed of 4g of helium
gas is 450 m/s. What is the value of total
21. A gas diffuse1/5 times as fast as hydrogen. If its
kinetic energy (J) of this sample?
molecular weight is 10y. What will be the value of y?
30. If the ratio of critical temperature to critical
22. The rate of diffusion of methane at a given
pressure for a real gas is mb/R, then what is
temperature is twice that of a gas X. If the molecular
the integer value of m?
weight of X is 8y then what will be the value of y?

ANSWER KEY
1 (a) 4 (b) 7 (b) 10 (d) 13 (c) 16 (b) 19 (b) 22 (8) 25 (4) 28 (1)
2 (d) 5 (c) 8 (c) 11 (d) 14 (a) 17 (c) 20 (d) 23 (4) 26 (9) 29 (405)
3 (b) 6 (b) 9 (b) 12 (d) 15 (c) 18 (c) 21 (5) 24 (7) 27 (3) 30 (8)
 18 CHEMISTRY

6
THERMODYNAMICS

MCQs with One Correct Answer 5. The amount of work done by 2 mole of an ideal gas
at 298 K in reversible isothermal expansion from 10
1. The internal energy change when a system goes
litre to 20 litre will be
from state A to B is 40 kJ/mol. If the system goes
(a) 3.4 kJ (b) –3.4 kJ
from A to B by a reversible path and returns to
(c) 4.0 kJ (d) –4.0 kJ
state A by an irreversible path what would be the
6. A gas expands reversibly from state A to state
net change in internal energy ?
B by three paths 1, 2 and 3 as shown in the
(a) > 40 kJ (b) < 40 kJ
figure. If w1, w2 and w3 respectively be the work
(c) Zero (d) 40 kJ
done by the gas along three paths then
2. A gas absorbs 200 J heat and undergoes
simultaneous expansion against a constant P
A
external pressure of 105 Pa. The volume changes
from 4L to 5L. The change in internal energy is 3
2
(a) 300 J (b) 100 J 1
(c) –300 J (d) – 100 J B
3. When 110 g of manganese (At. mass = 55) dis- V
solves in dilute HNO3 at 27°C under atmospheric (a) w1 > w2 > w3 (b) w1 < w2 < w3
pressure, the work done in the process is : (c) w1 = w2 = w3 (d) w2 < w3 < w1
(a) 2494.2 J (b) – 2494.2 J 7. 10 mole of an ideal gas expand isothermally and
(c) – 4988.4 J (d) 4988.4 J reversibly from a pressure of 10 atm to 1atm at
4. Workdone for the conversion of 0.5 mole of 300 K. What is the largest mass which can lifted
water at 100ºC to steam at 1 atm pressure is (heat through a height of 100 meter?
of vaporisation of water at 100ºC is 40670 J mol–1) (a) 31842 kg (b) 58.55 kg
(a) –1.54 kJ (b) 1.54 kJ (c) 342.58 kg (d) 6051 kg
(c) 1.25 kJ (d) –1.35 kJ
Thermodynamics 19
–1
8. Given that C + O 2 ® CO 2 : D H º = - x kJ D eg H Cl = –349 kJ mol ,
–1
2 CO + O 2 ® 2CO 2 : DH º = - y kJ D hyd H Cl – = –381 kJ mol , will be
the enthalpy of formation of carbon monoxide (a) + 152 kJ mol–1 (b) – 850 kJ mol–1
(c) – 610 kJ mol –1 (d) + 120 kJ mol–1
will be
12. The specific heat of a monoatomic gas at con-
2x - y y - 2x stant pressure is 248.2 J kg–1 K–1 and at con-
(a) (b)
2 2 stant volume it is 149.0 J kg–1 K–1. The mean
(c) 2x – y (d) y – 2x molar mass of the gas is
9. The enthalpy changes for the following (a) 83.8 g mol–1 (b) 84.0 g mol–1
processes are listed below : (c) 82 g mol –1 (d) 80 g mol–1
Cl2(g) ® 2Cl(g), 242.3 kJ mol–1 13. The values of standard enthalpy of formation
I2(g) ® 2I(g), 151.0 kJ mol–1 of SF6(g), S(g)and F(g) are : – 1100, 275 and
ICl(g) ® I(g) + Cl(g), 211.3 kJ mol–1 80 kJ mol–1 respectively. The average S–F bond
I2(s) ® I2(g), 62.76 kJ mol–1 energy in SF6 will be
Given that the standard states for iodine and (a) 309 kJ (b) 315 kJ
chlorine are I2(s) and Cl 2(g), the standard (c) 320 kJ (d) 300 kJ
enthalpy of formation for ICl(g) is : 14. Given the following entropy values (in J K–1 mol–1)
(a) +16.8 kJ mol–1 at 298 K and 1 atm :H2(g) : 130.6, Cl2(g) : 223.0,
(b) +244.8 kJ mol–1 HCl(g) : 186.7.The entropy change (in J K–1 mol–1)
(c) –14.6 kJ mol–1 for the reaction
(d) –16.8 kJ mol–1 H 2 ( g ) + Cl 2 ( g ) ¾¾® 2 HCl ( g ) is
10. The quantity of heat (in J) required to raise the (a) +540.3 (b) +727.0
temperature of 1.0 kg of ethanol from 293.45 K to (c) –166.9 (d) +19.8
the boiling point and then change to liquid to 15. One mole of CH3COOH undergoes dimerization
vapour at that temperature is closest to in vapour phase at 127°C as:
[Given, boiling point of ethanol 351.45 K. Specific
ˆˆ† ( CH 3 COOH ) ( g )
2CH 3COOH ( g ) ‡ˆˆ
heat capacity of liquid ethanol 2.44 J g–1 k–1. 2
Latent heat of vaporisation of ethanol 855 J g–1] if dimer formation is due to two H-bonds involved
(a) 142 × 102 (b) 9.97 × 102 in dimer, each of 33 kJ stength and the degree of
(c) 142 × 105 (d) 9.97 × 105 dimerisation of acetic acid 98.2%. The change in
11. Oxidising power of chlorine in aqueous solution standard entropy during dimerization is
can be determined by the parameters indicated (a) –104 JK–1 mol–1 (b) –120 JK–1 mol–1
below: (c) 135 JK–1 mol–1 (d) 108 JK–1 mol–1
16. For a spontaneous process
1
1 Ddiss H D eg H (a) enthalpy change of the system must be
2
Cl2 (g) ¾¾¾¾ ® Cl(g) ¾¾¾ ® Cl – (g) negative.
2
(b) entropy change of the system must be
D H positive.
Hyd
¾¾¾¾ ® Cl– (aq)
(c) entropy change of the surrounding must
using the data, be positive.
–1 (d) en tropy ch ange of the syst em pl us
D diss H Cl = 240 kJ mol ,
2 surrounding must be positive.
 20 CHEMISTRY

17. At the sublimation temperature, for the process Pressure

(Pa)
ˆˆ† CO2(g)
CO2(s) ‡ˆˆ 10
A B
(a) DH, DS and DG are all positive 8

(b) DH > 0, DS > 0 and DG < 0 6

(c) DH < 0, DS > 0 and DG < 0
4
(d) DH > 0, DS > 0 and DG = 0 C
18. The factor of DG values is important in (2, 2) 4 6 8 10 12 Volume
(m3)
metallurgy. The DG values for the following
23. At constant volume, 4 mol of an ideal gas when
reactions at 800ºC are given as : heated from 300 K to 500 K changes its internal
S2 (s) + 2O 2 (g) ¾¾
® 2SO 2 (g) ; DG = – 544 kJ energy by 5000 J. The molar heat capacity at
constant volume is ______.
® 2ZnS(s) ; DG = – 293 kJ
2Zn(s) + S2 (s) ¾¾ 24. A perfect gas undergoes a reversible adiabatic
® 2ZnO(s) ; DG = – 480 kJ
2Zn(s) + O 2 (g) ¾¾ expansion from (300 K, 200 atm) to (90 K, 10
atm). The atomicity of gas will be
Then DG for the reaction : 25. A mixture of ferric oxide, Fe2O3, and aluminium,
2ZnS(s) + 3O 2 (g) ¾¾
® 2ZnO(s) + 2SO 2 (g) Al, is used in solid fuel rockets. The fuel value
will be : per cc of the mixture is
Heats of formation and densities are as follows :
(a) –357 kJ (b) –731 kJ
H f (Al2O3) = 399 kcal/mol;
(c) –773 kJ (d) –229 kJ
H f (Fe2O3) = 199 kcal/mol;
19. Given that the molar combustion enthalpy of
Density of Fe2O3 = 5.2 g/cc;
benzene, cyclohexane, and hydrogen are x, y,
Density of Al = 2.7 g/cc.
and z, respectively, the molar enthalpy of
hydrogenation of benzene to cyclohexane is 26. x g sample of NH4NO3 is decomposed in a Bomb
calorimeter. The temperature of calorimeter
(a) x - y + z (b) x - y + 3z
increase by 4°C. The heat capacity of the system
(c) y - x + z (d) y - x + 3z is 125 kJ/°C. The value of x is
20. For vaporization of water at 1 atmospheric (Given molar heat of decomposition of NH4NO3
pressure, the values of DH and DS are 40.63 at constant volume is 400 kJ mol–1)
kJmol–1 and 108.8 JK–1 mol–1, respectively. The 27. A heat engine is operating between 500K to
temperature when Gibbs energy change (DG) for 400K. If the engine absorbs 100 J heat, the
this transformation will be zero, is: impossible amount of heat rejected by the engine
(a) 293.4 K (b) 273.4 K is 20TJ, then the value of T is ________
(c) 393.4 K (d) 373.4 K. 28. One mole of a real gas undergoes a change of
state A to B with a change in internal energy
Numeric Value Answer P

B (350 K)
21. For a dimerization reaction, 2A(g) ® A 2 (g), at 4

3
298K, DUQ = -20 kJmol–1, DSQ = -30 JK–1 mol–1,
(atm)

2
then the DG Q will be ___________ J. 1 A (200 K)
22. The magnitude of work done by a gas that V
0 1 2 3 4 5 6 7 8
undergoes a reversible expansion along the (litre)
path ABC shown in the figure is ________ DE = 50 L – atm. What is the value of change
in enthalpy in L – atm?
Thermodynamics 21
29. A 20g piece of iron (specific heat capacity The standard molar enthalpies of formation,
= 0.5 J/g °C) at 200°C is immersed in 100g water
D H0f for all the compounds are given below..
of 27°C.
What will be the temperature (°C) of this DH°f [C3H5(NO3)3] = – 364 kJ/mol
system at thermal equilibrium? DH°f [CO2(g)] = – 393.5 kJ/mol
30. Nitroglycerine (MW = 227.1) detonated DH°f [H2O(g)] = – 241.8 kJ/mol
according to the following equations, DH°f [N2(g)] = 0 kJ/mol
1 DH°f [O2(g)] = 0 kJ/mol
2C3H5(NO3)3(l) ¾¾ ® 3N2(g) + O2(g)
The enthalpy change when 10 g of nitroglycerine
2
+ 6CO2(g) + 5H2O(g) is detonated as

ANSWER KEY
1 (c) 4 (a) 7 (b) 10 (d) 13 (a) 16 (d) 19 (b) 22 (48.00) 25 (4) 28 (76)
2 (b) 5 (b) 8 (b) 11 (c) 14 (d) 17 (d) 20 (d) 23 (6.25) 26 (1) 29 (31)
3 (c) 6 (b) 9 (a) 12 (a) 15 (a) 18 (b) 21 (–13538) 24 (1) 27 (4) 30 (62.5)
 22 CHEMISTRY

7
EQUILIBRIUM

MCQs with One Correct Answer concentration

1. For the synthesis of ammonia by the reaction NH3

Molar

ˆˆ† 2NH in the Haber process, the

N2 + 3H2 ‡ˆˆ H2
3 (d)
attainment of equilibrium is correctly predicted N2
by the curve
time
2. Two moles of PCl5 were heated in a closed vessel
concentration
Molar

H2 of 2L. At equilibrium 40% of PCl5 is dissociated

(a) N2 into PCl3 and Cl2. The value of equilibrium
NH3 constant is
(a) 0.53 (b) 0.267
time
(c) 2.63 (d) 5.3
3. K1 and K2 are equilibrium constant for reactions
concentration
Molar

H2 (i) and (ii)

(b) N2 ˆˆ† 2 NO (g)
N2(g) + O2 (g) ‡ˆˆ ...(i)
NH3 1 1
ˆˆ†
NO(g) ‡ˆˆ N 2 (g) + O 2 (g) ...(ii)
time
2 2
Then,
concentration

NH3 2
Molar

æ ö
N2 (a) K1 = ç 1 ÷ (b) K1 = K22
(c) çK ÷
è 2ø
H2
1
(c) K1 = (d) K1 = (K2)0
time K2
Equilibrium 23

4. PCl5 is dissociating 50% at 250°C at a total If the KP of the reaction is 1.1 × 10–3, calculate
pressure of P atm. If equilibrium constant is Kp, the amount of nitric oxide produced in terms of
then which of the following relation is numerically volume percent.
correct – (a) 1.67 % (b) 1.23 %
(a) Kp = 3P (b) P = 3Kp (c) 1.33 % (d) 1.54%
2 KP 2P 10. At a certain temperature and 2 atm pressure
(c) P = (d) Kp = equilibrium constant (KP) is 25 for the reaction
3 3
ˆˆ† SO3 ( g ) + NO ( g )
SO2 ( g ) + NO 2 ( g ) ‡ˆˆ
5. 1.0 mole of AB5 (g) is placed in a closed
container under one atmosphere and at 300K. It Initially if we take 2 moles of each of the four
is heated to 600K, when 20% by mass of it gases and 2 moles of inert gas, what would be
dissociates as the equilibrium partial pressure of NO2?
(a) 1.33 atm
AB5 (g) ¾
¾® AB(g) + 2 B2 (g).
(b) 0.1665 atm
The resultant pressure is (c) 0.133 atm
(a) 1.2 atm (b) 2.4 atm (d) None of these
(c) 1.4 atm (d) 2.8 atm 11. The equilibrium constant for a reaction,
6. For the reaction C(s) + CO 2(g) ® 2CO(g), ˆˆ† 2NO(g) is 4 × 10–4 at 2000
N2(g) + O2(g) ‡ˆˆ
Kp = 63 atm at 1000 K. If at equilibrium : PCO = 10 K. In the presence of catalyst, the equilibrium is
PCO2, then the total pressure of the gases at attained 10 times faster. The equilibrium constant
equilibrium is in presence of catalyst at 2000 K is :
(a) 6.3 atm (b) 6.93 atm (a) 10 × 10–4 (b) 4 × 10–2
(c) 0.63 atm (d) 0.693 atm (c) 4 × 10 –4 (d) 40 × 10–4
7. The value of Kp for the equilibrium reaction 12. For the manufacture of ammonia by the reaction
N 2 O4 (g) ƒ 2NO2 (g) is 2. ˆˆ† 2NH 3 + 2 kcal
N 2 + 3H 2 ‡ˆˆ
The percentage dissociation of N2O4(g) at a
pressure of 0.5 atm is the favourable conditions are
(a) 25 (b) 88 (a) low temperature, low pressure and catalyst
(c) 50 (d) 71 (b) low temperature, high pressure and catalyst
8. For the decomposition of the compound, (c) high temperature, low pressure and catalyst
represented as (d) high temperature, high pressure and catalyst
13. For the reaction
NH2COONH4(s) ƒ2NH3(g) + CO2(g)
the Kp = 2.9 × 10–5 atm3. If the reaction is started ˆˆ† XO (s ) + CO 2 ( g ) ,
XCO3 ( s ) ‡ˆˆ
with 1 mol of the compound, the total pressure at
Kp = 1.642 atm at 727°C. If 4 moles of XCO3(s)
equilibrium would be :
was put into a 50 litre container and heated to
(a) 1.94 × 10–2 atm (b) 5.82 × 10–2 atm
727°C. What mole percent of the XCO3 remains
(c) 7.66 × 10–2 atm (d) 38.8 × 10–2 atm
unreacted at equilibrium?
9. Air containing 79% of nitrogen and 21% of oxy-
(a) 20
gen by volume is heated at 2200 K and 1 atm
(b) 25
until equilibrium is established according to the
(c) 50
reaction
(d) None of these
ˆˆ† 2NO(g)
N2(g) + O2(g) ‡ˆˆ
 24 CHEMISTRY

14. The figure shows the change in concentration 19. Among the following, the correct statement is:
of species A and B as a function of time. (a) pH decreases when solid ammonium
The equilibrium constant Kc for the reaction chloride is added to a dilute aqueous
solution of NH3
(b) pH decreases when solid sodium acetate is
added to a dilute aqueous solution of acetic
0.4 M B
acid
0.3 M (c) pH decreases when solid NaCl is added to
Concentration

a dilute aqueous solution of NaOH

0.2 M (d) pH decreases when solid sodium oxalate is
added to a dilute aqueous solution of oxalic
0.1 M A acid
20. Solubility products of CuI and Ag2CrO4 have
Time almost the same value (~ 4 ´ 10-12). The ratio of
solubilities of the two salts (CuI:Ag2CrO4) is
closest to
ˆˆ† 2B ( g ) is :
A ( g ) ‡ˆˆ (a) 0.01 (b) 0.02
(a) Kc > 1 (b) K < 1 (c) 0.03 (d) 0.10
(c) K = 1 (d) data insufficient Numeric Value Answer
15. The degree of dissociation of acetic acid in a 0.1
21. In the reaction PCl5 ƒ PCl3 + Cl2, the amount of
M solution is 1.32 × 10 –2 . Find out the each PCl5, PCl3 and Cl2 is 2 mole at equilibrium and
dissociation constant of the acid.
total pressure is 3 atm. What will be the value of Kp?
(a) 1.50 × 10–4 (b) 1.80 × 10–16
22. For the reaction : SnO2(s)+2H2(g) ƒ
(c) 1.76 × 10–5 (d) 1.2 × 10–3 2H2O(g) + Sn(s)
16. At 25° C, the solubility product of Hg2Cl2 in The value of 2 × KP at 900 K where the equilibrium
water is 3.2 × 10–17 mol3 dm–9. What is the steam hydrogen mixture was 45% H2 by volume is
solubility of Hg2Cl2 in water at 25° C?
23. For a reaction X + Y ƒ 2Z, 1.0 mol of X, 1.5 mol
(a) 1.2 × 10–12 M (b) 3.0 × 10–6 M
(c) 2 × 10 M–6 (d) 1.2 × 10–16 M of Y and 0.5 mol of Z were taken in a 1 L vessel and
17. Solid AgNO3 is slowly added to a solution allowed to react. At equilibrium, the concentration
containing each of 0.01 M NaCl and 0.001 M NaBr. of Z was 1.0 mol L–1. The equilibrium constant of
What will be the concentration of Cl– ions in x
the reaction is . The value of x is _________.
solution when AgBr will just start to precipitate? 15
24. A soft drink was bottled with a partial prssure
Ksp (AgBr) = 3.6 × 10–13, Ksp (AgCl) = 1.8 × 10–10.
of CO 2 of 3 bar over the liquid at room
(a) 1.8 × 10–7 (b) 3.6 × 10–10
temperature. The partial pressure of CO2 over
(c) 0.01 (d) 2 × 10–4
the solution approaches a value of 30 bar when
18. A buffered solution is prepared by mixing equal
44g of CO2 is dissolved in 1 kg of water at room
volumes of
temperature. The approximate pH of the soft
(a) 0.2 M NH4OH and 0.1 M HCl
drink is ______ × 10–1.
(b) 0.2 M NH4OH and 0.2 M HCl
(First dissociation constant of
(c) 0.2 M NaOH and 0.1 M CH3COOH
H2CO3 = 4.0 × 10–7; log 2 = 0.3; density of the
(d) 0.1 M NH4OH and 0.2 M HCl
soft drink = 1g mL–1)
Equilibrium 25

25. If the solubility product of
AB2 is 3.20 × 10–11M3, then the solubility of AB2
in pure water is ______ × 10–4 mol L–1.
[Assuming that neither kind of ion reacts with
water]
26. Calculate the pH at the equivalence point when a
solution of 0.01 M CH3COOH is titrated with a
solution of 0.01 M NaOH. pKa of CH3COOH is 4.74.
27. A buffer solution is prepared by mixing 0.1 M
ammonia and 1.0 M ammonium chloride. At 298 K,
the pKb of NH4OH is 5.0. The pH of the buffer is
28. Calculate the pOH of a solution at 25°C that
contains 1× 10– 10 M of hydronium ions, i.e.
H3O+.
29. Calculate pH of a resultant solution of 25 mL of
0.1 M HCl, 50 mL of 0.02 M HNO3 and 25 mL of
0.1 M NaOH.
30. 0.1 M NaOH is titrated with 0.1 M HA till the end
point; Ka for HA is 5.6 × 10–6 and degree of
hydrolysis is less compared to 1. Calculate pH
of the resulting solution at the end point.

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

8
REDOX REACTIONS

MCQs with One Correct Answer 4. Oxidation numbers of chlorine atoms in CaOCl2
are
1. Which reaction involves neither oxidation nor
(a) 0, 0
reduction?
(b) –1, –1
(a) CrO 24 - ¾¾
® Cr2O 72 - (c) –1, +1
(d) None of these
(b) Cr ¾¾
® CrCl3 5. In the reaction

3Br2 + 6CO 32 - + 3H 2 O ® 5Br - + BrO3– + 6HCO 3-

(c) ® Na +
Na ¾¾
(a) bromine is oxidised and carbonate is
(d) 2S2 O32 - ¾¾
® S4 O 62 - reduced.
2. In the reaction (b) bromine is reduced and water is oxidised
(c) bromine is neither reduced nor oxidised
Cr2 O 72 - + 14 H + + 6 I - ¾
¾® 2Cr 3+ + 7 H 2 O + 3I 2
(d) bromine is both reduced and oxidised
Which element is reduced 6. The oxidation state of the most electronegative
(a) I (b) O element in the products of the reaction between
(c) H (d) Cr BaO2 and H2SO4 are
3. Which one of the following reaction involves (a) 0 and –1 (b) –1 and – 2
oxidation-reduction ? (c) – 2 and 0 (d) – 2 and +1
(a) H 2 + Br2 ® 2HBr 7. Which of the following substances acts as an
(b) oxidising as well as a reducing agent?
NaBr + HCl ® NaCl + HBr
(a) Na 2O (b) SnCl2
(c) HBr + AgNO3 ® AgBr + HNO3
(c) Na 2O 2 (d) NaNO 2
(d) 2NaOH + H 2SO4 ® Na 2SO4 + 2H 2O
Redox Reactions 27

8. Which of the following reactions depicts the (a) (i), (ii) and (iii) (b) (i) and (ii)
oxidising property of SO2 ? (c) (i) only (d) (ii) and (iii)
(a) SO 2 + H 2 O ® H 2 SO 3 13.
–
E Values of some redox couples are given
(b) 2H 2S + SO 2 ® 3S + 2H 2O below. On the basis of these values choose the
(c) Cl 2 + SO 2 ® SO 2 Cl 2 correct option.
–
(d) 2MnO 4– + 5SO 2 + 2H 2 O ® E values : Br2/Br – = + 1.90; Ag+ /Ag(s) = + 0.80
Cu2+ /Cu(s) = + 0.34; I2(s) /I– = 0.54
5SO 24– + 2Mn 2+ + 4H +
(a) Cu will reduce Br – (b) Cu will reduce Ag
9. The most powerful oxidizing agent from the
(c) Cu will reduce I – (d) Cu will reduce Br2
following is
14. Standard reduction electrode potentials of three
(a) H3BO3 (b) HPO3
metals A, B & C are respectively + 0.5 V, – 3.0 V &
(c) H3PO4 (d) H2SO4 –1.2 V. The reducing powers of these metals are
10. Which one of the following reactions involves (a) A > B > C (b) C > B > A
disproportionation? (c) A > C > B (d) B > C > A
(a) 2H2SO4 + Cu ® CuSO4 + 2H2O + SO2 15. The formal oxidation numbers of Cr and Cl in the
(b) As2O3 + 3H2S ® As2S3 + 3H2O ions Cr2O72– and ClO3–, respectively are
(c) 2KOH + Cl2 ® KCl + KOCl + H2O (a) + 6 and +7 (b) +7 and +5
(d) Ca3P2 + 6H2O ® 3Ca(OH)2 + 2PH3 (c) +6 and +5 (d) +8 and +7
11. In the standardization of Na2S2O3 using K2Cr2O7
Numeric Value Answer
by iodometry, the equivalent weight of K2 Cr2 O7 is
(a) Molecular weight/2 16. In the chemical reaction,
(b) Molecular weight/6 K 2 Cr2 O7 + X H 2SO 4 + YSO2 ®
(c) Molecular weight/3
K 2SO4 + Cr2 (SO4 )3 + Z H 2O
(d) Same as molecular weight
12. Which of the following statements are correct X, Y and Z is
concerning redox properties? 17. Atomic number of an element is 22. The highest
(i) A metal M for which E° for the half life O.S. exhibited by it in its compounds is
reaction M n+ + ne – ‡ˆˆ ˆˆ† M is very 18. The number of electrons required to balance the
following equation
negative will be a good reducing agent.
(ii) The oxidizing power of the halogens NO3– + 4H + + e – ¾¾
® 2H 2 O + NO is -
decreases from chlorine to iodine.
19. The O.N. of nitrogen in NO3- is
(iii) The reducing power of hydrogen halides
increases from hydrogen chloride to -
20. The oxidation state of iodine in H4 IO6 is
hydrogen iodide

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

9
HYDROGEN

MCQs with One Correct Answer 4. Which hydride is an ionic hydride?

1. When same amount of zinc is treated separately (a) H 2S (b) TiH 1.73
with excess of sulphuric acid and excess of (c) NH 3 (d) NaH
sodium hydroxide solution the ratio of volumes 5. The reagent commonly used to determine
of hydrogen evolved is hardness of water titrimetrically is
(a) 1 : 1 (b) 1 : 2 (a) oxalic acid
(c) 2 : 1 (d) 9 : 4 (b) sodium thiosulphate
2. 2 g of aluminium is treated separately with excess (c) sodium citrate
of dilute H2SO4 and excess of NaOH. The ratio (d) disodium salt of EDTA
of the volumes of hydrogen evolved is 6. Pure water can be obtained from sea water by
(a) 2 : 3 (b) 1 : 1 (a) centrifugation
(c) 2 : 1 (d) 1 : 2 (b) plasmolysis
3. Consider the following statements : (c) reverse osmosis
1. Atomic hydrogen is obtained by passing (d) sedimentation
hydrogen through an electric arc. 7. Chemical A is used for water softening to remove
2. Hydrogen gas will not reduce heated temporary hardness. A reacts with sodium
aluminium oxide. carbonate to generate caustic soda. When CO2
3. Finely divided palladium adsorbs large is bubbled through a solution of A, it turns
volume of hydrogen gas cloudy. What is the chemical formula of A.
4. Pure nascent hydrogen is best obtained by (a) CaCO3
reacting Na with C2H5OH (b) CaO
Which of the above statements is/are correct ? (c) Ca(OH)2
(a) only 1 (b) only 2 (d) Ca(HCO3)2
(c) 1, 2 and 3 (d) 2, 3 and 4
Hydrogen 29
8. Which of the following statements do not define 17. A, 6 volume sample of H2O2
the characteristic property of water “Water is a (a) will contain 6% V/V of H2O2
universal solvent” (b) will contain 6% W/V of H2O2
(a) It can dissolve maximum number of compounds (c) would give 6 volumes of oxygen per unit
(b) It has very low dielectric constant volume of H2O2 sample at STP
(c) It has high liquid range (d) would give 6 volumes of oxygen per unit
(d) None of these weight of H2O2 sample at STP
9. The amount of H2O2 present in 1 litre of 1.5 N 18. In water-gas shift reaction, hydrogen gas is
H2O2 solution, is produced from the reaction of steam with
(a) 25.5 g (b) 3.0 g (a) methane (b) coke
(c) 8.0 g (d) 2.5 g (c) carbon monoxide (d) carbon dioxide
10. The volume strength of 1.5 N H 2O2 solution is 19. Treatment with lime can remove hardness of
(a) 8.4 (b) 8.0 water caused by
(c) 4.8 (d) 3.0 (a) CaCl2 (b) CaSO4
11. In lab H2O2 is prepared by (c) Ca(HCO3)2 (d) CaCO3
(a) cold H2SO4 + BaO2 20. Permanent hardness of water can be removed
(b) HCl + BaO2 by
(c) conc. H2SO4 + Na2O2 (a) heating
(d) H2 + O2 (b) treating with sodium acetate (CH3CO2Na)
12. The strength in volumes of a solution containing (c) treating with Ca(HCO3)2
30.36 g/L of H2O2 is (d) treatment with sodium hexametaphosphate
(a) 10 V (b) 5 V (Na6P6O18)
(c) 20 V (d) None of these Numeric Value Answer
13. 20 Volume H2O2 solution has a strength of about
(a) 30% (b) 6% 21. At room temperature, the ratio of ortho to para
(c) 3% (d) 10% hydrogen is n : 1. what is the value of n?
14. H2O2 is a 22. If 1 L of hard water (contains CaSO4) requires
(a) weak acid (b) weak base 0.286 g of washing soda (Na2CO3 . 10H2O) for
(c) neutral (d) None of these softening process. What is the hardness of
15. H2O2 ® 2H+ + O2 + 2e– ; E° = –0.68 V. This water in ppm?
equation represents which of the following 23. 3 Samples of H2O2 are labelled as 10 vol., 15 vol.
behaviour of H2O2 ? and 20 vol. 100 mL. of each sample is mixed.
(a) Reducing (b) Oxidising What is the volume strength of resulting
(c) Acidic (d) Catalytic solution?
16. Heavy water reacts respectively with CO2, SO3, 24. Ordinary water contains traces of heavy water.
P2O5 and N2O5 to give the compounds This is about 1part in n ×1000 parts. What is the
(a) D2CO3, D2SO4, D3PO2, DNO2 integer value of n?
(b) D2CO3, D2SO4, D3PO4, DNO2 25. What is the amount of energy released (in KJ)
(c) D2CO3, D2SO3, D3PO4, DNO2 on combustion of 1 g of H2 gas?
(d) D2CO3, D2SO4, D3PO4, DNO3

ANSWER KEY
1 (a) 4 (d) 7 (c) 10 (a) 13 (b) 16 (d) 19 (c) 22 (100) 25 (143)
2 (b) 5 (d) 8 (b) 11 (a) 14 (a) 17 (c) 20 (d) 23 (15)
3 (c) 6 (c) 9 (a) 12 (a) 15 (a) 18 (c) 21 (3) 24 (6)
 30 CHEMISTRY

10
THE S-BLOCK ELEMENT

MCQs with One Correct Answer 4. The stability of the following alkali metal
chlorides follows the order
1. Which of the following is not correct ?
(a) LiCl > KCl > NaCl > CsCl
heat (b) CsCl > KCl > NaCl > LiCl
(a) 2Li 2 O ¾¾¾® Li 2 O 2 + 2Li
673K
(c) NaCl > KCl > LiCl > CsCl
heat (d) KCl > CsCl > NaCl > LiCl
(b) 2K 2 O ¾¾¾® K 2 O 2 + 2K
673K 5. Sodium sulphate is soluble in water whereas
heat barium sulphate is sparingly soluble because
(c) 2Na 2 O ¾¾¾® Na 2 O 2 + 2Na (a) the hydration energy of sodium sulphate is
673K
more than its lattice energy
heat
(d) 2Rb 2 O ¾¾¾® Rb 2 O 2 + 2Rb (b) the lattice energy of sodium sulphate is
673K
equal to its hydration energy
2. An inorganic compound which on heating first
(c) the hydration energy of sodium sulphate is
melts, then solidifies and liberates O2 gas, the
less than its lattice energy
inorganic compound is
(d) None of these
(a) Al2O3 (b) KMnO4
6. Sodium thiosulphate, Na2S2O3. 5H2O is used in
(c) MnO2 (d) KClO3
photography to
3. The element which on burning in air gives
(a) reduce the silver bromide grains to metallic
peroxide is
silver
(a) lithium
(b) convert the metallic silver to silver salt
(b) sodium
(c) remove undecomposed AgBr as soluble
(c) rubidium
silver thiosulphate complex.
(d) caesium
(d) remove reduced silver
The s-Block Element 31

7. Li has the maximum value of ionisation potential 13. Which one of the following salts does not impart
among alkali metals i.e. lithium has the minimum colour to the flame ?
tendency to ionise to give Li+ ion. Thus, in aq. (a) KI (b) LiCl
solution lithium is (c) CaCl2 (d) MgCl2
(a) Strongest reducing agent 14. Lithopone is
(b) Poorest reducing agent (a) BaO + ZnSO4
(c) Strongest oxidising agent (b) BaS + ZnSO4
(d) Poorest oxidising agent (c) ZnS + BaSO4
8. Which of the following statements about Na2O2 (d) ZnO + BaSO4
is not correct? 15. Philosopher's wool on heating with BaO at
(a) It is diamagnetic in nature 1100°C produces:
(b) It is derivative of H2O2 (a) Ba + ZnCl2
(b) BaCdO2
(c) Na 2O2 oxidises Cr 3+ to CrO24 - in acid
(c) BaZnO2
medium. (d) BaO2+ Zn
(d) It is the super oxide of sodium 16. Metallic magnesium is prepared by
9. Causticisation is a process in which (a) reduction of MgO by coke
(a) soap is prepared by treating vegetable oils (b) electrolysis of aqueous solution of
with caustic soda Mg(NO3)2
(b) paper is formed (c) displacement of Mg by iron from MgSO4
(c) petroleum is treated with caustic soda solution
before fractional distillation (d) electrolysis of molten MgCl2
(d) caustic soda is manufactured by treating 17. Which of the following sulphates have the
sodium carbonate with lime. highest solubility in water?
more CO (a) MgSO4 (b) BaSO4
10. KO2 + CO2 + H2O ¾¾ ¾ ¾¾ 2®
[X] + [Y]
(c) CaSO4 (d) BeSO4
Products [X] and [Y] are respectively :
18. Which of the following metal carbonate is
(a) K2CO3, O2
decomposed on heating?
(b) KHCO3, O2
(a) MgCO3 (b) Na2CO3
(c) KOH, K2CO3
(c) K2CO3 (d) Rb2CO3
(d) KHCO3, H2O
19. Which of the following has correct increasing
11. Which property of sodium is being used in street
basic strength?
lights ?
(a) MgO < BeO < CaO < BaO
(a) It shows photoelectric effect
(b) BeO < MgO < CaO < BaO
(b) It has low melting point
(c) BaO < CaO < MgO < BeO
(c) Sodium atom emits photons in the yellow
(d) CaO < BaO < BeO < MgO
region of visible spectrum, due to
20. Thermal stability of alkaline earth metal
electrically stimulated transitions
carbonates decreases in order
(d) Sodium vapours show golden colour
(a) BaCO3 > SrCO3 > CaCO3 > MgCO3
12. Which of th e following compounds are
(b) BaCO3 > SrCO3 > MgCO3 > CaCO3
paramagnetic in nature?
(c) CaCO3 > SrCO3 > MgCO3 > BaCO3
(a) KO2 (b) K2O2
(d) None of these
(c) Na2O2 (d) Rb2O2
 32 CHEMISTRY

21. Chemical A is used for water softening to remove 24. Equimolar solutions of the following compounds
temporaryhardness. Areacts with Na2CO3 to generate are prepared separately in water. Which will have
caustic soda. When CO2 is bubbled through A, it turns the lowest pH value ?
cloudly. What is the chemical formula of A (a) BeCl2 (b) SrCl2
(a) CaCO3 (b) CaO (c) CaCl2 (d) MgCl2
(c) Ca(OH)2 (d) Ca(HCO3)2 25. 100 mL of tap water containing Ca(HCO3)2 was
22. Which of the following is used as a scavenger in titrated with N/50 HCl with methyl orange as
metallurgy? indicator. If 30 mL of HCl were required, calculate
(a) Be (b) Mg the temporary hardness as parts of CaCO3 per
(c) Ca (d) Sr 106 parts of water.
23. Hesenclever ’s process is a method for the (a) 150 ppm (b) 300 ppm
manufacture of (c) 450 ppm (d) 600 ppm
(a) NaOH (b) HNO3
(c) H2SO4 (d) Bleaching powder

ANSWER KEY
1 (a) 4 (d) 7 (a) 10 (b) 13 (d) 16 (d) 19 (b) 22 (c) 25 (b)
2 (d) 5 (a) 8 (d) 11 (c) 14 (c) 17 (d) 20 (a) 23 (d)
3 (b) 6 (c) 9 (d) 12 (a) 15 (c) 18 (a) 21 (c) 24 (a)
 THE p-BLOCK ELEMENTS 11
(GROUPS 13 AND 14)

MCQs with One Correct Answer (a) as a catalyst

(b) to make the fused mixture very conducting
1. H3BO3 on heating up to 373 K yields
(c) to increase the temperature of the melt.
(a) boric anhydride (d) to decrease the rate of oxidation of carbon
(b) orthoboric acid at the anode.
(c) metaboric acid
5. The dissolution of Al(OH)3 by a solution of
(d) tetraboric acid
NaOH results in the formation of
2. Aluminium chloride exists as dimer, (Al2Cl6) in
solid state as well as in solution of non-polar (a) [Al(H 2 O) 4 (OH )]2 +
solvents such as benzene. When dissolved in
(b) [Al(H 2 O) 2 (OH) 4 ]-
water, it gives
(a) [Al(OH) 6 ]3- + 3HCl (c) [Al(H 2O)3 (OH )3 ]
3+ -
(b) [ Al( H 2 O ) 6 ] + 3Cl (d) [Al(H 2 O) 6 (OH) 3 ]
3+
(c) Al + 3Cl -
R.T.
(d) Al2 O3 + 6HCl 6. BX3 + NH3 ¾¾¾
® BX3.NH3 + Heat of
3. In reaction adduct formation (DH)
BF3 + 3LiBH4 ® 3LiF + X ; X is The numerical value of DH is found to be
(a) B4H10 (b) B2H6 maximum for :
(c) BH3 (d) B3H8 (a) BF3
4. The role of fluorspar ( CaF2) which is added in (b) BCl3
small quantities in the electrolytic reduction of (c) BBr3
alumina dissolved in fused cryolite (Na3AlF6) is (d) BI3
 34 CHEMISTRY

7. When aluminium is heated in atomoshere of 13. PbO2 is obtained from

nitrogen it forms : (a) the reaction of PbO with HCl
(a) AlN (b) Al2N (b) thermal decomposition of Pb(NO 3 )2 at
(c) Al3N (d) Al2N3 200 °C
8. Diborane is prepared on large scale by (c) the reaction of Pb3O4 with HNO3
450 K (d) the reaction of Pb with air at room
(a) 2BF3 (g) + 6LiH(s) ¾¾¾®
temperature
B2 H6 (g) + 6LiF(s) 14. An allotrope of carbon which exhibits only two
types of C - C bond distance of 143.5 pm and
450 K
(b) 2BCI3 (g) + 6LiH(s) ¾¾¾® 138.3 pm, is
(a) charcoal (b) graphite
B2 H 6 (g) + 6LiCl(s)
(c) diamond (d) fullerene
450 K
(c) 2BF3 (g) + 6NaH ¾¾¾® 15. A solid element (symbol Y) conducts electricity
B2 H 6 + 6NaF
and forms two chlorides YCln (colourless
450 K
(d) 2BCl3 + 6NaH ¾¾¾® B2 H 6 + 6NaCl
volatile liquid) and YCl n - 2 (a colourless solid).
9. Silicon dioxide is formed by the reaction of
To which one of the following groups of the
(a) SiCl4 + H2O
periodic table does Y belong?
(b) SiO2 + HF
(a) 13 (b) 14
(c) SiO2 + NaOH
(c) 15 (d) 16
(d) SiCl4 + NaOH
16. The reducing power of divalent species
10. SiF4 gets hydrolysed giving........
decreases in the order
(a) SiO2 (b) Si(OH)2F2
(a) Ge > Sn > Pb
(c) H2SiF6 (d) Si(OH)4
(b) Sn > Ge > Pb
11. Soldiers of Napolean army while at alps during
(c) Pb > Sn > Ge
freezing winter suffered a serious problem as
(d) None of these
regards to the tin buttons of their uniforms.
17. The gas evolved on heating CaF2 and SiO2
White metallic tin buttons got converted to grey
with concentrated H2SO4, on hydrolysis gives
powder. This transformation is related to
a white gelatinous precipitate. The precipitate
(a) a change in the partial pressure of oxygen
is
in the air
(a) hydrofluorosilicic acid
(b) a change in the crystalline structure of tin
(b) silica gel
(c) an interaction with nitrogen of the air at
(c) silicic acid
very low temperatures
(d) calciumfluorosilicate
(d) an interaction with water vapours contained
18. On heating Pb(NO3)2, the products formed are:
in the humid air
(a) PbO, N2, O2 (b) Pb (NO2)2, O2
12. The tendency of X in BX3 (X = F, Cl, OMe, NMe)
(c) PbO, NO2, O2 (d) Pb, N2, O2
to form a p - bond with boron follows the order
19. The product of the following reaction are:
(a) BCl3 < BF3 < B(OMe)3 < B(NMe2)3
D
(b) BF3 < BCl3 < B(OMe)3 < B(NMe2)3 SiO2 + C ¾¾® Pr oducts
(c) BCl3 < B(NMe2)3 < B(OMe)3 < BF3 (a) SiC and CO2 (b) SiO and CO
(d) BCl3 < BF3 < B(NMe2)3 < B(OMe)3 (c) SiC and CO (d) Si and CO
The p-Block Elements (Groups 13 and 14) 35

20. What is not correct about carbon monoxide ?
(a) Carbon in CO is sp hybridised and is linear
molecule
(b) CO is a ligand because it has a lone pair of
electrons on the carbon atom
(c) CO is the reducing agent in metallurgy of
iron
(d) CO has the structure C = O
Numeric Value Answer
21. In aluminates, the coordination number of Al is
22. How many oxides of the following are non-
amphoteric in nature?
CO2, SiO2, SnO2 and CaO
23. How many orbitals of boron are involved in
hybridisation in B2H6?
24. In a molecule of C60 Buckminsterfullerene, what
is the sum of six-membered and five-membered
rings?
25. What is the sum for the molecular masses of
constituents of producer gas?

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

ORGANIC CHEMISTRY- 12
SOME BASIC PRINCIPLES
AND TECHNIQUES

MCQs with One Correct Answer (a) III > II > I (b) II > I > III
(c) II > III > I (d) I > II > III
1. The IUPAC name of
3. Which of the following will show tautomerism ?
NH2 COOH
O

COOH NH2 (a)

(a) o, o¢ – diamino – o, o¢ – dicarboxy biphenyl
(b) 6, 6¢ – diamino diphenyl – 2, 2¢ – O
dicarboxylic acid
(c) diamino dicarboxy biphenyl (b) O = =O
(d) none of these
O
2. The order of stability of the following tautomeric
compounds is :
OH O (c)
| ||
CH 2 = C - CH 2 - C - CH 3
I O
O O
|| ||
CH3 - C- CH 2 - C- CH 3 O
II
OH O
| || (d)
CH 3 - C = CH - C - CH 3
III O
Organic Chemistry-Some Basic Principles and Techniques 37

4. In the given conformation, if C2 is rotated about is in the order of :

C2 – C3 bond anticlockwise by an angle of 120º (a) (B) > (A) > (C) (b) (C) > (B) > (A)
then the conformation obtained is (c) (A) > (C) > (B) (d) (A) > (B) > (C)
4 7. Chlorine in vinyl chloride is less reactive because
CH3
H H (a) sp2 - hybridised carbon has more acidic
character than sp3 - hybridised carbon
3
2 (b) C - Cl bond develops partial double bond
H H character
(c) of resonance
CH31 (d) All are correct
(a) fully eclipsed conformation
8. Most stable carbocation is
(b) partially eclipsed conformation
(a) p—NO2—C6H4—CH2+
(c) gauche conformation
(b) C6H5CH2+
(d) staggered conformation
(c) p—Cl—C6H4—CH2+
5. Indicate whether each of the following pairs are
(d) p–CH3O—C6H4—CH2+
identical or not?
9. Rate of the reaction
F O O –
R – C + Nu R – C + Z is fastest
Br H F Z Nu
CH2Br when Z is
(I) H3C
H CH3 (a) OC2H5 (b) NH2
F
H (c) Cl (d) OCOCH3
10. The replacement of chlorine of chlorobenzene
Cl to give phenol requires drastic conditions, but
H H
CH2CH3 Cl the chlorine of 2,4-dinitrochlorobenzene is
(II) Cl
Cl readily replaced since,
CH3 H CH3 CH CH
Cl 2 3 (a) nitro groups make the aromatic ring electron
rich at ortho/para positions
CH3 CH3 (b) nitro groups withdraw electrons from the
meta position of the aromatic ring
H Br Br H
(c) nitro groups donate electrons at meta
(III) CH H H CH3 position
3
(d) nitro groups withdraw electrons from ortho/
Br Br
para positions of the aromatic ring
(a) I-enantiomers; II-diastereomers; III- 11. CH 3 Br + Nu - ¾ ¾® CH 3 - Nu + Br -
enantiomers The decreasing order of the rate of the above
(b) I-identical; II-enantiomers; III-enantiomers reaction with nucleophiles (Nu–) A to D is
(c) I-enantiomers; II-diastereomers;III-identical [Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–]
(d) I-enantiomers; II-identical; III-identical (a) A > B > C > D
6. Base strength of : (b) B > D > C > A
(A) H3CCH 2- , (B) H 2C = CH - and (c) D > C > A > B
(d) D > C > B > A
(C) H - C º C -
 38 CHEMISTRY

12. In the below mentioned compounds the

decreasing order of reactivity towards 2
O O
electrophilic substitution is ..
..
– 1
(i) (ii) OOC
3
SO3–
OCH3 CH3 4

(a) 3 > 4 > 1 > 2 (b) 4 > 3 > 2 > 1

(iii) (iv) (c) 4 > 3 > 1 > 2 (d) 3 > 4 > 2 > 1
CF3 16. The major product of the following reaction is –
(a) (iv) > (i) > (ii) > (iii) Me Br
(b) (ii) > (iii) > (i) > (iv) F
– +
(c) (iii) > (i) > (iv) > (ii) Ph S Na
¾¾¾¾¾¾¾¾ ®
(d) (i) > (ii) > (iii) > (iv) dimethylformamide
13. The correct order of stability of the following NO2
carbanions is Me SPh
Me SPh
- – F
F
(i) RCH 2 (ii)
(a) (b)
– – NO2
(iii) (iv) NO2

(a) III > IV > I > II (b) I > II > III > IV Me Br
Me Br
(c) I > III > II > IV (d) IV > III > II > I SPh
SPh
14. Which of the following is not a resonance form
of the enolate ion formed in the following acid (c) (d)
base equilibrium? NO2
O 17.
NO2

CH 3 CH3 CH3 CH3

+ NaOH CH3O NO2
O
H Cl CH3
O O–
on hydrolysis, in aqueous acetone will give
CH 3 CH 2 (i)
:

(a) (b)
O O CH3 CH3 CH 3
O– O–
CH3O NO2

CH 3 CH 3 H OH CH3
(c) (d)
(ii)
O O–
15. The structure drawn below has four nucleophilic CH3 CH3 CH 3
sites, arrange them in order of decreasing CH3O NO2
nucleophilicity.
OH H CH3
Organic Chemistry-Some Basic Principles and Techniques 39

(iii)
CH3 CH3 CH 3 (b) S
CH
CH3O NO2 S
H
H CH3 OH
(a) Mixture of (i) and (ii) (c) N
CH
(b) Mixture of (i) and (iii) N
(c) Only (iii) H
(d) Only (i)
H
(d) O
18. H H CH
x z N

y H
22.
+
H H O –H OH
Arrange the (C – H) bonds x, y and z in || CH3 CH3
decreasing order of their bond dissociation CH3— C — N CH3— C — N
CH3 + CH3
energies in homolysis. (I) (II)
(a) y > x > z (b) z > x > y
(c) z > y > x (d) y > z > x OH
19. + CH3
CH3— C N
CH3
NH; N (III)
, The correct stability order of the given canonical
O structure is :
(x) (y) (z) (a) I > II > III (b) III > I > II
The correct order of decreasing basic strengths (c) I > III > II (d) II > III > I
of x, y and z is: 23. X and Y
(a) x > y > z (b) x > z > y H Cl
H H3C H
(c) y > x > z (d) y > z > x Cl
Cl
20. Arrange the following (w, x, y, z) in decreasing
H3C H CH3
order of their boiling points: CH3 Cl
X Y
are
N N (a) enantiomers
OH O CH3 (b) diastereomers
H
(c) constitutional isomers
(w) (x) (y) (z)
(d) conformers
(a) w > x > z > y (b) w > x > y > z
24. The higher stabilities of tert-butyl cation over
(c) w > z > y > x (d) w > z > x > y
iso-propyl cation and trans-2- butene over propene,
21. Which of the following compounds has most
respectively, are due to orbital interactions involving.
acidic hydrogen?
(a) s ® p and s ® p*
(b) s ® vacant p and s ® p
(a) O (c) s ® s* and s ® p
CH
O (d) s ® vacant p and s ® p*
 40 CHEMISTRY

25. The most acidic proton and the strongest, nu- 28. IUPAC name of the following compound
cleophilic nitrogen in the following compound
O
O
b c
N N CH3
a H H
HO
N
H is
respectively, are
(a) 1 -hydroxycyclohex-4-en-3-one
(a) Na – H; Nb (b) Nb – H; Nc
a c
(b) 1 -hydroxycyclohex-3-en-5-one
(c) N – H; N (d) Nc – H; Na
(c) 3-hydroxycyclohex-5-en-1-one
26. The chlorine atom of the following compound
c (d) 5-hydroxycyclohex-2-en-1 one
Cl 29. The absolute configurations of the following
d b compounds
Cl Cl
H CH2SH HO H
O Cl
a H3C CH2OH H3C CH2SH
that reacts most readily with AgNO3 to give a respectively, are
precipitate is (a) R and R (b) S and S
(a) Cla (b) Clb (c) R and S (d) S and R
(c) Cl c (d) Cld
27. The lower stability of ethyl anion compared to a
30. O ,
methyl anion and the higher stability of ethyl
radical compared to methyl radical, respectively, b +
H
are due to c ¾¾¾ ®
(a) + I- effect of the methyl group in ethyl anion N
s ® p-orbital conjugation in ethyl radical d
(b) – I - effect of the methyl group in ethyl CH3
anion and s ® s* p-conjugation in ethyl
radical Identify the site, where attack of H+ is most
(c) + I effect of the methyl group in both cases favourable.
(d) + I- effect of the methyl group in ethyl anion (a) a (b) b
and s ® s* conjugation in ethyl radical. (c) c (d) d

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

MCQs with One Correct Answer (a) I > III > II > IV (b) IV > II > I >III
(c) III > I > II > IV (d) II > IV > I > III
1. On mixing a certain alkane with chlorine and
5. Which of the following reagents convert
irradiating it with ultraviolet light, it forms only
propene to 1-propanol?
one monochloroalkane. This alkane could be
(a) H2O, H2SO4
(a) pentane (b) isopentane
(b) Aqueous KOH
(c) neopentane (d) propane
(c) MgSO4, NaBH4/H2O
2. cis-2-Butene has higher boiling point than the
(d) B2H6, H2O2, OH–
trans-analog. It is because of
6. When hydrochloric acid gas is treated with
(a) hydrogen bonding in the cis-isomer
propene in presence of benzoyl peroxide, it gives
(b) higher molecular mass of the cis-isomer
(a) 2-Chloropropane
(c) van der Waal forces in the cis-isomer
(b) Allyl chloride
(d) polarity in the cis-isomer.
(c) n-Propyl chloride.
3. 2-Butene can be obtained by the electrolysis
(d) No reaction
of an aqueous solution of
7. 1, 3-Butadiene when treated with Br 2 gives
(a) 1, 2-Dimethylmaleic acid
(a) 1, 4-dibromo-2-butene
(b) 2, 2-Dimethylbutandioic acid
(b) 1, 3-dibromo-2-butene
(c) 3, 3-Dimethylbutandioic acid
(c) 3, 4-dibromo-1-butene
(d) 2, 3-Dimethylbutandioic acid
(d) 2, 3-dibromo-2-butene
4. The decreasing order of reactivity of hydrogen
8. Addition of Br 2 to trans-2-butene would give a
bromide on the following alkenes is
product which is
CH2= CH2, CH3CH2CH = CH2, CH2= CHCl,
(a) chiral (b) meso
I II III
(c) racemic (d) optically active
(CH3)2C = CH2
IV
 42 CHEMISTRY

9. Reaction of hydrogen bromide with propene in 13. In the presence of peroxide, HCl and HI do not
the absence of peroxide is a/an give anti-Markownikoff’s addition of alkenes
(a) free radical addition because:
(b) nucleophilic addition (a) One of the steps is endothermic in HCl
(c) electrophilic substitution and HI
(d) electrophilic addition (b) Both HCl and HI are strong acids
10. One mole of propanone and one mole of (c) HCl is oxidizing and the HI is reducing
formaldehyde are the products of ozonolysis of (d) All the steps are exothermic in HCl and HI
one mole of an alkene. The alkene may be 14. The reaction of
(a) 2-methylpropene
(b) 2, 2-dimethyl-1-butene CH3CH=CH OH with HBr gives
(c) propene
(d) 2-butene
11. The compound shown below (a) CH3CHBrCH2 OH
O NO
2

(b) CH3CH2CHBr OH
can be readily prepared by Friedel-Craft’s
reaction between
(a) benzene and 2-nitrobenzoyl chloride (c) CH3CHBrCH2 Br
(b) benzyl chloride and nitrobenzene
(c) nitrobenzene and benzoyl chloride
(d) benzene and 2-nitrobenzyl chloride (d) CH3CH2CHBr Br
CH2 – CH = CH2
12. 15. Among the following sets, the most stable ionic
species are
on mercuration-demercuration produces the –
+
major product:
(a) and
CH2 – CH – CH3
(a)
OH + +
+
(b) and
CH2 – CH2 – CH2 – OH
(b)
– –

(c) and
CH2 – CH – CH2
(c)
OH OH +
–
(d) and
CH2 – COOH
(d)
Hydrocarbons 43

CH 2 - CH 2 - CH 2 Cl
CH3
|
16. Isopropene, CH 2 = C - CH = CH 2 is treated
(b)
with HCl, the products formed will be a mixture of
CH3 Cl
| |
(i) CH3 - C - CH = CH 2 CH - CH2 - CH3
|
Cl
(c)
CH3
|
(ii) CH 2=C - CH = CH3 CH 2 - CH = CH 2
|
Cl Cl
CH3 (d)
|
(iii) CH 3 - C = CH - CH 2Cl
20. The major product of the following reaction
CH3
| Br 1. excess alc. KOH
(iv) ClCH 2 - C = CH - CH 3 ¾¾¾¾¾¾¾® is
Br 2. NaNH 2
(a) (i) and (iii) (b) (ii) and (iii) Ph
3. H3O+
(c) (ii) and (iv) (d) All the four. H
17. 1, 3-Butadiene is treated with hot KMnO4/NaIO4,
H
the product(s) formed is(are) (a) Ph H (b) Ph
(a) 2HCHO + OHC – CHO Br
(b) 2HCOOH + HOOC–COOH Br Br
(c) 2CO2 + HOOC–COOH H H
(d) 4CO2 (c) Ph (d) Ph
Br H
Ph Ph Ph Ph MeO
21. The addition of HI in the presence of peroxide
18.
catalyst does not follow anti-Markovnikov's rule
Ph
(I) (II) (III) (IV) because
(a) HI is a strong reducing agent.
Order of rate of electrophilic addition reaction
(b) H-I bond is too strong to be broken
with HBr will be
homolytically.
(a) IV > I > III > II (b) I > II > III > IV
(c) I atom combines with H atom to give back HI.
(c) I > III > II > IV (d) IV > I > II > III
CH 2 - CH = CH 2 (d) Iodine atom is not reactive enough to add
across a double bond.
22. Which of the following alcohols cannot be
19. + HCl ¾¾
® X, X is prepared from hydration of an alkene?

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

23. In which of the following reaction, H

Markovnikov’s rule is violated? (c) C H
HBr C
(a) CH3— O — CH CH2 ¾¾¾
CCl4
®
CH3
HBr
(b) CH3— NH — CH CH2 ¾¾¾
CCl4
®
H
H
(c) CH3—S—CH
HBr
CH2 ¾¾¾ ® C H
CCl4 C
HBr
(d) O2N — CH CH2 ¾¾¾
CCl4
®
(d)
24. Me H Me

H 27. Among the following compounds, the decreasing

order of reactivity towards electrophilic
Me H substitution is
Hydrogenation of the above compound in the
presence of poisoned palladium catalyst gives
(a) an optically active compound
(b) an optically inactive compound
CH3 OCH3 CF3
(c) a racemic mixture I II III IV
(d) a diastereomeric mixture (a) III > I > II > IV (b) IV > I > II > III
25. The compound X in the following reaction is (c) I > II > III > IV (d) II > I > III > IV
2 (i) H /Pt 28. Bromination of ethyl benzene in presence of light
CH3C º CCH3 ¾¾¾¾¾
®X gives
(ii) Br2
(a) d-2, 3-Dibromobutane C2 H5
(b) l-2, 3-Dibromobutane Br
(c) dl-2, 3-Dibromobutane (a)
(d) meso-2, 3 Dibromobutane.
C 2 H5

26. C CH
(b)
(i) NaNH , NH H
¾¾¾¾¾¾® 2
(ii) CH Br
3
(A) ¾¾¾¾¾¾ 2
Linder catalyst
® (B) ;
3 Br
Product (B) is: Br

C C CH3 CH - CH 3
(c)

(a) (d) Both (a) and (b)

29. Which of the following would not give 2-
phenylbutane as the major product in a Friedel-
H CH3 Crafts alkylation reaction ?
(a) 1-butene + HF
C C
(b) 2-butanol + H2SO4
(b)
H (c) Butanoyl chloride + AlCl3 then Zn, HCl
(d) Butyl chloride + AlCl3
Hydrocarbons 45

30. In the following reaction, P gives two products 33. How many number of moles of H2 is used for
Q and R, each in 40% yield the complete hydrogenation of the given
compound in the presence of a metal catalyst?
1. O3
OMe ¾¾¾¾¾® Q + R Me CN
2. Zn, H2O

40% 40% Me CN
P
(MW = 210) 34. Consider the following reaction scheme
If the reaction is carried out with 420 mg of P.
the reaction yields 108.8 mg of Q. The amount Br /CCl NaNH
¾¾¾
2
¾¾
4
® A ¾¾¾¾
2
®B
of R produced in the reaction is closest to D

(a) 97.6 mg (b) 108.8 mg

(c) 84.8 mg (d) 121.6 mg NaOD/D O HgSO 4/H 2SO 4
D ¬¾¾¾¾¾ 2
(excess)
¾ C
Numeric Value Answer
31. On conversion into the Grignard reagent How many deutrium are present in th e
followed by treatment with water, how many alkyl compound D?
bromides would yield isopentane? 35. Total no. of alkynes that on catalytic reduction
32. Number of hydrocarbons formed when C2H5Br gives 3-ethyl-4-methylheptane ______.
and CH3–CH2–CH2–Br are treated with Na in
the presence of dry ether is ______.

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

ENVIRONMENTAL 14
CHEMISTRY

MCQs with One Correct Answer 5. Which is a dangerous radiological pollutant?

(a) C14 (b) S35
1. In Antarctica, ozone depletion is due to the
(c) Sr90 (d) P32
formation of following compound
6. Which of the following is the coldest region of
(a) acrolein
atmosphere?
(b) peroxyacetyl nitrate
(a) Thermosphere (b) Mesosphere
(c) SO2 and SO3
(c) Troposphere (d) Stratosphere
(d) chlorine nitrate
7. Green house gases –
2. Classical smog occurs in places of
(a) allow shorter wavelength to enter earth's
(a) excess SO2 (b) low temperature
atmosphere while doesn't allow longer wave-
(c) high temperature (d) excess NH3
length to leave the earth's atmosphere.
3. Which gas is responsible for ‘ Bhopal Gas
(b) allow longer wavelength to enter earth at-
Tragedy’ in 1984?
mosphere while doesn't allow shorter wave-
(a) C O
length to leave the surface
(b) Methyl isocyanate
(c) don't have wavelength specific behaviour.
(c) SO2 and NO2
(d) show wavelength specific behaviour near
(d) Ethyl isocyanate
the earth while far from earth these have
4. CFC which is a main reason behind air pollution, is
wavelength independent behaviour.
produced by
8. Formation of London smog takes place in
(a) sewage pollutant
(a) winter during day time
(b) aerosols
(b) summer during day time
(c) industrial remains
(c) summer during morning time
(d) all the these
(d) winter during morning time
Environmental Chemistry 47

9. Which of the following statement is false ?
(a) The average residence time of NO is one
month
(b) Limestone acts as a sink for SOx
(c) SOx can be removed from fuel gases by
passing through a solution of citrate ions
(d) Ammonia acts as a sink for NOx
10. When rain is accompanied by a thunderstorm,
the collected rain water will have a pH value
(a) slightly lower than that of rain water without
thunderstorm
(b) slightly higher than that when the
thunderstorm is not there
(c) uninfluenced by occurrence of thunderstorm
(d) which depends upon the amount of dust in air
11. Which causes death of fish in water bodies
polluted by sewage?
(a) Foul smell (b) Pathogens
(c) Herbicides (d) Decrease in D.O.
12. Negative soil pollution is
(a) reduction in soil productivity due to erosion
and over use
(b) reduction in soil productivity due to
addition of pesticides and industrial wastes
(c) converting fertile land into barren land by
dumping ash, sludge and garbage
(d) None of the above
13. The quantity of DDT in food chain
(a) decreases (b) remains same
(c) increases (d) changes
14. Minamata disease is a pollution related disease
results from
(a) oil spills into sea
(b) accumulation of arsenic into atmosphere
(c) release of industrial waste mercury into
water bodies
(d) release human organic waste into drinking
water
15. Lichens do not like to grow in cities
(a) because of absence of the right type of
algae and fungi
(b) because of lack of moisture
(c) because of SO2 pollution
(d) because natural habitat is missing

ANSWER KEY
1 (a) 3 (b) 5 (c) 7 (a) 9 (a) 11 (d) 13 (c) 15 (c)
2 (b) 4 (b) 6 (b) 8 (d) 10 (a) 12 (a) 14 (c)
 48 CHEMISTRY

15
THE SOLID STATE

MCQs with One Correct Answer 4. The second order Bragg diffraction of X-rays
with = 1.00 Å from a set of parallel planes in a
1. The pure crystalline substance on being heated
metal occurs at an angle 60º. The distance
gradually first forms a turbid liquid at constant
between the scattering planes in the crystal is
temperature and still at higher temperature
(a) 0.575 Å
turbidity completely disappears. This behaviour
(b) 1.00 Å
is a characteristic property of substance forming.
(c) 2.00 Å
(a) Allotropic (b) Liquid
(d) 1.15 Å
(c) Isomeric (d) Isomorphous
5. A compound is formed by elements A and B.
2. Which of crystal systems contains the maximum
The crystalline cubic structure has the A atoms
number of Bravais lattices?
at the corners of the cube and B atoms at the
(a) Cubic
body centre. The simplest formula of the
(b) Hexagonal
compound is
(c) Triclinic
(a) AB (b) A6B
(d) Orthorhombic
(c) AB6 (d) A8B4
3. How many unit cells are present in a cube-
6. Total volume of atoms present in a face-centred
shaped ideal crystal of NaCl of mass 1.00 g ?
cubic unit cell of a metal is (r is atomic radius)
[Atomic masses : Na = 23, Cl = 35.5]
(a) 5.14 × 1021 unit cells 12 3 16 3
(a) pr (b) pr
(b) 1.28 × 1021 unit cells 3 3
(c) 1.71 × 1021 unit cells 20 3 24 3
(c) pr (d) pr
(d) 2.57 × 1021 unit cells 3 3
The Solid State 49

7. If calcium crystallizes in bcc arrangement and 13. The edge length of unit cell of a metal having
the radius of Ca atom is 96 pm, then the volume molecular weight 75 g/mol is 5Å which
of unit cell of Ca is crystallizes in cubic lattice. If the density is 2g/
(a) 10.9 × 10–36 m3 cc then find the radius of metal atom.
(b) 10.9 × 10–30 m3 (NA = 6 × 1023). Give the answer in pm.
(c) 21.8 × 10–30 m3 (a) 217 pm (b) 210 pm
(d) 21.8 × 10–36 m3 (c) 220 pm (d) 205 pm
8. The number of unit cells in the Ca atom lies on 14. The number of atoms in 100 g of an fcc crystal
the surface of a cubic crystal that is 1.0 cm in with density, d = 10 g/cm3 and cell edge equal to
length is 100 pm, is equal to
(a) 9.17 × 1023 (a) 1 × 1025 (b) 2 × 1025
(b) 9.17 × 1022 (c) 3 × 10 25 (d) 4 × 1025
(c) 2 × 9.17 × 1023 15. The cubic unit cell of a metal (molar mass = 63.55g
(d) 2 × 9.17 × 1022 mol–1) has an edge length of 362 pm. Its density
9. The radii of Na+ and Cl– ions are 95 pm and 181 pm is 8.92g cm–3.
respectively. The edge length of NaCl unit cell is The type of unit cell is
(a) 276 pm (b) 138 pm (a) primitive (b) face centered
(c) 552 pm (d) 415 pm (c) body centered (d) end centered
10. An alloy of copper, silver and gold is found to 16. In A B ionic compound, radii of A+ and B– ions
+ –

have cubic lattice in which Cu atoms constitute are 180 pm and 187 pm respectively. The crystal
ccp. If Ag atoms are located at the edge centres structure of this compound will be
and Au atom is present at body centre, the alloy (a) NaCl type (b) CsCl type
will have the formula (c) ZnS type (d) similar to diamond
(a) CuAgAu 17. Which set of following characteristics for ZnS
(b) Cu4Ag4Au crystal is correct?
(c) Cu4Ag3Au (a) Coordination number (4 : 4); ccp; Zn2+ ion
(d) Cu4Ag6Au in the alternate tetrahedral voids
11. A solid is made of two elements X and Z. The (b) Coordination number (6 : 6); hcp; Zn2+ ion
atoms Z are in ccp arrangement while the atoms in all tetrahedral voids.
X occupy all the tetrahedral sites. What is the (c) Coordination number (6 : 4); hcp; Zn2+ ion
formula of the compound? in all octahedral voids
(a) XZ (b) XZ2 (d) Coordination number (4 : 4); ccp; Zn2+ ion
(c) X2Z (d) X2Z3 in all tetrahedral voids.
12. The pyknometric density of sodium chloride 18. In a normal spinel type structure , the oxide ions
crystal is 2.165 × 103 kg m–3 while its X-ray density are arranged in ccp whereas 1/8 tetrahedral holes
is 2.178 × 103 kg m–3. The fraction of unoccupied are occupied by Zn 2+ ions and 50% of octahedral
sites in sodium chloride crystal is holes are occupied by Fe3+ ions .The formula of
(a) 5.96 × 10–3 the compound is
(b) 5.96 × 104 (a) Zn 2 Fe 2O 4 (b) ZnFe 2 O 3
(c) 5.96 × 10–2
(d) 5.96 × 10–1 (c) ZnFe 2O 4 (d) ZnFe 2O 2
 50 CHEMISTRY

19. A molecule A2B (Mwt. = 166.4) occupies 24. If NaCl is doped with 10– 4 mol % of SrCl2, the
triclinic lattice with a 5 Å, b = 8 Å, and c = 4 Å. concentration of cation vacancies will be
If the density of AB2 is 5.2 g cm– 3, the number (NA = 6.02 × 1023 mol–1)
of molecules present in one unit cell is (a) 6.02 × 1016 mol–1
(a) 2 (b) 3 (b) 6.02 × 1017 mol–1
(c) 4 (d) 5 (c) 6.02 × 1014 mol–1
20. A mineral having the formula AB2 crystallizes in ccp (d) 6.02 × 1015 mol–1
lattice with A atoms occupying the lattice points. 25. In a solid lattice the cation has left a lattice site
Pick out the correct statements of the following and is located at an interstitial position, the
(a) 100% occupancy of tetrahedral voids, C.N. lattice defect is
of B = 4 (a) Interstitial defect (b) Vacancy defect
(b) 100% occupancy of octahedral voids, C.N. (c) Frenkel defect (d) Schottky defect
of B = 4 Numeric Value Answer
(c) 50% occupancy of tetrahedral voids, C.N.
26. Pottasium has a bcc structure with nearest
of A = 4
neighbour distance 4.52 Å. Its atomic weight is
(d) 100% occupancy of octahedral voids, C.N.
39. Its density (in kg m–3) will be
of A = 4
27. KCl crystallises in the same type of lattice as
21. Schottky defect in crystals is observed when
does NaCl. Given that r + / r - = 0.55 and
(a) an ion leaves its normal site and occupies Na Cl
an interstitial site r /r = 0.74. Calculate the ratio of the edge
K+ Cl-
(b) unequal number of cations and anions are length of the unit cell for KCl to that of NaCl.
missing from the lattice 28. A metal has a fcc lattice. The edge length of the
(c) density of the crystal increases unit cell is 404 pm. The density of the metal is
(d) equal number of cations and anions are 2.72 g cm-3. The molar mass of the metal is :
missing from the lattice (NA Avogadro’s constant = 6.02 × 1023 mol–1)
22. To get a n- type semiconductor, the impurity to 29. The edge length of unit cell of a metal having
be added to silicon should have which of the molecular weight 75 g/mol is 5Å which
following number of valence electrons crystallizes in cubic lattice. If the density is 2 g/
(a) 1 (b) 2 cc and the radius of metal atom is 4.33 xpm. (NA
(c) 3 (d) 5 = 6 × 1023). Find the value of x.
23. Non stoichiometric defects are formed by 30. In face centred cubic (fcc) crystal lattice, edge
(a) s- block elements length is 400 pm. The diameter of greatest sphere
(b) p-block elements is 29.29 d pm which can be fit into the interstitial
(c) either s-block elements or d-block elements void without distortion of lattice. Find the value
(d) only d-block elements. of d.?

ANSWER KEY
1 (b) 4 (d) 7 (b) 10 (c) 13 (a) 16 (b) 19 (b) 22 (d) 25 (c) 28 (27)
2 (d) 5 (a) 8 (b) 11 (c) 14 (d) 17 (a) 20 (a) 23 (d) 26 (910) 29 (5)
3 (d) 6 (b) 9 (c) 12 (a) 15 (b) 18 (c) 21 (d) 24 (b) 27 (1.123) 30 (4)
 SOLUTIONS
16

MCQs with One Correct Answer pressure ( in mm Hg) of X and Y in their pure
states will be, respectively:
N N N (a) 300 and 400 (b) 400 and 600
1. If 50 mL H2SO4, 30 mL HNO3, 10 mL
10 3 2 (c) 500 and 600 (d) 200 and 300
HCl is mixed and solution is made to 1L. Then 4. Equal masses of a solute are dissolved in equal
normality of resultant solution is amount of two solvents A and B, respective
N N molecular masses being MA and MB. The relative
(a) (b) lowering of vapour pressure of solution in
20 40
solvent A is twice that of the solution in solvent
N B. If the solutions are dilute, MA and MB are
(c) (d) N
50 related as
2. When a gas is bubbled through water at 298 K,
(a) M A = MB (b) 2M A = M B
a very dilute solution of the gas is obtained.
Henry’s law constant for the gas at 298 K is 100 (c) M A = 2M B (d) M A = 4M B
kbar. If the gas exerts a partial pressure of 1 bar, 5. When two liquids A and B are mixed they form
the number of millimoles of the gas dissolved in an ideal solution. At certain temperature the V.P.
one litre of water is of the solution, that contains 3 moles of A and 1
(a) 0.555 (b) 5.55 mole of B was found to be 550 mm of Hg. The
(c) 0.0555 (d) 55.5 vapour pressure of a solution containing
3. Two liquids X and Y form an ideal solution. At 4 moles of A and 1 mole of B was found to be 560
300 K, vapour pressure of the solution mm of Hg. The vapour pressure of pure liquid A
containing 1 mol of X and 3 mol of Y is 550 mm is
Hg. At the same temperature, if 1 mol of Y is (a) 200 mm (b) 300 mm
further added to this solution, vapour pressure (c) 400 mm (d) 600 mm
of the solution increases by 10 mm Hg. Vapour
 52 CHEMISTRY

6. Two components A and B form an ideal solution. 11. 0.010M solution an acid HA freezes at –0.0205ºC. If
The mole fractions of A and B in ideal solution Kf for water is 1.860 K kg mol–1, the ionization
are XA and XB, while that of in vapour phase, constant of the conjugate base of the acid will be
these components have their mole fractions as (assume 0.010 M = 0.010 m)
YA and YB. Then, the slope and intercept of plot (a) 1.1 × 10–4 (b) 1.1 × 10–3
(c) 9.0 × 10 –11 (d) 9.0 × 10–12
1 1 12. DTf /Kf has the same value of 1 mol kg–1 for 8%
of vs. will be:
YA XA AB2 and 10% A2B by mass of solvent, both AB2
and A2B being non- electrolytes. Atomic masses
PAo PBo - PAo PBo PAo - PBo of A and B will be respectively
(a) , (b) , (a) 20, 40 (b) 20, 50
PBo PBo PAo PAo (c) 40, 20 (d) 50, 40
13. The vapour pressure of a solvent decreases by
PBo PBo PAo 10 mm of Hg when a non-volatile solute was
(c) , (d) PAo - PBo , added to the solvent. The mole fraction of the
PAo PBo - PAo PBo
solute in the solution is 0.2. What should be the
7. The total vapour pressure of a 4 mole % solution mole fraction of the solvent if the decrease in
of NH3 in water at 293 K is 50.0 torr. The vapour the vapour pressure is to be 20 mm of Hg ?
pressure of pure water is 17.0 torr at this (a) 0.8 (b) 0.6
temperature. Applying Henry’s and Raoult’s (c) 0.4 (d) 0.2
laws, the total vapour pressure for a 5 mole % 14. Which of the following pairs of solution are
isotonic at the same temperature ?
solution is
(a) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4
(a) 58.25 torr (b) 33 torr
(b) 0.1 M NaCl and 0.1 M Na2SO4
(c) 42.1 torr (d) 52.25 torr (c) 0.1 M urea and 0.1 M MgCl2
8. Vapour pressure of benzene at 30°C is 121.8 mm (d) 0.2 M urea and 0.1 M NaCl
Hg. When 15 g of a non-volatile solute is 15. 23.5 g of phenol was dissolved in 500 g of a
dissolved in 250 g of benzene its vapour solvent having depression constant Kf of 12.0
pressure decreased to 120.2 mm Hg. The K Kg mol–1. If the depression in freezing point
molecular weight of the solute is (Mo. wt. of of solution was found to be 3.60 K, the percent
solvent = 78) dimerization of phenol in the solvent is
(a) 356.2 (b) 456.8 (a) 89 (b) 85
(c) 530.1 (d) 656.7 (c) 80 (d) 92
9. A solution of urea (mol. mass 56 g mol -1) boils 16. A certain non-volatile electrolyte contains 40%
carbon, 6.7% hydrogen and 53.3% oxygen. An
at 100.18°C at the atmospheric pressure. If Kf
aqueous solution containing 5% by mass of of
and Kb for water are 1.86 and 0.512 K kg mol-1
the solute boils at 100.15°C. The molecular
respectively, the above solution will freeze at formula of the compound is
(a) 0.654°C (b) - 0.654°C (Kb = 0.51°C/m)
(c) 6.54°C (d) - 6.54°C (a) HCHO (b) CH3OH
10. p1, p2, p3 and p4 atm are the osmotic pressures of (c) C2H5OH (d) C6H12O6
5% (mass/volume) solutions of urea, fructose, 17. A storage battery contains a solution of H2SO4
sucrose and KCl respectively at certain 38% by weight. At this concentration, van’t Hoff
temperature. The correct order of their factor is 2.50. The temperature of which the
magnitudes is : battery contents freeze is
(a) p1 > p4 > p2 > p3 (b) p1 > p4 > p2 > p3 (K¢f = 1.86 K mol–1 kg)
(c) p4 > p1 > p2 > p3 (d) p4 > p1 > p3 > p2 (a) 225.45 (b) 235.85
(c) 249.92 (d) 243.92
Solutions 53
18. An industrial waste water is found to contain Numeric Value Answer
8.2% Na 3PO4 and 12% MgSO4 by mass in
21. Two liquids A and B are miscible in all
solution. If % ionisation of Na 3PO4 and MgSO4
proportions and form ideal solution. At 350 K
are 50 and 60 respectively then its normal boiling
the vapour pressure of pure A is 24.0 kPa and
point is [Kb(H2O) = 0.50 K kg mol–1] :
that of pure B is 12.0 kPa. A mixture of 60% (by
(a) 102.3°C (b) 103.35°C
mole) of A and 40% of B is distilled at this
(c) 101.78°C (d) None of these
19. The plot of total vapour pressure as a function temperature. A small amount of distillate is
of mole fraction of the components of an ideal collected and redistilled at the same
solution formed by mixing liquids X and Y is temperature. The mole percent of A in the
second distillate at initial stage is ________.
22. Two beaker A and B present in a closed vessel.
Total vapour
pressure

Beaker A contains 152.4 g aqueous solution of

(a) urea, containing 12 g of urea. beaker B contains
0 1 196.2 g glucose solution, containing 18 g of
Mole fraction of c glucose. Both solutions allowed to attain the
equilibrium. The mass % of glucose in its
solution at equilibrium is _______.
Total vapour
pressure

23. A solution containing 10 g per dm3 of urea

(b) (molecular mass = 60 g mol–1) is isotonic with a 5%
0 1
solution of a non-volatile solute. The molecular
Mole fraction of c mass of this non-volatile solute is _______.
24. The freezing point of 0.08 molal NaHSO4 is –
0.345°C. If assume 100% ionisation of NaHSO4,
Total vapour
pressure

calculate the percentage of HSO4– , ions that

(c) transfers a proton to water. (Kf for H2O = 1.86 K
molality–1).
0 1
Mole fraction of c 25. 2 g of benzoic acid dissolved in 25 g of C6H6
shows a depression in freezing point equal to
1.62 K. Molal depression constant of C6H6 is
Total vapour
pressure

4.9 K mol–1 kg. The percentage association of

(d) acid if it forms double molecule in solution
is ________.
0 1
Mole fraction of c 26. The amount of urea to be dissolved in 500 c.c. of
water (K = 1.86°C mol–1) to produce a depression
20. The values of the Henry’s law constant of Ar,
CO2, CH4, and O2 in water at 25 °C are 40.30, of 0.186°C in the freezing point is ________.
27. 0.400 g of an acid HA (mol. mass = 80) was
1.67, 0.41.and 34.86 kbar, respectively. The order
dissolved in 100 g of water. The solution
of their solubility in water at the same
temperature and pressure is showed a depression of freezing point of 0.12
(a) Ar > O2 > CO2 > CH4 K. The dissociation constant (in multiple of
(b) CH4 > CO2 > Ar > O2 10–3) of the acid at about 0°C, given Kf (water)
(c) CH4 > CO2 > O2 > Ar = 1.86 K Kg mol–1 is (Assume molarity of solution
(d) Ar > CH4 > O2 > CO2 » molality)
 54
28. An element X (Atomic mass = 25) exists as X4
is benzene. 51g of saturated solution of X in
benzene was added to 50.0 g of pure benzene. The
resulting solution showed a depression of freezing
point of 0.55 K. The solubility of X per 100 g of
benzene is (Kf for benzene = 5.5 K kg mol–1)
29. At 10°C, the osmotic pressure of urea solution
is 500 mm. The solution is diluted and the
CHEMISTRY
temperature is raised to 25°C, when the osmotic
pressure is found to be 105.3 mm. Determine
extent of dilution.
30. A solution containing 28 g phosphorus in
315 g CS2 (b. pt. 46.3°C) boils at 47.98°C. K¢b
for CS2 is 2.34 K mol–1 kg. _______ are the
no. of atom of phosphorus present in its
molecular formula.

ANSWER KEY
1 (c) 4 (c) 7 (a) 10 (c) 13 (b) 16 (d) 19 (b) 22 (14.49) 25 (99.2) 28 (2)
2 (a) 5 (d) 8 (a) 11 (c) 14 (a) 17 (d) 20 (c) 23 (300) 26 (3) 29 (5)
3 (b) 6 (b) 9 (b) 12 (c) 15 (c) 18 (c) 21 (0.857) 24 (31.9) 27 (6) 30 (4)
 ELECTROCHEMISTRY
17

MCQs with One Correct Answer (a) – 0.22 V (b) + 0.22 V

(c) – 0.44 V (d) + 0.44 V
1. Small quantities of solutions of compounds TX, 5. The equilibrium constant for the
TY and TZ are put into separate test tubes disproportionation reaction
containing X, Y and Z solution. TX does not +
react with any of these. TY reacts with both X 2+
2C u (aq) ¾¾® Cu (s ) + Cu (aq )
and Z. TZ reacts with X. The decreasing order
at 25°C (E o Cu + / Cu = 0.52V,
of state of oxidation of the anions X–, Y–, Z– is
(a) Y–, Z–, X– (b) Z–, X–, Y– EoCu2+ / Cu = 0.16V) is
–
(c) Y , X , Z – – (d) X–, Z–, Y– (a) 6 ´ 10 4 (b) 6 ´ 10 6
2. Following cell has EMF 0.7995V.
(c) 1 .2 ´ 10 6 (d) 1.2 ´ 10 -6
Pt | H2 (1 atm) | HNO3 (1M) || AgNO3 (1M) | Ag
6. The electrode potentials for
If we add enough KCl to the Ag cell so that the
Cu2+(aq) + e– ¾ ¾ ® Cu+(aq)
final Cl– is 1M. Now the measured emf of the cell
and Cu (aq) + e ¾¾
+ – ® Cu (s)
is 0.222V. The Ksp of AgCl would be – are + 0.15 V and + 0.50, respectively. The value
(a) 1 × 10–9.8 (b) 1 × 10–19.6 of E° 2+ will be :
–10 Cu /Cu
(c) 2 × 10 (d) 2.64 × 10–14 (a) 0.500 V (b) 0.325 V
3. Sn + 2e ¾¾
4+ – ® Sn E° = 0.13 V
2+
(c) 0.650 V (d) 0.150 V
Br2 + 2e ¾¾
– ® 2Br– E° = 1.08 V 7. Calculate DG° for the reaction :
Calculate Keq for the cell formed by two electrodes Cu2+ (aq) + Fe (s) ƒ Fe2+ (aq) + Cu (s)
(a) 1041 (b) 1032
–32 Given that : E ° 2 + = + 0.34 V,,
(c) 10 (d) 10–42 Cu /Cu
4. The standard reduction potential for Cu 2 + /Cu Eo = -0.44 V
Fe2 + /Fe
is + 0.34. The reduction potential at pH = 14 for
(a) 180.55 kJ (b) 140.35 kJ
the above couple. (Ksp Cu (OH ) 2 = 1 × 10 -19 ) is: (c) –130.15 kJ (d) –150.54 kJ
 56 CHEMISTRY

8. The e.m.f. of the cell Zn | Zn 2+ (0.01M) | | Fe2+ equivalent conductance of 0.01 N NH4OH is
(0.001M) | Fe at 298 K is 0.2905 then the value of 9.30 ohm–1 cm2 eq–1, then the degree of ionization
equilibrium for the cell reaction is
of NH4OH at this temperature would be
0.32 0.32
(a) 0.04 (b) 0.1
(a) e 0.0295 (b) 10 0.0295
(c) 0.39 (d) 0.62
0.26 0.32 14. Dissociation constant of a weak acid (HA) in
(c) 10 0.0295 (d) 10 0.0591
terms of L ¥
m and L m is:
9. For a cell reaction
cL ¥
m
2H 2 ( g ) + O2 ( g ) ¾¾
® 2H 2 O ( l ) (a) Ka =
( L m - L¥ )
D rS°298 = - 0.32 kJ / K .
cL 2m
What is the value of D r S°298 ( H 2 O, l ) ? (b) Ka =
Given :
¥
Lm (
L ¥m - L m )
O 2 ( g ) + 4H + ( aq ) + 4e - ¾¾
® 2H 2 O ( l ) ;
Ka =
c L¥
m( )2
E° = 1.23 V
(a) – 285.07 kJ/mol (b) – 570.14 kJ/mol
(c)
L¥ (
¥
m L m - Lm )
(c) 285.07 kJ/mol (d) None of these
(d) None of these
10. If 0.01 M solution of an electrolyte has a
15. Given the ionic equivalent conductivities for the
resistance of 40 ohms in a cell having a cell
following ions:
constant of 0.4 cm–1, then its molar conductance
l°eq K+ = 73.5 cm2 ohm– 1 eq– 1
in ohm–1 cm2 mol–1 is
l°eq Al3+ = 149 cm2 ohm– 1 eq– 1
(a) 102 (b) 104
(c) 10 (d) 103 l°eq SO42– = 85.8 cm2 ohm– 1 eq– 1
11. When electric current is passed through acidified The L°eq for potash alum (K2 SO4. Al2(SO4)3.
water, 112 mL of hydrogen gas at STP collected 24H2O) is
at the cathode in 965 seconds. The current (a) 215.92 (b) 348.3
passed in amperes is (c) 368.2 (d) 108.52
(a) 1.0 (b) 0.5 16. On passing a current of 1.0 ampere for 16 min and
(c) 0.1 (d) 2.0 5 sec through one litre solution of CuCl2, all copper
of the solution was deposited at cathode. The
12. L ClCH 2COONa = 224 ohm -1cm 2g eq -1,
strength of CuCl2 solution was (Molar mass of
L NaCl = 38.2 ohm -1cm 2g eq -1, Cu= 63.5; Faraday constant = 96500 Cmol–1)
(a) 0.01 N (b) 0.01 M
L HCl = 203 ohm -1cm 2g eq -1,
(c) 0.02 M (d) 0.2 N
What is the value of LClCH2COOH 17. Given the following molar conductivities
(a) 288.5 ohm–1cm2g eq–1 at 25°C:, HCl, 426W–1 cm2mol–1; NaCl, 126W–1
(b) 289.5 ohm–1cm2g eq–1 cm2 mol–1; NaC (sodium crotonate), 83 W–1
(c) 388.8 ohm–1cm2g eq–1 cm2mol–1. What is the dissociation constant of
(d) 59.5 ohm–1cm2g eq–1 crotonic acid, if the conductivity of a 0.001 M
13. Equivalent conductance at infinite dilution, l° crotonic acid solution is 3.83 × 10–5 W–1cm–1?
of NH4Cl, NaOH and NaCl are 128.0, 217.8 and (a) 10–5 (b) 1.11 × 10–5
109.3 ohm –1 cm 2 eq –1 r espectively. The (c) 1.11 × 10–4 (d) 0.01
Electrochemistry
18. A lead storage battery containing 5.0 L of (1N)
H 2SO 4 solution is operated for 9. 65 × 10 s
with a steady current of 100 mA. Assuming
volume of the solution remaining constant,
normality of H 2SO 4 will
(a) remain unchanged (b) increases by 0.20
(c) increase by unity (d) decrease by 0.40
19. In an electrolysis experiment current was passed
for 5 hours through two cells connected in series.
The first cell contains a solution of gold and the
second contains copper sulphate solution. 9.85 g
of gold was deposited in the first cell. If the oxidation
number of gold is +3, the amount of copper
deposited on the cathode of the second cell and
magnitude of the current in amperes is.
(1 faraday = 96,500 coulombs)
(a) 4.95 g, 0.8 A (b) 5.5 g, 0.9 A
(c) 4.76 g, 0.8 A (d) 5.85 g, 0.5 A
20. For the electrochemical cell shown below
Pt | H2 (p = 1 atm) | H+ (aq., x M) |
| Cu2+ (aq., 1.0 M) | Cu(s)
The potential is 0.49 V at 298 K. The pH of the
solution is closest to:
[Given, standard reduction potential, E° for Cu2+ /
Cu is 0.34 V.
Gas constant, R is 8.31 J K–1 mol– 1
Faraday constant, F is 9.65 × 104 J V– 1 mol– 1]
(a) 1.2 (b) 8.3
(c) 2.5 (d) 8.2
Numeric Value Answer
21. What is the standard electrode porential for the
reduction of HClO?
HClO ( aq ) + H + -
( aq ) + 2e ¾¾
®
Cl - ( aq ) + H 2 O ( l )
Given : Cr 2+ ( aq ) ¾¾
® Cr3+ ( aq ) + e - ,
E° = 0.41 V
HClO ( aq ) + H + ( aq ) + 2Cr 2+ ( aq ) ¾¾
® to 1.2 g/mL of 19.6 % (w/w) H2SO4. What is the
2Cr3+ ( aq ) + Cl- ( aq ) + H 2 O ( l ) , E° = 1.80
57
22. What is the potential of an electrode (in V) which
5 originally contained 0.1 M NO 3- and 0.4 M H+
and which has been treated by 80% of the
cadmium necessary to reduce all the NO3- to
NO(g) at 1 bar?
Given : NO3- + 4H + + 3e - ¾¾ ® NO + 2H 2 O;
E° = 0.96 V; log 2 = 0.3
23. On passing current through two cells, connected
in series containing solution of AgNO3 and
CuSO4, 0.18 g of Ag is deposited. The amount of
the Cu (in g) deposited is:
24. Eocell = 0.74 V for the cell,
Cr | Cr3+ (1 M) || H+ (1 M) | Pt (H2) (1 bar) and
Eocell = 0.80 V for the cell (1 bar) Pt (H2) | H+ (1 M)
|| Ag+ (1 M) | Ag
What is the value of cell EMF for the cell
Ag | Ag+ (0.1 M) || Cr 3+ (0.1 M) | Cr ?
25. For Daniell’s cell, the reaction quotient is Q. A
variation of Ecell with log Q has been plotted. At
start, the molar concentration of CuSO4 and
ZnSO4 are equal. When concentration of Zn 2+
increases to 1.5 mol/L, the cell EMF becomes
1.07 V. What is the value of [Cu2+] at this point.
Take 2.303 RT/F = 0.06
1.1 V
Ecell
0
log Q
26. For a hydrazine fuel cell, following data are given
at 298 K:
o
E oN 2 H 4 /N 2 = -0.9 V, E 12 O2 /H2 O = +1.23 V
Assuming 60% efficiency, what is the maximum
amount of energy (in KJ) that can be obtained?
27. During discharging of lead storage battery, the
density of 38% H2SO4 (w/w)fell from 1.274 g/mL
number of faradays that have been exchanged
during the discharging process? (vol. of H2SO4
in lead storage battery = 2.36 L)
 58 CHEMISTRY

28. The photoelectric current from Na (work 29. For an electrochemical cell
function, w0 = 2.3 eV) is stopped by the output Sn(s)|Sn2+ (aq, 1M) ||Pb2+ (aq, 1M)|Pb(s) the
voltage of the cell [Sn 2+ ]
Pt(s)|H2(g, 1 bar)|HCl(aq., pH = 1)|AgCl(s)|Ag(s). ratio when this cell attains equilibrium
[Pb2+ ]
The pH of aq. HCl required to stop the is _______.
photoelectric current from K(w0 = 2.25 eV), all
30. When 9.65 ampere current was passed for
other conditions remaining the same, is
1.0 hour into nitrobenzene in acidic medium, the
__________ × 10–2 (to the nearest integer).
amount of p-amino-phenol (in g) produced
Given,
is _______.
RT
2.303 = 0.06 V; E 0AgCl|Ag|Cl- = 0.22 V
F

ANSWER KEY
1 (a) 4 (a) 7 (d) 10 (d) 13 (a) 16 (a) 19 (c) 22 (0.84) 25 (0.15) 28 (142)
2 (a) 5 (c) 8 (b) 11 (a) 14 (b) 17 (b) 20 (c) 23 (0.0529) 26 (76.43) 29 (2.15)
3 (b) 6 (b) 9 (a) 12 (c) 15 (a) 18 (d) 21 (1.39) 24 (1.5) 27 (6) 30 (9.81)
 CHEMICAL KINETICS
18

MCQs with One Correct Answer 4. The time taken for 90% of a first order reaction
to complete is approximately
1. The rate of the reaction 2N2O5 ® 4NO2 + O2 can (a) 1.1 times that of half-life
be written in three ways : (b) 2.2 times that of half-life
- d[N 2O5 ] d[NO 2 ] (c) 3.3 times that of half-life
= k [N 2O5 ] ; = k ¢ [N 2O 5 ]
dt dt (d) 4.4 times that of half-life
5. The initial rates of reaction
d[O 2 ]
= k ¢¢ [N 2O 5 ] 3A + 2B + C ¾¾ ® Products, at different initial
dt
concentrations are given below:
The relationship between k and k' and between Initial rate, [A]0, M [B]0, M [C]0, M
k and k¢¢ are: Ms –1
(a) k¢ = 2k ; k¢ = k (b) k¢ = 2k ; k¢¢ = k / 2 5.0 × 10–3 0.010 0.005 0.010
(c) k¢ = 2k ; k¢¢ = 2k (d) k¢ = k ; k¢¢ = k 5.0 × 10–3 0.010 0.005 0.015
2. A reaction proceeds by first order, 75% of this 1.0 × 10 –2 0.010 0.010 0.010
reaction was completed in 32 min. The time
1.25 × 10–3 0.005 0.005 0.010
required for 50% completion is
(a) 8 min (b) 16 min The order with respect to the reactants, A, B and
(c) 20 min (d) 24 min C are respectively
3. Cyclopropane rearranges to form propene (a) 3, 2, 0 (b) 3, 2, 1
(c) 2, 2, 0 (d) 2, 1, 0
¾¾
® CH3 - CH = CH 2 6. Consider the two hypothetical reactions given
This follows first order kinetics. The rate constant below :
is 2.714 × 10 –3 sec –1. The initial concentration I a A ® Products, k = x mol–1 L min–1
of cyclopropane is 0.29 M. What will be the II b B ® Products, k = y min–1
concentration of cyclopropane after 100 sec? The half-lives of both the reactions are the same,
(a) 0.035 M (b) 0.22 M equal to 1 hr when molar concentration of the
(c) 0.145 M (d) 0.0018 M reactant is 1.0 M in each case. If these reactions
 60 CHEMISTRY

are started at the same time taking 1M of the 10. A (aq) ¾¾ ® B(aq) + C(aq) is a first order
reactant in each case, the ratio [A]/[B] after 3 hr reaction.
will be : Time t ¥
(a) 0.5 (b) 4 mole of reagent n1 n2
(c) 1 (d) 2 Reaction progress is measured with the help of
7. For a h omogen eous gaseous reaction titration of reagent ‘R’. If all A, B and C react
A ¾¾ ® 3B, if pressure after time t was Pt and with reagent and have ‘n’ factors [n factor; eq.
after completion of reaction, pressure was P¥ mol. mass
then select correct relation mass = ] in the ratio of 1 : 2 : 3 with
n
the reagent, the k in terms of t, n 1 and n 2 is :
(a) 1 æ P¥ ö
k = ln ç ÷
t çè 3 ( P¥ - Pt ) ÷ø 1 æ n2 ö
(a) k = ln ç ÷
t è n 2 - n1 ø
1 æ 2P¥ ö
(b) k = ln ç ÷
t çè ( P¥ - Pt ) ÷ø 1 æ 2n 2 ö
(b) k = ln ç ÷
t è n 2 - n1 ø
1 æ 3P¥ ö
(c) k = ln ç ÷ 1 æ 4n 2 ö
t è 2P¥ - Pt ø (c) k = ln ç ÷
t è n 2 - n1 ø
1 æ 2P¥ ö
(d) k = ln çç ÷ 1 æ 4n 2 ö
t è 3 ( P¥ - Pt ) ÷ø (d) k = ln ç ÷
t è 5 (n 2 - n1) ø
8. For a first order homogeneous gaseous reaction,
11. The gaseous decomposition reaction,
A ¾¾ ® 2B + C then initial pressure was Pi while
A(g) ® 2B(g) + C (g) is observed to first order
total pressure after time ‘t’ was Pt. The right
over the excess of liquid water at 25°C. It is found
expression for the rate constants k in terms of
that after 10 minutes the total pressure of system
Pi, Pt and t is :
is 188 torr and after very long time it is 388 torr.
2.303 æ 2Pi ö The rate constant of the reaction (in hr –1) is :
(a) k= log ç ÷ [Given : vapour pressure of H2O at 25° is 28 torr
t è 3Pi - Pt ø (ln 2 = 0.7, ln 3 = 1.1, ln 10 = 2.3)]
2.303 æ 2Pi ö (a) 0.02 (b) 1.2
(b) k= log ç ÷ (c) 0.2 (d) 0.5
t è 2Pt - Pi ø
12. The decomposition of N2O5 according to the
2.303 æ Pi ö equation :
(c) k = log ç ÷
t è Pi - Pt ø 2N2O5(g) ® 4NO2(g) + O2(g)
(d) None of these is a first order reaction. After 30 min. from the
9. The reaction A (g) ¾¾ ® B (g) + 2C (g) is a start of the decomposition in a closed vessel,
first order reaction with rate constant the total pressure developed is found to be 284.5
2.772 × 10–3 s–1. Starting with 0.1 mole of A in 2 mm of Hg and on complete decomposition, the
litre vessel, find the concentration of A after 250 total pressure is 584.5 mm of Hg. the rate constant
sec when the reaction is allowed to take place at of the reaction is:
constant pressure and at 300 K? (a) 5.2 min–1 (b) 520 × 10–3 min–1
(a) 0.0125 M (b) 0.025 M
(c) 5.2 × 10–3 min–1 (d) 0.52 × 10–3 min–1
(c) 0.05 M (d) None of these
Chemical Kinetics
13. The activation energy for a simple chemical
reaction A ® B is Ea in forward direction. The
activation energy for reverse reaction
(a) is always double of Ea
(b) is negative of Ea
(c) is always less than Ea
(d) can be less than or more than Ea
14. The rate constant, the activation energy and
the arrhenius parameter of a chemical reaction
at 25°C are 3.0 × 10–4s–1, 104.4 kJ mol–1 and
6.0 × 1014 s–1 respectively. The value of the rate
constant as T ® ¥ is
(a) 2.0 × 1018 s–1 (b) 6.0 × 1014 s–1
(c) Infinity (d) 3.6 × 1030 s–1
15. The activation energy for a reaction is 9.0 kcal/
mol. The increase in the rate constant when its
temperature is increased from 298K to 308K is
(a) 63% (b) 50%
(c) 100% (d) 10%
16. A reaction rate constant is given by
k = 1.2 ´ 1014 e -25000 / RTsec -1 . It means
(a) log k versus log T will give a straight line
with a slope as –25000
(b) log k versus T will give a straight line with
slope as 25000
(c) log k versus log 1/T will give a straight line
with slope as –25000
(d) log k versus 1/T will give a straight line
17. What is the activation energy for a reaction if its
rate doubles when the temperature is raised from
20°C to 35°C? (R = 8.314 J mol–1 K–1)
(a) 269 kJ mol–1 (b) 34.5 kJ mol–1
(c) 15.1 kJ mol –1 (d) 342 kJ mol–1
18. The rate of decomposition for methyl nitrite and
ethyl nitrite can be given in terms of rate constant
(in sec–1) k1 and k2 respectively. The energy of
activations for the two reactions are 152.30 kJ
mol–1 and 157.7 kJ mol–1 as well as frequency
factors are 1013 and 1014 respectively for the
decomposition of methyl and ethyl nitrite. The
temperature at which rate constant same for the
two reactions will be:
(a) 285 K (b) 290 K
(c) 282 K (d) 275 K
61
19. A first order reaction A ® B requires activation
energy of 70 kJ mol–1. When a 20% solution of
A was kept at 25°C for 20 minute, 25%
decomposition took place. What will be the per
cent decomposition in the same time in a 30%
solution maintained at 40°C? Assume that
activation energy remains constant in this range
of temperature.
(a) 67.21 (b) 65.21
(c) 70.50 (d) 64.25
20. The activity of a radio nuclide (X100) is 6.023
curie at a time t. If the disintegration constant is
3.7 × 104 sec–1, the mass of X after t seconds is–
(a) 10–3g (b) 10–6g
(c) 10–14g (d) 10–15g
Numeric Value Answer
21. The gas phase decomposition of dimethyl ether
follows first order kinetics.
CH3 - O - CH3 (g) ® CH 4 (g) + H 2 (g) + CO(g)
The reaction is carried out in a constant volume
container at 500°C and has a half life of 14.5
minutes. Initially, only dimethyl ether is present
at a pressure of 0.40 atmosphere. What is the
total pressure (in atm) of the system after 12
minutes? Assume ideal gas behaviour.
22. A compound A dissociates by two parallel first
order paths at certain temperature
k (min -1 )
A(g) ¾¾¾¾¾
1 ® 2B(g) k1 = 6.93 × 10–3 min–1
k (min -1 )
A(g) ¾¾¾¾¾
2 ® C(g) k2 = 6.93 × 10–3 min–1
The reaction is started with 1 mole of pure ‘A’ in
1 litre closed container with initial pressure 2 atm.
What is the pressure (in atm) developed in
container after 50 minutes from start of
experiment?
23. The time required for 10% completion of a first
order reaction at 298 K is equal to that required
for its 25% completion at 308 K. If the pre-
exponential factor for th e reaction is
3.56 × 109 s–1, the rate constant (in kcal mol–1) at
318 K is:
 62 CHEMISTRY

24. For first order parallel reactions k1 and k2 are 4 28. Carbon monoxide reacts with O2 to form CO2:
and 2 min –1 respectively at 300 K. If the 2CO (g) + O2 (g) ® 2CO2 (g). Informations about
activation energies for the formation of B and C this reaction are given in the table below.
are respectively 30,000 and 38,314 joule/mol
respectively, the temperature (in K) at which B [CO] [O2 ] Rate of reaction
and C will be obtained in equimolar ratio is : mol/L mol/L (mol/L min)
B –5
k1 0.02 0.02 4 × 10
–4
A 0.04 0.02 1.6 × 10
–5
k2 0.02 0.04 8 × 10
C
25. The rate constant of a reaction increases by 7% What is the value for the rate constant for the
when its temperature is raised from 300 K to 310 reaction in properly related unit ?
29. Two I order reactions having same reactant
K, while its equilibrium constant increases by
concentrations proceed at 25°C at the same rate.
3%. The ratio of activation energy of the forward
The temperature coefficient of the rate of the first
and reverse reactions is: reaction is 2 and that of second reaction is 3. Find
26. In the age of the earth is 4.5 billion years and the the ratio of the rates of these reactions at 75°C.
half-life of 40K is 1.26 billion years, what percent 30. For the reaction, 2NO + H2 ® N2O + H2, the
of the earth’s original amount of 40K remains dP
value of - was found to be 1.5 Pa s–1 for a
today ? dt
pressure of 359 Pa of NO and 0.25 Pa s–1 for a
27. A reaction A + B ® Products
pressure of 152 Pa of NO. The pressure of H2
is first order w.r.t. each reactant, k being being constant. If pressure of NO was kept
5.052 × 10–3 M– 1 s– 1. If start is made with initial dP
concentration of A to be 0.1 M acid that of constant, the value of - was found 1.60 Pa
dt
B = 5.0 M, calculate the concentration of A (in s for a pressure of H2 289 Pa and 0.79 Pa s–1
–1

mM) remaining after 100 s. for a pressure of 147 Pa of H2. Calculate the
order of reaction.

ANSWER KEY
1 (b) 4 (c) 7 (d) 10 (d) 13 (d) 16 (c) 19 (a) 22 (2.5) 25 (1.8) 28 (5)
2 (b) 5 (d) 8 (a) 11 (b) 14 (b) 17 (b) 20 (d) 23 (18.39) 26 (8.42) 29 (8)
3 (b) 6 (d) 9 (a) 12 (c) 15 (a) 18 (c) 21 (0.75) 24 (378.74) 27 (8) 30 (3)
 SURFACE CHEMISTRY
19

MCQs with One Correct Answer area of the charcoal covered by each molecule
of acetic acid. Surface area of charcoal
1. The adsorption of a gas on a solid surface varies
= 3.01 × 102 m2/g.
with pressure of the gas in which of the following
(a) 0.5 × 10–19 m2 (b) 4 × 10–20 m2
manner –10
(c) 0.5 × 10 m 2 (d) 5 × 10–19 m2
(a) fast ® slow ® independent of the pressure 4. 3.6 gram of oxygen is adsorbed on 1.2 g of metal
(b) slow ® fast ® independent of the pressure powder. What volume of oxygen adsorbed per
(c) independent of the pressure ® fast ® slow gram of the adsorbent at 1 atm and 273 K?
(d) independent of the pressure ® slow ® fast
(a) 0.19 Lg–1 (b) 1 Lg–1
2. Consider the following statements about
Langmuir isotherm. (c) 2.1 L g–1 (d) None of these
I. The free gas and adsorbed gas are in 5. Which of the following is true in respect of
dynamic equilibrium. chemical adsorption?
II. All adsorption sites are equivalent. (a) DH < 0, DS > 0, DG > 0
III. The initially adsorbed layer can act as a (b) DH < 0, DS < 0, DG < 0
substrate for further adsorption (c) DH > 0, DS > 0, DG < 0
IV. The ability of a molecule to get adsorbed at (d) DH > 0, DS < 0, DG > 0
a given site is independent of the occupa-
6. In an experiment, 200 mL of 0.5 M oxalic acid is
tion of neighboring sites.
shaken with 10 g of activated charcoal and
The correct statements are filtered. The concentration of the filtrate is
(a) I, II, III and IV (b) I, II and IV reduced to 0.4 M. The amount of adsorption
(c) I, III and IV (d) I, II and III æxö
3 1g of charcoal adsorbs 100 mL 0.5 M CH3COOH ç ÷ is
èmø
to form a monolayer, and thereby the molarity of (a) 0.9 (b) 1.8
CH3COOH reduces to 0.49. Calculate the surface (c) 0.18 (d) 0.09
 64 CHEMISTRY

7. For a gas-solid adsorbent system, the adsorption (c) A catalyst makes the reaction more feasible
by making the DGº more negative
isotherm x = K p1/ n is applicable, where n = 5 in
m (d) A catalyst makes the equilibrium constant
the specified case. Point out the correct of the reaction more favourable for the
statement : forward reaction.
x 11. Flocculation value of BaCl2 is much less than
(a) Vs. p plot is a linear graph with slope
m that of KCl for sol A and flocculation value of
equal to 5 Na2SO4 is much less than that of NaBr for sol B.
x The correct statement among the following is
(b) log Vs. log p plot is a straight line with (a) Both the sols A and B are negatively
m
slope equal to 5 charged.
x (b) Sol A is positively charged and Sol B is
(c) log Vs. log p is a straight line with slope negatively charged.
m
(c) Both the sols A and B are positively
equal to 0.2
charged.
(d) none of these
(d) Sol A is negatively charged and sol B is
8. The curve that best describes the adsorption of
positively charged.
a gas (X g) on 1.0 g of a solid substrate as a
12. Freshly obtained SnO 2 is added to water
function of pressure (p) at a fixed temperature
containing a little HCl. The sol obtained would
4
3 be ................ due to preferential adsorbtion of
................... ions
2
(a) positively charged, H+
X
1 (b) negatively charged, SnO32–
(c) positively charged, Sn4+
(d) positively charged, Sn2+
P 13. One desires to prepare a positively charged sol
is
of silver iodide. This can be achieved by
(a) 1 (b) 2 (a) adding a little AgNO 3 solution to KI
(c) 3 (d) 4 solution in slight excess
9. Which one of the following is an example of (b) adding a little KI solution to AgNO3
homogeneous catalysis ? solution in slight excess
(a) Haber’s process of synthesis of ammonia (c) mixin g equal volumes of equimolar
(b) Catalytic conversion of SO2 to SO3 in solutions of AgNO3 and KI
contact process (d) None of these
(c) Catalytic hydrogenation of oils 14. 100 mL each of two sols of AgI, one obtained by
(d) Acid hydrolysis of methyl acetate adding AgNO3 to slight excess of KI and another
10. Which of the following statements about a obtained by adding KI to slight excess of AgNO3,
catalyst is/are true ? are mixed together. Then
(a) A catalyst accelerates the reaction by (a) The two sols will stabilize each other
bringing down the free energy of activation (b) The sol particles will acquire more electric
(b) A catalyst also takes part in the reaction charge
mechanism (c) The sols will coagulate each other mutually
(d) A true solution will be obtained
Surface Chemistry 65
15. Under the influence of an electric field, the the yellow part of the content to 100 mL of
particles in a sol migrate towards cathode. The 5% w/V saline solution and homogenize
coagulation of the same sol is studied using NaCl, with a mechanical shaker.
Na2SO4 and Na3PO4 solutions. Their coagulating (c) Keep the egg in boiling water for 10
values will be in the order minutes. After removing the shell, transfer
(a) NaCl > Na2SO4 > Na3PO4 the white part of the content to 100 mL of
(b) Na2SO4 > Na3PO4 > NaCl 5% w/V saline solution and homogenize
(c) Na3PO4 > Na2SO4 > NaCl with a mechanical shaker
(d) Na2SO4 > NaCl > Na3PO4 (d) Break an egg carefully and transfer only
the yellow part of the content to 100 mL of
16. To an emulsion of olive oil and water, stabilized
5% w/V saline solution and stir well.
by soap of alkali metals, a small amount of salts
of bivalent or tervalent cations is added. Then Numeric Value Answer
(a) stabilization of emulsion enhances
21. In an adsorption experiment, a graph between
(b) the emulsion breaks into the component log (x/m) versus log P was found to be linear
liquids with a slope of 45°. The intercept on the y axis
(c) reversal of phase to W/O type takes place was found to be 0.301. The amount of the gas
(d) the emulsion turns into a true solution adsorbed per gram of charcoal under a pressure
17. The density of gold is 19 g/cm3. If 1.9 × 10–4 g of of 3.0 atm is ________.
gold is dispersed in one litre of water to give a 22. 10% sites of catalyst bed have adsorbed by H2.
sol having spherical gold particles of radius 10 On heating H2 gas is evolved from sites and
nm, then the number of gold particles per mm3 of collected at 0.03 atm and 300 K in a small vessel
the sol will be :
of 2.46 cm3.
(a) 1.9 × 1012 (b) 6.3 × 1014 No. of sites available is 5.4 × 1016 per cm2 and
(c) 6.3 × 1010 (d) 2.4 × 106 surface area is 1000 cm2. Find out the no. of
18. The volume of a colloidal particle, VC as surface sites occupied per molecule of H2.
compared to the volume of a solute particle in a (Given NA = 6 × 1023)
true solution VS , could be
23. Considering Freundlich adsorption isotherm in
VC ~ 3 VC ~ - 3 this plot, find the extent of adsorption at a
(a) - 10 (b) - 10
VS VS pressure of 4 atm.

VC ~ 23 VC ~
(c) - 10 (d) -1
VS VS
19. In an experiment, addition of 4.0 mL of 0.005M 45°

BaCl2 to 16.0 ml of arsenius sulphide sol just

log (x/m)

causes the complete coagulation in 2 hrs. The 0.3

flocculating value of the effective ion is
(a) Cl–, 1.0 (b) Cl–, 2.0
log P
(c) Ba2+, 1.0 (d) Ba2+, 0.5
24. The density of gold is 19 g/cm3. 1.9 × 10–3 g of
20. The most appropriate method of making egg–
gold is dispersed in one litre of water to give a
albumin sol is :
sol having spherical gold particles of radius
(a) Break an egg carefully and transfer the 10.5 nm.
transparent part of the content to 100 mL of The gold particles are occupying 50% of the
5% w/V saline solution and stir well. available space. The number of gold particles
(b) Keep the egg in boiling water for 10 per mm3 is about 10n. Find the value of n.
minutes. After removing the shell, transfer
 66 CHEMISTRY

25. A cationic colloidal electrolyte forms micelle at
10–3 M concentration in water. Its 1 mm3 solution
contains 2 × 1013 micelle structures. What is the
number of cations contained in one micelle?
Take NA = 6 × 1023.
26. The coagulation of 400 mL of a positive colloid
took place when 1.46 g of HCl was added to it
without changing the volume much. What is
the flocculation value of HCl for the colloid?
27. The coagulation of 100 mL of a colloidal sol of
gold is completely prevented by addition of 250
mg of a substance to it before adding 10 mL of
1% NaCl solution. What is the gold number of
this substance?
28. A sample of 16 g charcoal was brought into
contact with CH4 gas contained in a vessel of 1
litre at 27 °C. The pressure of gas was found to
fall from 760 to 608 torr. The density of charcoal
sample is 1.6 g/cm3. What is the volume of the
CH4 gas adsorbed per gram of the adsorbent at
608 torr and 27 °C?
29. One gram of activated carbon has a surface area
of 1000 m2. Considering complete coverage as
well as monomolecular adsorption, how much
ammonia at 1 atm and 273 K would be adsorbed
44
on the surface of g carbon if radius of a
7
ammonia molecules is 10–8 cm.
30. A detergent (C12 H 25SO 4- Na + ) solution
becomes a colloidal sol at a concentration of
10–3 M. On an average 1013 colloidal particles
are present in 1 mm 3. What is the average
number of ions which are contained by one
colloidal particle (micelle)?

ANSWER KEY
1 (a) 4 (c) 7 (c) 10 (a) 13 (b) 16 (c) 19 (c) 22 (3) 25 (30) 28 (16.25)
2 (b) 5 (b) 8 (b) 11 (b) 14 (c) 17 (d) 20 (a) 23 (8) 26 (100) 29 (7.46)
3 (d) 6 (c) 9 (d) 12 (c) 15 (a) 18 (a) 21 (6) 24 (7) 27 (25) 30 (60)
 GENERAL PRINCIPLES
AND PROCESSES OF
20
ISOLATION OF
ELEMENTS

MCQs with One Correct Answer 5. Thomas slag is

(a) calcium silicate
1. Calcination is used in metallurgy for removal of (b) calcium phosphate
(a) moisture (b) water and CO2 (c) tricalcium phosphate and calcium silicate
(c) CO 2 and H 2S (d) H 2 O and H 2S (d) calcium ammonium phosphate
6. Which of the following pairs of metals is purified
2. Hydro-metallurgical process of extraction of
by van Arkel method ?
metals is based on
(a) Ga and In (b) Zr and Ti
(a) complex formation (b) hydrolysis (c) Ag and Au (d) Ni and Fe
(c) dehydration (d) dehydrogenation 7. Calcination is the process in which
3. The method of zone refining of metals is based on (a) ore is heated above its melting point to expel
the principle of H2O or CO2 or SO2
(a) greater solubility of the impurities in the (b) ore is heated below its melting point to expel
molten state than in the solid volatile impurities
(b) greater mobility of the pure metal than that (c) ore is heated above its melting point to
of the impurite remove S, As and Sb as SO2 ,As2O3 and
(c) higher melting point of the impurities than Sb2O3 respectively
that of the pure metal (d) ore is heated below its melting point to expel
H2O or CO2
(d) greater noble character of the solid metal
8. A sulphide ore is generally roasted to the oxide
than that of the impurities before reduction, because
4. In froth flotation process many chemicals (a) the enthalpy of formation of CO2 is more
(frother , collector, activator, and depressant) are than that of CS2
used. Which of the following is a frother: (b) a metal sulphide is generally more stable
(a) CuSO4 than the metal oxide
(b) NaCN + alkali (c) no reducing agent is found suitable for
(c) Pine oil reducing a sulphide ore
(d) Potassium xanthate. (d) a sulphide ore cannot be reduced at all
 68 CHEMISTRY

9. Nickel is purified by thermal decomposition of (C) In the extractive metallurgy of zinc, partial
its fusion of ZnO with coke is called sintering
(a) hydride (b) chloride and reduction of ore to the molten metal is
(c) azide (d) carbonyl called smelting.
10. The process of converting hydrated alumina into (D) Extractive metallurgy of silver from its ore
anhydrous alumina is called argentine involves complex formation and
(a) roasting (b) smelting displacement by more electropositive metal.
(c) dressing (d) calcination Choose the correct options –
11. The reduction of metal oxides is sometimes (a) A and B (b) B and C
done by aluminium in the (c) A, B and C (d) A, B, C and D
(a) Bayer reaction 17. Carbon cannot be used in the reduction of Al2O3
(b) Zilch reaction because
(a) the enthalpy of formation of CO2 is more
(c) Goldschmidt reaction
than that of Al2O3
(d) Silberschmidt reaction
(b) pure carbon is not easily available
12. Which of the following is chalcopyrite?
(c) the enthalpy of formation of Al2O3 is very
(a) CuFeS2 (b) FeS2
high
(c) KMgCl3.6H2O (d) Al2O3.2H2O
(d) it is an expensive proposition
13. Composition of azurite mineral is
18. Which of the following process is generally used
(a) CuCO3CuO
for the extraction of tin and lead from their chief
(b) Cu(HCO3)2. Cu(OH)2
ores ?
(c) 2CuCO3.Cu(OH)2
(a) carbon reduction and self-reduction
(d) CuCO3. 2Cu(OH)2
(b) self reduction and carbon-reduction
14. Cassiterite is concentrated by
(c) electrolysis and self-reduction
(a) levigation
(d) self-reduction and electrolysis
(b) electromagnetic separation
19. In order to refine “blister copper” it is melted in
(c) floatation
a furnace and is stirred with green logs of wood.
(d) liquefaction
The purpose is
15. One of the ores of lead is known as lead
(a) to expel the dissolved gases in blister
pyromorphite. What is approximate composition?
copper.
(a) Pb3O4.PbCl2 (b) PbSO4.Pb(OH)2
(b) to bring the impurities to surface and oxidize
(c) 3Pb3(PO4)2.PbCl2 (d) PbCO3.Pb(OH)2
them.
16. Consider the following statements – (c) to increase the carbon content of copper.
(A) In the Aluminothermite process, aluminium (d) to reduce the metallic oxide impurities with
acts as reducing agent. hydrocarbon gases liberated from the
(B) The process of extraction of gold involves wood.
the formation of [Au(CN) 2 ] – and 20. Muffle furnace is used in the metallurgy of
(a) Zn (b) Sn
[Zn(CN)4]2–.
(c) Pb (d) Cu

ANSW ER KEY
1 (b) 3 (a) 5 (c) 7 (d) 9 (d) 11 (c) 13 (c) 15 (c) 17 (c) 19 (d)
2 (a) 4 (c) 6 (b) 8 (a) 10 (d) 12 (a) 14 (b) 16 (d) 18 (a) 20 (a)
 THE P-BLOCK
ELEMENTS
21
(GROUP 15, 16, 17
AND 18)

MCQs with One Correct Answer (c) SbH3 > AsH3 < PH3 < NH3
(d) SbH3 < AsH3 < PH3 < NH3
1. NH4 ClO4 + HNO3 (dil.) ¾¾ ® HClO 4 + [X] 5. When PbO2 reacts with conc. HNO3 the gas
D
[X] ¾¾ ® Y(g) evolved is
[X] and [Y] are respectively – (a) NO2 (b) O2
(a) NH4NO3 & N2O (b) NH4NO2 & N2 (c) N2 (d) N2O
(c) HNO4 & O2 (d) None of these 6. When potassium ferrocyanide crystals are
heated with conc. H2SO4, the gas evolved is
2. In the reaction 4HNO 3 + P4 O10 ® 4HPO 3 + X ,
(a) SO2 (b) NH3
the product X is (c) CO2 (d) CO
(a) N2O5 (b) N2O3 7. Hydrolysis of one mole of peroxodisulphuric acid
(c) NO2 (d) H2O produce
3. Ammonia is generally manufactured for fertilizers (a) two moles of sulphuric acid
by the reaction (b) two moles of peroxomonosulphuric acid
(a) 2NH 4 Cl + Ca(OH)2 ® CaCl 2 + 2H 2 O (c) one mole of sulphuric acid and one mole of
+2NH3 peroxomonosulphuric acid
(b) By passing an electric discharge in a mixture (d) one mole of sulphuric acid, one mole of
of N2 and H2 peroxomonosulphuric acid and one mole of
(c) By passing a mixture of N2 and H2 under hydrogen peroxide.
high pressure and moderate temperature 8. [X] + H2SO4 ¾¾ ® [Y] , a colourless gas with
over a catalyst irritating smell
(d) None of these
[Y] + K 2 Cr2 O 7 + H 2SO 4 ¾¾® Green solution
4. Boiling / melting points of the following hydrides
follow in order The species [X] and [Y] are –
(a) SbH3 > AsH3 > PH3 < NH3 (a) SO32–, SO2 (b) Cl–, HCl
(b) SbH3 > AsH3 > PH3 > NH3 (c) S2–, H2S (d) CO32–, CO2
 70 CHEMISTRY

9. In the reaction 13. Which one of the following is correct pair with
+
HNO3 + HF ¾¾ ® H 2 NO3 + F- base is respect to molecular formula of Xenon compound
and hybridization state of Xenon in it?
(a) HF (b) HNO3 (a) XeF4, sp3 (b) XeF2, sp
(c) HF and HNO3 (d) None of these (c) XeF2, sp3d (d) XeF4, sp2
10. HBr and HI reduce sulphuric acid, HCl can reduce 14. What are the products formed in the reaction or
KMnO4 and HF reduces xenon hexafluoride with silicon dioxide ?
(a) XeSiO4 + HF (b) XeF2 + SiF4
(a) H2SO4 (b) KMnO4
(c) XeOF4 + SiF4 (d) XeO3 + SiF2
(c) K2Cr2O7 (d) None of these 15. Which of the following xenon-oxo compounds
11. When Br2 is treated with aqueous solutions of may not be obtained by hydrolysis of xenon
NaF, NaCl and NaI separately fluorides?
(a) F2, Cl2 and I2 are liberated (a) XeO2F2 (b) XeOF4
(b) only F2 and Cl2 are liberated (c) XeO3 (d) XeO4
(c) only I2 is liberated Numeric Value Answer
(d) only Cl2 is liberated 16. How many bonding electron pairs are there in
12. The ease of liquefaction of noble gases increases white phosphorus?
in the order 17. The number of S–S bonds in sulphur trioxide
(a) He < Ne < Ar < Kr < Xe trimer (S3O9) is _________
18. The number of P–O–P bonds in cyclic
(b) Xe < Kr < Ne < Ar < He
metaphosphoric acid is _________
(c) Kr < Xe < He < Ne < Ar 19. The number of P–O–P bonds in P4O10 is _______
(d) Ar < Kr < Xe < Ne < He 20. The number of Cl = O bonds in perchloric acid
is, "______."

ANSW ER KEY
1 (a) 3 (c) 5 (b) 7 (c) 9 (b) 11 (c) 13 (c) 15 (d) 17 (0) 19 (6)
2 (a) 4 (a) 6 (d) 8 (a) 10 (d) 12 (a) 14 (c) 16 (6) 18 (3) 20 (3)
 THE d-AND f-BLOCK
22
ELEMENTS

MCQs with One Correct Answer 5. A compound of a metal ion M x+ ( Z = 24 ) has a

1. What would happen when a solution of spin only magnetic moment of 15 Bohr
potassium chromate is treated with an excess of Magnetons. The number of unpaired electrons
dilute nitric acid? in the compound are
(a) 2 (b) 4
(a) Cr2 O 72- and H2O are formed
(c) 5 (d) 3
(b) CrO 24- is reduced to +3 state of Cr 6. In which of the following compounds manganese
(c) CrO 24- is oxidized to +7 state of Cr has oxidation number equal to that of iodine in
KIO4 ?
(d) Cr3+ and Cr2O 72- are formed (a) Potassium manganate
2. The correct order of ionic radii of Y3+, La3+, Eu3+ (b) Potassium permanganate
and Lu3+ is (c) Manganous chloride
(a) La 3+ < Eu 3+ < Lu 3+ < Y 3+ (d) Manganese chloride
7. When MnO2 is fused with KOH, a coloured
(b) Y 3+ < La 3+ < Eu 3+ < Lu 3+
compound is formed, the product and its colour
(c) Y 3+ < Lu 3+ < Eu 3+ < La 3+ is:
(d) Lu 3+ < Eu 3+ < La 3+ < Y 3+ (a) K2MnO4, purple green
(Atomic nos. Y =39, La = 57, Eu = 63, Lu = 71) (b) KMnO4, purple
3. Which of the following oxides of manganese is (c) Mn2O3, brown
amphoteric? (d) Mn3O4, black
(a) MnO 2 (b) Mn 2O3 8. If an aqueous solution of KCN is added to a
(c) Mn 2O7 (d) MnO solution of ferrous salt then the complex formed
4. Which of the following compound is called is represented by
Turnbull’s blue? 4- 3-
(a) é Fe ( CN ) ù (b) éFe ( CN ) ù
(a) Ferricyanide (b) Ferrous ferricyanide ë 6û ë 6û
3+ 2+
(c) Ferrous cyanide (d) Ferri-ferrocyanide (c) é Fe ( H 2O ) ù (d) éFe ( H2 O ) ù
ë 6û ë 6û
 72 CHEMISTRY

9. For the four successive transition elements (Cr, (c) Mercury (II) chloride and mercury
Mn, Fe and Co), the stability of +2 oxidation (d) Mercury
state will be there in which of the following order? 15. Consider the following statements
(a) Mn > Fe > Cr > Co (b) Fe > Mn > Co > Cr (I) La(OH) 3 is the least basic among
(c) Co > Mn > Fe > Cr (d) Cr > Mn > Co > Fe hydroxides of lanthanoids.
10. In neutral or faintly alkaline medium, thiosulphate (II) Zr4+ and Hf 4+ posses almost the same ionic
is quantitatively oxidized by KMnO4 to radii.
(a) SO32– (b) SO42– (III) Ce4+ can as an oxidizing agent.
(c) SO2 (d) SO52– Which of the above is/are true ?
11. An excess of Na 2S2O3 reacts with aqueous (a) (I) and (III) (b) (II) and (III)
CuSO4 to give (c) (II) only (d) (I) and (II)
(a) CuS2O3 (b) Cu2S2O3
Numeric Value Answer
(c) Na2[Cu(S2O3)2] (d) Na4[Cu6(S2O3)5]
12. Which of the following oxides of Cr is 16. The number of water molecule(s) directly bonded
amphoteric to the metal centre in CuSO4.5H2O is
(a) CrO2 (b) Cr2O3 17. The oxidation number of Mn in the product of
(c) CrO5 (d) CrO3 alkaline oxidative fusion of MnO2 is
13. The roasting of HgS in air produces 18. What is the oxidation states of Cr in butterflystructure.
(a) HgO (b) HgSO3 19. Out of the following, how many oxides are acidic.
(c) HgSO4 (d) Hg MnO, Mn2O3, MnO2, MnO3, Mn2O7
14. Mercury (I) chloride sublimes, when this 20. A light blue coloured compound (A) on heating gives
compound is heated and the vapours it gives off
a block compound (B) which reacts with glucose to
are cooled the substance collected consists of
give a red compound (C). After the completion of
(a) Mercury (II) chloride
reaction, how many metal oxides are formed?
(b) Mercury (I) and Mercury (II), chlorides

ANSW ER KEY
1 (a) 3 (a) 5 (d) 7 (a) 9 (a) 11 (d) 13 (d) 15 (b) 17 (6) 19 (3)
2 (c) 4 (b) 6 (b) 8 (a) 10 (b) 12 (a) 14 (d) 16 (4) 18 (6) 20 (2)
 COORDINATION 23
COMPOUNDS

MCQs with One Correct Answer achiral ligands), the correct statement, among
the following, is
1. Which one is the most likely structure of CrCl3. (a) MX4Y2 has 2 geometrical isomers one of
6H2O if 1/3 of total chlorine of the compound is which is chiral.
precipitated by adding AgNO3 (b) MX4Y2 has 2 geometrical isomers both of
(a) CrCl3.6H2O which are achiral.
(c) MX4Y2 has 4 geometrical isomers all of
(b) [Cr(H2O)3Cl3].(H2O)3
which are achiral.
(c) [CrCl2(H2O)4] Cl.2H2O (d) MX4Y2 has 4 geometrical isomers two of
(d) [CrCl(H2O)5] Cl2.H2O which are chiral.
2. The octahedral complex CoSO4Cl.5 NH3 exists 4. Which of the following coordination
in two isomeric fonns X and Y. Isomer X reacts compounds will give precipitate with an
with AgNO3 to give a white precipitate, but does aqueous solution of AgNO3?
not react with BaCl2. Isomer Y gives white (a) [Cr(NH3)6]Cl3 (b) [Cr(NH3)3Cl3]
precipitate with BaCl2 but does not react with (c) [Cr(NH3)5Cl]SO4 (d) Na3[Cr(CN)6]
AgNO3. 5. Oxidation state of “V” in Rb4K[HV10O28] is
Isomers X and Y are (a) + 5 (b) + 6
(a) ionization isomers 7
(c) + (d) + 4
(b) linkage isomers 5
(c) coordination isomers 6. The complex that can exhibit linkage isomerism is
(d) solvate isomers (a) [Co(NH3)5(H2O)]CI3
3. For an octahedral complex MX 4Y2 (M = a (b) [Co(NH3)5(NO2)]C12
transition metal, X and Y are monodentate (c) [Co(NH3)5(NO3)](NO3)2
(d) [Co(NH3)5Cl]SO4
 74 CHEMISTRY

7. The complex having the highest spin only 14. K 3[Al(C 2O 4 )3 ] is called
magnetic moment is
(a) [Fe(CN)6]3– (b) [Fe(H2O)6]2+ (a) Potassium aluminooxalate
(c) [MnF6] 4– (d) [NiCl4]2– (b) Potassium trioxalatoaluminate (III)
8. Which of the following complex will show (c) Potassium aluminium (III) oxalate
geometrical as well as optical isomerism (d) Potassium trioxalatoaluminate (VI)
(en=ethylenediammine) 15. When AgNO 3 is added to a solution of
(a) Pt(NH3)2Cl2 (b) [Pt(NH3)Cl4] Co(NH3)5Cl3, the precipitate of AgCl shows two
(c) [Pt(en)3]4+ (d) [Pt(en)2Cl2] ionizable chloride ions. This means :
9. In which of the following pairs both the (a) Two chlorine atoms satisfy primary
complexes show optical isomerism ? valency and one secondary valency
(a) cis-[Cr(C2O4)2Cl2]3+, cis [Co(NH3)4Cl2] (b) One chlorine atom satisfies primary as well
(b) [Co(en)3]Cl3, cis-[Co(en)2Cl2]Cl as secondary valency
(c) [PtCl(dien)]Cl, [NiCl2Br2]2- (c) Three chlorine atoms satisfy primary
(d) [Co(NO3)3(NH3)3], cis - [Pt(en)2Cl2]
valency
10. When 0.01 mole of a cobalt complex is treated
(d) Three chlorine atoms satisfy secondary
with excess silver nitrate solution, 4.305 g silver
valency
chloride is precipitated. The formula of the
16. Among the following, the pair of paramagnetic
complex is
(a) [Co(NH3)3Cl3] complexes is
(b) [Co(NH3)5Cl]Cl2 (a) K3[Fe(CN)6] and K3 [CoF6]
(c) [Co(NH3)6]Cl3 (b) K3[Fe(CN)6] and [Co(NH3)6]Cl3
(d) [Co(NH3)4Cl2]NO3 (c) K4[Fe(CN)6] and K3[CoF6]
11. Which of the following complexes does not show (d) K4[Fe(CN)6] and [Co(NH3)6]Cl3
the geometric isomerism ?
17. The tetrahedral [CoI 4 ]2 - and square planar
(a) Pt( NH3 ) 2 Cl 2
[Pd Br4 ]2 - complex ions are respectively
(b) [Pt( NH 3 ) ( NH 2 OH) ( NO 2 ) (C 6 H 5 N)] NO 2
(a) low spin, high spin
(c) Pt ( NH 2 CH 2COO) 2 (b) high spin, low spin
(d) [Cu ( NH 3 ) 4 ] Cl 2 (c) both low spin
12. [Co(NH3)4(NO2)2]Cl exhibits (d) both high spin
(a) linkage isomerism, ionization isomerism and 18. Crystal field stabilization energy for high spin
geometrical isomerism d 4 octahedral complex is:
(b) ionization isomerism, geometrical isomerism (a) – 1.8 Do (b) – 1.6 Do + P
and optical isomerism (c) – 1.2 Do (d) – 0.6 Do
(c) linkage isomerism, geometrical isomerism 19. Low spin complex of d 6-cation in an octahedral
and optical isomerism field will have the following energy :
(d) linkage isomerism, ionization isomerism and
optical isomerism -12 -12
(a) Do + P (b) D o + 3P
13. Which one of the following has the highest molar 5 5
conductivity?
(a) Diamminedichloroplatinum (II) -2 -2
(c) D o + 2P (d) Do + P
(b) Tetraamminedichlorocobalt (III) chloride 5 5
(c) Potassium hexacyanoferrate (II) (D 0= Crystal Field Splitting Energy in an
(d) Hexaaquachromium (III) chloride octahedral field, P = Electron pairing energy)
Coordination Compounds 75

20. In which of the following octahedral complex
species the magnitude of Do will be maximum ?
(a) [Co (H 2 O)6 ]2+ (b) [Co(CN)6 ]3-
(c) [Co(C2 O4 )3 ]3- (d) [Co (NH3)6]3+
Numeric Value Answer
21. The number of unpaired electrons in the complex
ion [CoF6]3– is (Atomic no.: Co = 27)
22. The possible number of isomers of the complex
23. The total number of coordination sites in
ethylenediaminetetraacetate (EDTA4–) is ______.
24. Considering that D 0 > P, the magnetic moment
(in BM) of [Ru(H2O)6]2+ would be __________.
25. The volume (in mL) of 0.125 M AgNO3 required
to quantitatively precipitate chloride ions in 0.3
g of [Co(NH3)6]Cl3 is _______.
M [Co(NH ) ]Cl3 = 267.46 g/mol
36

[MCl2Br2]SO4 is ________. MAgNO3 = 169.87 g/mol

ANSWER KEY
1 (c) 4 (a) 7 (c) 10 (c) 13 (c) 16 (a) 19 (b) 22 (4) 25 (26.92)
2 (a) 5 (a) 8 (d) 11 (d) 14 (b) 17 (b) 20 (b) 23 (6)
3 (b) 6 (b) 9 (b) 12 (a) 15 (a) 18 (d) 21 (4) 24 (0.0)
 76 CHEMISTRY

HALOLALKANES AND
24
HALOARENES

MCQs with One Correct Answer 6. Consider the reactions :

(i) C H OH
2 5
1. (CH3)3CMgCl on reaction with D2O produces : (CH 3 )2 CH - CH 2Br ¾¾¾¾¾ ®
(a) (CH3)3CD (b) (CH3)3OD (CH3 )2CH - CH 2OC2H5 + HBr
(c) (CD3)3CD (d) (CD3)3OD
C H O-
2. CH 3 - CH 2 - C H - CH 3 obtained by (ii) 2 5
(CH 3 ) 2 CH - CH 2 Br ¾¾¾¾¾ ®
|
Cl (CH 3 )2CH - CH2OC2 H5 + Br -
chlorination of n-butane, will be
The mechanisms of reactions (i) and (ii) are
(a) l-form (b) d-form
(c) meso form (d) racemic mixture respectively :
3. Most reactive halide towards SN1 reaction is (a) SN1 and SN2 (b) SN1 and SN1
(a) n-Butyl chloride (b) sec-Butyl chloride (c) SN2 and SN2 (d) SN2 and SN1
(c) tert-Butyl chloride (d) Allyl chloride
4. Arrange the following halides in the decreasing 7. Which one of the following alkyl halides has the
order of SN1 reactivity : lowest boiling point?
(a) n-Butyl chloride
CH3CH 2CH 2Cl, CH2 = CHCH(Cl)CH3 , (b) iso-Butyl chloride
I II
(c) sec-Butyl chloride
CH 3CH 2CH (Cl)CH 3 (d) tert-Butyl chloride
III 8. Although hexafluoroethane (C2F6, b.p. –79ºC) and
(a) I > II > III (b) II > I > III ethane (C2H6, b.p. – 89ºC) differ very much in
(c) II > III > I (d) III > II > I their molecular weights, their boiling points differ
5. The compound most reactive towards S N1 only by 10ºC. This is due to
reaction is (a) low polarizability of F
(a) Me 3COCH 2 Cl (b) MeOCH 2 Cl (b) nearly similar size of F and H
(c) C 6 H 5CH 2 CH 2 Cl (d) Cl (c) both (a) and (b)
(d) Neither of the two
Halolalkanes and Haloarenes 77

CH2CN
9. O2N COCl + R (b)

O2N COCH2CH3 I
CH2CN
The reagent R may be (c)
CH3CH2MgBr CH3 CH2Li
I II CN
(CH3CH2)2Cd (CH3CH2)2CuLi
CH2Cl
III IV (d)
(a) I or II (b) I or II or III
CN
(c) III or IV (d) Any of the four
10. Pick up the final product in the following reaction. I
12. Which of the following is fast de-brominated ?
Br
H O
(a) (b)
O ¾®[ ] ¾¾2¾® Product
+ C 2 H 5 MgBr ¾
Br
C2H5 Br
(c) (d)
(a)
Br
13. Which of the following is least reactive towards
nucleophilic substitution with aq. KOH ?
OH
Cl Cl
(b) NO2
OH
(a) (b)

NO2 NO2
(c) Br Cl
C2H5 OH

(c) (d)
(d)
OH OH OH
OH
11. The structure of the major product formed in the 14. Which of the following gives white precipitate
following reaction when treated with silver nitrate solution ?
CH2Cl (a) CHCl3
NaCN
is (b) CH 2 —— CHCH 2 Cl
DMF
(c) C6 H5CH 2Cl
I
Cl
CH2Cl
O2N NO2
(a)
(d)
CN
NO2
 78 CHEMISTRY

15. Chloropicrin is obtained by the reaction of 18.

(a) steam on carbon tetrachloride
(i) HCl/ZnCl2
(b) nitric acid on chlorobenzene CH3 H Product
(c) chlorine on picric acid
Ph – CH – C – CH2 – CH3 Product
(d) nitric acid on chloroform (ii) SOCl2
OH Product
Numeric Value Answer (iii) PCl5
(Optically pure
single stereoisomer)
CH3
Find the sum of total number of isomeric chlorides
16. obtained in these reactions (consider only the
H3C OH major products)
H +
Br , CCl 19. How many possible monochloro structural
¾¾
¾®[F] ¾¾2¾ ¾
¾4 ® C H Br
isomers are expected to form on free radical
-H 2O 14
428432
5 such products . chlorination of (CH3)2CH CH2CH3?
are possible
20. The total number of monohalogenated organic
How many structures for F are possible? products in the followin g (including
17. Find the number of total number of structural and stereoisomers) reaction is __________.
configurational isomers of a bromo compound, (i) H /Ni/Δ
C5H9Br, formed by the addition of HBr to 2- A ¾¾¾¾¾
2
®
(ii) X 2 /Δ
pentyne respectively. (Simplest optically
active alkene)

ANSW ER KEY
1 (a) 3 (c) 5 (b) 7 (d) 9 (c) 11 (b) 13 (d) 15 (d) 17 (6) 19 (4)
2 (d) 4 (c) 6 (a) 8 (c) 10 (b) 12 (c) 14 (d) 16 (3) 18 (4) 20 (8)
 ALCOHOLS, PHENOLS 25
AND ETHERS

MCQs with One Correct Answer CH3 - CH 2 - CH 2 - CH 2

|
1. Which one of the following is not formed when OH
(I)
glycerol reacts with HI ?
(a) CH3 — CHI — CH3 OH
(b) CH3 — CH = CH2 |
CH3 - CH 2 - CH - CH3
(c) CH2OH — CHI — CH2OH
(d) CH2 = CH — CH2I (II)
2. The reaction of Lucas reagent is fastest with:
OH OH
(a) (CH3 ) 2CHOH (b) CH3(CH 2 )2OH |
CH 2 = CH - CH - CH3
(c) CH3CH 2OH (d) (CH3 )3COH (III) (IV)
3. Following compounds are given:
(a) I > III > II > IV (b) IV > III > II > I
(i) CH3CH2OH (ii) CH3COCH3
(c) IV > II > III > I (d) III > IV > II > I
(iii) CH 3 - CHOH (iv) CH3OH 5. The product of the following reaction is
(i ) BH 3 / THF
CH 3 ¾¾ ¾ ¾ ¾ ¾
¾ ®
-
(ii ) H 2 O 2 , OH
Which of the above compound(s), on being
warmed with iodine solution and NaOH, will give (a) 1-Pentanol (b) 2-Pentanol
iodoform? (c) Pentane (d) 1,2-Pentanediol
(a) (i) and (ii) 6. In the following sequence of reactions,
(b) (i), (iii) and (iv) CH 3 - CH - CH 3 ¾¾¾¾
HNO
2 ® A ¾¾ ¾¾¾
®B
Oxidation
(c) (i) only |
(d) (i), (ii) and (iii) NH 2
i ) CH MgI
4. Which of the following is the correct order for B ¾¾ ¾3¾¾® C
ii ) H 3O +
ease of dehydration– the compound C formed will be
 80 CHEMISTRY

(a) Butanol-1 +
(b) Butanol-2
(c) 2-Methylpropanol-1 (a) (b)
(d) 2-Methyl-2-propanol +
7. Ethanol when reacted with PCl5 gives A, POCl3 + +
and HCl. A reacts with silver nitrite to form B (c) (d)
(major product) and AgCl. A and B respectively
are
(a) C2H5Cl and C2H5OC2H5
Conc. H2SO4
(b) C2H6 and C2H5OC2H5 12. Major product is
(c) C2H5Cl and C2H5NO2
(d) C2H6 and C2H5NO2
8. Arrange the following alcohols in order of OH
increasing ease of dehydration
CH 3CH 2 OH C 6 H 5 CH 2 OH
I II (a) (b)
Cl 3CCH 2 OH F3CCH 2 OH
III IV
(a) II < I < IV < III (b) IV < III < II < I
(c) IV < III < I < II (d) II < I < III < IV
(c) (d)
(i) B 2H 6
9. – X . The compound
2 2 13. Anisole is treated with HI under two different
X is conditions.
HI ( g ) conc . HI
CH3 CH3 C + D ¬¾¾¾ C 6 H 5 OCH 3 ¾¾ ¾¾® A + B
(a) H (b) H The nature of A to D will be
OH H (a) A and B are CH3I and C6H5OH, while C and
D are CH3OH and C6H5I
H OH
(b) A and B are CH3OH and C6H5I, while C and
CH3 D are CH3I and C6H5OH
(c) HO (d) Both (b) and (c) (c) Both A and B as well as both C and D are
CH3I and C6H5OH respectively.
H (d) A and B are CH3I and C6H5OH, while there
H is no reaction in the second case.
10. Which of the following is most reactive towards OH
aqueous HBr ? Br
(a) 1-Phenyl - 2- propanol 14. H2O
(b) 1- Phenyl - 1- propanol
(c) 3-Phenyl - 1 - propanol
(d) 2- Phenyl - 1 - propanol The driving force in the above reaction is
11. Which carbocation is more likely to be formed in (a) conver sion of 1º carbocation to 2º
carbocation
OH
(b) conver sion of 1º carbocation to 3º
+ carbocation
the dehydration of H
(c) releif in steric strain due to expansion of ring
(d) both a & c
Alcohols, Phenols and Ethers 81

O (a) 2, 4, 6-tribromophenol
NaOH (b) p-bromophenol
15. CH3CH2 – C — CH2 ¾¾¾¾
18
® (c) o- and p-bromophenol
H 2O
CH3 (d) m-bromophenol
18. Arrange the following phenols in order of their
Major product is increasing acidity.
OH OH OH
18
OH OH NO2
| |
(a) CH3CH 2 - C - CH 2
|
NO2
CH3
NO2
I II III
18
OH OH (a) I > III > II (b) I > II > III
| | (c) III > I > II (d) III > II > I
(b) CH3 CH 2 - C - CH 2
|
14
CH3 CH2
O
OH OH heat
| | 19. H3C CH3 ¾¾¾
® P. P is
(c) CH3 CH 2 - C - CH 2
|
CH3

18
OH 18
OH OH 14
| | (a) H3C CH2
(d) CH3 CH 2 - C - CH 2
|
CH3

16. Which of the carbocations is more likely to be CH3

formed when is heated with conc (b)

OH

H2SO4 ?

(a) (b) +
+ OH
14
(c) H3C
(c) both in equal amounts (d) None
17. Phenol on reaction with Br2 in non-polar aprotic
solvent furnishes
CH3
 82 CHEMISTRY

Numeric Value Answer

(d) H+ Br2, CCl4

[F] ¾¾¾¾® C 4H 8Br 2
21. (– H2O) 5 isomers
OH
How many structures are possible for F ?
22. How many of the following phenols will give
lower yield during Kolbe-Schmidt reaction ?
OH OH OH

CH3OH CH3OH , and

20. Y ¬¾¾¾ H2C — CHCH 3 ¾¾¾® H+
X
CH 3 ONa
O
CH3 OCH3 NO2
Here X and Y respectively are
(a) CH2 – CHCH3 and HOCH2 – CHCH3 23. What is the total number of stereoisomers of the
product ‘Q’?
OCH3 OH OCH3
(b) HOCH – CHCH and CH – CHCH
2 3 2 3

OCH3 OCH3 OH
24.
(c) CH2 – CHCH3 in both cases

OCH3 OH
How many carbon atoms are present in the ring
(d) HOCH – CHCH in both cases
2 3 of reactant ether?
25. How many moles of CH4 will evolve from the
OCH3 following reaction?

ANSWER KEY
1 (c) 4 (b) 7 (c) 10 (b) 13 (c) 16 (b) 19 (d) 22 (1) 25 (3)
2 (d) 5 (a) 8 (c) 11 (c) 14 (c) 17 (c) 20 (b) 23 (3)
3 (d) 6 (d) 9 (b) 12 (c) 15 (b) 18 (c) 21 (3) 24 (4)
 ALDEHYDES, KETONES 26
AND CARBOXYLIC ACIDS

MCQs with One Correct Answer (a) CH3COOH (b) CH3CH2NHOH

(c) CH3CONH2 (d) CH3CHO
1. Suggest appropriate structures for the missing 3. Which of the following reactions can produce
final compound. (The number of carbon atom R – CO – Ar?
remains the same throughout the reaction) AlCl3
(a) ArCOCl + H - Ar ¾¾¾ ®
CH3 (b) RCOCl + ArMgX ®
(c) ArCOCl + RMgX ®
AlCl
CH3 (d) RCOCl + H - Ar ¾¾ ¾ 3®

4. The suitable reaction steps to carry out the

dil. KMnO HIO OH - following transformation
¾¾¾¾¾
4 ® A ¾¾¾®
4 B ¾¾¾® C
O ? ? H
CHO ¾¾¾® ¾¾¾®
O
(a) (b)
CH3
CH3 (a)
(i ) BH 3 , THF
¾¾ ¾ ¾ ¾ ¾¾® ¾¾¾®
PCC
(ii ) H 2O 2 , NaOH CH 2Cl 2

CHO (i ) BH , THFHIO4
CHO (b) ¾¾ ¾ ¾
3 ¾ ¾¾®
¾¾¾ ®
(c) (d) (ii ) H 2O 2 , NaOH

(c) H O, H SOPCC
CHO ¾¾¾¾¾¾
2 2 4®
¾¾¾®
CH 2Cl 2
2. Identify the product C in the series OsO K Cr O , H SO
Na / C2 H5OH HNO 2 Cu / 573K (d) ¾¾¾¾¾¾¾¾¾
4
– ® ¾¾¾¾¾¾¾
2 2 7 2 4®
CH 3CN ¾¾¾¾¾¾
® A ¾¾¾¾
® B ¾¾¾¾¾
®C (CH 3 )3 C.COOH, OH H 2O
 84 CHEMISTRY
11. If 3-hexanone is reacted with NaBH4 followed
O
by hydrolysis with D2O, the product will be
OH - (a) CH3CH2CH(OH)CH2CH2CH3
5. 2 ¾¾¾® Product is (b) CH3CH2CD(OH)CH2CH2CH3
D
(c) CH3CH2CH(OD)CH2CH2CH3
(d) CH3CH2CD(OD)CH2CH2CH3
(a) 12. Consider the following statements :
I. Acetoph enone can be pr epared by
O oxidation of 1-phenylethanol
II. Acetoph enone can be pr epared by
(b) reaction of benzaldehyde with methyl
magnesium bromide
III. Acetophenone can be prepared by Friedel-
Craft’s reaction of benzene with acetyl chloride
(c) IV. Acetoph enone can be pr epared by
O distillation of calcium benzoate
Which of the above statements are correct ?
(a) II and III (b) I and IV
(d) O (c) I and III (d) III and IV
13. Arrange the following in order of decreasing acidity
6. Which gives lactic acid on hydrolysis after
O
reacting with HCN ?
(a) HCHO (b) CH3CHO (A) O O
(B)
(c) C6H5CHO (d) CH3COCH3
7. The reactant (X) in the reaction
CH COONa CH 2
(X) ¾¾¾¾¾
3 ¾® Cinnamic acid, is
(CH CO) O
3 2

COOH CHO (C)

(a) (b)
(a) C > A > B (b) C > B > A
CH 3 CH2OH (c) A > C > B (d) A > B > C
14. Which one of the following compounds will be
(c) (d) most readily dehydrated?
OH
8. The increasing order of the rate of HCN addition
to compound A – D is
(a) CH3
(A) HCHO (B) CH3COCH3 O
(C) PhCOCH3 (D) PhCOPh O
(a) D < C < B < A (b) C < D < B < A
(c) A < B < C < D (d) D < B < C < A
9. Oxidation of acetaldehyde with selenium dioxide (b) CH3
OH
produces
(a) ethanoic acid (b) methanoic acid O
(c) glyoxal (d) oxalic acid
10. The reaction of C6H5CH = CHCHO with NaBH4 (c) H3 C
gives OH
(a) C6H5CH2CH2CH2OH
(b) C6H5CH = CHCH2OH
O OH
(c) C6H5CH2CH2CHO
(d) C6H5CH2CHOHCH3 (d) CH3
Aldehydes, Ketones and Carboxylic Acids 85
15. The order of stability of the following tautomeric 20. Which of the following will undergo alkaline
compounds is : hydrolysis most rapidly ?
OH O COOCH3 COOCH3
| ||
CH 2 = C - CH 2 - C - CH 3
I
O O (a) (b)
|| ||
CH3 - C- CH2 - C- CH 3
II CH3
OH O COOCH3
| || COOCH3
CH 3 - C = CH - C - CH 3
III
(a) III > II > I (b) II > I > III (c) (d)
(c) II > III > I (d) I > II > III
16. In the following reaction
Br / P excess NH Cl NO2
RCH 2 COOH ¾¾¾¾
2 ® X ¾¾¾¾¾
3® Y
21. Acidic hydrolysis is minimum in
The major compounds X and Y are
OCOR OCOR
(a) RCHBrCONH2 ; RCH(NH2)COOH
(b) RCHBrCOOH ; RCH(NH2)COOH
(c) RCH2COBr ; RCH2COONH4 (a) (b)
(d) RCHBrCOOH ; RCH2CONH2 NO2
17. The correct order of increasing acid strength of OCOR OCOR
the compounds
(A) CH3CO2H (B) MeOCH2CO2H
Me (c) (d)
(C) CF3CO2H (D) CO2H
Me
is NO2 OC2H5
(a) D < A < B < C (b) A < D < B < C
22. The major product of the following reaction,
(c) B < D < A < C (d) D < A < C < B
18. Which of the following on oxidation followed O
NaBH4
CO2H ¾¾®
by hydrolysis gives pyruvic acid ? is
(a) Acetaldehyde cyanohydrin
(b) Acetone cyanohydrin
(c) Formaldehyde cyanohydrin OH
(d) None of these (a) CO2H
19. An organic compound ‘A’ on treatment with NH3
gives ‘B’ which on heating gives ‘C’, ‘C’ when OH
treated with Br 2 in the presence of KOH OH
(b)
produces ethylamine. Compound ‘A’ is:
(a) CH3COOH O
(b) CH3 CH2 CH2 COOH OH
(c)
(c) CH3 – CHCOOH
CH3 CO2H
(d)
(d) CH3CH2COOH
 86 CHEMISTRY
23. Reaction of phenol with NaOH followed by heating O
with CO2 under high pressure, and subsequent H
acidification gives compound X as the major (a) H
product, which can be purified by steam O
distillation. When reacted with acetic anhydride O
in the presence of a trace amount of conc. H2SO4, (b)
compound X produces Y as the major product. H CN
Compound Y is O
O H
(c) EtO
OH O O O
O O
(a) CO2H (b) O H
(d) HO
O
O
Numeric Value Answer
OH
O
26. 1, 2-Diethylbenzene on ozonolysis gives how
many different products?
(c) (d) 27. How many products are formed when ethanal
O
reacts with propanal in the presence of a base?
O O 28. The amount (in mol) of bromoform (CHBr 3)
CO2H
produced when 1.0 mole of acetone reacts
24. The product of which of the following reactions completely with 9.0 mole of bromine in the
forms a reddish brown precipitate when presence of aqueous NaOH is
subjected to Fehling’s test? 29. Number of possible geometrical isomers for [X]
CO, HCl
(a) ¾¾¾¾¾¾® CHO
anh. AlCl3 , CuCl OH
V
+ CH3COCH3 [X]
?
Cl
(b) + (CH3CH2)2Cd ¾¾¾®
O OH
CO2H CN
1. PCl 5
(c) ¾¾¾¾¾¾¾®
2. H 2 , Pd-BaSO4
30. HO CN
1. O3 COOC2H5 O
(d) ¾¾¾¾®
2. Zn/H2 O
Å
H3O
25. The major product of the following reaction ¾¾¾D
® [P]
O
excess DIBAL-H
Number of moles of NaOH required to neutral-
EtO CN ¾¾¾¾¾¾® ize one mole of [P]
toluene, –78 °C
then H3O +
is

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

MCQs with One Correct Answer The increasing order of their boiling point is
(a) III < II < I (b) I < II < III
1. The end product (Y) in the reaction sequence (c) II < III < I (d) II < I < III
CH 3 CONH 2 ¾¾¾
PO
2 5 ® X ¾¾¾¾ Sn / HCl
® Y , is : 5. Which of the following reactions will not give a
D primary amine?
(a) ethane nitrile (b) acetic acid Br / KOH
(a) CH 3 CONH 2 ¾¾2¾ ¾
¾®
(c) ethanamine (d) chloroethane
2. The end product of the reactions is (b) LiAlH
CH 3 CN ¾¾ ¾¾
4®

HNO PCl H.NH

C2 H5 NH 2 ¾¾¾
2
® A ¾¾¾
5
® B ¾¾¾2¾
®C (c) LiAlH
CH 3NC ¾¾¾¾
4®

(a) ethyl cyanide (b) ethyl amine (d) CH 3CONH 2 ¾¾ ¾¾

4® LiAlH
(c) methyl amine (d) acetamide
6. NaCN Ni / H
3. The correct order of basicities of the following CH 3 CH 2 Cl ¾¾ ¾
¾® X ¾¾ ¾
¾2®Y

compounds is acetic anhydride

¾¾ ¾ ¾ ¾ ¾ ¾® Z
NH Z in the above reacting sequence is
1. CH3 - C 2. CH3 - CH2 - NH2 (a) CH 3CH 2CH 2 NHCOCH 3
NH2 (b) CH 3CH 2 CH 2 NH 2
(c) CH3CH 2 CH 2CONHCH3
O
|| (d) CH 3CH 2 CH 2 CONHCOCH 3
3. (CH3)2NH 4. CH 3– C–NH 2
7. Identify the prdouct C in the series
(a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4 Na/C H OH HNO
CH3CN ¾¾¾¾¾¾
2 5
® A ¾¾¾¾
2®B
(c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4
4. n-Butylamine(I), diethylamine(II) and ¾¾¾¾¾
Cu/573K
®C
N, N-dimethylethyl amine(III) have the same (a) CH 3COOH (b) CH3CH2NHOH
molar mass.
(c) CH 3CONH 2 (d) CH 3CHO
 88 CHEMISTRY

8. The major organic product formed from the

following reaction : NHCH3 NHCH3

O (i) CH NH NO
3 2
¾¾¾¾¾¾¾® ...... (b) +
(ii) LiAlH4, (iii) H 2O
is
NO
O – NHCH3
OH
(a)
N CH3
(c)
(b)
NCH3
CH3
H
N N=O
H (d)
NCH3
(c) 11. In a set of reactions m-bromobenzoic acid gave
OH a product D. Identify the product D.

H COOH
NCH3 SOCl NH NaOH
(d) ¾¾®
2
B ¾¾®
3
C ¾¾® D
Br 2
OH Br

SO2NH2 COOH
(i) H2O 2
9. ¾¾¾® Product P is (a) (b)
(ii) heat

CH3 N(CH3)2 Br NH2

NH2 CONH2
(a) N (b) (c) (d)
CH3 CH3
Br Br

(c) (d)
12. NH2
10. Predict the product:
(I)
NHCH 3 + NaNO 2 + HCl (CH CO) O ,Pyridine
(i) LiAlH 4
3 2
¾¾¾¾¾¾¾¾® (II) ¾¾¾¾¾ ® III
(ii) H 2O

¾¾¾® Product The basicity order of I, II and III is –

CH3 (a) III > I > II (b) I > II > III
N NO2 (c) III > II > I (d) II > III > I
(a)
Amines 89
13. What could be the product for the following
NH2 NH2
reaction?
N(CH3)2 (c) X = Y=
O2N
NaNO ,HCl O O
¾¾¾¾¾
2 ¾® Product ?
NH2
+
Cl N2 Z=
O2N
OH

(a) (b) O

NO2
H H
N (CH3)2 N N

(c) (d) X= O Y= O
NO
NO2
NH2
CH3
Z=
+
N
(d) NO 15. The correct order of basicity of the following
CH3 amines

14. The major products X, Y and Z in the following NH2 NH2

sequence of transformations
O O
NH2 O I II
conc. HNO 3
¾¾¾¾® X ¾¾¾¾®
conc. H2SO 4 NH2 NH2
15 °C

conc. HNO aq. NaOH H3C O2N

X Y ¾¾¾® Z
are III IV

NH2 NH2 is
(a) X= Y= (a) I > II > III > IV (b) I > III > II > IV
NO2
(c) III > II > I > IV (d) IV > III > II > I
O O
NH2 Numeric Value Answer
Z = HO 16. How many of the following method(s) is/ are
NO2
used for eliminating nitrogen of an amine present
O
outside the ring?
H H Hofmann elimination, Cope elimination and Emde
N N
degradation
(b) X= O Y= O 17. How many of the following compounds can be
O 2N

NH2
methylated by diazomethane ?
C2H5COOH, C2H5NH2 , C6H5OH and
Z=
O 2N CH3COCH2COOC2H5
 90 CHEMISTRY

18. Starting with nitrobenzene, what is the minimum 19. Find the total number of bromine atoms present
number of following reagents required to in the end product of following scheme of
convert it to P-dinitrobenzene? reactions.

(a) Conc. HNO3 + Conc. H2SO4, NH2

(b) NH3 Br2 Diazotisation CuBr
(c) C2H5OK H2O

(d) Sn + HCl Br 2
NO2 Sn/HCl
(e) NaNO2 + HBF4 H2O
(f) NaNO2 + Cu NH2
(i) HNO2, 0°C
(g) (CH3CO)2O + Pyridine 20. NH2 (ii) dil. H2SO4, D; (iii) HI, D
(h) H3O+
How many hydrogen atoms are present in the
final product of above reaction?

ANSWER KEY
1 (c) 3 (d) 5 (c) 7 (d) 9 (d) 11 (c) 13 (c) 15 (b) 17 (3) 19 (5)
2 (b) 4 (a) 6 (a) 8 (b) 10 (d) 12 (a) 14 (b) 16 (2) 18 (6) 20 (7)
 BIOMOLECULES
MCQs with One Correct Answer
1. What will happen when D-(+)-glucose is treated
with methanolic —HCl followed by Tollens’
reagent ?
(a) A black ppt. will be formed
(b) A red ppt. will be formed
(c) A green colour will appear
(d) No characteristic colour or ppt. will be
formed.
2. Which one of the following statements is not
true regarding (+) lactose ?
(a) On hydrolysis (+) lactose gives equal
amount of D(+) glucose and D(+)
galactose.
(b) (+) Lactose is a b-glycoside formed by the
union of a molecule of D(+) glucose and a
molecule of D(+) galactose.
(c) (+) Lactose is a reducing sugar and does
not exhibit mutarotation.
(d) (+) Lactose, C12H22O11 contains 8-OH
groups.
3. The term anomers of glucose refers to
(a) enantiomers of glucose
(b) isomers of glucose that differ in
configuration at carbon one (C-1)
28
(c) isomers of glucose that differ in
configurations at carbons one and four
(C-1 and C-4)
(d) a mixture of (D)-glucose and (L)-glucose
4. The linkage between the two monosaccharide
units in lactose is
(a) C1 of b-D-glucose and C4 of b-D-galactose
(b) C1 of b-D-galactose and C4 of b-D-glucose
(c) C1 of a-D-galactose and C4 of b-D-glucose
(d) C1 of b-D-galactose and C4 of a-D-glucose
5. Natural glucose is termed D-glucose because :
(a) – OH on the second carbon is on the right
side in Fischer projection
(b) – OH on the sixth carbon is on the right
side in Fischer projection.
(c) – OH on the fifth carbon is on the right side
in Fischer projection.
(d) It is dextrorotatory.
6. Which of the following statement is not correct?
(a) Amylopectin is a branched polymer of a -
glucose.
(b) Cellulose is a linear polymer of b-glucose
(c) Glycogen is the food reserve of plants
(d) All proteins are polymers of a - amino acids.
 92 CHEMISTRY

7. Fructose reduces Tollen’s reagent due to: 9. An organic compound with the formula C6H12O6
(a) en olisation of fructose followed by forms a yellow crystalline solid with
conversion to glucose (having aldehydic phenylhydrazine and gives a mixture of sorbitol
group) by the base present in Tollen’s and mannitol when reduced with sodium. Which
reagent among the following could be the compound?
(b) asymmetric carbons (a) Fructose (b) Glucose
(c) primary alcoholic group (c) Mannose (d) Sucrose
(d) secondary alcoholic group 10. Statement-1 : Treatment of D-glucose with dilute
8. Cellulose upon acetylation with excess acetic alkali affords an equilibrium mixture consisting
anhydride/H2SO4 (catalytic) gives cellulose of D-mannose, D-fructose and starting substance
triacetate whose structure is
D-glucose.
(a)
Statement-2 : The reaction involves an
AcO intermediate in which hybridisation of C2
O
O
changes from sp3 to sp2.
AcO H
H
O
(a) Statement-1 is True, Statement-2 is True;
AcO
H H O
OAc H H Statement-2 is a correct explanation for
H
H
O
OAc H H OAc Statement-1.
O H
(b) Statement-1 is True, Statement-2 is True;
OAc H H OAc
O H Statement-2 is NOT a correct explanation
H OAc for Statement-1.
(c) Statement -1 is True, Statement-2 is False.
(b) (d) Statement -1 is False, Statement-2 is True.
AcO 11. Which of the statements about "denaturation"
O given below are correct ?
AcO H O
H (A) Denaturation of proteins causes loss of
O
AcO H O
OH H H secondary and tertiary structures of the
H
H O protein.
H OH H H OH
O H (B) Denturation leads to the conversion of
O OH H
H
H OH double strand of DNA into single strand
(C) Denaturation affects primary strucrture
H OH
which gets distorted
(c) (a) (B) and (C)
AcO
(b) (A) and (C)
AcO
AcO
O H O (c) (A) and (B)
H H H O
H
H
O H H (d) (A), (B) and (C)
O OAc H O OAc H H 12. During the process of digestion, the proteins
O OAc H
H OAc
present in food materials are hydrolysed to
H OAc
H OAc amino acids. The two enzymes involved in the
(d) process
AcO
AcO Proteins ¾Enzyme( A)
¾ ¾ ¾¾® Polypeptides
AcO O
O H
H H H O
O Enzyme(B)
H
H
H H
¾¾¾ ¾¾® Amino acids
O H H H
O H H
O H H
are respectively
OAc OAc
OAc OAc (a) Diastase and lipase
OAc OAc
(b) Pepsin and trypsin
Biomolecules
(c) Invertase and zymase
(d) Amylase and maltase
13. In both DNA and RNA, heterocyclic base and
phosphate ester linkages are at –
(a) C5' and C1' respectively of the sugar
molecule
(b) C1' and C5' respectively of the sugar
molecule
(c) C '2 and C5' respectively of the sugar
molecule
(d) C5' and C '2 respectively of the sugar
molecule
14. Match List I (name of vitamin) with List II
(deficiency result/disease) and select the correct
answer using the codes given below the lists :
List I List II
I. Ascorbic acid A. Beri-beri
II. Retinol B. Cracked lips
III. Riboflavin C. Scurvy
IV. Thiamine D. Night blindness
(a) I - B, II - A, III - C, IV - D
(b) I - A, II - B, III - C, IV - D
(c) I - D, II - C, III - B, IV - A
(d) I - C, II - D, III - B, IV - A
15. Chargaff’s rule states that in an organism
(a) amount of adenine (A) is equal to that of
guanine (G) and the amount of thymine (T)
is equal to that of cytosine (C)
(b) amount of adenine (A) is equal to that of
cytosine (C) and the amount of thymine
(T) is equal to that of guanine (G)
(c) amount of adenine (A) is equal to that of
thymine (T) and the amount of guanine
(G) is equal to that of cytosine (C)
(d) amount of all bases are equal
16. Essential amino acids cannot be made by our
body. Which of the following is not essential
amino acid?
(a) Leucine (b) Lysine
(c) Serine (d) Histidine
93
17. How many peptide bond(s) is/are present in the
following structure?
(a) One
(b) Two
(c) Three
(d) None of these
18. The average energy of each hydrogen bond in
A–T pair is x kcal mol–1 and that in G–C pair is y
kcal mol–1. Assuming that no other interaction
exists between the nucleotides, the approximate
energy required in kcal mol–1 to split the following
double stranded DNA into two single strands is
A T A T G C A G
T A T A C G T C
[Each dashed line may represent more than one
hydrogen bond between the base pair]
(a) 10x + 9y (b) 5x + 3y
(c) 15x + 6y (d) 5x + 45y
19. A tetrapeptide is made of naturally occurring
alanine, serine, glycine and valine. If the C-
terminal amino acid is alanine and the N-terminal
amino acid is chiral, the number of possible
sequences of the tetrapeptide is
(a) 12 (b) 8
(c) 6 (d) 4
20. Which one of the following is NOT correct?
(a) D(–) Fructose exists in furanose structure
(b) D (+) Glucose exists in pyranose structure
(c) In sucrose the two monosaccharides are
held together by peptide linkage
(d) Maltose is a reducing sugar
Numeric Value Answer
21. A strongly alkaline solution of a
monoaminodicarboxylic acid contains how
many basic groups ?
22. How many dipeptides are possible from two
molecules of a typical a-amino acid ?
 94 CHEMISTRY

23. The optical rotation of a–D fructose is –21° and
that of its b-form is –133°. The equilibrium
mixture of these anomers has an optical rotation
of –92°. What is the % of a–form (upto one
decimal place) in its equilibrium mixture?
24. Consider all possible optical isomers of glucose
individually. How many moles of periodic acid
will be consumed by reaction of one mole of
each optical isomer with it?
25. Starch is a polymer of two components: amylose
and amylopectin. In the structure of
amylopectin straight chain is formed by
Ca – Cb glycosidic linkage and branching
occurs by Cc – Cd glycosidic linkage. What is
the value of a + b + c + d?

ANSWER KEY
1 (d) 4 (b) 7 (a) 10 (a) 13 (b) 16 (c) 19 (d) 22 (1) 25 (12)
2 (c) 5 (c) 8 (a) 11 (c) 14 (d) 17 (b) 20 (c) 23 (36.6)
3 (b) 6 (c) 9 (a) 12 (b) 15 (c) 18 (a) 21 (3) 24 (80)
 POLYMERS
29

MCQs with One Correct Answer (b) thermosetting polymer

(c) homopolymer
1. The turbidity of a polymer solution measures
(d) copolymer
(a) the light scattered by a solution
6. Which one of the following sets forms the
(b) the light absorbed by a solution
biodegradable polymer?
(c) the light transmitted by a solution
(d) none of the above (a) CH2 = CH – CN and CH2 = CH – CH = CH2
2. On the basis of mode of formation, polymers (b) H2N – CH2 – COOH and
can be classified? H2N–(CH2)5 – COOH
(a) as addition polymers only
(c) HO – CH2 – CH2 – OH and
(b) as condensation polymers only
(c) as copolymers
(d) both as addition and condensation HOOC COOH
polymers
3. Which of the following polymers do not involve
cross linkages? (d) CH = CH2 and
(a) Melmac (b) Bakelite
(c) Polythene (d) Vulcanised rubber CH2 = CH – CH = CH2
4. Which one of the following is not an example of 7. PVC is a
chain growth polymer? (a) thermoplastic polymer
(a) Neoprene (b) Buna-S (b) compound polymer
(c) PMMA (d) Glyptal (c) thermosetting polymer
5. —[NH(CH 2 ) 6 NHCO(CH 2 ) 4 CO—
]n is a (d) simple polymer

(a) addition polymer

 96 CHEMISTRY

8. The synthetic polymer which resembles natural 13. Which of the following statements is false?
rubber is (a) Artificial silk is derived from cellulose.
(a) neoprene (b) chloroprene (b) Nylon-66 is an example of elastomer.
(c) glyptal (d) nylon (c) The repeat unit in natural rubber is isoprene.
9. Which of the following is not a biopolymer ? (d) Both starch and cellulose are polymers of
(a) Proteins (b) Rubber glucose.
(c) Cellulose (d) RNA 14. The condensation of hexamethylenediamine
10. The process of heat-softening, moulding and with sebacoyl chloride at 525 K gives
cooling to rigidness can be repeated for which (a) nylon-6,20 (b) nylon-6,01
plastics (c) nylon-6,10 (d) none of these
(a) thermoplastics 15. The monomer(s) used in the preparation of orlon,
(b) thermosetting plastics a substitute for wool is/are
(c) both (a) and (b) (a) caprolactam
(d) neither (a) nor (b) (b) tetrafluoroethene
11. Which one of the following statement is not true? (c) styrene and 1, 3-butadiene
(a) In vulcanization the formation of sulphur (d) acrylonitrile
bridges between different chains make rubber 16. Polymer obtained by condensation
harder and stronger. polymerization is
(b) Natural rubber has the trans -configuration (a) Polythene
at every double bond. (b) Teflon
(c) Buna-S is a copolymer of butadiene and (c) Phenol-formaldehyde
styrene. (d) Nitrile rubber
(d) Natural rubber is a 1, 4 - polymer of isoprene. 17. Polyvinyl alcohol can be prepared by
12. Which of the following is not correctly matched? (a) polymerization of vinyl alcohol
(a) Terylene (b) alkaline hydrolysis of polyvinyl acetate
(c) polymerization of acetylene
O O
(d) reaction of acetylene with H2SO 4 in
–OCH2–CH2–C– –C – presence of HgSO4
n 18. Structure of some important polymers are given.
Which one represents buna-S?
(b) Neoprene — CH2 — C = CH — CH2 — CH3
Cl (a) (– CH2 – C = CH – CH2 –) n
n

(c) Nylon-66 (b) (– CH2 – CH = CH – CH2 – CH – CH2 –)n

O O C6H5
–NH–(CH2)6–NH –C –(CH2)4– C–O –n
(c) (– CH2 – CH = CH – CH2 – CH – CH2 –)
n
CN
CH3
(d) PMMA – CH2–C Cl

COOCH3 n (d) (– CH2 – C = CH – CH2 –)n

Polymers 97

19. Match List-I (Monomer) with List II (Polymer) 20. Statement-1 : Vinylidene chloride forms isotactic,
and select the correct answer using the codes syndiotactic and atactic polymers.
given below the lists: Statement-2 : Vinylidene chloride does not
List I List II contain chiral carbon.
I. Hexamethylenediamine A. Bakelite (a) Statement-1 is True, Statement-2 is True;
II. Phenol B. Dacron Statement-2 is a correct explanation for
III. Phthalic acid C. Glyptal Statement-1.
IV. Terephthalic acid D. Melamine (b) Statement-1 is True, Statement-2 is True;
E. Nylon Statement-2 is NOT a correct explanation
Codes: for Statement-1.
(a) I-E, II-A, III-B, IV-C
(c) Statement -1 is True, Statement-2 is False.
(b) I-E, II-A, III-C, IV-B
(d) Statement -1 is False, Statement-2 is True.
(c) I-D, II-C, III-A, IV-B
(d) I-D, II-C, III-B, IV-A

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

CHEMISTRY IN 30
EVERYDAY LIFE

MCQs with One Correct Answer 6. Which of the following acts as an antioxidant in
edible oils ?
1. Substances used for bringing down temperature
(a) Vitamin B (b) Vitamin C
in high fever are called
(c) Vitamin D (d) Vitamin E
(a) pyretics (b) antipyretics
7. The drug which is effective in curing malaria is
(c) antibiotics (d) antiseptics
2. Amoxycillin is semi-synthetic modification of (a) quinine (b) aspirin
(a) penicillin (b) streptomycin (c) analgin (d) equanil
(c) tetracyclin (d) chloroampheniol 8. Which of the following is an antidiabetic drug?
3. Barbituric acid and its derivatives are well (a) Insulin (b) Penicillin
known
(c) Chloroquine (d) Aspirin
(a) antipyretics (b) analgesics
(c) antiseptics (d) traquillizers 9. Further growth of cancerous cells in the body is
4. A medicine which promotes the secretion of arrested by
urine is called (a) physiotherapy (b) chemotherapy
(a) uretic (b) monouretic (c) electrotherapy (d) psychotherapy
(c) diuretic (d) triuretic 10. Sulphaguadine is used for
5. A drug effective in the treatment of pneumonia, (a) dysentery (b) urinary infections
bronchitis, etc, is (c) antiseptic (d) antipyretic
(a) streptomycin
11. H1 – Receptor antagonists is a term associated
(b) chloramphenicol
with :
(c) penicillin
(a) Antiseptics (b) Antihistamins
(d) sulphaguanidine
(c) Antacids (d) Analgesics
Chemistry in Everyday Life 99

12. Which one of the following can possibly be used 14. Structuraly biodegradable detergents, should
as analgesic without causing addiction and contain
(a) normal alkyl chain
mood modification?
(b) branched alkyl chain
(a) Diazepam (c) phenyl side chain
(b) Morphine (d) cyclohexyl side chain
(c) N-acetyl-para-aminophenol 15. Match the chemicals in Column I with their
(d) Tetrahydrocannabinol uses in Column II.
13. Antiseptics and disinfectants either kill or
Column I Column II
prevent growth of microorganisms. Identify
(A) Sodium perborate (I) Disinfectant
which of the following statements is not true:
(B) Chlorine (II) Antiseptic
(a) Chlorine and iodine are used as strong
(c) Bithional (III) Milk bleaching agent
disinfectants.
(D) Potassium stearate (IV) Soap
(b) Dilute solutions of boric acid and hydrogen
Peroxide are strong antiseptics. (a) A - I, B - II, C - III, D - IV
(c) Disinfectants harm the living tissues. (b) A - II, B - III, C - IV, D - I
(d) A 0.2% solution of phenol is an antiseptic (c) A - III, B - I, C - II, D - IV
while 1% solution acts as a disinfectant. (d) A - IV, B - I, C - II, D - III

ANSW ER KEY
1 (b) 3 (d) 5 (c) 7 (a) 9 (b) 11 (b) 13 (b) 15 (c)
2 (a) 4 (c) 6 (d) 8 (a) 10 (a) 12 (c) 14 (b)
 100 CHEMISTRY

PRACTICAL CHEMISTRY
31

MCQs with One Correct Answer 4. The prussian blue colour obtained in the Lassaigne’s
test for nitrogen is due to the formation of
M (a) Iron (II) hexacyanoferrate (III)
1. A solution of 10 mL FeSO4 is titrated with
10 (b) Iron (III) hexacyanoferrate (II)
KMnO4 solution in acidic medium the amount (c) Iron (III) hexacyanoferrate (III)
of KMnO4 used will be (d) Iron (II) hexacyanoferrate (II)
(a) 5 mL of 0.1 M (b) 10 mL of 0.1 M 5. A metal X on heating in nitrogen gas gives Y.Y
(c) 10 mL of 0.5 M (d) 10 mL of 0.02 M on treatment with H2O gives a colourless gas
2. A red solid is insoluble in water. However, it which when passed through CuSO4 solution
becomes soluble if some KI is added to water. gives a blue colour, Y is
Heating the red solid in a test tube results in (a) Mg(NO3)2 (b) Mg3N2
liberation of some violet coloured fumes and (c) NH3 (d) MgO
droplets of metal appear on the cooler part of 6. Soda extract is prepared by –
the test tube. The red solid is – (a) fusing soda and mixture and then extracting
(a) KI (b) Pb3O4 with water
(c) (NH4)2Cr2O7 (d) HgI2 (b) dissolving NaHCO3 and mixture in dil. HCl
3. The following figure shows a reaction scheme (c) boiling Na2CO3 and mixture in dil. HCl
for a compound X, identify X. (d) boiling Na 2CO3 and mixture of salt in
Water Flame test distilled water
Colourless solution X Red colour
7. The salt used for performing bead test in
heat with dil. HCl qualitative inorganic analysis is :
White precipitate Brown gas evolved (a) K2SO4.Al2 (SO4)3.24H2O
(b) FeSO4.(NH4)2SO4.4H2O
(a) CaBr2 (b) Ca(NO3)2
(c) Na(NH4)HPO4.4H2O
(c) Ca(NO2)2 (d) Mg(NO3)2
(d) CaSO4.2H2O
Practical Chemistry 101
8. H2S gas when passed through a solution of (a) Prussian blue - Fe4[Fe(CN)6]3. xH2O
cations containing HCl precipitates the cations (b) Black - PbS
of second group in qualitative analysis but not (c) Violet colour - [Fe(CN)5NOS]4–
those belonging to the fourth group. It is because (d) Yellow - (NH4)2MoO4
(a) presence of HCl decreases the sulphide ion 14. A is a lighter phenol and B is an aromatic
concentration. carboxylic acid. Separation of mixture of A and B
(b) solubility product of group II sulphides can be carried out easily by using a solution of
is more than that of group IV sulphides. (a) sodium hydroxide
(c) presence of HCl increases the sulphide ion (b) sodium sulphate
concentration. (c) calcium chloride
(d) sulphides of group IV cations are unstable (d) sodium bicarbonate
in HCl.
15. To detect iodine in presence of bromine, the sodium
9. An organic compound contains 46.78% of a
extract is treated with NaNO2 + glacial acetic acid +
halogen X. When 2.00 g of this compound is
CCl4. Iodine is detected by the appearance of
heated with fuming HNO3 in the presence of
(a) yellow colour of CCl4 layer
AgNO3, 2.21 g AgX was formed. The halogen X is
[Given: atomic weight of Ag = 108, F = 19, (b) purple colour of CCl4
Cl = 35.5, Bi = 80, I = 127] (c) brown colour in the organic layer of CCl4
(a) F (b) Cl (d) deep blue colour in CCl4
(c) Br (d) I 16. In Kjeldahl’s method for the estimation of N2,
10. In a titration experiment, 10 mL of an FeCl2 potassium sulphate and copper sulphate are
solution consumed 25 mL of a standard K2Cr2O7 used. On the basis of their functions which of
solution to reach the equivalent point. The standard the following statement(s) is/are correct?
K2Cr2O7 solution is prepared by dissolving 1.225 g I. Potassium sulphate raises the bpt. and
of K2Cr2O7 in 250 mL water. The concentration of ensures complete reaction.
the FeCl2 solution is closest to II. Copper sulphate acts as catalyst.
[Given: molecular weight of K2Cr2O7 = 294 g mol–1] III. Potassium sulphate acts as catalyst and
(a) 0.25 N (b) 0.50 N copper sulphate raises the bpt.
(c) 0.10 N (d) 0.04 N (a) Only III is correct
11. Sodium nitroprusside, when added to an alkaline (b) I and II are correct
solution of sulphide ions, produces purple (c) Only II is correct
colour ion due to the formation of (d) None of the given option is correct
(a) Na[Fe(H2O)5NOS] 17. Which of the following compound will give white
(b) Na2[Fe(H2O)5NOS] precipitate on heating with HNO3 followed by
(c) Na3[Fe(CN)5NOS] addition of silver nitrate?
(d) Na4[Fe(CN)5NOS] (a) (C2H5)3NHCl
12. In the estimation of sulphur by Carius method,
(b) 2, 4, 6- Trinitrochlorobenzene
0.480 g of an organic compound gives 0.699 g of
(c) Both (a) and (b)
barium sulphate. The percentage of sulphur in
(d) Neither (a) nor (b)
this compound is
18. The ammonia evolved from the treatment of 0.30
(Atomic masses : Ba = 137, S = 32, O = 16)
(a) 20% (b) 15% g of an organic compound for the estimation of
(c) 35% (d) 30% nitrogen was passed in 100 mL of 0.1 M sulphuric
13. The colour of the solution/precipitate obtained acid. The excess of acid required 20 mL of 0.5 M
in the elemental analysis of an organic sodium hydroxide solution for complete
compound and the molecule/ion responsible for neutralization. The organic compound is
the colour are given below. Choose the (a) urea (b) benzamide
incorrectly matched pair (c) acetamide (d) thiourea
 102 CHEMISTRY

19. A sample of 0.5 g of an organic compound was
treated according to Kjeldahl’s method. The
ammonia evolved was absorbed in 50 mL of 0.5 M
H2SO4. The remaining acid after neutralisation by
ammonia consumed 80 mL of 0.5 M NaOH. The
percentage of nitrogen in the organic compound is
(a) 14 (b) 28
(c) 42 (d) 56
20. Which one among the following is not correct?
(a) Alumina can be used as adsorbent
(b) Glycerol is purified by steam distillation
(c) Water trapped in the chromatographic filter
paper acts as stationary phase
(d) In TLC the thickness of the adsorbent layer
is about 0.2 mm thickness
21. Diazo compounds, sometimes do not respond
Lassaigne’s test for nitrogen because
(a) these are quite stable compounds and do
not decompose to elemental nitrogen
(b) these contain very little carbon
(c) these form organometallic compounds with
sodium
(d) their nitrogen contents is removed, during
heating, in the form of nitrogen gas
22. One gram of an organic nitrogen-containing
compound, on heating, decomposes to give 0.2
g of nitrogen. What should be nature of the
compound ?
(a) C3H7N2Cl
(b) C6H5N2Cl
(c) (CH3)3N
(d) Given data is insufficient.
23. In Lassaigne's test for the detection of halogens,
the sodium fusion extract is first boiled with
concentrated nitric acid. This is
(a) to remove silver halides
(b) to decompose Na2S and NaCN, if present
(c) to dissolve Ag2S
(d) to dissolve AgCN, if formed
24. In the test of basic radical which reagent is used
in IVth group?
(a) H2S + HCl
(b) NH4OH + NH4Cl
(c) NH4OH + NH4Cl + H2S gas
(d) NH4OH + NH4Cl + (NH4)2CO3
25. When excess of dilute NH4OH is added to an
aqueous solution of copper sulphate, an intense blue
colour is obtained. This is due to the formation of
(a) CuSO4 (b) Cu(OH)2
(c) [Cu(NH3)4]2+ (d) (NH4)2SO4
Numeric Value Answer
26. 3.92 g of ferrous ammonium sulphate react
N
completely with 50 mL KMnO4 solution.
10
The percentage purity of the sample is
27. When 1.4 g of a nitrogen containing organic
compound is heated with CuO in an atmosphere
of CO2 224 mL of free N2 gas is liberated at STP.
The percentage of nitrogen in the compound is
28. 0.25 g of an organic compound on Kjeldahl's
analysis gave enough ammonia to just neutralize
10 cm3 of 0.5 M H2SO4. The percentage of
nitrogen in the compound is
29. In Duma's method of estimation of nitrogen 0.35
g of an organic compound gave 55 mL of nitrogen
collected at 300 K temperature and 715 mm
pressure. The percentage composition of
nitrogen in the compound would be : (Aqueous
tension at 300 K = 15 mm)
30. 2.79 g of an organic compound when heated in
Carius tube with conc. HNO3 and H3PO4 formed
converted into MgNH4.PO4 ppt. The ppt. on
heating gave 1.332 g of Mg 2 P 2 O 7. The
percentage of P in the compound is

ANSW ER KEY
1 (d ) 4 (b ) 7 (c) 10 (a) 13 (d ) 1 6 (b) 19 (b ) 22 (b) 25 (c) 28 (56)
2 (d ) 5 (b ) 8 (a) 11 (d ) 14 (d ) 1 7 (c) 20 (b ) 23 (b) 26 (50) 29 (16.46)
3 (c) 6 (d ) 9 (c) 12 (a) 15 (b ) 1 8 (a) 21 (d ) 24 (c) 27 (20) 30 (13.33)
Some Basic Concepts of Chemistry 103

Hints & Solutions

CHAPTER
Some Basic Concepts
1 of Chemistry

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

\ Equivalent weight of metal

358
Moles of prop-1-ene = = 0.085 mole æ Mass of Metal ö
42 =ç ÷ ´ 35.5
è Mass of chloride ø
0.085
% yield = ´ 100 = 85%
47.22
0.1 = ´ 35.5 = 31.76
7. (b) Using the relationship 52.78
11. (b) Volume of a spherical water droplet
Mol. mass of oxide mass of oxide
= 4 3 4
Mass of metal in molar mass mass of metal pr = p (1)3
=
3 3
4 x + 96 10
= Þ x = 24 4
4x 5 V= p cm3
3
8. (a) No. of molecules in different cases
Mass of spherical water droplet
(a) Q 22.4 litre at STP contains
= 6.023 × 1023 molecules of H2 4 4
= P × V = 1´ p = p g
15 3 3
\ 15 litre at STP contains = ´ 6.023 ´ 10 23
22.4 18 g of water = 1 mol
= 4.03 × 1023 molecules of H2 no. of moles of water in a spherical water droplet
(b) Q 22.4 litre at STP contains 4p 2p
= 6.023×1023 molecules of N2 = =
3 ´ 18 27
5
Q 5 litre at STP contains = ´ 6.023 ´ 10 23 heat
22.4 12. (a) 2KClO3 ¾¾¾
® 2KCl + 3O 2
= 1.344 × 1023 molecules of N2 2 ´ 122.5 g 3´32 g
245 96
(c) Q 2 g of H2= 6.023×1023 molecules of H2
48 g of oxygen will be produced from 122.5 g of
0.5
Q 0.5 g of H2= ´ 6.023 ´ 10 23 KClO3
2
\ Amount of 80% KClO3 needed
= 1.505 × 1023 molecules of H2
(d) Similarly 10 g of O2 gas 100
= ´ 122.5 = 153.12 g
80
10
= ´ 6.023 ´ 10 23 molecules of O2
32 10
13. (b) Meq. of CaCO 3 = × 1000 = 200
= 1.88 × 1023 molecules of O 50
2
Thus (a) will have maximum number of molecules Meq. of HCl = 250 × 1 = 250
– Meq. of HCl left in the solution = 250 – 200 = 50
COO –
9. (b) 5 – +2 MnO4 + 16 H+ ¾®
16 H \ Meq. of KOH requred V × 2 = 50
COO \ V = 25 mL
oxalate ion
14. (c) The relation between molarity (M) and
2+
2 Mn +10CO2+8H2O molality (m) is
From above equation 2 moles MnO4 required to
d = M æç
1 M ö
+ 2 ÷ , M2 = Mol. mass of solute
oxide 5 moles of oxalate. è m 1000 ø
Thus number of moles of MnO4 required to On putting value
oxidise one mole of oxalate = 2/5 = 0.4
1.252 = 3 æç
10. (b) Suppose weight of metallic chloride = 100 g 1 58.5 ö
+ ÷
Then weight of metal = 47.22 g è m 1000 ø
Weight of chlorine = 100 – 47.22 = 52.78 g on solving m = 2.79
Some Basic Concepts of Chemistry 105

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

Þ Mass of acetic acid

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

2 Structure of Atom

- Ze 2 é1 1 ù
1. (d) In S.I. units the P.E. = . For Li2+, Z = 3. or E = 13.6 ê - ú eV [Q n1 = 1]
4peo r 2
ëê1 n 2 ûú
-3e 2
\ P.E. = . é 1ù
4pe 0r or 12.72 = 13.6 ê1 - 2 ú [Q E = 12.72 eV]
ë n2 û
20
2. (a) 10
Ne contains 10 protons and 10 neutrons 1 12.72
or 1- =
\ M1 = 10 mp + 10mn n 22 13.6
40
20
Ca contains 20 protons and 20 neutrons 1 13.6 - 12.72 0.88 1
or = = ;
\ M2 = 20 mp + 20 mn n 22 13.6 13.6 16
\ M2 =2M1
or n 22 ; 16
3. (d) Isodiaphers have same difference of
number of neutrons and protons or (A – 2Z) or n22 ; 4
must be same. The transition n4 ¾¾ ® n3 will give the longest
4. (c) Energy of an electron at infinite distance from wave length.
the nucleus is zero. As an electron approaches 6. (d) Total energy of a revolving electron is the
the nucleus, the electron attraction increases and sum of its kinetic and potential energy.
hence the energy of electron decreases and thus Total energy = K.E. + P. E.
becomes negative. Thus as the value of n
e 2 æ e 2 ö e 2 - 2e 2
decreases, i.e. lower the orbit is, more negative is = + ç- ÷ =
2r è r ø 2r
the energy of the electron in it.
5. (b) The energy associated with radiation of e2
wave length 975 Å is given by =-
2r
12400
E= eV = 12.72 eV 7. (a) The frequency distribution of the emitted
975
[For a radiation of wavelength x Å, we radiation from black body depends only on its
temperature. The maximum value of intensity of
12400
know E = eV] radiation emitted will be more for higher
x
temperature. Thus, correct representation is
é1 1ù shown in option (a).
E = 13.6 ê 2 - 2 ú eV 8. (b) The maximum number of electrons in the
ë n1 n 2 û
shell with principle quantum number (n) is 2n2.
 108 CHEMISTRY

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

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

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

®

of this 6.8 eV is converted to K.E.

6.8 eV Þ 6.8 ´ 1.6 ´ 10–19 J; ®r
æ 1ö 18. (b) Given E1 = 25eV E2 = 50 eV
6.8 ´ 1.6 ´ 10–19 = K.E. Þ çè ÷ø mv
2
2 hc hc E1 l 2
E1 = E2 = \ =
2KE 2 ´ 1.088 ´ 10
-18 l1 l2 E 2 l1
v= = -31
m 9.1 ´ 10
l 2 25 1
\ = = \ l1 = 2l 2
= 1.54 ´ 106 m/s l1 50 2
Structure of Atom 109
19. (b) Cathode rays are independent of the nature E1 : E2 = 1 : 2 or E2 = 2E1
of the gas and electrodes placed in discharge Thus, energy of the radiation with wavelength
tube. They travel in a straight line in the absence 400 nm is twice that of the radiation of wavelength
of external electrical or magnetic field. 800 nm.
20. (c) Energy emitted by the bulb = 600 W = 600 23. (3) In the 1st Bohr orbit of H :
Js–1 (1W = 1 Js–1) n = 2.18 ´ 106 ms–1.
l = 331.3 × 10–9 m Now, let us consider that in Li2+ the electron is
in nth orbit. Speed of electron in n th Bohr orbit
hc
Energy of one photon = hv = of Li2+ is
l
3
n = (Li2+) = 2.18 ´ 106 ´
6.62 ´ 10 -34 ´ 3 ´ 108 n
=
331.3 ´ 10-9 Now, applying the condition of equal speed :
= 0.059 ´ 10–17 » 0.06 ´ 10 -17 J 3
2.18 ´ 106 ´ = 2.18 ´ 106 Þ n = 3
No. of photon emitted from the lamp per second n

600 hc 6.63 ´ 10 -34 ´ 3 ´ 108

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

0.001 = 1.93 ´ 10–18 J

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

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

1 2 1 ( n 0 = Threshold frequency)
E= mv Þ E1 - E2 = m(v12 - v22 )
2 2
æ 3 ´ 108 ö
hc h æ 1 2
1 ö 4.806 × 10–17 = 6.626 × 10 34 çç n – ÷
–10 ÷
Þ = çç 2 - 2 ÷÷ è 1500 ´10 ø
l 2m è l1 l 2 ø
= 6.626 × 10–34 ( n – 2 × 1015)
1 h æ 1 1 ö 1 4.806 ´10 –17
Þ = ç 2 - 2 ÷ -6 2 n – 2 × 1015 = = 72.53 ´ 1015
l 2 mc è 4 6 ø (10 ) 6.626 ´10 – 34

1 h æ 20 ö 1 Þ n = 7.45 × 1016 Hz
Þ = ç ÷
l 2mc è 36 ´16 ø 10-12 hc
29. (6.604) DE = E3 – E2 = hn = or
l
mc æ 36 ´ 16 ö -12 mc
l= ç ÷10 m = ´ 576 ´10-11 m
h è 10 ø h hc
l=
E3 - E2
Þ x = 576
Given E2 = – 5.42 × 10–12 erg
1 æ 1 1ö E3 = – 2.41 × 10–12 erg
27. (653.4) v = = RZ 2 ç 2 – 2 ÷
l è n1 n2 ø
6.626 ´ 10 -27 ´ 3 ´ 1010
\ l=
1 æ 1 1 ö 5 -2.41 ´ 10 -12 - (–5.42 ´ 10 -12 )
= R ´ 12 ç 2 – 2 ÷ = 36 R
lH è2 3 ø
19.878 ´ 10 -17
= = 6.604 × 10–5 cm = 6.604Å
1 æ 1 1 ö 363
2 3.01 ´ 10 -12
= R ´ 11 ç 2 – 2 ÷ = R
l Na+ è1 2 ø 4 30. (80) Let the % of isotope with At. wt. 10.01 = x
\ % of isotope with At. wt. 11.01 = (100 – x)
363R
x ´ 10.01 + (100 - x) ´ 11.01
lH At. wt. of boron =
Hence = 4 = 653.4 100
l + 5R
Na
36 x ´ 10.01 + (100 - x) ´ 11.01
Þ 10.81 =
28. (7.45) 100
K.E. of photoelectron = e– × stopping potential \ x = 20
= 1.602 × 10–19 × 300 Hence % of isotope with At. wt. 10.01 = 20%
= 4.806 × 10–17 J \ % of isotope with At. wt. 11.01 = 100 – 20 = 80%
 CHAPTER Classification of
Elements & Periodicity
3 in Properties
1. (d) Most of the transition metal compounds
(ionic as well as covalent) are coloured both
in the solid state and in aqueous solution in
contrast to the compounds of s and p-block
elements due to the presence of incomplete
d-subshell.
2. (c) In iso-electronic species, cation with
greater positive charge will have a smaller radius
and anion with greater negative charge will have
the largest radius.
Thus, the order of ionic radii will be,
N3– > O2– > F– > Na+
3. (c) Elements (a), (b) and (d) belong to the same
group since each one of them has two electrons
in the s sub shell. In contrast, element (c) has
seven electrons in the valence shell and hence
does not lie in the same group in which elements
(a), (b) and (d) lie.
4. (c) atomic number 9 is for F so its halogen
series.
5. (a) There are four elements which is lighter
than the rare–earth elements that are:
(i) eka – boron (Eb) – scandium
(ii) eka – aluminium (Ea) – Gallium
(iii) eka – manganese (Em) – Technetium
(iv) eka – Silicon (Es) – Germanium
6. (b) The atomic number 85 lies in the sixth period
and since the next halogen, if discovered, will lie
in the 7th period. Hence, its atomic number must
be 85+32=117.
7. (c) Atomic number of the given element = 15;
group no. = 10 + 5 (valence electrons) = 15,
period = 4th Therefore atomic number of the
element below the above element = 15 + 18 = 33.
8. (a) O– – and F– are isoelectronic. Hence have
same number of shells, therefore greater the
nuclear charge smaller will be the size i.e.,
O– – > F–
further Li+ and B3+ are isoelectronic, therefore
Li+ > B3+
Hence the correct order of atomic size is.
O-- > F– > Li+ > B3+
9. (a) Ionisation potential of nitrogen is more than
that of oxygen. This is because nitrogen has
more stable half-filled p-orbitals. (N = 1s2, 2s2,
2p3, O = 1s2, 2s2, 2p4)
10. (a) In Cu it has completely filled d-orbital so
highest energy is absorbed when it convert in
Cu+ ion.
11. (b) K+ ® K2+ + e–. Since e– is to be removed
from stable configuration.
12. (b) Along the period, I.P. generally increases
but not regularly. Be and B are exceptions. First
I.P. increases in moving from left to right in a
period, but I.P. of B is lower than Be.
13. (b) IE2 of Mg is lower than that of Na because
in case of Mg+, 3s-electron has to be removed
whereas in case of Na+, an electron is removed
from the stable inert gas configuration which is
difficult.
 112
14. (b) In case of Ne, the electron is being removed
from a species with a charge of +1 whereas in case
of Na+, the electron is being removed from a species
with charge of + 2. Hence IE1 of Na+ > IE1 of Ne.
15. (a) Zero, because of the stable electronic
configuration the noble gases do not show any
force of attraction towards the incoming electron.
16. (a) Acidic character of oxide µ Non-metallic
nature of element.
Non-metallic character increases along the
period. Hence order of acidic character is
Cl2O7 > SO2 > P4O10.
17. –
(a) O ion exerts a force of repulsion on the
incoming electron. The energy is required to
overcome it.
18. (c) Basicity of oxides decreases in a period and
increases in a group.
\ SnO2, Al2O3 and ZnO are amphoteric oxides.
CHEMISTRY
19. (a) (i) < (iii) < (ii) < (iv). In case of half filled or
completely filled subshell, not easy to add elec-
tron so (i) & (iii) has less tendency to accept
electron. Thus option (a) is correct.
20. (c) The basic character of metal oxides
decreases from left to right in a period and
increases down the group.
21. (106) Unh = Un – nil – hexium = 106
22. (731) The I.E. of Ag will be less than Cu, due
to bigger size of Ag. From Ag to Au, 14f
electrons are added, which provides very poor
shielding effect. Therefore, due to high nuclear
charge, the I.E. of Au > Ag. Correct order: Au
(890) > Cu (745) > Ag (731).
23. (7) Long form of periodic table contains 18
groups and 7 periods (completely filled)
24. (7) Third period contains total 8 elements but
‘Si’ is metalloid.
25. (2) (iv) Li < Li+ (vii) Ba < Sr
 CHAPTER
Chemical Bonding and
4 Molecular Structure

1. (c) Percent ionic character is given by 1

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

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

p*2p2x = p *2 py2
O atom O atom
 114 CHEMISTRY
+ 8. (b) As the size of anion increases polarizibility
··
3. I3+ I- I -I sp3 hybridisation of anion increase. Among given anions I– has
·· maximum size.
F
F F
S S
S F
I 9. (d) F F F
F
I ÐFSF < 109°28' ÐFSF = 90°
I
144 42444 3 F
Bent geometry F
S S
4. SeF4 sp3d
see–saw F
F S F
CH4 sp3 tetrahedral F
Thus, option (a) is correct ÐFSF < 109°28' ÐFSF < 90°
5. (b) I
s
H— C— s ss s s s s s 10. (d)
p C— C —
p C— C —
p C— C —
p C—H + –
s s s s s s s s I I
H H H H H H H H I
1, 3, 5, 7 - octatetraene I I
17 s and 4 p 3 3
6. (a) R—N==C==O Hyb. : sp Hyb. : sp d
Nitrogen has 2 sigma bond and a lone pair of m¹0 m= 0
electron Planar Planar
\ hybridisation is sp2. Carbon has 2 sigma bond
\ hybridisation is sp. Oxygen has 1 sigma bond 11. (c) IO 2 F2- : Hyb. sp3 d , [ º sp x p y p z d 2 ]
z
and two lone pair of electron \ hybridisation is sp2.
ClF4- 3 2
: Hyb. sp d [ º sp x p y p z d d ]
NOTE: p-bonding electron does not take part x2 - y 2 z 2
in hybridisation.
7. (b) The delocalised pp - pp bonding between IF7 : Hyb. sp3 d 3.[ sp x p y p z d d d ]
x 2 - y 2 xy z 2
filled p-orbital of F and vacant p-orbital of B leads dxy : orbital has two nodal planes xz and yz.
to shortening of B–F bond length which results 12. (b) SO3
in higher bond dissociation energy of the B–F
bond.
s bond = 3 ü
ý number of covalent bond = 6
p bond = 3 þ
F 1
Lone pair = = ( 6 - 6) = 0
B F 2
F Hybridization = 3 + 0 = 3 (sp2)
Unhybridized p–orbitals left = 1 so pp–pp = 1
Vacant Filled
p bond = 3
2p-orbital 2p-orbital pp – dp = 3 – 1 = 2
Thus, SO3 has 3s, one pp–pp and two pp – dp
F F bonds.
+
B=F B–F 13. (c) H +2 : (s1s1)
+
F F
1 1
+ +1/3 \ B.O. = (1 - 0) =
F F 2 2
+1/3
B–F
+1/3
B F H -2 : (s1s 2 )(s *1s1 )
F F 1 1
\ B.O. = (2 - 1) =
2 2
Chemical Bonding and Molecular Structure 115

Even though the bond order of H +2 and H-2 are F

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

20. (a) F – pp-pp bond(s) = 0

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

z2
p

sp 3 s
-d
pp

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

P ® sp 3d , bent, T-shape, planar

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

23. (2) XeO4 , XeF7+ NO3- ¾¾

® sp 2 , planar
F F
O F F ® sp 3d , see-saw, non-planar
XeO2 F2 ¾¾
Xe I
Sn
O F F PCl+4 ¾¾
® sp 3 , tetrahedral, non-planar
F3 Cl Cl
2 3 2
sp d sp sp d CH3+ ¾¾
® sp 2 , Trigonal planar
polar polar polar a = 4, b = 5, c = 3
O
a+b
+ so, =3
Xe c
I 26. (6) (p x , p y , d xy , d yz , d xz , d )
O x 2 –y 2
I I O O
3 3 27. (21) Molecular orbital electronic configuration
sp sp
of these species are :
polar non-polar
O -2 (17e- ) = s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , s2 p2z ,
Chemical Bonding and Molecular Structure 117

p2 p 2x = p 2 p 2y , p * 2 px2 = p * 2 p1y m= m12 + m 22 + 2m1m 2 cos q

O 2 (16e- ) = s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , s2 pz2 , = 1.62 + 1.62 + 2 ´ 1.6 ´ 1.6 ´ cos(120) = 1.6 D
p2 px2 = p2 p 2y , p * 2 p1x = p * 2 p1y 29. (50) The hybridization of S in SF6 is sp3d2.
O 22- (18e- ) = s1s 2 , s *1s 2 , s2s 2 , s * 2 s 2 , s2 pz2 , 3
% p character = ×100 = 50
6
p2 px2 = p2 p 2y , p * 2 px2 = p * 2 p 2y 30. (1200) 1
Therefore number of antibonding electrons are Na(s) + Cl (g)
2 2
7, 6 and 8 respectively and the sum is 21. 1 DHf
DHsub DH diss
28. (1.6) The substituent in o– and p– position, 2
will cancel each others dipole moment.
Na(g) Cl(g)
X Na+Cl–(s)
1 I.E.1 –e– –D Heg +e–
X X
6 2
Na+(g) Cl–(g) –U
5 3
4
X 1
DHf = DHsub + DHdiss + I.E.1 – DHeg – U
The angle between 2 and 6 positions is 120°. 2
The resultant dipole moment generated by these
1
two is: Þ –200 = 650 + × 400 + 500 – 350 – U
2
Þ U = 1200 kJ/mol
 118 CHEMISTRY

CHAPTER

States of Matter
5
1. (a) Given initial volume (V1) = 600 c.c.; Initial
pressure (P1) = 750 mm of Hg and final volume 28
(c) For CO, t2 = (5s) ¹ 25s
(V2) = 500 c.c. according to Boyle’s law, 2
P1V1 = P2V2
or 750 × 600 = P2 × 500 44
(d) For CO2, t2 = (5s) ¹ 55s
2
750 ´ 600
or P2 = = 900 mm of Hg 5. (c) According to question :
500
For initial stage of a gas,
Therefore increase of pressure = (900 – 750) P1 = 1 atm, V1 = 24.6 litres,
= 150 mm of Hg T1 = 273 + 27 = 300 K
16 1 For final stage of a gas,
2. (d) n of O 2 = =
32 2 P2 = 10 atm, V2 = ?
3
n of H 2 = T2 = 327 + 273 = 600 K
2
3 1 By gas equation,
Total no. of moles = + = 2
2 2 P1V1 P2 V2
The total volume occupied = 2 × 22.444.8L T1
= T2
= 44800mL
3. (b) Pressure exerted by hydrogen will be 1 ´ 24.6 10 ´ V2
proportional to its mole fraction. =
300 600
w
2 8 24.6 ´ 600
Mole fraction of H2 = w w = Þ V2 =
9 300 ´10
+
16 2
= 4.92 litres.
r M2
4. (b) Under identical conditions, 1 = 6. (b) At the same conditions of T and P, V µ n
r2 M1
14 1 1
As rate of diffusion is also inversely proportional nN = = ; VN 2 µ
2 28 2 2
t2 M2 36 3 3
to time, we will have,
t1
= M1 nO 3 = = ; VO 3 µ
48 4 4
4 1 4 2
(a) Thus, For He, t2 = (5s) = 5 2s ¹ 10s Hence , VN /VO = ´ =
2 2 3 2 3 3
(b) For O2, t2 = 32 \ 3VN 2 = 2VO3
(5s) = 20s
2
States of Matter 119

7. (b) The correct graph which represents the van der Actual volume to be transferred into balloons
Waal’s gas under the given condition is option (b). = 51324 – 2820 mL = 48504 mL
[Q 2820 mL of H2 will remain in cylinder]
nRT 4×0.0821×300 3
8. (c) Total pressure; P = = 4 3 4 22 æ 21 ö
V 100 Volume of one balloon = pr = ´ ´ ç ÷
3 3 7 è2ø
= 0.985 atm.
é diameter ù
nA 1 êQ r = 2 ú
pA = . P = × 0.985 = 0.246 atm. ë û
n A +n B 4 = 4851 ml = 4.851L
nB 3 48504
pB = n + n . P = 4 × 0.985 = 0.739 atm. No. of balloons that can be filled up =
4851
A B
= 9.999 = 10
Total partial pressure (PA + PB) = 0.985 atm.
11. (d) Let V mL of gas is effused
9. (b) First we should calculate the number of
V / 220 dO
moles of the gas under the given conditions by 2
= Þ dmix = 1.936 g/L
the relation PV = nRT V / 200 d mix
Here P = 7.6 × 10–10 mm Hg Let density of ozone is d. In 100 volume ozonised
7.6 ´ 10-10 oxygen, 60% O2 and 40% by volume O3 is present
= atm. = 1 × 10–12 atm. \ Mass of mixture = mass of ozone + mass of
760
V = 1 litre oxygen
T = 273 + 0 = 273K 100 × 1.936 = 40 × d + 60 × 1.6
R = 0.082 litre atm./K/mol \ Density of O3 is 2.44 g/L
Putting the values in equation 12. (d) From ideal gas equation
PV 1 ´ 10-12 ´ 1 PV = nRT
n= = moles Maximum number of moles in container,
RT 0.082 ´ 273
Now since 1 mole contains = 6.023 × 1023 molecules PV 2 ´ 2.4
n= = = 0.18 moles
RT 0.0821´ 298
10-12
moles will have Maximum weight of N2 in container
0.082 ´ 273
= 0.183 × 28 = 5.127 g
6.023 ´ 1023 ´ 10-12 Hence, at 5.127 g exploding can occur. Thus, the
= molecules maximum amount of nitrogen that can be safely
0.082 ´ 273
put in this container at 298 K temperature and exert
= 2.7 × 1010 molecules pressure less than 2 atm will be closest to 4.2 g.
10. (d) No. of balloons that can be filled PM
V of H 2 available 13. (c) Density (r) = (1 bar = 0.987 atm)
= RT
V of one balloon 4 ´ 0.987 ´ 28
Calculation of total volume of hydrogen in the rN =
2 R ´ 300
cylinder at N.T.P. Let the molar mass of gas be x
PV
1 1 P2V2 2 ´ 0.987 ´ x
T1
= T rgas =
2 R ´ 300
P1 = 1 atm P2 = 20 atm Given rgas = rN × 2
2
V1 = ? V2 = 2.82 l
2 × 0.987 × x 4 × 0.987 × 28
T1 = 273 K T2 = 273 + 27 = 300 K = ×2
R × 300 R × 300
20 ´ 2.82 ´ 273
\ V1 = = 51.324 l = 51324 mL \ x = 112 g/mol.
300 ´ 1
 120 CHEMISTRY

14. (a) Given T = 27 °C = 27 + 273 = 300 K

V = 10.0 L ( U rms ) H 2 ´ 5 =
TH 2
´
28
\
Mass of He = 0.4 g ( U rms ) H 2 TN 2 2
Mass of oxygen = 1.6 g
Mass of nitrogen = 1.4 g TH 2
5
nHe = 0.4/4 = 0.1 = 1 = T ´ 14
nO = 1.6/32 = 0.05 N2
2
nN = 1.4/28 = 0.05
2
n total = nHe + nO + nN = 0.1 + 0.05 + 0.05 = 0.2 TH 2
2 2
= 5 = T ´ 14
nRT 0.2 ´ 0.082 ´ 300 N2
P= = = 0.492 atm
V 10 TN × 5 = TH × 14
2 2
15. (c) Draw a line at constant P parallel to volume \ T N > TH
2 2
axis. Take volume corresponding to each
PVm
temperature. 19. (b) Compressibility factor Z =
RT
From volume axis, V1 > V2 > V3
Hence, T1 > T2 > T3. PVm æ Vm ö æ a ö
= -
RT çè Vm - b ø÷ èç RTVm ø÷
1 1 Z=
16. (b) PV = mNu2 = mu2
3 3
or u = 3 PV /M
1 a
1 = - ... (i)
at STP, u a b RTVm
M 1-
i.e., higher the molar mass lesser will be the value Vm
of urms. Considering the equation (i) the value of
Molecular masses of H2, N 2, O 2 and HBr compressibility factor Z decreases as the value
are 2,28,32 and 81. Hence the correct order is of ‘b’ decreases and the value of compressibility
HBr < O2 < N2 < H2. factor Z decreases as the value of ‘a’ increases
3 3 w at constant temperature and fixed volume.
17. (c) K.E.= nRT; K.E(H2 ) = × × R × 300;
2 2 2 3 3000 ´ 2
20. (d) K = n T RT Þ n T =
3 w 2 3 ´ 250 ´ 8.314
K.E.(CH4) = × × R × 600;
2 16 3
3 × 103 = n × 8.314 × 250
K.E.(H 2 ) 2 T
Hence K.E.(CH ) = 4 x 30 - x 2
4 + =
20 40 8.314
3RT % Ne = 28.3
18. (c) U rms
M 1
21. (5) rg = .r
5 H2
( Urms ) H 2 = TH2 ´ M N2 ; 2
= U Mg é rH 2 ù
( rms ) N2 M H2 TN2 = ê ú = (5)2 = 25; Mg = 2 × 25 = 50
M H2
ëê rg ûú
(Urms)H2 = 5 (Urms)N2 10 y = 50 Þ y = 5
States of Matter 121

rCH 4 Mx Mx 26. (9) V, n constant.

22. (8) =2= =
rx M CH 4 16 , or Mx = 64
Pi Pf T æ 109 ö
8y = 64 Þ y = 8 Þ Pf = f Pi = ç ÷ Pi
Ti = Tf Ti è 100 ø
3RTx 2RTy
23. (4) vrms of X = M x ; vmp of Y = My 9
Þ Pincreases = DP = Pf – Pi = Pi
Given vrms = vmp 100
3RTx 2RTy \ % Pressure increases
Þ Mx = My DPf 9Pi
2RTyM x = P ´ 100 = 100P ´ 100%
2 ´ 60 ´ 40 i i
Þ My = = =4
3RTx 3 ´ 400 X%=9%
24. (7) Equation of line is = X=9
10 - 2
p–2= ( V - 15)
4 - 15 u12 N1 + u 22 N 2
(4, 10) 27. (3) urms =
8 N1 + N 2
p–2= - ( V - 15 )
11
8V 15 ´ 8 P
p= 2- + u12 N1 + u 22 N 2
11 11 Þ u 2rms =
(15,2) N1 + N 2
æ 142 8V ö
p= ç - ÷
è 11 11 ø V
4 ´ 7 2 + 6u 22 54
1 æ 142V 8V2 ö 25 = Þ u2 = 3ms -1
f(T) = nR çç 11 - 11 ÷÷ 10 6
è ø 28. (1) Average kinetic energy depends only on
d ( F (T)) 1 æ 142 8V 2 ö the temperature. Thus, n = 1
= nR çç 11 - 11 ÷÷ = 0
dV è ø 3RT
29. (405) mrms =
142 M
V= = 8.875
11´ 16 3RT
142 8 8.875 71 450 =
p= - ´ = 4 ´ 10 -3
11 11 16 11 (molecular mass of He = 4 ¥ 10–3 kg)
PV 71 142 RT = 270
TMax = = ´ = 700
nR 11 16 ´ 0.0821 3 3 4
Þ 7 × 102 K Total K.E. of He gas = nRT = ´ × 270 = 405 J
2 2 4
25. (4) Pi = 722 mm Pf = 760 mm 8a a
Ti = 107 + 273 = 380 K Pf = 100 K 30. (8) Tc = 27 Rb and Pc = 27 b 2
di = lg/cm3 df = ? Tc é Tc mb ù
8b
Þ êQ = ú
Pc = R
d i Ti R d f Tf R
Pi = Pf
ë Pc R û
mb 8b
æ Pf öæ Ti ö æ 760 öæ 380 ö 3 Þ =
Þ df = ç P ÷ç T ÷ d i = ç 722 ÷ç 100 ÷ ´1g / cm R R
è i øè f ø è øè ø \ m= 8
= 4 g/cm3
 122 CHEMISTRY

CHAPTER

Thermodynamics
6
reversible path
1. (c) w = Pext × volume change
= 1 × 15.3 = 15.3 litre-atm
A B = 15.3 × 101.3 J = 1549.89 J
‘w’ should be negative as the work has been
done by the system on the surroundings.
irreversible path w = –1549.89 J = –1.54 kJ
For a cyclic process the net change in the internal 5. (b) Amount of work done in reversible
energy is zero because the change in internal isothermal expansion
energy does not depend on the path.
V2
2. (b) DU = q + w = q - PDV w = –2.303nRT log V
1
= 200J - 105 Pa ´ (5 - 4) ´10 -3 m3
20
(Q 1L = 10–3m3) w = –2.303 × 2 × 8.314 × 298 log
10
= 200J - 100 Pa m3 = –2.303 × 2 × 8.314 × 298 × 0.3010
= 200 J – 100 J = 100 J (Q 1J = Pa m3) = –3434.9 J = –3.4 kJ
i.e., work is done by the system.
3. (c) ®;
Mn(s) + 2HNO 3 (aq) ¾¾ 6. (b) w = Area of P-V curve. As area under graph
Mn(NO3 )2 (aq) + H 2 (g) 3 is maximum and area under graph 1 is minimum,
so w3 is maximum and w1 is minimum \
110 w1<w2<w3
Moles of H2 = Moles of Mn = =2
55 P
7. (b) w = - nRT ln 1
Work done due to expansion P2
= – PDV = –DnRT = – 2 × 8.314 × 300 = – 4988.4J
4. (a) Volume of 0.5 mole of steam at 1 atm pressure 10
= -10 ´ 8.314 ´ 300ln
1
nRT 0.5 ´ 0.0821 ´ 373
= = = 15.3 L
P 1.0 = – 57441.43 J
w = – mgh
Change in volume = vol. of steam – vol. of water
\ m × 9.81 × 100 = 57441.42
= 15.3 –negligible = 15.3 L
m = 58.55 kg
Work done by the system,
Thermodynamics 123

8. (b) Given C + O2 ® CO2 , DHº = -x kJ ....(i) where M is the molar mass of the gas.
Similarly, Cv = 149 × M J. kg–1
2CO2 ® 2CO + O2 , DHº = +y kJ … (ii) Cp – Cv = R
or CO2 ® CO + 1/ 2O 2 , DHº = + y / 2kJ ...(iii) \ 248.2 × M – 149M = 8.314
By adding no. (i) and (iii) eq. 8.314
M= = 0.0838 kg/mol
1 248.2 - 149
C + O 2 + CO 2 ¾¾
® CO 2 + CO + O 2
2 Molar mass of the gas = 83.8 g/mol
13. (a) Given S(s) + 3F2(g) ® SF6(g) ;
1
C + O 2 ¾¾
® CO , D H = –1100 kJ ......(i)
2
S(s) ® S(g); D H = 275 kJ .....(ii)
y - 2x 1/2 F2(g) ® F(g); D H = 80 kJ .....(iii)
DHº = y / 2 - x = kJ
2 To get SF6(g) ® S(g) + 6F(g) we can proceed
as (ii) + 6 ´ (iii) – (i)
9. (a) I 2 ( s ) + Cl2 ( g ) ¾¾
® 2ICl( g ) \ SF6(g) ® S(g) + 6F(g); DH= 1855 kJ
D rH = [DH(I2 (s) ®I2 (g)] + DHI–I + DHCl–Cl] Thus average bond energy for S-F bond
– [DHI – Cl] 1855
= = 309.16 kJ
= 151.0 + 242.3 + 62.76 –2 × 211.3 = 33.46 6
33.46 14. (d) Entropy change
D f H°(ICl) = = 16.73 kJ / mol
2 DS = DSproduct - DSreactant
10. (d) Given, mass of ethanol = 1kg = 1000 g
= 2 (186.7) – (223 + 130.6)
Latent heat of vaporisation of ethanol
= 373.4 – 353.6
= 855 Jg–1
= 19.8 JK–1 mol–1
Specific heat capacity of ethanol = 2.44 J/gK–1
Heat, q = mcDT + heat of vaporisation 15. (a) ˆˆ† ( CH 3COOH ) ( g )
2CH 3COOH ( g ) ‡ˆˆ 2
= 1000 × 2.44 (351. 45 – 293.45 + 855 × 1000 J)
= 9.97 × 105 J 1 0
0.982
11. (c) The energy involved in the conversion of 1 – 0.982 2
1
2
Cl2 (g) to Cl–1 (aq) is given by ( CH3COOH )2 0.982
K= = = 1515.4
( CH3COOH ) 2 ´ ( 0.018)2
2
1
DH = D dissH (–) (–)
+ D eg H Cl (–)
+ D hyd H Cl
2 Cl 2 Now, DH° for dimerization = – 2 × 33 kJ = – 66 kJ
Thus, DG° = DH° – TDS°
Substituting the values from given data, we get
– 2.303 RT log K° = DH° – TDS°
DH = æç ´ 240 ö÷ + (–349) + (–381)kJmol –1
1 – 2.303 × 8.314 × 400 × log (1515.4)
è2 ø = – 66 × 103 – 400 × DS°
= (120 – 349 – 381) kJ mol–1 – 242359.2 = – 66000 – 400 DS°
= – 610 kJ mol–1 41640.8
DS° = - = -104 JK –1 mol –1
12. (a) Molar heat capacity at constant pressure, 400
Cp = 248.2 × M J.kg–1
 124 CHEMISTRY
16. (d) For a spontaneous process, 22. (48.00)
DS = (DSsystem + DSsurrounding) > 0 Work done is given by the area under the trapezium.
17. (d) Since the process is at equilibrium DG = 0 and 1
for DG = 0, the conditions should be DH > 0, DS > 0. \ |w| = (6 + 10) × 6 = 48 J
2
18. (b) For the reaction 23. (6.25) DU = nCvDT
2 ZnS ® 2 Zn + S2 ; DG1º = 293 kJ .......(i) 5000 = 4 × Cv (500 – 300)
2 Zn + O2 ®2 ZnO ; DG2º = –480 kJ .......(ii) Cv = 6.25 JK–1 mol–1
S2 + 2 O2 ®2 SO2 ; DG3º = –544 kJ ......(iii) 24. (1) For reversible adiabatic process
DGº for the reaction g 1– g
æ T1 ö æ P2 ö T1 P
2 ZnS + 3O2 ®2 ZnO + 2SO2 ç ÷ = ç ÷ or g log = 1 – g log 2
can be obtained by adding eqn. (1), (2) and (3) T
è 2ø è 1ø P T 2 P1
Þ DGº = 293 – 480 – 544 = – 731 kJ 300 10
g log = 1 – g log
90 200
15 g (log10 – log3) = 1 – g (log10 – log200)
19. (b) C6H6 + O ® 6CO2 + 3H2O; x ...(i)
2 2 g = 1.66
C6H12 + 9O2 ® 6CO2 + 6H2O; y ...(ii) Atomicity = 1
25. (4) In Fe2O3 + 2Al ® 2Fe + Al2O3
1 2 × 56 + 48 = 160 2 × 27 = 54
H2 + O2 ® H2O; ...(iii)
2 Heat of reaction = 399 – 199 = 200 kcal [Al and
C6H6 + 3H2 ® C6H12; DH ...(iv) Fe are in their standard states]
To get equation (iv), (i) + 3 × (iii) – (ii) 54
Volume of Al = = 20 cc
C6H6 + 3H2 ® C6H12 2.7
Molar enthalpy of hydrogenation of benzene to 160
Volume of Fe2O3 = = 30.77 cc
cyclohexane = x – y + 3z 5.2
Total volume = 20 + 30.77 = 50.77 cc
1atm
H2O(l) ‡ˆˆˆ
20. (d) ˆˆˆˆ †
ˆ H2O(g) 200
\ Fuel value per cc = = 3.94 ; 4 kcal/cc
DH = 40630 J mol
–1 50.77
–1 –1 26. (1) Qv = 1.25 × 4 = 5
DS = 108.8 JK mol
x
DG = DH - TDS Qv = 5 = ×400
80
When DG = 0, DH - TDS = 0 Þ x=1
400 1
DH 40630 J mol -1 27. (4) hmax = 1 - = = 20%
500 5
T= = = 373.4 K.
DS 108.8J mol-1 Source
100J
21. (– 13538)
From DH° = DU° + Dn g RT H.E. 20J Max

DH° = -20 ´1000 - 1´ 8.314 J / mol.K ´ 298 K 80J Min

Sink
= –22477.57 J
80
DG° = DH° – TDS° = -22477.57 - (298 ´ -30) T=
20
= – 13538 J
T= 4
Thermodynamics 125

28. (76) DH = DE + W = – 2361 – 1209 + 728

= DE + (P2V2 – P1V1) = – 2842 kJ/mol
= 50 + (4 × 7 – 1 × 2) For 2 moles of nitroglycerine enthalpy
= 76 L – atm = – 2842 kJ/mol.
29. (31) At equilibrium \ For 1 mole of nitroglycerine enthalpy
Heat lost by iron = Heat gain by water
-2842
20 × 0.5 × (473 – T) = 100 × 4.2 × (T – 300) = = – 1421 kJ/mol.
2
Þ T = 304 K = 31°C
227.1 g of C3H5(NO3)3 has enthalpy
1 = – 1421 kJ/mol.
30. (62.5) 2C3H5(NO3)3 (l) ¾® 3N2(g) + O2(g)
2 \ 10 g of C3H5(NO3)3 has enthalphy
+ 6CO2(g) + 5H2O(g)
1421
DH°reaction = SH°f(P) – SH°f(R) =- × 10 = – 62.5 kJ/mol
227.1
1
DH°reaction = 3 × 0 + × 0 + 6 × – 393.5
2
+ 5 × – 241.8 – (2 × – 364)
 126 CHEMISTRY

CHAPTER

7 Equilibrium

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

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

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

K2 = ; \ K1 = 2
[NO] K2
100(PCO 2 ) 2
4. (b) PCl5 ƒ PCl3 + Cl2 or 63 = or 63 = 100 PCO 2
PCO 2
Moles at equilibrium
1 1 1
2 2 2 63
PCO2 = = 0.63 atm
Mole fraction at equilibrium 100
1 1 1
3 3 3 PCO = 10PCO 2 = 10 × 0.63 = 6.3 atm
Partial pressure at equilibrium
Ptotal = PCO + PCO = 0.63 + 6.3 = 6.93 atm
P P P 2
3 3 3
7. (d) ˆˆ† 2NO 2 (g)
N 2 O 4 (g) ‡ˆˆ
P P
´ Initial moles 1 0
P
\ Kp = 3 3 = Moles at eqm. (1 – a) 2a
P/3 3
(a = degree of dissociation)
Equilibrium 127

Total number of moles at equil.

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

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

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

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

Total no. of moles of gases at equilibrium

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

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

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

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

s1 s2
15. (c) ˆˆ† CH COO– + H+
CH3COOH ‡ˆˆ 3
0.1 0 0
K sp = s1 ´ s1
1
Initial concentration
Þ4× 10–12 = s12
0.1(1 – 0.0132) 0.1 × 0.0132 0.1 × 0.0132 s1 = 2 × 10–6 mol/L
at eqb. Ksp(Ag2CrO4) = 4 × 10–12
[CH 3COO - ] [H + ] Ag2CrO4 ® 2Ag + + CrO24 +
Ka =
[CH3COOH] 2 's 2 ' s2

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

= = 1.76 × 10–5 2 2 2
0.1(1 – 0.0132)
4 × 10–12 = 4s23
s23 = 10–12
Equilibrium 129

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

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

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

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

X + Y ˆˆ† 2 Z
‡ˆˆ Let acid be = V mL
t =0 1 mol 1.5 mol 0.5 mol V mL of 0.01 M CH3COOH will require V mL of
0.01 M NaOH. But CH3COONa formed will make
t = teq 1– x 1.5 – x 0.5 + 2x
solution alkaline due to hydrolysis.
0.5 + 2x = 1; x = 0.25
 130 CHEMISTRY

28. (4) Given [H3O+] = 1 × 10–10 M

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

8 Redox Reactions

1. (a) Ox. no. of Cr on both side is + 6. 8. (b) SO2 oxidises H2S to S, since the O.N. of S
2. (d) 2I - ® I2 is oxidation (loss of electrons) ; change from –2 to 0.
Cr (+6) changes to Cr (+3) by gain of electrons. 9. (d) In H 2SO4 , sulphur is in highest oxidation
Hence Cr is reduced.
state (+6), hence H2SO4 will be strongest
3. (a) In a redox reaction, one molecule is oxidised
oxidising agent.
and other molecule is reduced i.e. oxidation
10. (c) A reaction in which a substance undergoes
number of reactants are changed.
simultaneous oxidation and reduction is called
0 0 +1 -1 disproportionation reaction. In these reactions
H2 + Br2 ¾¾
® 2 HBr
the same substance simultaneously acts as an
Here H2 is oxidised and Br 2 is reduced, thus it is oxidising agent and as a reducing agent. Here Cl
oxidation-reduction reaction. undergoes simultaneous oxidation and
4. (c) CaOCl2 or Ca (OCl) Cl is the mixed salt of reduction.
Ca(OH)2 with HCl and HOCl. 0 -1 +1
2KOH + Cl2 ® KCl+ KOCl + H 2O.
0
5. (d) 3B r2 + 6CO32– + 3H 2O ® 11. ( b) The reaction involve 6 electrons, i.e.
Cr2O72– accepts 6 electrons for its reduction to Cr3+
-1 +5
5 B r – + Br O3– + 6HCO3– 2Cr2 O 72- + 14H + + 6I - ® 2Cr 3+ + 7H 2 O + 3I2
O.N. of Br2 changes from 0 to –1and +5 hence it ˆˆ† M, for this reaction,
12. (a) (i) Mnn+ + ne– ‡ˆˆ
is reduced as well as oxidised.
high negative value of E° indicates lower
6. (b) BaO2 + H2SO4 ® BaSO4 + H2O2
reduction potential, that means M will be a good
The most electronegative element O is present
reducing agent.
in BaSO4 and H2O2, where its O.N. are – 2 and
– 1 respectively. Stronger reducing agent Þ Easy to oxidise
7. (d) In Na2O, SnCl2 and Na2O2 central atom is ß
either in lowest or highest oxidation state, so it Lower reduction potential Ü higher oxidation potential
can function either as an oxidising or a reducing (ii) Element F Cl Br I
agent but not both. However, the oxidation state Reduction +2.87 +1.36 +1.06 +0.54
of N in NaNO2 is +3 which lies between its potential
highest (+5) and lowest (–3) values. (E° volt)
 132 CHEMISTRY

As reduction potential decreases from fluorine

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

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

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

9 Hydrogen

1. (a) Zn + H2SO4 ® ZnSO4 + H2 11. (a) H2SO4 + BaO2 ® BaSO4 + H2O2

Zn + 2NaOH ® Na2ZnO2 + H2
Molar mass
\ Ratio of volumes of H2 evolved is 1 : 1 12. (a) Equivalent weight =
Valence factor
2. (b) 2Al + 3H 2SO4 ® Al2(SO4 )3 + 3H 2

2Al + 2NaOH + 2H 2O ® 2NaAlO2 + 3H 2 1´ 2 + 16 ´ 2

=
2
The ratio of volumes of hydrogen evolved is 1:1.
3. (c) Pure hydrogen is evolved by reacting Eq. wt. of H2O2 = 17
absolute alcohol and Na 30.36
N= = 1.78 N
C2 H5OH + Na ® C2 H5ONa + ½H 2 17
other statements are correct. Volume strength = 5.6 × normality
4. (d) All metal hydrides are ionic in nature. = 5.6 × 1.78 = 10 V
5. (d) It forms calcium and magnesium complex 13. (b) Q 22.4L O2 at S.T.P. is obtained from = 68 g
with Ca2+ and Mg2+ ions present in hard water. H2O2
6. (c) Sea water is purified by reverse osmosis.
68
7. (c) Ca(OH) 2 is used for the softening of \ 1L O2 at S.T.P. is obtained from = gHO
22.4 2 2
temporary hard water.
\ 20L O2 at S.T.P. is obtained from
Ca(OH) 2 (aq) ¾¾
® CaCO3 (s) + H 2O( l )
Cloudiness 68
8. (b) Water has high dielectric constant i.e., 78.39 = ´ 20 g H O = 60.71 g of H O
22.4 2 2 2 2
C2/Nm2, high liquid range and can dissolve
Therefore, strength of H2O2 in 20 volume H2O2
maximum number of compounds. That is why it
= 60.71g/L
is used as universal solvent.
\ 1000 mL O2 at S.T.P. is obtained from = 60.71 g
9. (a) Molecular weight of H2O2 = 34
H2O2
Equivalent weight of H2O2 = 17
\ 100 mL O2 at S.T.P. is obtained from
\ 1 L of 1 N H2O2 has = 17 g of H2O
\ 1 L of 1.5 N H2O2 has = 1.5 × 17 = 25.5 g of H2O2 60.71
= ´ 100 = 6.071% H O
1000 2 2
Vol. strength
10. (a) Normality of H2O2 =
5.6 14. (a) H 2O 2 ® H 2O + [O]
Volume of normal (1N) H2O2 solution = 5.6 volumes. weak acid
\ Volume of strength of 1.5 N H2O2 15. (a) As H2O2 is loosing electrons so it is acting
= 1.5 × 5.6 = 8.4 volumes. as reducing agent.
 134 CHEMISTRY

16. (d) The D2O reacts with given compounds as

0 × 286
follows: 0.286 g Na2CO3 . 10H2O º = 10–3moles
286
D2O + CO2 ® D2CO3
D2O + SO3 ® D2SO4 Moles of CaCO3 = 10–3 moles
3D2O + P2O5 ® 3D3PO4 Mass of CaCO3 º 10–3 × 100 = 10–1g
D2O + N2O5 ® 2DNO3 1n 1000 g of hard water º 10–1g of CaCO3
17. (c) 6 volume H2O2 would give 6 volumes of
10-1
O2 per unit volume of H2O2 106g of hard water º × 106
1000
18. (c) In water gas shift reaction carbon
monoxide reacts with steam at high temperature º 100g. of CaCO3
to produce carbondioxide and hydrogen. ppm hardness = 100
19. (c) Lime can remove temporary hardness of 23. (15) Volume strength = 5.6 × N
water which is caused due to bicarbonate salt
10 15 20
of Ca and Mg. Thus N1 = , N2 = , N3 =
5.6 5.6 5.6
20. (d) When sodium hexametaphosphate is added
After mixing total volume = 300 mL
to hard water it combines with Ca2+, Mg2+ ions
N1V1 + N2V2 + N3V3 = NV
present in hard water and forms a complex. These
complexes with soap readily produce lather. 10 15 20
´ 0.1 + ´ 0.1 + ´ 0.1 = 0.3 × N
Na2[Na4(PO3)6] + 2Ca2+ ® 5.6 5.6 5.6
Na2[Ca2(PO3)6] + 4Na+
Na2[Na4(PO3)6] + 2Mg ® 2+ 10 +15 + 20 0.1 15
N= ´ =
Na2[Mg2(PO3)6] + 4Na+ 5.6 0.3 5.6
21. (3) The ratio of ortho to para hydrogen can
15
never be more than 3 : 1. Volume strength = 5·6 × = 15
22. (100) Molecular mass of Na2CO3 . 10H2O = 286 5×6
Molecular mass of CaCO3 = 100 24. (6) 6000 parts of ordinary water (H2O) contains
CaSO4 + Na2CO3 . 10H2O ® 1 part of heavy water (D2O).
CaCO3 + Na2SO4+10H2O 25. (143) 1 g of H2 gas, release 143 kJ of energy.
 CHAPTER

10 The s-Block Element

1. (a) Lithium does not form peroxide. 11. (c) The property of sodium atom to emit
photons in yellow region of visible spectrum,
heat
2. (d) 2KClO 3 ¾¾¾® 2KCl + 3O 2 due to electrically stimulated electron transitions
solid melts solid
is used in street lights.
3. (b) Sodium metal on burning in air gives 12. (a)
sodium peroxide. 13. (d) Halides of group I an d II impart
4. (d) Stability of a compound depends upon its characteristic colour to the flame due to low IE
enthalpy of formation DHf. The more negative of the central atom. However, ionization energy
value of DHf shows more stability of a compound. of Be and Mg atoms is high due to their small
Thus KCl is more stable than LiCl , size, hence they can't be excited to higher levels
DH f for LiCl = -408 kJ/mol by Bunsen burner flame. Thus, their halides
DH f for KCl = -436 kJ/mol don't impart colour to flame.
14. (c) ZnS + BaSO4 is lithopone. It is used as white
5. (a) If lattice energy is less than hydration pigment.
energy, the ionic compound will be soluble in 15. (c) Philosopher’s wool is ZnO
water.
1100°C
6. (c) The unreacted AgBr is removed by soluble ZnO + BaO ¾¾¾¾
® BaZnO2
complex formation
MgCl2 ¾¾¾¾¾® Mg 2+ + 2Cl-
Electrolysis
16. (d)
AgBr + 2Na 2S2 O3 ® Na 3[Ag(S2 O3 ) 2 ] + NaBr (Molten) Cation Anion
7. (a) The ionisation potential value of lithium is
Anode ® 2Cl– ® 2Cl + 2e–, Cl + Cl ® Cl2
maximum among alkali metals i.e., its tendency
Cathode ® Mg+2 + 2e– ® Mg
to ionise to give Li+ ions should be the minimum
17. (d) BeSO4 is most soluble because hydration
i.e. Li should be the poorest reducing agent. But,
energy is more than lattice energy.
lithium is the strongest reducing agent in aq.
BeSO > MgSO > CaSO > SrSO > BaSO
solution. This is due to the largest value of ¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾
4 4 4 4 4 ®
Hydration energy decreases hence,solubility decreases.
hydration energy of Li+ ions.
8. (d) Na 2 O 2 is per oxide of sodium not Heat
18. (a) MgCO3 ¾¾¾
® MgO + CO 2
superoxide. The formula of sodium superoxide
is NaO2. The metal whose oxide is stable, has its
9. (d) Na2CO3 + Ca(OH)2 ® 2NaOH + CaCO3 carbonate unstable
10. (b) 19. (b) The basic character of oxides increases
down the group.
 136 CHEMISTRY

20. (a) increase in size which results in decrease of

ionization energy which weakens the strength
21. (c) Ca(HCO3 )2 + Ca(OH)2 ¾¾
®
temp. hardness of M – O bonds in MOH and thus increases the
2CaCO3 ¯ +2H 2 O basic strength.
Be(OH) 2 Mg(OH)2 Ca(OH)2 Sr(OH) 2 Ba(OH)2
Ca(OH) 2 + Na 2CO3 ¾¾
® 2NaOH + CaCO 3
Caustic soda Amphoteric Weak base Strong base
A

Ca(OH) 2 + CO 2 ¾¾
® CaCO3 ¯ + H 2 O Hence, Be(OH)2 will have lowest pH.
A milkiness 25. (b) 30 mL N/50 HCl º 30 mL N/50 Ca(HCO3)2
22. (c) º 30 mL N/50 CaCO3 º 100 mL tap water
23. (d) Hasenclever and Batchmann’s methods are Mass of CaCO3 in 100 mL tap water
used for the manufacture of bleaching powder.
E´ N´V 50 ´ 30
24. (a) Metal halide on hydrolysis with water form = = = 0.03 g
1000 50 ´ 1000
corresponding hydroxides.
The basic strength of hydroxide increases as we Þ hardness = 300 ppm
move down in a group. This is because of the
 CHAPTER The p-Block
11 Elements
(Groups 13 and 14)
1. (c) H3BO3 on heating at 373K yields metaboric Although transitions of white to grey tin occurs
acid (HBO2) at any temperature below 15.2°C, it becomes rapid
only at –50°C, unless a catalyst is present. During
373K
H3BO3 ¾¾¾® HBO2 + H2O the conversion of white tin to grey tin (in cold
D
metaboric acid countries) volume increases. Grey Sn is very
(orthorombic form)
brittle easily crumbles down to powder. This
2. (b) Al2Cl6 + 12H2O 2[Al(H2O)6]3+ + 6Cl– phenomenon is called tin diseases, tin past or
tin plague.
3. (b)
12. (a) Lesser electronegativity of X and similar
4. (b) CaF2 when added to fused cryolite, lowers size of valence shell of X and B favours back
the m.p. and increases the conductivity. bonding.
Cl and F are more electronegative than
5. (b) Al(OH)3 + OH - ® [Al(OH) 4 ]-
OMe and NMe group and Cl have large size of
3p-orbital.
[Al(OH) 4 (H 2 O) 2 ]-
2H O
¾¾¾®
2
Among B(OMe)3 and B(NMe2)3, N in NMe is
6. (d) Lewis acidic strength : BF3 < BCl3 < BBr3 < BI3 less electronegative than O in OMe group. Thus,
As BI3 is strongest lewis acid among all boron the tendency to form p-bond with boron follows
halides therefore, heat of adduct formation will the order.
the maximum numerically, for BI3. BCl3 < BF3 < B(OMe)3 < B(NMe2)3.
13. (c) Pb3O4 + 4HNO3 ®
7. (a) 2Al + N 2 ¾¾ D
® 2AlN 2Pb(NO3)2 + PbO2 + 2H2O
8. (a) 14. (d) Fullerene contains both single and double
9. (a) bond with C-C at a distance of 143.5 pm and
D 138.3 pm.
SiCl 4 ( s) + 2H 2O(l) ¾¾¾¾ ® Si(OH) 4 ( aq)
-4HCl
Silicic acid 15. (b) SnCl4 is colourless volatile liquid and SnCl2
D
¾¾
® SiO 2 .xH2O( s) is colourless solid Sn conducts electricity and it
Silica gel belongs to 14 group.
10. (d) It is hydrolysed with water to form a Si(OH)4. 16. (a) The stability of +2O.S. follows the order
15.2°C 164°C Pb 2 + > Sn 2 + > Ge 2 +
ˆˆˆˆˆ†
11. (b) a-tin ‡ˆˆˆˆ ˆˆˆˆˆ
†
ˆ b-Sn ‡ˆˆˆˆ
ˆ
(Grey) Hence reducing power Ge > Sn > Pb
(White)
(most common and stable) 17. (d) 2CaF2 + SiO 2 + H 2SO 4 ¾¾
®
232°C
ˆˆˆˆˆ
g -Sn ‡ˆˆˆˆ †
ˆ Liquid tin hydrolysis
(Brittle)
SiF4 + H 2O + CaSO4 ¾¾¾¾¾ ® CaSiF6
(Rhombic)
 138 CHEMISTRY
D 1 22. (3) CO2, SiO2 acidic CaO basic and SnO2
18. (c) Pb(NO3 ) 2 ¾¾® PbO + 2NO2 + O 2
2 amphoteric.
19. (c) SiO2 + 3C ¾¾® SiC + 2CO
¬
23. (4) Boron in B2H6 is sp3 hybridised and hence
20. (d) CO molecule is linear (C = O) and it is four orbitals are involved.
supposed that carbon atom in it is sp-hybridised. 24. (32) It contains 20 six-membered rings and 12
CO is electron deficient molecule and has p five-membered rings.
acceptor properties. Due to presence of pair of
Total no. of rings = 20 + 12 = 32
electrons, it acts as ligand or Lewis base. In
metallurgy it is used as reducing agent. 25. (56) Producer gas is CO + N2.
21. (6) In aqueous solution the probable aluminate Sum of molecular mass = (16 + 12) + (14 + 14)
species is [Al(H2O)2(OH)4], hence, co-ordination = 56
number of Al is 6.
 CHAPTER Organic Chemistry-
Some Basic Principles
12 and Techniques
1. (b) It is biphenyl derivative 4. (c) Any conformation between two extreme
NH 2 COOH positions
5' 6' 2 3
i.e. eclipsed and staggered is known as Gauche
4' 4 or Skew form.
1' 1 C4
3' 2' 6 5 CH3
H
COOH N H 2 H H H3C H
2. (a) Enolic form predominates in compounds C3
H
60º C4 C3
containing two carbonyl groups separated by a C2
C2
– CH2 group. This is due to following two factors. H H
(i) Presence of conjugation which increases
stability. CH3 H3C H
C1 C1
(ii) Formation of intramolecular hydrogen
bond between enolic hydroxyl group and
second carbonyl group which leads to H
H
stablisation of the molecule.
H Hence the H H H
H
correct answer is III > C
II3> I. 60º 60º
O OH C2
C2 C
3
H H
3. (a) H3C
C4 CH3
C1
O O (Gauche conformation)
are tautomers.
a
F F
H
c CH3Br
5. (c) (I) Br H c
º H Me & b
Me
H CH3 F
a
H CH2Br
b

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

diastereomers

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

+ +
6. (d) The amount of s-character in various hybrid CH2 CH2
orbitals is as follows.
sp = 50%, sp2 = 33% and sp3 = 25%
Therefore s-character of the C – H bond in
acetylene (sp) is greater than that of the C – H
bond in alkene (sp2 hybridized) which in turn NO2
NO2 intensifies Benzyl stable
has greater s character of the C–H bond than in due to resonance
+ve charge on benzyl cation
alkanes. Thus owing to a high s-character of the due to –I and –M effects
C – H bond in alkynes, the electrons constituting +
CH2 +
CH2
this bond are more strongly held by the carbon
nucleus with the result the hydrogen present on
such a carbon atom can be easily removed as
proton. The acidic nature of three types of C – H
bonds follows the following order Cl : OCH
.. 3
-C º C - H > - C = C - H > - C - C - H Cl intensifies +ve Positive charge of
charge on C benzyl cation is
Further, as we know that conjugate base of a due to –I effect more dispersed due
to +M effect of the
strong acid is a weak base, hence the correct –OCH3 group
order of basicity is 9. (c) Cl– is the best leaving group among the
- - - given option.
H - C º C < CH 2 = CH < CH 2 - CH3 10. (d) —NO2 group is electron attractive group,
.. -
.. + so it is able to deactivate the benzene ring.
7. (c) CH2 = CH - Cl
.. « CH 2 - CH = Cl
: :
.. Cl
a double bond is formed between C and Cl. Hence NO2
it is less reactive due to resonance.
8. (d) The stability of carbonium ion is influenced
NO2
by both resonance and inductive effect.
Organic Chemistry-Some Basic Principles and Techniques 141

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

OCH3 CH3 CF3

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

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

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

O –
O H3C H CH3
CH 3 CH 3 aq .acetone
(B)¾¾¾¾¾® CH3O NO2
( H 2O )

O O HO H CH3
O
(ii)
CH 3

–O
 142 CHEMISTRY

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

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

·· H
O
delocalised l.p. sp2 -hybridised sp3-hybridised CH2
'N' l.p.
H3C C+
20. (d) B.P. µ extent of H bonding µ surface area
of molecule. CH2
Most acidic H
(Hyper-conjugation in tert-butyl carbocation)
H
Whereas, trans-2-butene is more stable than
21. (b) S propene because of hyper-conjugation between
C
S s and p*-orbitals.
empty 3 d orbitals H
– S
C + H+ HH
S H C
Stabilise by simple resonance C C
and 'd ' – orbital resonance. H H C H
22. (b) Structure III and I has complete octet for
all atoms III is more stable than I because 25. (b) H
O
N + > O + is the stability order..
b c
23. (d) H Cl N N
CH3
a H H
H Cl N
H3C H
Cl H
H CH3 In the given compound most acidic proton will
H3C be Nb — H. This is because its conjugate base
CH3 Cl
(X) (Y) will be most stable and the most nucleophilic
nitrogen will be Nc, because the lone pair of
Both X and Y are conformers of each other, where
electrons present on this N is localised.
X is eclipsed and Y is staggered form.
Organic Chemistry-Some Basic Principles and Techniques 143

26. (a) The reaction between haloalkane and 29. (d)

AgNO3 gives carbocation intermediate. So, H CH2SH HO H
more easily it will be formed, more readily it will
react to give precipitate. H3C CH2OH H3C CH2SH
In the given compound I II
c
Cl Cl
a Fischer projection of the above compounds are:
d d
(3)
b b
Cl Cl Cl Cl CH3
¾¾¾®
(1)
O a O + H
Cl a
CH2SH
Cl (4)
d b
Cl Cl CH2OH
¾¾¾® (2)
O I
+ So I should be 'R' but here, lower priority group
O being electronegative, will attract electron is on horizontal line. Therefore configuration will
density and cleave C–Cla bond density easily. be reversed i.e. correct configuration 'S'.
27. (a) The lower stability of ethyl anion (CH3CH2–) (3)
compared to methyl anion (CH3–) is because of + CH3
I-effect of methyl group of ethyl anion. The
(1) (4)
higher stability of ethyl radical compared to
HO H
methyl radical is due to s an d p-orbital
conjugation is ethyl radical.
H CH2OH
H H (2)
C C ¬¾® H C CH2
II
H
II should be 'S', lower priority group is on
H H horizontal line i.e. 'R'
Hyper conjugation
in ethyl radical 30. (a)
O Me — N: O Me — N O
–

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

CHAPTER

Hydrocarbons
13
1. (c) In neopentane all the H atoms are same (1º). 6. (a) Peroxide effect is observed only in case of
CH3 HBr. Therefore, addition of HCl to propene even
|
CH 3 - C - CH 3 in the presence of benzoyl peroxide occurs
|
CH3 according to Markovnikoff’s rule :
2. (d) In trans-isomer polarity developed by one HCl
—CH3 group is cancelled by polarity of the CH 3 - CH = CH 2 ¾¾¾¾¾¾®
(C 6H 5CO) 2O 2
order —CH3 group placed in opposite direction
CH3 – CHCl – CH3
while the cis-isomer is polar although weak causing
7. (a) The intermediate 2º carbocation shows
high boiling point than the trans-isomer.
resonance
3. (d)
2 1 Br +
CH3CHCOONa CH3CH CH 2 = CH - CH = CH 2 ¾¾¾
®
——® + CO2 + 2NaOH + H2 + +
CH3CHCOONa
é ù
3 4
CH3CH ê CH 2 Br - CH - CH = CH 2 « CH 2 Br - CH = CH - CH 2 ú
4. (b) The relative reactivities of alkenes towards ë û
HX are directly related to the stabilities ofé the + + ù
ê CH 2 Br - CH - CH = CH 2 « CH 2 Br - CH = CH - CH 2 ú
intermediate carbocations. Isobutene (IV) formsë û
the most stable 3° carbocation followed by Br -
¾¾¾ ® CH 2 Br - CH = CH - CH 2 Br
butene-1 (II) which forms 2° carbocation.
1,4 - Dibromo - 2- butene
Ethylene (I) and vinyl chloride (III), both form 1°
carbocation, but the carbocation from vinyl 8. (b) Always remember cis-2-butene + Br2 ®
chloride will be less stable because electron- Racemic-2, 3-dibromobutane
withdrawing halogen intensifies the positive charge trans-2-Butene + Br2 ® Meso-2, 3-dibromobutane.
and thus destabilizes the carbocation. Hence 9. (d) Addition of hydrogen halide to alkene is
vinyl chloride will be less reactive than ethylene. an example of electrophilic addition involving
B H carbocations as intermediates.
5. (d) 6CH3 - CH = CH 2 ¾¾¾®
2 6
ether, 0°C HBr
1-Propene CH3 CH CH2 ¾¾¾¾¾¾
In absence of
®
H O peroxide
2(CH3CH 2CH 2 )3B ¾¾¾®
2 2
OH- CH3 —CH—CH3
6CH 3CH 2 CH 2 OH + 2H 3 BO3 ½
Propanol Br
(Markownikoff 's addition)
Hydrocarbons 145
–
10. (a) +

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

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

OH CH3—C—CH = CH2 + CH3— C = CH—CH2

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

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

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

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

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

H 27. (a) :OCH3

:
BH2 CH3
(1) B 2H 6
¾¾¾¾®

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

¾¾®

– –
Br Br

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

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

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

cis-alkene adds bromine in anti manner forming C6H5COCH2CH2CH3 ————®
racemic product.
C6 H5 CH 2 CH 2CH 2CH 3
Butyl benzene
Hydrocarbons 147

31. (4) All alkyl bromides having carbon skeleton of

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

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

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

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

1. (a) In Antarctica ozone depletion is due to
formation of acrolein.
2. (b) 3. (b) 4. (b) 5. (c)
6. (b) The coldest region is mesosphere (temp. –
27ºC to – 92ºC)
7. (a) Radiation coming from sun or outerspace
have high energy or short wavelength, which
are allowed to enter by green house gases.
However, radiation emitted by earth is in infrared
region, having long wavelength, are reflected
back by the envelope of green house gases.
8. (d) London smog is formed in morning during
winter.
9. (a) The average residence time of NO is 4 days.
10. (a) Normal rain water has pH 5.6.
Thunderstorm results in the formation of NO
and HNO3 which lowers the pH.
11. (d) Decrease in D.O causes death of fish.
12. (a) 13. (c) 14. (c)
15. (c) Because they are very sensitive to sulphur
dioxide and in cities the amount of SO2 is high
so lichen do not grow in cities.
 CHAPTER

The Solid State

15
1. (b) Liquid crystals on heating first become Therefore contribution of each atom A at the
turbid and then clear. 1
2. (d) Orthorhombic system has 4 bravais lattice: corner = . Since number of atoms per unit cell
8
(i) primitive (ii) bcc (iii) fcc (iv) end centred
3. (d) Since in NaCl type of structure 4 formula units 1
is 8, therefore total contribution = 8 ´ = 1 . Wee
form a cell. 8
58.5 gm. of NaCl = 6.023 × 1023 atoms also know that atoms in the body centre,
6.023 ´1023 therefore number of atoms of B per unit cell = 1.
1 gm of NaCl = atoms Thus formula of the compound is AB.
58.5
6. (b) The face centered cubic unit cell contains 4
4 atoms constitute 1 unit cell atom
6.023 ´ 1023 4 16
\ atoms constitute \ Total volume of atoms = 4 ´ pr 3 = pr 3
58.5 3 3

6.023 ´1023 4 ´ 96
= = 2.57 × 1021 unit cells. 7. (b) For bcc lattice, 3a = 4R Þ a = pm
58.5 ´ 4 3
4. (d) Order of Bragg diffraction (n) = 2; = 221.7 pm
Wavelength (l) = 1Å and angle (q) = 60º. (where R is the radius of Ca atom)
We know from the Bragg’s equation Colume of unit
nl = 2d sin q cell = a3 = (211.7 × 10–12)3 m3 = 10.9 × 10–30 m3
or 2 × 1 = 2d sin 60º 8. (b) Volumeof crystal = (1.0 cm)3 = (10–2 m)3 = 10–6 m3
Number of unit cells
3 2
Þ 2 ´1 = 2.d. Þ d= = 1.15Å
2 3 10-6 m3
= = 9.17 ´ 1022
(where d = Distance between the scattering 10.9 ´ 10 -30 m3
planes) 9. (c) In a fcc lattice, the distance between the
5. (a) Atoms are present in the corners of cube = cation and anion is equal to the sum of their
A and atom present at body centre = B. radii, which is equal to half of the edge length of
We know that a cubic unit cell has 8 corners. unit cell,
 150 CHEMISTRY

i.e. r+ + r- =
a
(where a = edge length) r´ a 3 ´ N A ´ 10-30
2 14. (d) M=
Z
r+ = 95 pm, r– = 181 pm
Edge length = 2r+ + 2r– = (2 × 95 + 2 × 181) pm 10 ´ (100)3 ´ 6.02 ´ 1023 ´10-30
= = 15.05
= (190 + 362) pm = 552 pm. 4
\ Number of atoms in 100 g
10. (c) Number of Cu-atoms per unit cell
1 1 6.02 ´1023
= ´8 + ´6 = 4 . = ´100 = 4 × 1025
8 2 15.05

1 ZM
Number of Ag-atoms per unit cell = ´ 12 = 3 15. (b) r=
4 NA V
Number of Au-atoms per unit cell = 1 (at body rN A V
Z=
centre) M
Formula : Cu4 Ag3 Au
8.92 ´ 6.02 ´10 23 ´ (362)3 ´10 -30
11. (c) Let the number of Z atoms in the ccp = =4
63.55
arrangement = 100
\ It has fcc unit cell
Thus the number of tetrahedral sites = 200
Since all the tetrahedral sites are occupied by X 180
16. (b) r+ / r- = = 0.962 which lies in the
atoms, the number of X atoms = 200 187
Hence ratio of X : Z = 2 : 1 range of 0.732 – 1.000, hence co-ordination
Thus the formula is X2Z number = 8 i.e., the structure is CsCl type.
12. (a) Fraction of unoccupied sites in NaCl crystal 17. (a) ZnS has cubic close packed (ccp) structure.
The S2– ions are present at the corners of the
2.165 ´ 103
=1- cube and at the centre of each face. Zinc ions
2.178 ´ 103
occupy half of the tetrahedral sites. Each zinc
ion is surrounded by four sulphide ions which
2.178 ´ 103 - 2.165 ´ 103 0.13 ´103
= = are disposed towards the corners of a regular
3 2.178
2.178 ´ 10
tetrahedron. Similarly, S2– ion is surrounded by
130 four Zn 2+ ions.
= = 5.96 × 10–3 18. (c) Number of O-atoms per unit cell
2178
1 1
ZM = ´8 + ´6 = 4 .
13. (a) r= 8 2
NA V Number of octahedral holes per unit cell
= 1× 4 = 4
rN A V 2 ´ 6 ´10 23 ´ (5 ´10 -8 ) 3
Z= =
M 75 50 ´ 4
Number of Fe3+ ions per unit cell = =2
Z = 2, which represents bcc structure 100

3 3 Number of tetrahedral voids per unit cell

\ r= a= ´ 5 = 2.165Å = 216.5 pm
4 4 = 2 × 4 = 8.
» 217 pm
The Solid State 151

26. (910) For bcc,

1
Number of Zn2+ ions per unit cell = ´ 8 =1
8 3 2d 2 ´ 4.52
d= a or a = = = 5.219Å
Hence, formula : ZnFe2O4 2 3 1.732
19. (b) Volume of unit cell = a × b × c = 522 pm
= 5 × 10– 8 × 8 × 10– 8 × 4 × 10– 8
= 1.6 × 10– 22 cm3 z´ M
r=
Mass of unit cell = 1.6 × 10– 22 × 5.2 a ´ N A ´10-30
3

= 8.32 × 10– 22 g
Number of molecules in one unit cell 2 ´ 39
=
(522) ´ (6.023 ´ 10 23 ) ´10-30
3
8.32 ´10 – 22 g
= =3
166.4 g mol –1 = 0.91g / cm3 = 910 kg m -3
20. (a) Number of A cations per unit cell = 4
r r
Number of B anions per unit cell must be Na + K+
27. (1.123) = 0.55 and = 0.74
=2×4=8 r - r -
Cl Cl
Number of tetrahedral voids per unit cell
=2× 4=8 r r
Na + K+
Number of octahedral voids per unit all + 1 = 0.55 + 1 and + 1 = 0.74 + 1
r r
= 1 × 4 = 4. Cl- Cl-
Hence, occupancy of tetrahedral voids = 100%
21. (d) If in an ionic crystal of the type A+, B–, equal r +r r +r
Na + Cl- K+ Cl-
= 1.55 and = 1.74
number of cations and anions are missing from r - r -
Cl Cl
their lattice sites so that the electrical neutrality
is maintained. The defect is called Schottky Now edge length ratio of KCl and NaCl is
defect. 1.74 rK + + rCl- r
Cl-
22. (d) For n-type, impurity added to silicon should = ´ = 1.123
1.55 r - r +r
Cl Na + Cl-
have more than 4 valence electrons.
28. (27) Density is given by
23. (d) In non stoichiometric defects ratio of cation
and anion is not same that is represented by Z´ M
d= ; where Z = number of formula units
chemical ideal formula, this is due to variable NA a 3
oxidation nos of cation. Transition elements
show variable oxidation nos. present in unit cell, which is 4 for fcc
a = edge length of unit cell. M = Molecular mass
24. (b) Since each Sr ++ ion provides one cation
vacancy, hence 4´ M

( )
2.72 = 6.02 ´1023 ´ 404 ´ 10-10 3
Concentration of cation vacancies = mole % of
SrCl2 added
(Q 1pm = 10-10 cm)
-4
10
=10–4mole%= ´ 6.023 ´1023 = 6.023 ´ 1017
100 2.72 ´ 6.02 ´ (404)3
M= = 26.99 = 27 g mole–1
7
25. (c) Frenkel defect. 4 ´ 10
 152 CHEMISTRY

216.5
3 x=
29. (5) For bcc ; r = a; 43.3
2 x= 5
30. (4) For an octhedral void a = 2 (r + R)
n´M d ´ N Av ´ a3
d= or n = In fcc lattice the largest void present is octahedral
N Av ´ a3 M
void. If the radius of void sphere is R and of
lattice sphere is r,
2 ´ 6 ´ 1023 (5 ´10-8 )3 2 ´ 400
Þ n= =2 Then, r = = 141.42 pm (a = 400 pm)
75 4
Applying condition for octahedral void,
Therefore Metal crystallizes in BCC structure
2 (r + R) = a
and for a BCC lattice 3a = 4r \ 2 R = a – 2r = 400 – 2 × 141. 42
\ Diameter of greatest sphere = 117.16 pm
3 3´5 117.16
r= a= = 2.165Å = 216.5 pm d= =4
4 4 29.29
 CHAPTER
Solutions
16
1. (c) Applying the law of equivalence,
PA° + 4PB° = 560 ´ 5 ...(ii)
N1V1 + N2 + V2 + N3 + V3 = NRVR
Subtract (i) from (ii)
N N N
´ 50 + ´ 30 + ´ 10 = NR × 1000
10 3 2 \ PB° = 560 ´ 5 - 550 ´ 4 = 600
5N + 10N + 5N = 1000 × NR
Q PA° = 400
N
Þ NR =
50 ΔP n
4. (c) For dilute solution, Þ solute
2. (a) KH = 100 kbar = 105 bar, = 1 bar P° n solvent
P = KH × xA For solution in A,
P 1
xA = = = 10 -5 ΔPA W/M W MA
K H 100 ´ 103 = = × ........(i)
P°A WA /MA M WA
1000
Moles of water = = 55.5 ΔPB W MB
18 For solution in B, = × ........(ii)
P°A M WB
Weight of water = 1000 g (Q 1000 mL = 1000 g)
ΔPA /P°A M W M
x From (i) and (ii), =2= A B = A
Mole fraction = 10–5 = ΔPB /P°B M BWA MB
55.5 + x
As 55.5 >>> x, thus neglecting from denominator (WA = WB) MA = MB
x 5. (d) From the given data
10–5 = Þ x = 55.5 × 10–5 moles
55.5 In case I
or 0.555 millimoles. 3 mole of + 1 mole of B, V.P. = 550 mm
3. (b) Ptotal = PA° XA + PB°X B Using the equation
P = P°
A.xA + P°
B.xB, we have
1 3
550 = PA° ´ + PB° ´
4 4 3 1 é 3 1ù
550 = PAo ´ + PBo ´ ê= 4 , = 4 ú
4 4 ë û
PA° + 3PB° = 550 ´ 4 ...(i)
or 550 = 0.75 P°
A + 0.25 P°
B
In second case
In case II
1 4
Ptotal = PA° ´ + PB° ´ 4 mole of A + 1 mole of B; V.P. = 560 mm
5 5
\ 560 = P°
A × 0.80 + P°
B × 0.20
 154 CHEMISTRY

= (842 torr) (0.05) = 16.15 torr

é 4 1 ù
ê x A = 5 or 0.8 and x B = 5 = 0.20 ú Thus, Ptotal (5 mole % solution)
ë û
Solving the above two equations, we get = PNH 3 + Pwater = 42.1 + 16.15 = 58.25 torr

P°
A = 600 mm of Hg
8. (a) Given vapour pressure of pure solvent (P°)
= 121.8 mm Hg;
6. (b) \ PA = PAo X A ,
Weight of solute (w) = 15 g
PB = PBo X B Weight of solvent (W) = 250 g; vapour pressure
of solution (P) = 120.2 mm Hg and Molecular
(Po
A and PBo = v.p. of pure A and B ) weight of solvent (M) = 78 from Raoult’s law.
P° - P w M
PA = = ´
YA = P° m W
PA + PB
121.8 - 120.2 15 78
= ´
PAo X A 121.8 m 250
Þ
PAo X A + PBo (1 - X A )
15 ´ 78 121.8
or m = ´ = 356.2
250 1.6
PAo X A
Þ YA =
(
X A PAo - PBo + PBo) 9. (b) As DTf = Kf.m
DTb = Kb.m

1 æ PAo - PBo ö PBo 1 DTf DTb

Þ =ç ÷+ . Hence, we have m = =
YA çè PAo ÷ø PAo X A Kf Kb

Kf
PBo PAo - PBo or DTf = DTb
So, slope is and intercept = Kb
PAo PA°
Þ [DTb = 100.18 - 100 = 0.18°C]
7. (a) The given data are
Pwater = 17.0 torr; 1.86
= 0.18 × = 0.654°C
0.512
Ptotal (4 mole % solution)
As the freezing point of pure water is 0°C,
= PNH3 + Pwater = 50.0 torr DTf = 0 –Tf
0.654 = 0 – Tf
X NH3 = 0.04 and Xwater = 0.96
\ Tf = – 0.654
Now according to Raoult’s law; Thus the freezing point of solution will be
– 0.654°C.
°
Pwater = X water Pwater
5
10. (c) Moles of urea = ; moles of fructose
= 0.96 × 17.0 torr = 16.32 torr 60
Now Henry’s law constant for ammonia is 5 0.08 ´ 1000
= ; Curea = Þ 0.833
PNH3 180 100
33.68 torr
K H ( NH3 ) = = = 842 torr
X NH3 0.04 5
moles of sucrose = ;
342
Hence, for 5 mole % solution, we have
1000
PNH3 = K H ( NH3 ) X NH3 Csucrose = 0.0146 × = 0.146
100
Solutions 155
moles of KCl(effective) Total ions produced = 3
5 5 0.134 ´ 1000
\ 0.1 M Ca(NO3)2 and 0.1 M
= 2´ = ; = 1.34 Na2SO4 are isotonic.
74.5 37.25 100
15. (c) Molality of solution,
pµC
this order is p4 > p1 > p2 > p3 23.5 ´ 1000
= = 0.5 (mol. mass = 94)
94 ´ 500
11. (c) ΔTf (normal) = K f m = 1.86 × 0.01 = 0.0186 ;
ˆˆ† ( C 6 H 5OH )
2C6 H 5OH ‡ˆˆ
ΔTf(obs) 0.0205 2
i= = = 1.10 = 1 + a ; a = 0.1
ΔTf(nor) 0.0186 (a = degree of dimerization)
Van’t Hoff factor of phenol,
Ca 2 0.01 ´ 0.12 1
Ka = = = ´ 10 -3 ; é æ 1ö ù é æ 1ö ù a
1- a 1 - 0.1 9 = ê1 – ç1 – ÷ a ú = ê1 – ç1 – ÷ a ú = 1 –
ë è n ø û ë è 2ø û 2
Kw Hence
Kb = = 1.0 ´ 10 -14 ´ 9 ´ 103 = 9 ´ 10 -11
Ka
æ aö æ aö
12. (c) Let x and y be the molar masses of A and B DTf = iK f m = ç1 – ÷ ´ 12.0 ´ 0.5 = ç 1 – ÷ ´ 6.0
è 2ø è 2ø
respectively.
DTf 8 ´ 1000 80 æ aö
Then, = m = 1= = … (i) 3.60 = ç 1 – ÷ ´ 6.0 Þ a = 0.80
Kf (x + 2y) ´ 100 x + 2y è 2ø
\ 80% of phenol is present in dimeric form.
DT 10 ´ 1000 100 16. (d) Mole ratio of C : H : O is 1 : 2 : 1 so empirical
And f = m = 1 = = … (ii)
Kf (2x ´ y) ´ 100 2x + y formula is CH2O
Solving (i) and (ii), x = 40; y = 20 DTb 0.15
13. (b) According to Raoult's law m= Þ Þ 0.294;
Kb 0.51
DP n
= (mole fraction of solute) 5 1000
P° n+N 0.294 = ´ ; M » 180
M 95
10 M = molarmass of solute
=0.2 \ P° = 50 mm of Hg
P°
(CH2O)n = 180 or 30 × n = 180 or n = 6;
For other solution of same solvent \ molecular formula is C6H12O6.
20 n 17. (d) Given,
= (Mole fraction of solute)
P° n+N WH 2 SO 4 = 38 g, WH 2 O = 100 - 38 = 62 g

20 1000 ´ K ¢ f ´ w
Þ = Mole fraction of solute \ DTf =
50 mW
Þ Mole fraction of solute = 0.4
1000 ´ 1.86 ´ 38
As mole fraction of solute + mole fraction of DTf = \ DTf Normal = 11.633
98 ´ 62
solvent = 1
Hence, mole fraction of solvent = 1 – 0.4 = 0.6 DTf exp
14. (a) The solution which provide same number Now, = i = 2.50
DTf N
of ions are isotonic.
Ca(NO3)2 ¾® Ca2+ + 2 NO3– \ DTexp = 11.633 × 2.50 = 29.08
Total ions produced = 3 \ f. pt. = 273 – 29.08 = 243.92 K
Na2SO4 ¾® 2 Na+ + SO42–
 156 CHEMISTRY

18. (c) For Na3PO4, i = 1 + 3a = 1 + 3 × 0.5 This distillate is redistilled.

= 2.5; for MgSO4, i = 1 µ = 1 + 0.6 = 1.6 P¢A = Partial vapour pressure of
100 g solution contains 8.2 g Na3PO4 and 12 g
A = P°
Ax¢A = 24 × 0.75 = 18 k Pa
MgSO4
DTb = Kb.m.i = P¢B = Partial vapour pressure of
B = P°
BxB = 12 × 0.25 = 3 kPa
é effective no.of moles of (Na 3PO 4 + MgSO 4 ) ù
Kb.ê ´ 1000 ú Mole fraction of A in second distillate = mole
êë mass of solvent ( in g ) úû
fraction of A in the vapour above first distillate

é 8.2 12 ù P 'A 18
= = = 0.857
ê 164 ´ 2.5 + 120 ´ 1.6 ú PA¢ + P¢B 18 + 3
DTb = 0.50 ê ú ´ 1000 = 1.78°C
ê 79.8 ú Hence, mole % of A in 2nd distillate = 85.7
ë û
22. (14.49) Mole fraction of urea in its solution
Tb = 100 + 1.785 Þ 101.78°C
12
19. (b) Total vapour pressure of solution varies
= 60 Þ 0.025
linearly with mole fraction of component c. 12 140.4
+
Thus, correct graph is given in option (b). 60 18
20. (c) Henry's law; P = KHXgas Mole fraction of glucose
1 18
µ
Herry'slaw constant (K H ) 180
= Þ 0.01
18 178.2
Solubility of gas µ Parital pressure of gas +
180 18
KH : Ar > O2 > CO2 > CH4
Q Mole fraction of glucose is less so vapour
4.30 34.86 1.67 0.41
pressure above the glucose solution will be
Solubility: Ar < O2 < CO2 < CH4
higher than the presure above urea solution, so
60 some H2O molecules will transfer from glucose
21. (0.857) Mole fraction of A, xA = = 0.60;
100 to urea side in order to make the solutions of
P° equal mole fraction to attain equilibrium, let x
A = 24.0 k Pa
moles H2O transferred
40
Mole fraction of B, xB = = 0.40; 0.2 0.1
100 \ = Þx =4
0.2 + 7.8 + x 0.1 + 9.9 - x
P°
B = 12.0 k Pa
now mass of glucose solution
PA = Partial vapour pressure of A at 350 K
Þ 196.2 – 4 × 18 Þ 124.2
= P°
AxA = 24 × 0.60 = 14.4 k Pa
18
PB = Partial vapour pressure of B at 350 K wt. % of glucose = ´ 100 Þ 14.49
124.2
= P°
BxB = 12 × 0.40 = 4.88 k Pa 23. (300) Osmotic pressure of urea from the formula
Mole fraction of A in vapour, i.e., first distillate
nRT
pV = nRT Þ p =
PA 14.4 14.4 V
x¢A = = = = 0.75
PA + PB 14.4 + 4.8 19.2
10
Mole fraction of B in first distillate x¢B = 1 – 0.75 Þ ´ .0821 ´ T [1 dm3 = 1 litre]
60
= 0.25
5% solution means
Solutions 157
100 mL º 5g mN a
1000 mL º 50 g/L = 1- a +
m exp n
Osmotic pressure of solution having non-
volatile solute For dimer formation n = 2
a
50 1-
p2 = × .0821 × T 2 =1 - a
M i=
1 2
For isotonic solution, p1= p2
122.0 a
10 50 =1 - (mN = 122.0 for C6H5COOH)
´ .0821 ´ T = ´ .0821 ´ T 241.98 2
60 M
a
M = 300 g mol–1 or 1 - = 0.504
2
24. (31.9) NaHSO 4 ¾® Na + + HSO -4 \ a = 0.992 or 99.2%
1 0 0 26. (3) Given, W = 500 cc = 500 g
0 1 1 (Q density of water = 1g/cc)
Weight
HSO4- + H 2O ¾® H3O+ + SO 4- As, Density =
Volume
1 0 0
1g
1– h h h Weight = Density × Volume = ´ 500cc = 500g
cc
\ Total particles after dissolution of
w = amount of urea = ?
2+h Kf = 1.86°C; DTf = 0.186°C
NaHSO4 = 1 + 1 – h + h + h = 2 + h; i=
1 m = Molecular mass of urea = 60
=2+h 1000´ K f ´ w
Now, DTf = Kf × molality × i m=
W ´ DT f
0.345 = 1.86 × 0.08 × (2 + h)
\ 2 + h = 2.319 1000 ´ 1.86 ´ w
\ h = 0.319 60 =
500 ´ 0.186
i.e., 31.9% of HSO4– shows proton transfer to 60 = 20 × w
H2O.
60
25. (99.2) Given, w = 2 g, W = 25 g, DT = 1.62, \ w= = 3g
20
K’f = 4.9
0.4 ´ 1000
1000 ´ K ¢ f ´ w 27. (6) Molality (m) of solution = = 0.05
Q DT 80 ´ 100
m´W
ΔTf (normal) = Kf × m = 1.86 × 0.05 = 0.093 K
1000 ´ 4.9 ´ 2
1.62 = Van’t Hoff factor,
25 ´ m
\ mexp = 241.98 ΔTf (observed) 0.12
i= = = 1.290
ΔTf (normal) 0.093
nC6H5COOH ƒ ( C6H5COOH ) n
Before association 1 0 ˆˆ† H3O+ + A-
HA + H2O ‡ˆˆ

a i – 1 1.290 – 1
After association (1 – a) a= = = 0.29
n n –1 2 –1
\ Total number of mole at equilibrium
Ca 2 0.05 ´ 0.292
Ka = = = 5.92 ´ 10 –3
a 1– a 1 – 0.29
= 1- a +
n
 158 CHEMISTRY
28. (2) Let x g be the mass of element in 51.0 g
105.3
of saturated solution. ´ V2 = n ´ R ´ 298 ...(ii)
760
Mass of benzene in 51.0 g of saturated solution
= 51.0 – x g 1 V 283 105.3
\ By Eqs. (i) and (ii), we get V = 298 ´ 500
Total mass of benzene containing x g of solute 2
= 50 + 51 – x = (101 – x) g V1 1
=
1000K f WB 1000 ´ 5.5 ´ x V2 5
DTf = = = 0.55 (given)
M B WA 4 ´ 25 ´ (101 – x ) \ V2 = 5V1
i.e., Solution was diluted to 5 times.
Þ x = 1.0 g
Hence, solubility 30. (4) 1000 ´ K 'b ´ w
DT =
m´W
WB ´ 100 1
= = ´ 100 = 2.0 g
WA ( 51 – 1) 1000 ´ 2.34 ´ 28
1.68 =
m ´ 315
29. (5) For initial solution,
\ mexp = 123.80
500
Q p= atm, T = 283 K mN a
760 =1 - a +
mexp n
500
´ V1 = n ´ R ´ 283 ...(i) mN 1
760 =
Q a = 1 \ mexp n (mN of P = 31)
After dilution, let volume becomes V2 and
temperature is raised to 25°C, i.e., 298 K. 31 1
\ =
105.3 123.80 n
p= atm
760 \n»4
 CHAPTER
Electrochemistry
17
1 - ( -2 ´ 96500 ´ 0.95)
1. (a) Oxidising tendency µ = = 32.13
Electrode potential 2.303 ´ 8.314 ´ 298
TX ¾¾
® No reaction Keq = antilog 32.682 » 1032
TY ¾¾
® X, Z
4. (a) When pH = 14 [H + ] = 10-14 and [OH - ] = 1 M
TZ ¾¾
®X
Þ order of electrode potential is K sp = [Cu 2 + ] [OH - ]2 = 10 -19
TY < TZ < TX
Þ Order of oxidation of the anion is 10 -19
Y – > Z– > X–
\ [Cu 2+ ] = = 10 -19
- 2
[OH ]
2. (a) 2Ag+ + H2 ¾¾ ® 2H+ + 2Ag
The half cell reaction
0.0591 [H + ]2 Cu 2+ + 2e - ¾
¾® Cu
E = E° - log
2 PH 2 ´ [Ag+ ]2 0.059 1
E = E° – log
2 [Cu 2+ ]
0.0591 1
0.222 = 0.7995 - log 0.059 1
2 [Ag + ]2 = 0.34 – log = – 0.22 V
2 10 -19
[Ag+] = 10–9.8 5. (c) The reaction
Ksp = [Ag+] [Cl–] = (10–9.8) × (1) = 10–9.8
(b) Sn 4 + + 2e - ¾¾ 2 Cu + (aq) ¾
¾® Cu(s) + Cu 2 + (aq)
3. ® Sn 2+ ; E ° = 0.13V
Br2 + 2e- ¾¾
® 2Br - ; E ° = 1.08V 0.059 [Cu 2+ ]
° –
Ecell = E cell log
E° value shows Br 2 has higher reduction 1 [Cu + ]2
potential. At equilibrium Ecell = 0
Hence
\ ° = 0.059 log Keq
E cell
Ecell = E - - E +4 +2
Br2 / Br Sn / Sn
0.52 – 0.16
= 1.08 – 0.13 = 0.95 V or, log Keq =
0.059
Now -D G = nF Ecell
\ Keq = 1.2 ´ 10 6
n = 2, F = 96500
-DG = 2 ´ 96500 ´ 0.95 kJ / mol. 6. (b) Cu 2 + + 1e - ¾¾
® Cu +
E1o = 0.15V; DG1o = - n1E1o F
Also, DG = -2.303RTlog K eq
Cu + + 1e - ¾¾
® Cu
DG E2o = 0.50V; DG2o = - n2 E2o F
log K eq = -
2.303 ´ R ´ T
Cu 2+ + 2e - ¾¾
® Cu DG° = DG°1 + DG °2
 160 CHEMISTRY

– nE° F = –1 n1 E1o F + (–1) n2 E2o F = (– 474.78) + 298 × (– 0.32)

– nE° F = –1 (n1 E1o F + n2 E2o F) = – 570.14 kJ/mol
n1 E1o + n2 E2o 0.15 ´1 + 0.50 ´1 \ Df H°298 = -285.07 kJ / mol
E° = =
n 2 10. (d) Molarity = 0.01 M ; Resistance = 40 ohm;
Þ 0.325 l -1
Cell constant = 0.4cm .
7. (d) The cell reactions are : A
® Fe 2 + ( aq) + 2e -
At anode : Fe( s) ¾¾ Specific conductivity (k )

At cathode : Cu 2 + ( aq) + 2e- ¾¾ cell constant 0.4

® Cu ( s) = = = 0.01 ohm -1 cm -1
resistance 40
We know that :
o 1000k
DG° = - nF Ecell ; n = 2 mol Molar conductance ( Ù m ) =
Molarity
o
Ecell = [ E o 2+ - E o 2+ ] 1000 ´ 0.01
(Cu /Cu) (Fe /Fe) = = 103 ohm -1 cm 2 mol -1
= (+ 0.34 V) – (– 0.44 V) = + 0.78 V 0.01
F = 96500 C mol–1 11. (a) 2H+ + 2e– ¾¾ ® H2
o 2
\ DG° = -nFEcell
EH (Eq. wt) = =1 g
= – (2 mol) × (96500 C mol–1) × (+0.78 V) 2
= – 150540 CV = – 150540 J (Q 1 CV = 1 J) 22400
= – 150.54 kJ = = 11200 mL (STP)
2
8. (b) For this cell, reaction is;
Zn + Fe2+ ® Zn2+ + Fe 96500´112
Total charge passed = = 965
0.0591 c 0.0591 c 11200
E = E° - log 1 ; E° = E + log 1 Q = It = 965
n c2 n c2
965
0.0591 10 -2 I= = 1amp.
E° = 0.2905 + log -3 = 0.32 V. 965
2 10
12. (c) ClCH 2COONa + HCl ®
0.0591
E° = log K eq ClCH 2COOH + NaCl
2
LClCH 2COONa + LHCl = LClCH 2COOH + L NaCl
0.32 ´ 2 0.32
log K eq = =
0.0591 0.0295 224 + 203 = LClCH 2COOH + 38.2
0.32
L ClCH 2COOH = 427 - 38.2
\ K eq = 10 0.0295 .
9. (a) We know = 388.8 ohm -1cm 2 g eq -1

® 4H + + 4e - ; E = 0.0 V
2H 2 ( g ) ¾¾ 13. (a) Λ¥ ¥
eq (NH 4 OH) = Λeq (NH 4 Cl) +

O2 ( g ) + 4H + ( aq ) + 4e- ¾¾
® 2H 2O ( l ) ; E = 1.23 V Λ¥ ¥
eq (NaOH) - Λ eq (NaCl)
® 2H 2O ( l ) ; E °cell = 1.23 V
2H2 ( g ) + O2 ( g ) ¾¾
= 129.8 + 217.8 - 109.3 = 238.3 ohm -1cm 2 eq -1
DG°298 = - nFE° = -4 ´ 96500 ´ 1.23 = -474.78 kJ L eq 9.30
a= = = 0.04
Df H°298 = Dr G °298 + T.D rS°298 L¥aq 238.3
Electrochemistry 161
= (426 + 83 – 126) W–1 cm2mol–1
14. (b) ˆˆ† H + ( aq ) + A - ( aq )
HA ( aq ) ‡ˆˆ = 383 W–1 cm2mol–1
c (1-a ) ca ca The molar conductivity of HC,

ca 2 L k 3.83 ´ 10 -5 W -1cm -1
Ka = ; where a = m L m ( HC) = = ´ 1000
C 0.001
1- a L¥m
= 38.3 W–1 cm2mol–1
2 The degree of dissociation,
æ Lm ö

\ Ka =
c
çè L ¥ ÷ø
m a= =
( 38.3 W-1cm 2mol-1 )
L m ( HC )
= 0.1
m ( HC ) ( 383 W cm mol )
L¥
æ Lm ö -1 2 -1
1-
çè L ¥ ÷ø
m
Ca 2 (10 ) ( 0.1)
-3 2
K = = = 1.11 ´ 10-5
cL 2m a
1- a 1 - 0.1
=
L¥
m ( L¥
m - Lm ) 18. (d) Pb + SO -4 - ¾
¾® PbSO 4 + 2 e -
15. (a) (Eq. = Charge on the ion/Total charge) PbO 2 + 4 H + + SO -4 - + 2 e - ¾
¾® PbSO 4 + 2 H 2 O
1 1 1
[K+] = mole × 2 = mole = Eq.
8 4 4 Pb + PbO 2 + 2H 2SO 4 ¾
¾® 2PbSO 4 + 2 H 2 O

6 3 The reaction indicates that 2 moles of H 2SO 4

[Al3+] = = Eq.
8 4 corresponds to 2 × 96500 C and 2 mol H 2SO 4
8 º 4 equiv. of H 2SO 4 .
[SO42–] = = 1 Eq.
8
2 × 96500 C consumed 4 equiv. of H 2SO 4
Leq° K2SO4.Al2(SO4)3.24H2O
-3
= leq° (K+) + leq° (Al3+) + leq° (SO42–) and 100 × 10 × 9.65 ´ 10 5 C consumed

1 3 4 ´ 100 ´ 10 -3 ´ 9.65 ´10 5

= × 73.5 + 149 × + 85.8 × 1 = = 2 equiv. H 2SO 4
4 4 2 ´ 96500
= 18.375 + 111.75 + 85.8 = 215.92 2
\ Decrease in normality = = 0.40
16. (a) By Faraday's I st law of electrolysis, 5
W Q 19. (c) Gold deposited in the first cell = 9.85 g
= (where Q = it = charge of ion )
E 96500 At. wt. of Gold = 197, Oxidation number of gold = +3
We know that no. of gram equivalent 197
Eq. Wt. of Gold =
W it 1 ´ 965 1 3
= = = =
E 96500 96500 100 W = Zit
(where i = 1 A, t = 16 × 60 + 5 = 965 sec.) (where W stands for the weight of ions
Since, we know that deposited, i for current and t for time and Z for
1 electro-chemical equivalent of the electrolyte.)
No. of gram equivalent Q Charge required to deposit 1 g eq. of gold
Normality = = 100 = 1F = 96,500 C
Volume (in litre) 1
\ Charge required to deposit 9.85 g of gold or
= 0.01 N
17. (b) The molar conductivity of the dissociated 9.85 96,500 ´ 9.85 ´ 3
g eq. of gold = C
form of crotonic acid is 197 / 3 197
Lm(HC) = Lm(HCl) + Lm(NaC) – Lm(NaCl) = 14475 C
 162 CHEMISTRY

According to Faraday’s second law, é NO- ù remaining = 0.02 M; é H + ù remaining=0.08M

ëê 3 ûú ëê ûú
Wt. of Cu Wt . of Gold
=
Eq. wt. of Cu Eq. wt. of Gold 0.0591 1
E - E° - log
Þ Wt. of Cu deposited NO3- |NO NO3- |NO 3 4
é NO ù é H + ù
0 -
êë 3 úû êë úû
9.85 ´ 3 63.5
= ´ = 4.76 g
197 2 0.0591 1
= 0.96 - log = 0.84 V
Q 14475 193
3 ( 0.02)( 0.08)4
Current = = A= A = 0.80 A 23. (0.0529) Using Faraday’s second law of
t 5 ´ 3600 240
electrolysis,
20. (c) Cu2+ (aq) + H2 2H+ + Cu(s)
For the given electrochemical cell Weight of Cu deposited Equ. wt. of Cu
=
Pt | H2 (p = 1 atm) | Weight of Ag deposited Equ. wt. of Ag
H+ (aq. xM) || Cu2+ (aq. 1.0 M) | Cu(s)
w Cu 63.5 1
0.0591 [H + ]2 Þ = ´
log 0.18 2 108
Ecell = E°cell –
n [Cu 2+ ] 63.5 ´ 18
Þ wCu = = 0.0529 g.
0.0591 x 2 2 ´108 ´ 100
0.49 = 0.37 – log 24. (1.5)
2 1
For the cell:
0.0591 (anode) (cathode)
0.49 = 0.37 – × 2 log x
2 Cr | Cr3+ (1 M) || H+ (1 M) | Pt (H2) (1 bar)
0.15 = – 0.0591 × log x o
Eocell = E - Eo
2.54 = – log x H + /H 2 Cr 3+ /Cr
Also, – log [H+] = pH o
\ pH = – log x 0.74 = 0 – E Cr 3+
/Cr
Þ pH = 2.54 » 2.5
E oCr 3+ /Cr = –0.74 V
21. (1.39) Cr 2+ ( aq ) ¾¾
® Cr 3+ ( aq ) + e- ,E ° = 0.41 V For the cell:
...(i) (anode) (cathode)
(1 bar) Pt (H2) | H+ (1 M) || Ag+ (1 M) | Ag
HClO ( aq ) + H + ( aq ) + 2Cr 2+ ( aq ) ¾¾
® o o
Eocell = E Ag+ /Ag – E H+ /H 2
2Cr3+ ( aq ) + Cl- ( aq ) + H 2O ( l ) , E ° = 1.8V ...(ii)
o
[Reaction (i)] × – 2 + [Reaction (ii)] we get. 0.80 = E Ag + /Ag – 0
o
HClO ( aq ) + H + ( aq ) + 2e - ¾¾
® Cl- ( aq ) + H 2O ( l ) E Ag +
/Ag = +0.80 V

DG ° = -2FE ° - 2 ( -1 ´ FE° ) For the cell:

(anode) (cathode)
-2FE ° = -2F (1.8 ) + 2F ( 0.41) Ag | Ag+ (0.1 M) || Cr 3+ (0.1 M) | Cr
E° = + 1.8 – 0.41 = 1.39 V Reduction at cathode:
22. (0.84) After addition of Cd and its oxidation (i) Cr3+ + 3e–® Cr; E oCr3+ /Cr = - 0.74 V
into Cd2+.
Oxidation at anode:
NO3- ( aq ) + 4H + ( aq ) + 3e- ¾¾
® NO ( g ) + 2H 2O ( l ) o
(ii) Ag ® Ag+ + e–; E Ag + /Ag = + 0.80 V
0.1 – x 0.4 – 4x;
where x = 0.08 eq. (i) + 3 × eq. (ii)
Electrochemistry 163
Cr3+ + 3 Ag ® Cr + 3 Ag+; n = 3
O2 + 4 H+ + 4e– ® 2 H2O, E o = +1.23 V
o o
Eocell = E Cr 3+
/Cr
- E Ag +
/Ag
Oxidation at anode:
Eocell = -0.74 - 0.80 = -1.54 V -2 o
N 2 H 4 ® N2
0.0591 [Ag + ]3 o
Ecell = Eocell - l og N2 H4 ® N2 + 4 H+ + 4e– E , = -0.9 V
n [Cr3+ ]
Overall cell reaction:
0.06 (0.1) 3 0.06 N2 H4 (aq) + O2(g) ® N2(g) + 2H2O (l); n = 4
= -1.54 - log = -1.54 - × (-2)
3 (0.1) 3 o o
Eocell = E 12 O2 / H 2O - E N2 /N 2 H4
= -1.5 V
25. (0.15) = (1.23 - 0.9)V = + 0.33 V
Cell reaction for Daniell’s cell: Maximum available potential Eocell = 0.33 V
Zn (s) + Cu2+ (aq) ® Cu (s) + Zn 2+ (aq)
Maximum amount of energy = -DG
[Zn 2+ ]
Reaction quotient Q = = nF E o = 4 × 96500 × 0.33 J =1,27,380 J
[Cu 2+ ]
Assuming 60% efficiency
At start, Q = 1 as [Zn2+] = [Cu2+]
also log Q = 0 at point O for Q = 1 60
Wmax = 127380 × J = 76.43 KJ
This is the maximum EMF, the cell can generate. 100
As the reaction proceeds, [Zn 2+] will increase 27. (6) Molecular mass of H2SO4 = 98 g/mol
and [Cu2+] will decrease. Thus, the value of Q Molarity of initial solution
will increase and the cell EMF will decrease.
%W/W ´ 10 ´ d 38 ´ 10 ´ 1.274
0.0591 [Zn 2 + ] = moleculer mass = = 4.94
log 98
Ecell = Eocell -
n [Cu 2 + ] Molarity of final solution
Ecell = 1.07 V, Eocell = 1.10 V, n = 2 19.6 ´ 10 ´ 1.2
= = 2.4 M
98
0.06 1.5 Decrease in amount of H2SO4 during this dis-
1.07 = 1.10 - 2 log
[Cu 2 + ] charging process
= (4.94 - 2.4) × 98 × 2.36 g = 6 × 98 g
1.5 Overall reaction during discharging
0.03 = 0.03 log
[Cu 2 + ] Pb(s) + PbO2(s) + 2H2SO4(aq.) ®
1.5 2PbSO4(s) + 2H2O(l); n = 2
log =1
[Cu 2 + ] \ For 1 mole of H2SO4 +•1 F is required
1.5 6 × 98 g H2SO4 = 6 moles of H2SO4
Þ = 10 Thus, number of Faradays required = 6
[Cu 2 + ]
28. (142)
Þ [Cu2+] = 0.15 mol/L Sodium metal :
26. (76.43)
E = E0 + (KE)max; E0cell = 0.22 V
Reduction at cathode:
-2
Cell reaction
o
O 2 ® 2H 2 O Cathode : AgCl(s) + e - ¾¾
® Ag(s) + Cl- (aq)
 164 CHEMISTRY

1 0.06 [P]
Anode : ® H + (aq) + e -
H 2 (g) ¾¾ E = E 0cell - log
2 n [R]
Overall :
0.06 [Sn 2+ ]
1
® Ag(s) + H + (aq) + Cl- (aq)
AgCl(s) + H2 (g) ¾¾ 0 = 0.01 - log
2 2 [Pb 2+ ]

0.06 0.06 [Sn 2+ ]

0
E cell = E cell - log[H + ][Cl- ] – 0.01 = – log
1 2 [Pb2+ ]
0.06 [Sn 2+ ]
E cell = 0.22 - log[10 -1 ][10 -1 ] 1
1 = log
3 [Pb 2+ ]
= 0.22 + 0.12 = 0.34 V
(KE)max = Ecell = 0.34 eV [Sb2+ ]
= 101/3 = 2.15
So, E = 2.3 + 0.34 = 2.64 eV = Energy of photon [Pb2+ ]
incident
30. (9.81) 9.65 ampere current was passed for 1.0
For potassium metal :
hour (3600 seconds)
E = E0 + (KE)max
Number of moles of electrons passed
2.64 = 2.25 + (KE)max
(KE)max = 0.39 = Ecell I(A) ´ t(s) 9.65A ´ 3600s
= = = 0.36 moles
Cell reaction 96500 96500

Cathode : AgCl(s) + e - ¾¾ NO2 NHOH

® Ag(s) + Cl- (aq)
1 Conc. H SO
Anode : ® H + (aq) + e -
H 2 (g) ¾¾ ¾¾¾¾¾¾
2 4®
4[H]
2 NH2
1
Overall : AgCl(s) + H 2 (g) ¾¾
® ¾¾¾¾¾¾¾
®
2 [Rearrangement]

Ag(s) + H + (aq) + Cl- (aq) OH

C 6 H 5 NO 2 + 4e - + 4H + ¾¾
®
0.06
0
E cell = E cell - log[H + ][Cl- ] p-Aminophenol + H 2O
1
Q 4 moles of electrons reduces 1 mole of
0.39 = 0.22 – 0.06 log [H+]2
nitrobenzene to p-aminophenol.
0.39 = 0.22 – 0.12 log[H+]
0.17 = 0.12 × pH 0.36
\ = 0.09
0.36 moles of electrons will reduce
pH = 17/12 = 1.4166 ; 1.42 = 142 × 10–2 4
29. (2.15) moles of nitrobenzene to p-aminophenol.
At equilibrium state Ecell = 0; E0cell = 0.01 V p-aminophenol molar mass = 109.14 g/mol
Mass of p-aminophenol obtained
Sn + Pb2+ ¾¾® Sn2+ + Pb = 109.14 g/mol × 0.09 mol = 9.81 g
 CHAPTER
Chemical Kinetics
18
1. (b) Rate of disappearance of reactants = Rate 0.27 0.29 0.29
Þ = log Þ 0.117 = log
of appearance of products 2.303 ( a - x) (a - x )
1 d[N 2O 5 ] 1 d[NO 2 ] d[O 2 ] Þ (a – x) = 0.22 M.
- = =
2 dt 4 dt dt 2.303 100
4. (c) t90% = log (I)
1 1 k 100 - 90
k [N 2 O5 ] = k ¢[N 2 O5 ] = k ¢¢[N 2 O5 ]
2 4 2.303 100
t50% = log (II)
k k¢ k 100 - 50
= = k ¢¢
2 4 t log10
k Dividing 90% =
k¢ = 2k, k¢¢ = t50% log 2
2
2. (b) Given: 75% reaction gets completed in \ t90% = 3.3t50%
32 min 5. (d) If rate = k[A]x [B]y [C]z
2.303 a 5.0 × 10–3 = k[0.010]x [0.005]y [0.010]z ...(i)
Thus, k = log 5.0 × 10–3 = k[0.010]x [0.005]y [0.015]z ...(ii)
t (a - x )
1.0 × 10–2 = k[0.010]x [0.010]y [0.010]z ...(iii)
2.303 100 1.25 = k[0.005]x [0.005]y [0.010]z ...(iv)
= log
32 (100 - 75) From 1st and 2nd sets of data - no change in rate
is observed with the change in concentration of
2.303 ‘C’. So the order with respect to ‘C’ is zero.
= log 4 = 0.0433 min–1
32 From 1st and 4th sets of data
Now we can use this value of k to get the value Dividing eq. (iv) by eq. (i)
x
of time required for 50% completion of reaction 1.25 ´ 10-3 é 0.005 ù
=
2.303 a 2.303 100 5.0 ´ 10 -3 êë 0.010 úû
t= log = log
k (a - x ) 0.0433 50 or 0.25 = (0.5)x or (0.5)2 = (0.5)x
\x=2
2.303 The order with respect to ‘A’ is 2 from the 1st and
= log 2 = 16 min
0.0433 3rd sets of data Dividing eq. (i) by eq. (iii)

5.0 ´ 10-3
y
2.303 a é 0.005 ù
3. (b) k= log =ê
t (a - x ) 1.0 ´ 10 -2
ë 0.010 úû
(a – x) is the concentration left after 100 sec. or (0.5)1 = (0.5)y Þ y = 1
2.303 0.29 The order with respect to ‘B’ is 1
2.7 ´ 10-3 = log So the order with respective the reactants A, B
100 ( a - x)
and C is 2, 1 and 0.
 166 CHEMISTRY

6. (d) Units of k indicate that reaction I is of Since volume is changing therefore half-life
second order and reaction II is first order. should be defined on the basis of moles, so
For I reaction, t1/2 µ 1/a, moles of A remaining after 250 sec. Also final
first t1/2 = 1 hr, second t1/2 = 2 hr volume of the container
1hr 2 hr n 0.05 + 0.15
[ A] = 1M ¾¾¾
® 0.5M ¾¾¾
® 0.25M Vf = f ´ Vi = ´ 2 = 4 litre
ni 0.1
1hr 1hr
[B] = 1M ¾¾¾
® 0.5M ¾¾¾
® 0.05
\ Final concentration of A = = 0.0125 M
1hr 4
0.25M ¾¾¾
® 0.125M
10. (d) Let n is the moles of reagent ‘R’ when R is
[ A] 0.25M reacted with A at time t = 0
= =2
[ B] 0.125M
A ¾¾
® B + C
7. (d) A ¾¾
® 3B; PT = P0 + 2x t =0 n 0 0
After time t, P0 - x 3x at t n -x 2x 3x
at t ® ¥ 0 2n 3n
P - P0 1 æ P ö
x= T k = ln ç 0 ÷ n2
2 t è P0 - x ø \ 5 n = n2 Þ n =
5
After long time, 0 3P0 n -n
n + 4x = n1 Þ x = 1
æ ö 4
P P¥
PT - ¥ ç ÷ 2.303 æ n ö
3 1 3
x= k = ln ç ÷ k= log ç ÷
2 t ç P¥ æ 3PT - P¥ ö÷ t èn-xø
ç 3 -ç ÷÷
è è 6 øø
1 æ 4n 2 ö
so k = ln ç ÷
t çè 5 ( n 2 - n1 ) ÷ø
æ ö
3PT - P¥ 1 ç P¥ / 3 ÷ 11. (b) A (g) ¾¾
® 2B (g) + C (g)
P¥ = 3Po x = k = ln ç ÷
6 t ç P¥ - PT ÷
Let initial pressure P0 0 0
è 2 2 ø After 10 min. (P0 – x) 2x x
After long time (t ® ¥) 0 2P0 P0
1 æ 2 P¥ ö as per given (P0 – x) + 2x + x + vapour
k = ln ç ÷ pressure of H2O = 188
t è 3( P¥ - PT ) ø
P0 + 2x = 160 and 3P0 + 28 = 388
so, P0 = 120 and x = 20 torr
8. (a) A ¾¾
® 2B + C
1 æ P ö
t=0 Pi 0 0 k = ln ç 0 ÷
t è P0 - x ø
t = t Pi - y 2y y
Total pressure Pt = Pi –y + 2y + y = Pi + 2y 1 æ 120 ö 1
Þ ln ç ÷ = ´ (ln 4 + ln 3 - ln10)
Pt - Pi 10 è 100 ø 10
=y
2 = 0.02 min–1 = 1.2 hr–1
12. (c) 2N2O5(g) ® 4NO2(g) + O2(g)
2.303 2Pi
k= log 2 mol of gaseous nitrogen pentoxide on complete
t 3Pi - Pt
decomposition gives 5 mol of gaseous products.
0.693 2
9. (a) t1/ 2 =
Therefore, initial pressure of N2O5 = 584.5 ×
k 5
0.693 = 233.8 mm Hg.
= = 250 sec
2.772 ´ 10 -3 Let x be the amount of N2O5 decomposed after
30 min.
Chemical Kinetics 167
\ After 30 min. 1
Pressure due to N2O5 = 233.8 – x As T® ¥, ®0
T
Pressure due to NO2 = 2x
x k2 104.4 ´ 103 J mol -1
and pressure due to O2 = \ log -4
=
2 3 ´ 10 2.303 ´ 8.314 ´ 298
Total pressure after 30 min
k2 k2
x log -4
= 18.297, = 1.98 ´ 1018
= 284.5 mm Hg = 233.8 – x + 2x +
2 3 ´ 10 3 ´ 10-4
3x
or 233.8 + = 284.5 k2 = (1.98 ´ 1018 ) ´ (3 ´ 10-4 ) = 6 ´ 1014 s -1
2
or x = 33.8 mm Hg k E éT - T ù
Hence pressure of N2O5 after 30 min. 15. (a) 2.303log 2 = a ê 2 1 ú
k1 R ë T1T2 û
= 233.8 – 33.8 = 200 mm Hg
k 9.0 ´ 103 é 308 - 298 ù
2.303 a 2.303 233.8 log 2 =
k= log = log k1 2.303 ´ 2 êë 308 ´ 298 úû
t ( a - x ) 30 200
k2
2.303 = 1.63; k2 = 1.63k1;
k= × 0.0679 = 5.2 × 10–3 min–1 k1
30
13. (d) The activation energy of reverse reaction Increase in k1 = k 2 - k1 ´ 100
k1
will depend upon whether the forward reaction
1.63k1 - k1
is exothermic or endothermic. = ´ 100 = 63.0%
k1
As DH = Ea (forward reaction) – Ea (backward
16. (c) k = 1.2 ´ 1014 e -25000 / RT sec -1 or
reaction)
For exothermic reaction 25000 1
log k = log 1.2 × 1014 - .
DH = –ve R T
\ –DH = Ea(f) – Ea(b)
or Ea(f) = Ea(b) – DH
\ Ea(f) < Ea(b) logk
for endothermic reaction
1/T
DH = + ve Equation of straight line
\ DH = Ea(f) – Ea(b) or Ea(f) = DH + Ea(b)
2500
\ Ea(f) > Ea(b). slope = -
R
14. (b) T2 = T (say), T1 = 25°C = 298K,
Ea = 104.4 kJ mol–1 = 104.4 × 103 J mol–1 k2 Ea æ1 1ö
17. (b) log = çè T - T ÷ø
k1=3 × 10 –4, k2 = ?, k1 2.303 R 1 2

k Ea é 1 1 ù Ea é 1 1 ù
log 2 = - log 2 = -
k1 2.303 R êë T1 T2 úû ê
2.303 ´ 8.314 ë 293 308 ú
û

k2 104.4 ´ 103 J mol-1 Ea 15

log = 0.3 = ×
3 ´10 -4 2.303 ´ (8.314 J K -1mol-1) 2.303 ´ 8.314 293 ´ 308
0.3 ´ 2.303 ´ 8.314 ´ 293 ´ 308
é 1 1ù Ea = .
êë 298 - T úû 15
= 34558 J mol–1 = 34.5 kJ mol–1
 168 CHEMISTRY

18. (c) k = Ae - E a /RT

6.023 ´ 3.7 ´ 1010
é -152300/ (8.314´T ) ùû or N =
For methyl nitrite k1 = 1013 × e ë 3.7 ´ 104
\ Mass of X100
For ethyl nitritek2 = 1014 × e éë -157700/ (8.314´T )ùû
if k1 = k2, then
é 6.023 ´ 3.7 ´ 1010 ù
1013 e[
-152300/(8.314 ´ T) ]
= 1014 e[
- 155700/(8.314 ´ T) ] 1
=ê 4 ú´ 23
´ 100
10 = e ( +157700 -152300)/(8.314 ´ T) ëê 3.7 ´ 10 ûú 6.023 ´ 10
157700 - 152300
or 2.303 log 10 =
8.314 ´ T = 10-15 g
\T = 282 K 21. (0.75) CH3.O.CH3 ® CH4 + CO + H2
Total conc.
19. (a) Given, A ¾¾ ®B Initial state a 0 0 0 a
and 20% solution of A decomposes 25% in 20 After 12 mts. a–x x x x a + 2x
minute at 25°C Calculation of initial concentration (a) of
\ Initial amount, a = 20 CH3OCH3
75 PV = nRT
\ Amount left, (a – x) = 20 ´ = 15
100 P
n
2.303 20 or =
\ k 25 = log10 (Q t = 20 minute) V RT
20 15
P 0.4
= 0.0144 minute–1 a= = = 6.31 × 10–3 moles L–1
RT 0.082 ´ 773
k E [T - T ]
Now, 2.303log10 40 = a 2 1 Calculation of k
k 25 R T1T2
0.693 0.693
k 70 ´ 103 é 313 - 298 ù k= = = 4.78 × 10–2 min–1
\ 2.303log10 40 = t½ 14.5
k 25 8.314 êë 313 ´ 298 úû
Substituting the values in the first order
k 40 equation.
= 3.872
k 25 2.303 a
k= log
\ k40 = 0.05575 min–1 (Q k25 = 0.0144) t a-x
Now suppose amount ‘m’ is left in 30% 2.303 a
solution in 20 minute at 40°C. 4.78 × 10–2 = log
12 a-x
2.303 a a
k 40 = log10
t ( x)
a -
a-x
= 1.77446

2.303 30
0.05575 = log10 6.31 ´ 10 -3
20 m a–x= moles L–1 = 3.556 × 10–3
1.77446
\ m = 9.838
\ % decomposition moles L–1
\ x = (6.310 – 3.556) × 10–3 moles/l
( a - m ) ´100 = 30 - 9.838 ´100 = 67.21%
= = 2.754 × 10–3 moles L
a 30
\ After 12 min.
20. (d) An activity of 6.023 curie means
6.023 × 3.7 × 1010 dps. Total no. of moles L–1
Activity = l × N = a + 2x = 6.31 × 10–3 + 2 × 2.754 × 10–3
\ 6.023 × 3.7 × 1010 = 3.7 × 104 × N = 11.818×10–3
Chemical Kinetics 169

n ' é ù
\ P= RT = 11.818 × 10–3 × 0.082 × 773 24. (378.74) ln k1 = E1 ê 1 - 1 ú ...(i)
V k R T T
1 ë 1 2û
= 0.75 atm
k' E é1 1 ù
22. (2.5) A ¾¾
1k
® 2B; A
k
¾¾
2
®C ln 2 = 2 ê - ú ...(ii)
a0 -x -y a0 -x -y y
k2 R ë T1 T2 û
2x
Solving we get (ii)–(i),
d [A] [ B] = 2k1 = 2x
= ( k1 + k 2 ) [ A] ; k' k ' æ E - E1 ö æ 1 1 ö
dt [C ] k 2 y ln 2 - ln 1 = ç 2 ÷ç - ÷
k2 k1 è R ø è T1 T2 ø
k x
= 1 = (for equimolar formation of B and C, k '2 = k1' )
k2 y
Q k1 = k 2 = x = y æ k ö æ 8314 ö ( T2 - 300 )
ln ç 1 ÷ = ç ÷
é A0 ù è k 2 ø è 8.314 ø 300 ´ T2
( k1 + k 2 ) t = ln ê ú
ë At û 2 æ T - 300 ö
ln 2 = (1000) ç 300 ´ T ÷
é A0 ù è 2ø
2 × 6.93 × 10–3 × 50 = ln ê ú
ë At û T2 = 378.74K
25. (1.8) Rate constant at 300 K = k
= [A] t =
[A0 ] = a
0 - x - y = a 0 / 2 (Q x = y ) \ Rate constant at
2
\ x = a0/4. Total moles in container é 7 ù
310 K = k + ê k ´ = 1.07 k
ë 100 úû
a0 – x – y + 2x +y = a0 + x = 1.25 a0
% increase in moles Þ 25, So final pressure k 2 Ea (f) [ T2 - T1 ]
Thus, 2.303log =
= 2 × 1.25 = 2.5 atm k1 R T2T1
23. (18.39) Let the initial concentration (A) = 100 1.07k Ea (f) é 310 - 300 ù
Final concentration at 298 K = 100 – 10 = 90 2.303 log =
k 2 êë 310 ´ 300 úû
Final concentration at 308 K = 100 – 25 = 75
Substituting the values in the 1st order rate \ Ea (f) = 1258.68 cal
reaction Now, equilibrium constant at 300 K = K¢
2.303 100 Equilibrium constant at 310 K
t= log ...(i) 3
k298 90 = K¢ + ´ K¢ = 1.03 K ¢
100
2.303 100 K 2 DH é T2 - T1 ù
t= log ...(ii) Using 2.303 log = ê ú
k308 75 K1 R ë T1T2 û

k308 1.03K¢ DH é 310 - 300 ù

From (i) and (ii) = 2.73 2.303log =
k 208 K¢ 2 êë 310 ´ 300 úû
Substituting the value in the following relation \ DH = 549.89 cal

2.303 R ´ T1 ´ T2 k Since, DH = E a (f) - Ea (b)

Ea = log 2
T2 - T1 k1
\ 549.89 = 1258.68 - E a (b)
2.303 ´ 8.314 ´ 298 ´ 308
= log 2.73 Ea (f )
308 - 298 \ Ea (b) = 708.79 cal = 1.8
Ea (b)
Ea = 76.62 kJ mol–1 = 18.39 kcal mol–1
 170 CHEMISTRY

26. (8.42) t = 4.5 billion years and T1/2 of 40K = 1.26 29. (8) For I order reaction r 1 = k[C]1
billion years. R1
éa - xù \ = k1 / k 2 = temperature coefficient
Then, percentage of 40K remaining ê a ú ´ 100 R2
ë û
2.303 a r35 k35
t= log Let temperature coefficient be a = =a
l a-x r25 k 25
l = 0.693 / T1/2 = 0.693 /1.26 = 0.55 r45 k 45 r45
= =a \ = a ´ a = a2
a a-x 1 r35 k35 r25
= 11.86 \ = = 0.0843
a-x a 11.86
r75
a-x Similarly, = a5
\ ´ 100 = 0.0843 ´ 100 = 8.42% r25
a
27. (8) Since [B] >>> [A], [B] remains practically For I reaction (r 75)I = 25 × (r 25)I
constant and the rate is dependent only on [A]. For II reaction (r 75)II = 35 × (r 25)II
The reaction is pseudo first order w.r.t. A.
(r75 )II 35
Rate = k [A][B] = k [A] × 5 = 5 k [A] = k’ [A] \ = = 7.594 » 8 [Q (r25 )I = (r25 )II ]
(r75 )I 25
2.303 C 2.303 C
k' = log o = log o
t Ct 100 Ct 1 dPNO dPH
2
30. (3) Rate of reaction = - =-
2 dt dt
Co 100 k' 100×5k
log = = For PH2 constant :
Ct 2.303 2.303
1 dPNO
100×5×5.052×10-3 - = 1.5 = k(359)m (PH2 ) n
= =1.0968 2 dt
2.303
1 dPNO m
- = 0.25 = k (152 ) (PH 2 ) n
Co C 0.1 2 dt
= 12.5 , Ct = o = =0.008M
Ct 12.5 12.5 m
1.5 æ 359 ö
Hence, concentration of the reactant A remaining \ =ç ÷ \ m= 2
0.25 è 152 ø
after 100 s = 0.008 M = 8 mM
dPH2
28. (5) Rate of reaction = k[CO]x[O2]y For PNO constant : - = 1.60 = (PNO)m ( 289 )
n
dt
4 × 10–5 = k (0.02)x(0.02)y ...(i)
–4 x
1.6 × 10 = k (0.04) (0.02) y ...(ii) dPH2 n
- = 0.79 = (PNO)m (147 )
–5 x
8×10 = k (0.02) (0.04) y ...(iii) dt
(i ) 1 = æ 1 öx 1.60 æ 289 ö
n

( ii ) 4 çè 2 ÷ø \ =ç ÷
0.79 è 147 ø
\ n=1
x= 2
1
( i) 1 = æ 1 öy \ Rate = k [ PNO ]2 é PH ù
ë 2û
( iii ) 2 çè 2 ÷ø \ Order of reaction = 2 + 1 = 3
y= 1
From eq. (1)
4 × 10–5 = k (0.02)2 (0.02)1
4 ´ 10 -5 10
k= = =5
4 ´ 10 -4 ´ 2 ´ 10 -2 2
 CHAPTER

Surface Chemistry
19
1. (a) Adsorption of a gas on solid is represented Volume of O2 per gram of adsorbent
by following equilibria,
ˆˆ† 3 0.0821 ´ 273
Gas (Adsorbate) + solid (Adsorbent) ‡ˆˆ = ´ = 2.10
Gas adsorbed on solid + Heat 32 1
Initially adsorption increases with increase in 5. (b) DH < 0, DS < 0, DG < 0
pressure at a particular temperature then got slow. 6. (c) Mass of oxalic acid adsorbed by 10 g
After attaining equilibrium adsorption become charcoal
independent of pressure.
= 200 ´ 10-3 (0.5 - 0.4) ´ 90 = 1.8 g
2. (b) The Langmuir isotherm assumes that the
gas attaches to the surface of adsorbent. The x 1 .8
= = 0 .18
free gas and adsorbed gas are in dynamic m 10
equilibrium. The surface of the adsorbent is 1 1
7. (c) The slope = = = 0.2
uniform that is, all the adsorption sites are n 5
equivalent. The ability of a molecule to get 8. (b) We know that, x/m = K.p1/n (n > 1)
adsorbed at a given site is independent of the
occupation of neighbouring sites. Thus, option x = Kp1/n
(b) is correct. m = 1g (given)
3. (d) Amount of CH3COOH adsorbed on 1g of The above relation between x and p will be
charcoal correctly represented by Freundlich absorption
1000mL -3
isotherm curve.
= (0.5 – 0.49 mol L–1) × 1000mL / L = 1 ´ 10 mol
So, No. of CH3COOH molecules in 1 ×10–3 mol
of acetic acid x
= 6.02 × 1023 mol–1 × 10–3 mol = 6.02 × 1020
Area occupied by one CH3COOH molecule

3.01 ´ 102 m 2 p
= = 5 ´ 10-19 m 2 9. (d) In acid hydrolysis of methyl acetate all are
6.02 ´ 1020
present in one phase (liquid)
Thus the surface area of the charcoal covered
10. (a)
by each CH3COOH molecule is 5 × 10–19 m2.
11. (b) In first case the given compounds have
3.6
4. (c) Mass of O2 per gram of adsorbent = =3 same anion but different cations having different
1.2
3 charge hence they will precipitate negatively
No. of moles of O2 per gram of adsorbent = charged sol i.e. ‘A’.
32
 172 CHEMISTRY

In second case the given compounds have 4 3 4

similar cation but different anion with different VC = pr = VC = p(10)3
3 3
charge. Hence they will precipitate positively
Particle size of true solution particle = 1mm
charged sol. i.e. ‘B’.
4 V
p(1)3 hence now C = 10
3
12. (c) ® Sn 4+ + 4H 2O ; Sn4+ ions
SnO2 + 4HCl ¾¾ VS =
VS
3
are preferentially adsorbed by SnO2 particles.
19. (c) As2S3 sol is negatively charged owing to
13. (b)
preferential adsorption of S2– ions. Cation would
KI + AgNO3 (slight excess) ¾¾
® AgI + KNO3 be the effective ion in coagulation.
Flocculating value = minimum milli mol of the
® Ag + + NO3- ;
AgNO3 ¾¾
4 ´ 0.005 ´ 103
AgI(s) + Ag ¾¾+
®[AgI]Ag + effective ion per litre of sol = = 1.0
4 + 16
14. (c) The sols obtained in the two cases will be 20. (a) Preparation of egg albumin sol. is done in
oppositely charged. following two steps.
15. (a) Since the sol particles migrate towards (i) Prepare 100 mL of 5% (w/V) solution of NaCl
cathode, they are positively charged. Hence, in water in a 250 mL beaker.
anions would be effective in coagulation. Greater (ii) Break one egg in a porcelain dish and
is the valence of effective ion, smaller will be its pipette out the albumin and pour it in sodium
coagulating value. chloride solution. Stir well to ensure the
16. (c) O/W type emulsion is stabilized by soaps preparation of sol.
of alkali metals whereas W/O type emulsions are
stabilized by soaps of bi and tervalent cations. x 1
21. (6) log = log K + log P
17. (d) Volume of gold dispersed in 1 L water m n
x
Mass 1.9 ´ 10- 4 g \ Plot of log versus log P is linear with slope
= m
= = 1 × 10–5 cm3
Density 19g cm -3 1
= and intercept = log K
n
Radius of gold sol particle
= 10 nm = 10 × 10–7 cm = 10–6 cm 1
Thus = tan q = tan 45° = 1 or n = 1
n
4 3
Volume of gol sol particle = pr log K = 0.301 or K = antilog 0.301 = 2
3
At P = 3 atm
4 22
= ´ ´ (10 -6 )3 = 4.19 × 10–18 cm3 x
3 7 = KP1/n = 2 ´ (3)1 = 6
m
\ No. of gold sol particles in 1 × 10–5 cm3
0.03 ´ 2.46 ´ 10 -3
1 ´ 10-5 12
22. (3) Adsorbed moles of H 2 =
0.0821 ´ 300
= = 2.38 ´ 10
4.19 ´ 10-18
= 3 × 10–6
\ No. of gold sol particles in one mm3 \ No. of adsorbed molecules of
12 H2 = 3 × 10–6 × 6 × 1023
2.38 ´ 10
= = 2.4 ´ 106
106 Þ = 18 × 1017
18. (a) Particle size of colloidal particle = 1mµ to Total no. of surface sites available
100 mµ (suppose 10 mµ) = 5.4 × 1016 × 1000
Surface Chemistry 173
Þ 5.4 × 1019 cm2
0.5 ´ 10-4
No. of surface sites that is occupied by Number of gold particles =
adsorption of 4.851 ´ 10-18
= 1.03 × 1013
10
H2 = ´ 5.4 ´ 1019 Gold particles are dispersed in a litre of water
100
i.e. 106 mm3.
Þ 5.4 × 1018 Number of gold particles in one mm3 of sol
No. of surface sites occupied by one molecule
1.03 ´ 1013
18
5.4 ´ 10 = = 1.03 × 107 » 107 per mm3
H2 = =3 106 mm 3
18 ´ 1017
Hence, n = 7.
x 25. (30) Before micelle formation, number of
23. (8) = K × P1/n
m particles of cationic colloidal electrolyte per litre
x 1
log = log P + log K = 10–3 × 6 × 1023 = 6 × 1020/L
m n
1 = 6 × 1020/106 mm3 = 6 × 1014/mm3
= tan 45° = 1 Number of micelles in 1 mm3 = 2 × 1013
n
Þ n=1 Thus, number of cations in one micelle
log K = 0.3
6 ´ 1014
at pressure P = 4 atm. = = 3 × 10 = 30.
x 2 ´ 1013
log = 1 × log 4 + 0.3
m 26. (100)
x
Þ log = 2 log 2 + log 2 (log 2 = 0.3) 1.46 g
m 400 mL of colloid requires =
x 36.5 g / mol
Þ log = 3 log 2 = log 8
m = 0.04 mol = 40 m-mol
x
Þ = 8. 40
m 1000 mL of colloid requires = ´ 1000
400
1.9 ´ 10-3 g = 100 m-mol
24. (7) Volume of gold = = 10–4 cm3
19 g / cm3 Flocculation value of HCl = 100
Radius of gold particle = 10.5 nm 27. (25) 10 mL of 1% NaCl solution º
= 10.5 × 10–7 cm. 1 mL of 10% NaCl solution
Volume of gold-sol particle For 100 mL of gold sol = 250 mg. of substance
4 3 4 22 required
= pr = ´ ´ (10.5 ´ 10-7 )3 cm. For 10 mL of gold sol = 25 mg. of substance
3 3 7
required
4 22 21 21 21 Hence, gold number = 25.
= ´ ´ ´ ´ ´ 10 -21 cm 3
3 7 2 2 2 28. (16.25) Final volume of gas, at 608 torr
= 4.851 × 10–18 cm3 pressure
As gold sol occupying 50% of the space, the P1V1
V2 = 760 ´ 1
=
1 P2 608
available volume = × 10–4 cm3
2 Þ 1.25 L or V2 = 1250 mL
 174 CHEMISTRY

Volume occupied by gas = Volume of vessel

44
– Volume occupied by charcoal ´ 10 7
= 7
No. of NH3 molecules adsorbed 22
16 ´ 10 -16
= 1000 - = 990 mL
1.6 7
Difference of volume is due to adsorption of Vol. of NH3 adsorbed at 1 atm 273 K
gas by charcoal.
\ Volume of gas adsorbed by charcoal 2 ´ 1023
= ´ 22.4 = 7.46 L
= 1250 – 990 Þ 260 mL 6 ´ 1023
Volume of the gas adsorbed per gram of charcoal 30. (60) No. of sodium lauryl sulphate molecules

=
260
= 16.25 mL / g at 608 torr and 27 °C. (CH3 (CH 2 )11SO4- Na + ) in 1 litre solution
16
= 10–3 × 6 × 1023 = 6 × 1020
29. (7.46) Total surface area of carbon No. of sodium lauryle sulphate molecules per
44 mm3 = 6 × 1014
= ´ 107 cm 2
7 No. of colloidal particles per mm3 = 1013
r = 10–8 cm No. of molecules per colloidal particle
22
-16 2 6 ´ 1014
Surface area of NH3 = pr2 = 7 ´ 10 cm = = 60
1013
 CHAPTER General Principles and
Processes of Isolation
20
of Elements
1. (b) Calcination is used for removal of volatile 11. (c) Fe2O3 (3 parts) + Al powder (1 part) is
impurities and decompose carbonates into their known as thermite
respective oxides. Fe2O3 + 2Al ® Al2O3 + 3 Fe
D
Al2O3 · 2H2O ¾¾ 12. (a) Chalcopyrite : CuFeS2
® Al2O3 + 2H2O
Fool's gold : FeS2
Bauxite Alumina
Carnalite : KMgCl3.6H2O
D Bauxite : Al2O3.2H2O
CaCO3 ¾¾
® CaO + CO2
Limestone Calcium oxide
13. (c) Azurite is a basic carbonate ore of copper.
2. (a) For example, Ag 2S is converted into 2CuCO3. Cu(OH)2
Na[Ag(CN) 2 ]. When Zn is added, Ag is 14. (b) Cassiterite contains the magnetic impuri-
displaced. ties of FeSO4 and thus concentrated by electro-
3. (a) Zone refining is based on the difference in magnetic separation.
solubility of impurities in molten and solid state 15. (c) Lead pyromorphite is a phosphate ore. It
of the metal. This method is used for obtaining can be represented as 3Pb3(PO4)2. PbCl2.
+3
metals of very high purity.
16. (d) (A) Cr2O3 + 2Al ¾¾
® Al 2O3 + 2Cr
4. (c) Froth reduces the surface tension of water
and the solution forms froth. (B) Au + 2CN - + H 2O + 1 O 2
2
5. (c) Tricalcium phosphate and calcium silicate
¾¾ ® [Au(CN) 2 ]- + 2OH -
is Thomas slag
6. (b) Zr and Ti are purified by van Arkel method. 2[Au(CN) 2 ]- + Zn ® [Zn(CN) 4 ]2 - + 2Au

Zr(s) + 2I 2 (g) ¾¾ ® ZrI 4 (g) (C) Statement is true

O2
On the hot
(D) Ag 2S + 4NaCN ¾¾¾ ® 2Na[Ag(CN) 2 ] + Na 2S
ZrI4 (g) ¾¾¾¾¾ ® Zr(s) + 2I 2 (g)
filament 2Na[Ag(CN) 2 ] + Zn ¾¾
® Na 2 [Zn(CN) 4 ] + 2Ag
7. (d) Calcination is a process of heating a 17. (c) The enthalpy of formation of Al2O3 is very
substance to a high temperature but below the high and therefore, it cannot be reduced by
melting or fusion point, causing loss of moisture, carbon. It is reduced by electrolytic method.
reduction or oxidation and dissociation into 18. (a) Generally tin is obtained by carbon
simpler substances. reduction and lead by self-reduction.
8. (a) The more stable CO2 has higher enthalpy SnO 2 ¾¾
® Sn + CO 2 (carbon reduction)
of formation than CS2 2PbO + PbS ¾¾
® 3Pb + SO2 (self-reduction)
9. (d) Ni is purified by Mond’s process by 19. (d) 2Cu2S + 3O2 ¾® 2Cu2O + 2SO2
decomposition of Ni(CO)4. 3Cu 2O + CH4 ¾¾® 6Cu + 2H 2O + CO
10. (d) Al2O 3.2H 2O ® Al 2O3 + 2H 2O (From green
logs of wood)
is calcination.
20. (a) It is used in metallurgy of Zn.
 176 CHEMISTRY

CHAPTER
The p-Block Elements
21 (Group 15, 16, 17 and 18)

1. (a) NH4ClO4 + HNO3 ® HClO4 + NH4NO3 3SO 2 + K 2 Cr2 O7 + H 2SO 4

D
NH4NO3 ¾¾ ® N2O + 2H2O
¾¾
® Cr2 (SO 4 )3 + K 2SO 4 + H 2O
2. (a) (Green)
3. (c) By Haber’s process. +
4. (a) 9. (b) In HNO3 + HF ® H 2 NO3 + F-
5. (b) PbO2 is a powerful oxidizing agent and HNO3 accepts H+ hence it is a base.
liberate O2 when treated with acids. 10. (d) HF does not act as reducing agent.
2PbO 2 + 4HNO3 ¾¾
® 11. (c) Br2 reacts with NaI only to get I2.
2NaI + Br2 ® 2NaBr + I2
2Pb(NO3 ) 2 + 2H 2 O + O 2 ­ 12. (a) As size increases, van der Waal's forces of
6. (d) K4 [Fe(CN)6 ] + 6H 2SO 4 + 6H 2O ® attraction between noble gas atoms also
increases. Consequently, ease of their
2K 2SO 4 + FeSO 4 + 6CO + 3 ( NH 4 )2SO4 liquefaction increases.
13. (c) Hybridisation in each case is
O O XeF4 sp3 d 2 , XeF2 sp3 d .

7. (c) HO S O O S OH + H2O ¾® 14. (c) 2XeF6 + SiO 2 ® SiF4 + 2XeOF4

15. (d) Partial

O O XeF6 + H 2 O ¾¾¾¾
® XeOF4 + 2HF
peroxodisulphuric acid
Partial
XeF6 + 2H 2 O ¾¾¾¾
® XeO 2 F2 + 4HF

O O Complete
XeF6 + 3H 2 O ¾¾¾¾® XeO3 + 6HF

HO S O OH + HO S OH 16. (6) The structure of white phosphorus (P4) is

O O P
peroxomonosulphuric acid sulphuric acid
P P

8. (a) SO32- + 2H + ¾¾
® H 2 O + SO 2 P
(X) (Y)
Hence bonding electron pairs are 6.
SO2 is a colourless gas with irritating smell.
The p-Block Elements (Group 15, 16, 17 and 18) 177

17. (0) S3O9 (also called a- sulphur trioxide) is an 18. (3) O O

–

ice like solid with the following molecular P

structure. O O
O O
P P
O O – –
O O O
S
O O
O O No. of P–O–P bonds = 3. It is the most stable
S S among all the cyclic metaphosphates
O O O 19. (6)
20. (3) The structure of perchloric acid is
There is no S–S bond is S3O9
O
Cl
O OH
O
The number Cl = O bond in HClO4 is 3.
 178 CHEMISTRY

CHAPTER
The d-and f-Block
22 Elements

1. (a) When a solution of potassium chromate is 8KMnO4 + 3Na2S2O3 + H2O ¾®

treated with an excess of dilute nitric acid. 3K2SO4 + 8MnO2 + 3Na2SO4 + 2KOH
Potassium dichromate and H2O are formed.
11. (d) CuSO 4 + Na 2S2 O 3 ¾¾
®
2K2CrO4 + 2HNO3 –––®
K2Cr2O7 + 2KNO3 + H2O CuS2O3 + Na 2SO4
Hence Cr2O72– and H2O are formed.
2. (c) In lanthanoid series there is a regular 2CuS2 O3 + Na 2S2 O 3 ¾¾
®
decrease in the atomic as well as ionic radii of
Cu 2S2O3 + Na 2S4O6
trivalent ions (M3+) as the atomic number
increases. Although the atomic radii do show
3Cu 2S2 O 3 + 2Na 2S2 O 3 ¾¾
®
some irregularities but ionic radii decreases from
La(103 pm) to Lu (86pm). Na 4 [Cu 6 (S2O3 )5 ]
3. (a) The more the oxidation state, the more is 12. (a) Acidic nature of oxides increases with the
the acid character, MnO, Mn2O3 are basic, MnO2 increase in O.S. of the metal atom e.g., Cr2O3 is
is amphoteric and Mn2O7 is acidic. basic. CrO2 is acidic, CrO5 is also acidic in
4. (b) Ferrous ferricyanide is known as Turbull’s nature.
blue 13. (d) 773-873K
HgS + O 2 ¾¾¾¾¾
® Hg + SO 2
5. (d) Magnetic moment m = n (n + 2 ) where n 14. (d) Hg 2 Cl2 ¾¾ D
® Hg + HgCl 2
15. (b) As a result of lanthanoid contraction Zr4+
= number of unpaired electrons 15 = n(n + 2 )
and Hf 4+ possess almost the same ionic radii.
\ n=3 Ce4+ is an oxidising agent. Ce4+ gains electron
6. (b) In KIO4 O.S of I is +7 and in KMnO4 O.S. of to acquire more stable Ce3+state. La(OH)3 is the
Mn is +7 most basic among lanthanoid hydroxides.
7. (a) Stable oxidation state of Mn in alkaline 16. (4) The number of water molecules directly
medium is +6. So, MnO2 is oxidised to K2MnO4 bonded to the metal centre in CuSO4.5H2O is 4.
by atmospheric oxygen in KOH medium.
2MnO 2 + 4KOH + O 2 ® 2K 2 MnO4 + 2H 2 O H2O OH2
4-
8. (a) Fe2 + + 6KCN ® éë Fe ( CN )6 ùû + 6K + 2+
9. (a) Cu SO42– . H2O
10. (b) In neutral or faintly alkaline medium
H2O OH2
thiosulphate is quantitatively oxidized by
KMnO4 to SO42–
The d-and f-Block Elements 179

17. (6) 2MnO 2 + 4KOH + O 2 ¾¾

® 19. (3) Lower O.S. compounds are basic and higher
2K 2 MnO4 + 2H 2O O.S. compounds are acidic.

Oxidation number of Mn in K2MnO4 is 6 +2 +3 +4 +6 +7

K2MnO4 ; 2 + x – 8 = 0 MnO, Mn 2 O 3 MnO2 , MnO 3 ,Mn 2O7
x=6 Neutral Acidic
18. (6) Butterfly structure (CrO5) is:
O–2 D
–1O O–1 20. (2) Cu(OH)2 ¾¾
® CuO + H 2 O ;
light blue black
Cr
–1O
+6 O –1
There are two peroxide (–O–O–) bond in CrO5 in 2CuO + glucose ¾¾
® Cu 2 O
red
which O.S. of each O-atom is –1.
Hence O.S. of Cr = +6.
 180 CHEMISTRY

CHAPTER
Coordination
23 Compounds

1. (c) The ions present in the ionisation sphere 4. (a) In [Cr(NH3)6]Cl3, the chloride ione are
are precipitated. Hence [CrCl2(H 2O) 4 ]Cl.2H 2O ionisable. As they are present outside the
contains 1/3 Cl in ionisation sphere to be coordination sphere.
precipitated by AgNO3 as AgCl
[Cr(NH3)6]Cl3 + 3AgNO3 —®
2. (a) CoSO4Cl. 5NH3 has two ionization isomers
[Cr(NH3)6]NO3 + 3AgCl¯
i.e. [Co(NH3)5SO4]Cl and [Co(NH3)5Cl]SO4.
white ppt.
On reacting them with AgNO 3 and BaCl 2
5. (a)
following reactions give white precipitate.
6. (b) Linkage isomerism arises in a coordination
(I) [Co(NH3)5SO4]Cl + AgNO3 ®
AgCl + [Co(NH3)5SO4]NO3 compound containing ambidentate ligand. Since
[White ppt] NO2 is an ambidentate ligand which can join to
(II) [Co(NH3)5Cl]SO4 + BaCl2 ® the metal atom through N or O-atom. Thus,
BaSO4 + [Co(NH3)5Cl]Cl2 [Co(NH3)5 (NO2)] Cl2 show linkage isomerism.
[White ppt] 7. (c) (a) [Fe(CN)6]3–
3. (b) MX4Y2 is an octahedral complex and it has The oxidation number of Fe in [Fe(CN)6]3– is +3.
Fe3+ : [Ar] 3d 5 4s0
two geometrical isomers i.e. cis and trans forms
3d 4s 4p
both of them are achiral.
As CN– is a strong ligand pairing will occur.
Y [Fe(CN)6]3–
X X
3d 4s 4p
M Plane of
symmetry
X X \ n = 1 Þ m = 1(1 + 2) = 3
Y
(b) [Fe(H2O)6]2+
trans The oxidation number of Fe in
(Achiral)
[Fe(H2O)6]2+ is +2.
X Fe2+ : [Ar] 3d 6 4s0
X Y As H2O is weak ligand, so pairing will not occur.
M Plane of [Fe(H2O)6]2–
symmetry 3d 4s 4p
X Y
X \ n=4 Þ m= 4(4 + 2) = 24
cis
(Achiral)
Coordination Compounds 181
(c) [MnF6]4– Hence, the compound has three ionisable
The oxidation number of Mn is +2. Cl atoms. Thus formula of the complex must be
Mn2+ : [Ar] 3d 5 4s0 [Co(NH3)6]Cl3.
As F– is a weak field ligand, so pairing will not 11. (d) (a) square planar - cis and trans isomers
occur. (b) square planar - 3 isomers (while NH3 at
[MnF6]4– position 1, groups NH2OH, NO2 and C 6 H 5 N can
3d 4s 4p
occupy position 3.
(c) 2 isomers (cis and trans)
\ n=5 Þ m= 5(5 + 2) = 35 12. (a) The given compound may have linkage
(d) [NiCl4]2– isomerism due to presence of NO2 group which
may be in the form –NO2 or –ONO.
In NiCl2–
4 , the oxidation number of Ni will be +2. It may have ionisation isomerism due to presence
Ni : [Ar] 3d 8 4s0
2+
of two ionisable group –NO2 and –Cl. It may
As Cl– is a weak field ligand, so pairing will not have geometrical isomerism in the form of cis-
occur. trans form as follows :
[NiCl4]2–
[Co(NH3)4Cl(NO2)]NO2 and [Co(NH3)(NO2)2]Cl
3d 4s 4p
Ionisation isomers.
[Co(NH3)5(NO2)2]Cl and [Co(NH3)5(ONO)2]Cl
n=2 Þ m= 2(2 + 2) = 8 Linkage isomers
Thus, [MnF6]4– will have the highest spin only NO2 NO2
magnetic moment.
H3N NH3 H3N NO2
8. (d) [Pt(en)2Cl 2] is a complex of the type
M(AA) 2 B 2 which is octahedral such Co Co
compounds exhibit optical and geometrical NH3 NH3 NH3 NH3
isomerism both.
9. (b) [Co(en)3]Cl3 NO2 NH3
Trans-form cis-form
en 3+ en 3+ Geometrical isomers
13. (c) K4[Fe(CN)6] produces maximum number of
en en ions (5) in the solution.
K4[Fe(CN)6] ‡ˆˆˆˆ† 4K+ + [Fe(CN)6] –4
en en 14. (b) IUPAC name is potassium
d -form mirror l -form trioxalatoaluminate (III).
[Co(en)2Cl2]Cl 15. (a) Since the precipitate of AgCl shows two
ionisable chloride ion the complex must have
+ en + the structure.
en
Cl Cl [Co(NH3 ) 5 Cl]Cl2 + 2AgNO3 ®
[Co(NH3 )5Cl](NO3 )2 + 2AgCl
Cl Cl
en
Hence two chlorine atoms satisfy the primary
en
mirror
valency and one secondary valency.
16. (a) K3[Fe(CN)6]
10. (c) Number of moles of AgCl
4.305 Let ‘x’ be the oxidation state of Fe
= = 0.03 mol
143.5 x + 6(–1) = –3
0.01 mol. of complex ® 0.03 mol of AgCl x = +3
1 mol. of complex ® 3 moles of AgCl
 182 CHEMISTRY

Fe(26) Þ [Ar] 3d 6 4s2 C2O42– < H2O < NH3 < CN –

hence the crystal field splitting will be maximum
Fe3+ Þ [Ar] 3d 5 : for [Co(CN)6]3–
21. (4) 22. (4)
CN- strong field ligand, hence pairing occurs.
23. (6)
\ K3(Fe(CN)6 : –5 3–
OOC – CH2 .1. .2. CH2 – COO
It is paramagnetic as it has 1 unpaired electron.
–6
N – CH = CH – N 4–
K3[CoF6] OOC – CH2 CH2 – COO
Let ‘x’ be the oxidation state of Co EDTA4– is a hexadentate ligand, since hexa
x + 6(–1) = –3 means six and the ligand attaches six times.
x = +3 24. (0.0)
Co(27) Þ [Ar] 3d 7 4s2 Ru 2 + = 4d 6 = t26g e0g since D 0 > P
No. of unpaired electrons = 0
Co3+ Þ [Ar] 3d 6 :
\ Magnetic moment = 0 B.M.
F– weak field ligand hence, no pairing occurs. 25. (26.92)
It is paramagnetic as it has 4 unpaired electron. [ML6]Cl3 + 3AgNO3 ¾® 3AgCl
17. (b) 0.3 g V mL, 0.125 M
18. (d) d 4 in high spin octahedral complex
0.3
eg – Number of moles of the complex =
267.46
t 2g Number of moles of AgNO3 = 0.125 × V × 10–3
CFSE = [0.6 × 1] + [–0.4 × 3] = – 0.6 D 0 0.3
× 3 = 0.125 × V × 10–3
19. (b) d 6 – t2g 2, 2, 2 eg 0,0 (in low spin) 267.46
12 0.3 ´ 3 ´ 1000
C.F.S.E = – 0.4 × 6D0 + 3P = - D + 3P Or, V = = 26.92 mL
5 0 267.46 ´ 0.125
20. (b) Crystal field splitting depends upon the
field strength of ligand. The field strength of
ligand D decreases as shown below
 CHAPTER
Halolalkanes and
24 Haloarenes

Though (ii) contains +ve charge on oxygen.

1. (a) (CH3 )3 C - MgCl + D 2O ¾¾
®
Since octet around each atom is complete the
(CH3 )3 C - D + Mg(OD)Cl structure II is more stable than I.
2. (d) 6. (a) A strong nucleophile favours the SN2 reaction
and a weak nucleophile favours the SN1 reaction.
Cl / hn
CH3 — CH2 — CH2 — CH3¾ ¾2¾¾ ® First reaction is SN1 reaction because C2H5OH
used as solvent which is a weak nucleophile.
CH3 CH3 Second reaction is SN2 reaction because C2H5O–
is strong nucleophile.
H — C — Cl + Cl — C — H
7. (d) The boiling points of alkyl chlorides
C2H5 C2H5 increases with increase in molecular weight. In
d l case of isomeric alkyl chloride, the order of
Racemic mixture boiling point is
50% d form + 50% l form primary > secondary > tertiary
Cl• may attack on either side and give a racemic
8. (c) Small difference in boiling points of C2F6
mixture of 2-chloro butane which contain 50% d
and C2H6 is due to the fact that (i) the F aton is
form and 50% l-form.
only slightly larger than H, and (ii) F has low
3. (c) More stable the carbocation, more reactive
polarizability
will be the parent alkyl halide towards SN1 reaction.
3° > Benzyl > Allyl > 2° > 1° > methyl 9. (c) Organomagnesium and organolithium
4. (c) Stability of the three corresponding compounds can’t be prepared from the alkyl (or
carbocations aryl) halide having –NO2 group. On the other
+ + hand, organocopper and organocadmium
CH 2 = CH C HCH3 > CH3CH 2 C HCH 3 compounds, do not react with the –NO2 group.
Allyl Carbocation 2° Carbocation 10. (b) When Grignard reagent reacts with an
+
epoxide, the alkyl group of the Grignard reagent
> CH3CH 2 C H 2
1° Carbocation goes to more substituted carbon atom.

Slow + – C 2 H5MgBr
5. (b) MeOCH 2 Cl ¾¾¾® MeO CH2 + Cl
(i)
O O
MgBr C2H 5
+
Me – O = CH2
H2 O
(ii) O C2H 5
H
 184 CHEMISTRY

11. (b)
CH3
CH2Cl CH2CN
® H Br
NaCN Br2
¾¾ ¾
¾®
DM F
¾¾¾
H Br
I I CH3
meso
Nuclear substitution will not take place.
So F can have three possible structures
12. (c) ¾¾
¾® + HBr 17. (6) Addition of HBr to 2-pentyne gives two
Br structural isomers (I) and (II)
It results in formation of more stable aromatic HBr
CH 3 - C º C - CH 2 CH3 ¾¾¾®
compound which is benzene. CH 3C(Br) = CHCH 2CH3 + CH3CH = C(Br)CH 2CH 3
13. (d) 14. (d) (I) (II)
15. (d) Chloropicrin is nitrochloroform. It is obtained Each one of these will exist as a pair of geometrical
by the nitration of chloroform with HNO3. isomers. Thus, there are two structural and four
configurational isomers. (total 6)
(conc.) HNO
HCCl3 ¾¾¾¾¾¾
3
® O2NCCl3 18. (4)
Chloroform Chloropicrin CH3
HCl/ZnCl2
Ph – C – CH2 – CH2– CH3
CH3 (i) S N1
16. (3) H+ Cl
¾¾¾
®
OH (±) mixture (two products)
CH 3
C H3 H CH3 H
SOCl2
CH3 CH 2 CH =CH 2 + CH3CH =CHCH3 Ph – CH – C – CH2 – CH3 (ii) S N1 Ph – CH – C – CH2 – CH3
Butene-1 Butene-2 OH Cl
E55555555555555555555555
(cis - and trans )
F Retention (one product)
F
CH3 Cl
PCl5
Ph – CH – C – CH2 – CH3
(iii) S N2
* HCH Br
Br2 H
CH3CH 2 CH =CH 2 ¾¾¾
® CH3 CH 2 C 2 Inversion (one product)
Butene-1 | Total no. of products is 4.
Br
( + ) - and (–) enantiomer 19. (4) In the given compound, there are four different
types of hydrogen atoms as shown below:
1 2 3 4
Br
¾¾¾
2® CH3 — CH— CH 2 — CH 3
|
CH 3

The replacement of each of these hydrogen

atoms will give the following four monochloro
derivatives.
(i) ClCH 2 — CH — CH 2 —CH3
|
CH3
1-chloro-2-methylbutane
Halolalkanes and Haloarenes 185

20. (8)
Cl H H
|
H2/Ni
(ii) CH3 — C — CH 2 — CH 3 CH3–C–CH=CH2 CH3–C–CH2–CH3
|
CH3 CH2–CH3 CH2

2-chloro-2-methylbutane CH3

(iii) CH3 — CH — CH — CH3 Cl 2/HCl

| |
CH3 Cl Cl
Cl
2-chloro-3-methylbutane +

(iv) CH3 —CH—CH2 —CH2 Cl (4) (1)

| 2 Pair of
enantiomers
CH3 Cl
1-chloro-3-methylbutane +
(d + l) CH2–Cl
(2) (1)
 186 CHEMISTRY

CHAPTER
Alcohols, Phenols
25 and Ethers

CH 2 OH CH 2 I +
| | CH3 - CH 2 - CH - CH 3
3HI - I2 (II)
1. (c) CHOH ¾¾¾ ® CHI ¾¾¾ ®
| |
CH 2 OH CH 2 I + +
CH 2 = CH - CH - CH3
CH 2 CH3
|| | (III) (IV)
H I (excess) - I2
CH ¾¾¾¾¾® CHI ¾¾¾ ®
| | (IV) is most stable due to resonance followed by
CH 2 I CH 2 I (III) which is allylic carbocation. Next is (II) as it
is a secondary carbocation and least stable is (I)
CH3 CH3 as it is a primary carbocation.
| |
HI
CH ¾¾®
5. (a) Hydroboration-oxidation leads to anti-
CHI Markownikoff’s hydration, thus
|| |
CH 2 CH3 (i) BH /THF
3 OH
¾¾¾¾¾®
\ All the compounds except (c), –
(ii) H2O/OH
CH2 OH - CHI - CH 2 OH ar e formed during
1-Pentanol
reaction of glycerol with excess HI.
6. (d)
2. (d) Lucas reagent is anhydrous ZnCl 2 and
conc. HCl. It is used to distinguish between 1°, NH2
2° and 3° alcohols. | HNO2 oxi.
CH3CHCH 3 ¾¾¾¾ ® CH3 C H CH3 ¾¾¾ ® CH3CO CH3
3° alcohols ® immediate turbidity |
2° alcohols ® turbidity after 5 minutes OH
1° alcohols ® No turbidity at room temp. OH
(i) CH3MgI
|
CH3 ¾¾¾¾¾ ® CH3 – C – CH3
| (ii) H3O+ |
CH 3 - C - OH is a tertiary alcohol hence it will CH3
| 2-Methyl –2 propanol
CH3 7. (c)
give fastest reaction with Lucas reagent. PCl
3. (d) Among the given compounds only C2 H5OH ¾¾¾
5 ® C H Cl + POCl + HCl
2 5 3
CH3OH does not give iodoform reaction. [A]
4. (b) The ease of dehydration can be determined AgNO
by seeing the stability of carbocation as ¾¾¾¾
2 ® C H NO
2 5 2
intermediate. [B]
+ 8. (c) Higher the stability of the carbocation, more
CH3 - CH 2 - CH 2 - CH 2 easily it is formed and more will be the ease of
(I) its dehydration. Stability of the carbocations of
the corresponding alcohols is
Alcohols, Phenols and Ethers 187

+ + +
F3C CH2 < Cl3C CH2 < H3C CH2 < –H
+
Least stable due + ¾¾®
to intensification
of charge
+
C6H5 CH2 3º Carbocation More stable (alkene)
Most stable due 13. (c) Although in both cases products are CH3I
to resonance
and C6H5OH; the two reactions follow different
F3CCH 2OH < Cl3CCH 2 OH < H3CCH 2 OH
mechanism.
< C 6 H 5 CH 2 OH (Ease of dehydration) HI(g)
9. (b) Hydroboration – oxidation reaction of C6 H5 – O – CH3 ¾¾¾® CH3I + C6 H5OH
SN 2
alkenes leads to anti-Markovnikov’s hydration.
conc. HI
Further addition of water adds in syn-manner, C6 H5 – O – CH3 ¾¾¾¾ ® CH3 I + C6 H 5OH
i.e., H and OH are added to the same face of the SN 1
double bond leading trans-product. In short, Remember that during SN1 reaction, CH 3+
hydroboration-oxidation of alkenes is is formed because it is more stable than C 6 H 5+ .
regioselective as well as stereoselective.
10. (b) It is a nucleophilic substitution reaction, 1- 14. (c)
phenyl -1-propanol will be most reactive because +
of formation of more stable benzyl type of Br
–
carbocation. –Br
¾¾®
OH OH
3° Carbocation
C6H5CH2CHCH3 C6H5CHCH2CH3 (Four membered ring
with large strain)
1–Phenyl–2–propanol 1–Phenyl–1–propanol
C6H 5
+
C6H 5CH2CH2CH2OH
CH3CHCH 2OH ¾¾¾®
3–Phenyl–1–propanol
2–Phenyl–1–propanol
11. (c) 2° Carbocation
(Five membered ring
OH with less strain)
+
+
15. (b) Base catalysed epoxide opening is a typical
¾¾®
H
¾¾® SN2 reaction in which attack of the nucleophile
takes place at the less hindered expoxide.
2º Cabocation 16. (b)
6 2 6 17. (c) In presence of non-protic solvent such as
1 +
5 5 + CHCl3 or CCl4, concentration of electrophile (Br+) is
1 –H
+ ¾¾® less, hence reaction stops at the monobromo stage
4 2 18. (c) Observe the relative stability of their
4 3 3 corresponding conjugate bases.
12. (c) It is an example of dehydration of alcohol. – – –
The 2º carbocation formed at first stage O O O
rearranges to the more stable 3º. NO2
> >
+
1, 2 - Methyl
H ¾¾¾¾® NO2
¾¾® shift
NO2
I III II
+ Stabilised by both –I Stabilised by both –I Stabilised only
and – R effects of the and – R effects, but by –I effect
OH 2º Carbocation –NO2 group – I is less than in I
 188 CHEMISTRY
However, the acidity of the corresponding d+
CH OH
phenols will be different because of H–bonding H2C — CHCH 3 ¾¾¾®
3
H2C — CHCH 3
in the ortho isomer. +
OH OH
O +
OH H OH OCH3
NO2 H
> > +
–H
NO2 ¾¾® H2C — CHCH 3
NO2
III I II OH OCH3
19. (d) It is an example of Claisen rearrangement.
20. (b) In the acid-catalysed ring opening of an In case of CH3ONa, –OCH3, being a strong
unsymmetrical ethoxide, the nucleophile attacks nucleophile, opens the strained epoxide ring in
primarily at the more substituted carbon atom a direct SN2 reaction, i.e. by attacking at the least
because such atom of the protonated epoxide hindered carbon atom.
–
acquires a considerable positive charge. This CH3O
resembles like a more stable 2º or 3º carbocation H2C — CHCH3 ¾¾® CH3OCH2CHCH3
and hence the reaction is SN1 like. O
OH
H

+
H
21. (3) ¾¾ ¾® H + +
(– H2O)
H H
OH cis- Butene-2 trans-Butene-2 Butene-1
¾¾®

¾¾®

¾¾®
Br 2 Br2 Br2

Br Br Br

H +
Br H Br
H Br Br Br
H H
d- and l-forms meso- d- and l

22. (1) The corresponding phenoxide ion will be

less basic, hence equilibrium will not lie
favourably toward carboxylation.
–
O OH
COOH
2 chiral carbons and one plane of symmetry
+ CO2
Þ 3 stereoisomers.
®

NO2 NO2
Less basic due to —NO2 group
24. (4)
23. (3)

25. (3) 3 acidic hydrogens will produce, 3 moles

of methane gas.
 CHAPTER
Aldehydes, Ketones
26 and Carboxylic Acids

CH3 CH3
O
dil. KMnO OH
1. (a) ¾¾¾¾¾
4® H –
CH3 OH
–
O O+
CH3 OH
O O–
CH3
C=O
OH -
¾¾¾®
HIO 4 ¾¾¾¾¾¾¾®
aldol condensation
HOH
C=O O O
CH3 D
– H 2O
O
H OH

CH3 O OH
|| HCN |
2. (d) 6. (b) CH3 - C - H ¾¾¾® CH3 - C - H
Na /C2H5OH HNO 2 acetaldehyde |
CH3CN ¾¾¾¾¾¾
® CH3CH 2 NH 2 ¾¾¾¾
® CN
[A] OH
Cu / 573K Hydrolysis |
CH3CH2OH ¾¾¾¾¾
® CH3CHO ¾¾¾¾¾® CH3 - C - H
[B] [C] |
3. (a) ArCOR can be prepared by the COOH
Lactic acid
combination of ArH + R’COCl and not by
ArCOCl + RMgX because here the ArCOR 7. (b) Benzaldehyde forms cinnamic acid as
formed will further react with RMgX to form 3º follows.
alcohol, ArC(OH)R2 as the final products. CHO
4. (a)
CH COONa
+ (CH3CO)2O ¾¾¾¾®
3

(i) BH3 ,THF

¾¾¾¾¾®
(ii) H2 O2 ,NaOH OH
b
CH = CH.COOH
PCC H
OH ¾¾¾
®
CH 2 Cl 2 + CH3COOH
O
5. (c) In the presence of base, cyclohexanone Cinnamic
Cinnamic acid
show aldol condensation.
 190 CHEMISTRY
8. (a) Addition of HCN to carbonyl compounds can be removed as water. Moreover, the positive
is nucleophilic addition reaction. The order of charge on the intermediate carbocation is
reactivity of carbonyl compounds is relatively away from the C = O group.
Aldehydes (smaller to higher) Ketones (smaller 15. (a) Enolic form predominates in compounds
to higher), Then containing two carbonyl groups separated by a
HCHO > CH3COCH3 > Ph.COCH3 > PhCOPh – CH2 group. This is due to following two factors.
The lower reactivity of Ketones is due to (i) Presence of conjugation which increases
presence of two alkyl group which shows +I stability.
effect. The reactivity of Ketones decreases as (ii) Formation of intramolecular hydrogen bond
the size of alkyl group increases. between enolic hydroxyl group and second car-
9. (c) Selenium dioxide oxidises aldehydes and bonyl group which leads to stablisation of the
ketones at a-position to carbonyl group. molecule. Hence the correct answer is III > II > I.
CH 3CHO ® OHC.CHO 16. (b)
10. (a) Normally NaBH4 as well as LiAlH4 reduce RCH 2 COOH ¾¾¾¾¾¾
2 Br / P
® R - CH - COOH
only –CHO group without effecting carbon- HVZ reaction |
carbon double bond, however when it is present Br
in conjugation with benzene ring and aldehydic NH
'X'
group it is also reduced along with the reduction ¾¾¾¾ 3 ® R - CH COOH
(Excess) |
of –CHO group.
NH 2
NaBH
C 6 H 5 CH = CH CHO ¾¾¾¾
4
® C 6H 5CH 2CH 2CH 2OH 'Y'
11. (c) Remember that during reduction with 17. (a) The correct order of increasing acid
NaBH4, a hydride ion is transferred by NaBH4 strength
to carbonyl carbon and a proton (or deutron) is CF3 COOH > MeOCH2COOH > CH3COOH
transferred from the solvent (in the second step) > (Me)2CH.COOH
to carbonyl oxygen. Electron withdrawing groups increase the acid
strength and electron donating groups decrease
O O- the acid strength.
|| |
® C 2 H 5 - C H - C 2 H 5 ¾¾2¾® 18. (a)
NaBH 4 D O
C 2 H 5 - C - C 2 H 5 ¾¾ ¾¾
3- Hexanone ( - OD- ) OH O
| ||
OD [O] H + ,H 2O
CH3 C HCN ¾¾¾
® CH3 - C – CN ¾¾¾¾®
|
Acetaldehyde cyanohydrin
C2 H5 - C H - C2H 5
12. (c) O
Oxi
||
(I) CH 3CHOHC 6 H 5 ¾¾
¾® CH 3COC6 H 5 CH 3C – COOH
1 -phenyletha nol Acetophenone 19. (d) Since, C when heated with Br2 in presence
(II) C 6 H 5CHO + CH 3 MgBr ® C 6 H 5CHOHCH 3 of KOH produces ethylamine, hence it must be
1-phenylethanol propanamide and hence the organic compound
anh . AlCl 3 (A) will be propanoic acid. The reactions follows.
(III) C 6 H 6 + CH 3 COCl ¾¾ ¾ ¾
¾® C 6 H 5 COCH 3 NH
CH3 - CH 2 - COOH ¾¾¾
3
®
Acetophenone
(A)
distil
(IV) (C 6 H 5 COO) 2 Ca ¾¾ ¾® C6 H 5COC 6 H 5 + CaCO3 - + D
Cal. benzoate Benzophenone CH3 - CH 2 - CO O N H4 ¾¾
®
13. (a) (C) contains the most reactive methylene (B)

group followed by (A) then (B). KOH + Br

CH 3 - CH 2 - CONH 2 ¾¾¾¾¾
2
®
14. (d) The intermediate is carbocation which is Hoffmann
bromamide
destabilised by C = O group (present on reaction
a-carbon to the –OH group) in the first three
cases. In (d), a–hydrogen is more acidic which CH3 - CH 2 - NH 2
(Ethylamine)
Aldehydes, Ketones and Carboxylic Acids 191
20. (d) Hydrolysis is a nucleophilic substitution. O
Hence more is the electron deficiency of carbonyl CO2H
carbon, more will be the ease of hydrolysis ; – (c) PCl Cl
NO2 group is strongly electron-withdrawing due ¾¾¾
5
®
to –M and –I effects, hence it will produce
electron deficiency at carbonyl carbon to the
maximum extent. CHO
21. (d) H2, Pd-BaSO4
¾¾¾¾¾®
22. (a) O

CO2H
OH 31.O O
¾¾¾¾ ® O
(d) 2. Zn/H2O
NaBH CO2H
¾¾®
4

NaBH4 is a selective reducing agent which CH3 – C – CH2 – CH2 – CH2 – CH2 – C – H
reduces carboxyl group of aldehyde and ketone
to alcohol, but does not reduce COOH group O O
and double bond. Amongst the above formed product only CH3–
CO–CH2–CH2–CH2–CH2–CHO will give reddish
OH OH O
brown precipitate in Fehling’s solution.
(i) CO2, NaOH C OH
23. (a) ¾¾¾¾¾®
+
25. (a) DIBAL-H is a reducing agent it reduces RCN
H
to RCHO and esters i.e. RCOOR¢ to RCHO.
Salicylic acid Therefore,
(X)
O
O
O CH3 DIBAL-H
¾¾¾¾¾¾¾¾®
+
EtO CN Toluene, –78°C then H3O
conc. H2SO4 COOH
¾¾¾¾¾¾¾¾® O
O O
H
CH3 C O C CH 3 Methyl salicylate H
24. (d) (Y )
O
CHO
CO, HCl 26. (3)
(a) ¾¾¾¾¾® 1, 2– Diethylbenzene is a resonance hybrid of
anh. AlCl3, CuCl
the two structures which on ozonolysis give
different products.
Cl
(b) + (CH3CH2)2Cd¾¾® O
¾¾
¾3 ® 2CH CH COCHO + C HO
3 2
O |
I CHO
CH2CH3

O O CH 3CH 2C O CHO
¾¾®
¾3
| + 2 |
CH3CH 2CO CHO
II
 192 CHEMISTRY

27. (4) 2CH 3CHO ¾ ¾® 1st Product, O

2 CH 3CH 2 CHO ¾
¾® 2 nd Product c a
a 29. (4) [X] is b
CH3CH 2CHO + CH3CHO ¾¾
® 3rd Product
a Out of a, b, c only a and b can show geometrical
CH 3 C H 2 CHO + CH 3CHO ¾
¾® 4th Product isomer ism
28. (11) CH3 C CH3 + 3Br2 + 4NaOH G.I = 2n = 22 = 4
30. (3) Compound P contains three acidic groups
O
Acetone
O OH
– +
¾® CH3CONa + 3NaBr + 3H2O+ CHBr3
3 moles of bromine produces 1 mole of CHBr3.
1 HO [P]
\ 9 mole of bromine produces × 9 = 3 mole
3 COOH O
of CHBr3.
 CHAPTER
Amines
27
1. (c) Completing the given reaction we get 5. (c) CH3NC (methyl isocyanide) on reduction
P O with LiAlH4 gives secondary amine
CH 3 CONH 2 ¾¾¾
2 5®
D NaCN
6. (a) CH 3 CH 2 Cl ¾¾¾¾
® CH 3CH 2 CN
Sn/HCl X
CH 3 C º N ¾¾¾¾
® CH 3 CH 2 NH 2
Ni/H 2
Ethanamine ¾¾¾¾
® CH 3CH 2 CH 2 NH 2
2. (b) Y
HNO PCl (CH 3CO) 2 O
C2 H 5 NH 2 ¾¾¾
2
® C2 H 5OH ¾¾¾
5
® C2 H 5Cl ¾¾¾¾¾¾
® CH 3CH 2 CH 2 NHCOCH 3
Ethyl amine Ethyl alcohol
Z
NH
¾¾¾
3
® C2 H 5 NH 2 7. (d) CH 3CN ¾¾ ¾¾ ¾
Na / C2 H 5OH
¾® CH 3CH 2 NH 2
Ethyl amine
(A)
NH HNO2 Cu
3. (d) CH3 – C is most basic ¾¾ ¾
¾® CH 3CH 2OH ¾¾® CH 3CHO
NH2 ( B) 573 K ( C)
(CH3)2NH is less basic than CH3CH2NH2 due to 8. (b)
steric hindrance because of two bulky –CH3 O NCH3
CH3NH 2
groups on nitrogen atom.
4. (a) Structures of given amines are following
H3C — CH2 — CH2 — CH2 — NH2
LiAlH4/H2O
n-Butylamine (Primary amine) [H]
CH3CH2 — NH— CH2 — CH3
Diethylamine (Secondary amine) NHCH3
CH3

CH3 N C 2H 5 9. (d) The reaction involves Cope eliminiation

Ethyldimethylamine (Tertiary amine) (heating of a 3º amine oxide to form an alkene
Amines have ability to form intermolecular H- with the elimination of a 2º hydroxylamine).
bonding and the extent of H-bonding depends H 2O2
b b
upon number of H-atom present of N-atom.
Primary amines have two hydrogen atoms CH3 N(CH3)2 H3C
+
N (CH3)2
available for hydrogen bond formation, while 2° b
amines have only one hydrogen atom for O–
+(CH3)2NOH 3º Amine oxide
hydrogen bond formation. 3° amines do not have (acts its own base)
intermolecular association due to absence of
H heat
hydrogen atom. b b + HON (CH3)2
(Cope elimination)
Thus, order of boiling point of isomeric amines
is as follows: 3° < 2° < 1°. N (CH )2
 194 CHEMISTRY
10. (d) Secondary amine with (NaNO2 + HCl) gives 14. (b)
a nitroso product O
NHCH3 NaNO2/ HCl
¾
¾¾¾® H–N–C–CH3
NH2
CH3 (CH CO) O
3 2
| ¾¾¾¾¾
Pyridine
®
N–N=O
(X)
(Acetanilide)
N– Nitroso – N– methylaniline
11. (c) O

O H–N–C–CH3
COOH C – Cl
conc. NHO
¾ ¾¾¾¾¾¾¾ 3
®
conc. H SO 15°C(288 K)
SOCl2 NH3 2 4

Br Br NO 2
O NH2 (major)
(Y)
C NH2

NaOH
NH2
+Br2
aq. NaOH
Br Br ¾¾¾¾ ®
12. (a) NH2
NO2
(I) (Z)

3 (CH CO) O,Pyridine

2 NH2
¾¾¾¾¾¾¾¾® NH – C – CH 3
15. (b)
(II) O I
No resonance of lone pair of ‘N’
4®(i) LiAlH NH 2
¾¾¾¾¾ NH – CH2 – CH3
(ii) H 2 O
(III)

II
Product (II) is NH – C – CH3 and Resonance of lone pair of ‘N’
NH2
O
(II)
H3C III
+I of CH3 and resonance of lone pair of ‘N’
(III) is NH – CH2 – CH3
NH2
(III)
\ III > I > II, As + I effect increases the basic
strength and – R, – I effect shown by – COCH3 O2N
IV
reduces the basic strength.
13. (c) NaNO2, HCl Þ NO+ (as E+). –I effect of –NO2 and resonance of lone pair of ‘N’
Order of basic strength : I > III > II > IV
Amines 195
16. (2) Cope elimination is used for removing a 17. (3) Diazomethane is used for methylating acidic
nitrogen present outside the ring, while Hofmann groups ; compound IV has enolic —OH group,
elimination is used for removing nitrogen present hence it can also be methylated by CH2N2.
inside as well as outside the ring.
18. (6) NO2 NH2 NHCOCH3

Sn + HCl (CH3CO)2O Conc. HNO3

D Pyridine Conc. H2SO4, D

(Nitrobenzene)

NHCOCH3 NH2 N2BF4 NO2

+
H3O NaNO2 NaNO2
–CH 3COOH HBF 4 Cu, D

NO2 NO2 NO2 NO2

(p-dinitrobenzene)
+ –
19. (5) NH2 NH2 N Cl
Br Br Br Br
Br 2 Diazotisation
H2O

NO2 NO2 NO2

Br Br
Br Br Br Br
Sn/HCl CuBr

NH2 NO2
Br
Br Br
Br 2
(5 bromine atoms)
H2O
Br Br
NH2

NH2 N N
HNO 2
20. (7)
NH2 0°C N N –2N2

OH
dil. H2SO4 HI
D D
CH2—OH
OH

CH2—I
 196 CHEMISTRY

CHAPTER
Biomolecules
28
1. (d) Reaction of D-(+)-glucose with methanolic — 1
CHO
HCl leads to formation of methyl glucoside (C 1—OH
2
group is methylated) which, being acetal, is not H – C – OH
hydrolysable by base, so it will not respond Tollen’s 3
HO – C – H
reagent.
¾ ¾ ® H – C – OH ¾ ¾ ®
4
2. (c)
5
H OH H – C – OH
CH2OH 6
O CH2OH
HO OH H
H H
O Open chain form of D-(+)-Glucose
OH H H
H O OH (negligible % at equilibrium)
H H
H OH CH2OH H6 H
CH2OH
(Lactose) 4
All reducing sugar shows mutarotation. 5 O
3. (b) Cyclization of the open chain structure of D- HO 2
1 OH
(+)-glucose has created a new stereocenter at C 1 HO 3

which explains the existence of two cyclic forms of OH

H H
D-(+)-glucose, namely a– and b–. These two cyclic
H
forms are diastereomers, such diastereomers which
differ only in the configuration of chiral carbon b -D-(+)-Glucopyranose
developed on hemiacetal formation (it is C1 in glucose m.p. 150°C; [a ]D = +18.7°
and C 2 in fructose) are called anomers and the (67% at equilibrium)
hemiacetal carbon (C1 or C2) is called the anomeric 4. (b) Lactose is obtained by the condensation of one
carbon. molecule of b-D-galactopyranose (C1—b) unit and
H6 H one molecule of b-D-glucopyranose (C4—b) unit.
CH2OH 6
4 CH2OH 6
5 O CH 2OH
HO 5
2 O 5
HO 3 1 H O
HO H
OH H H HO
4 1
H H O 4 1
OH H OH H OH
3 2
H H H
3 2
a -D-(+)-Glucopyranose
m.p. 146°C; [a ]D = +112.2° H OH
H OH
(36% at equilibrium) b–D–Galactose b–D–Glucose

Lactose
5. (c) Fischer gave the prefix “D” to compounds
whose bottom chiral has its OH to the right. So natural
glucose is called D-glucose or dextrose.
Biomolecules 197
Structure of D-Glucose : Pepsin/HCl
1 Proteins ¾¾¾¾¾®
CHO Stomach
2
H OH Proteases and Peptones
3
HO H Trypsin
¾¾¾¾¾¾¾¾¾¾
® Peptides
4 Chemotrypsin
H OH (Pancreatic juice Intestine)
5
H OH Peptidases
¾¾¾¾¾
® Amino acids
6CH OH (Intestine)
2
13. (b) In DNA and RNA heterocyclic base and
D-Glucose phosphate ester are at C1' and C5' respectively of the
6. (c) Glycogen is called animal starch and is found in
sugar molecule.
all animal cells. It constitutes the reserve food material.
7. (a) HO
| N
8. (a) Cellulose is a polysaccharide composed of only 5
HO – P – O – C H 2
O N
4¢
D-glucose units. Every adjacent glucose units are || C
N
N
joined by b-glycosidic linkage between C 1 of one O C¢
H H
glucose and C4 of the next. H
C3––– C2 H
Thus in every glucose units only three –OH
groups are free to form triacetate. OH OH
HO 6
14. (d) Ascorbic acid - Scurvy
5
HO 6 H O Retinol - Night blindness
H O
HO 6
5
O 1 Riboflavin - Cracked lips
H 4
5 H 1
O OH H H Thiamine - Beri-Beri
O
H
H
O
4
OH H
3 2 15. (c)
1 H H OH
4
O
3 2 16. (c) Leucine, Lysine and Histidine are essen-
OH H H H OH
3 2
tial amino acids.
H OH

(CH3CO)2O, H2SO4
17. (b) The group represents a pep-

tide linkage.
(–OH = –OCOCH 3 )
9. (a) Since the compound forms a yellow crystalline H O
solid, i.e. osazone with phenylhydrazine, it may be N OH
an aldohexose or a ketohexose. Further, since on H2N N
reduction, compound forms a mixture of sorbitol and
O H O
mannitol, it must be a ketohexose, i.e. fructose. Recall
that glucose on reduction gives only one alcohol glucitol Hence, 2 peptide linkages.
(Sorbitol) 18. (a) Number of H-bonds in each A–T pair = 2
10. (a) Statement-2 is the correct explanation of Number of H-bonds in G–C pair = 2
statement-1. The given double stranded DNA has 5
11. (c) When the proteins are subjected to the action of A–T and 3 G–C pairs.
heat, mineral acids or alkali, the water soluble form of \ Total number of H-bonds in 5 A–T pair
= 5 ´ 2 = 10
globular protein changes to water insoluble fibrous
Total number of H-bonds in 3G–C pair
protein. This is called denaturation of proteins. = 3 ´ 3 = 9 Average energy of 10 H-bonds in
During denaturation secondary and tertiary structures A–T pair = 10x
of protein destroyed but primary structures remains Average energy of 9 H-bonds in G–C pair = 9y.
intact. Thus, the approximate energy required to split
12. (b) Pepsin and Trypsin are two enzymes involved the double stranded DNA in two single strands
in the process (hydrolysis of proteins) = 10x + 9y.
 198 CHEMISTRY
19. (d) It is given that C-terminal amino acid is 22. (1) Two molecules of an a-amino acid will form
alanine and N-terminal amino acid is chiral, thus only one dipeptide, recall that four different
glycine can’t be N-terminal amino acid as it is an dipeptides are formed when two a-amino acids are
achiral amino acid. different.
Thus it can have 4 possible sequences of the 23. (36.6)
tetrapeptide as follows: Let x be the % of a–form in the equilibrium
(i) Ala-Gly-Ser-val
(ii) Ala-Gly-Val-Ser –21x – 133 (100 – x) = –92 × 100
(iii) Ala-Ser-Gly-Val x = 36.6%
(iv) Ala-Val-Gly-Ser 24. (80) Each mole of glucose will consume 5 moles
20. (c) In sucrose the two monosaccharides are held of HIO4.
together by glycosidic linkage and not by peptide
linkage.
21. (3) In strongly alkaline solution of an amino acid,
all of its —COOH groups are converted into —COO.
Thus a strongly alkaline solution of a
monoaminodicarboxylic acid will have one —NH 2
and two —COO– groups, all of which are basic in Glucose has 4 chiral centres No. of optical
nature. Further remember that a —NH2 is more basic isomers = 24 = 16.
than a –COO– group. Total moles of HIO4 consumed = 16 × 5 = 80.

25. (12)

The straight chain linkage is between C1 – C4 and branching linkage is between C1 – C6.
Hence, a + b + c + d = 1 + 4 + 1 + 6 = 12
 CHAPTER
Polymers
29
1. (a) Molecules of a polymer, being large in size, This is inferior to natural rubber but is more
scatter light resistant to aerial oxidation and to other
2. (d) solvents.
3. (c) Polythene is a linear polymer 9. (b) Since proteins, cellulose and RNA control
4. (d) Glyptal is an example of a step growth various activities of plants and animals, they are
polymer called biopolymers.
5. (d) The given compound is a copolymer of 10. (a)
hexamethyline diamine and adipic acid. It is 11. (b)
actually Nylon-66. CH2
CH3 H
6. (b) Biodegradable polymer is Nylon-2-Nylon-6 C=C
– CH2 CH2 CH 3
which is copolymer of glycine (H2N – CH2–
COOH) and amino caproic acid (H2N–(CH2)5 –
CH2 CH3 H
COOH). C=C C=C
nH2N – CH2 – COOH + nH2N – (CH2)5– COOH H CH2
CH2–
Glycine Amino caproic acid Natural rubber
(All cis configuration)

All statements except (b) are correct

12. (a) Terylen e is prepared by condensing
O O dimethylterephthalate and ethylene glycol in
presence of a weak base, (calcium acetate).
–( HN – CH2 – C – HN – (CH2)5 – C –) n
Methanol is eliminated during condensation.
Nylon – 2 – Nylon – 6
7. (a) PVC is an example of thermoplastic polymer. nH3COOC COOCH3 + nHOCH2 – CH2 OH
8. (a) The synthetic polymer neoprene Dimethylterephthalate Ethylene glycol
(polychloroprene) is prepared by polymerisation
of chloroprene. –CH3OH —C — —C —OCH2 —OCH2—
2 O or peroxides
nCH 2 = C - CH = CH 2 ¾¾¾¾¾¾¾
® 300°C
O O
| Terylene n
Cl 13. (b) Nylon-66 is an example of first synthetic
Chloroprene
fibres produced from the simple molecules. It is
é
—CH 2 - C = CH-CH 2 —
ù
prepared by condensation polymerisation of
ê | ú
ëê Cl ûú n adipic acid and hexamethylene diamine.
Neoprene
 200 CHEMISTRY

O
||
O
||
18. (b) nCH 2 = CH - CH = CH 2 + n
14. (c) H 2 N - (CH 2 - )6 NH 2 + Cl - C - (CH 2 )8 - C - Cl 1, 3-Butadiene
Hexamethylene diamine Sebacoyl chloride
CH = CH2
O O
|| ||
D Na, Heat
¾¾® —
[ HN - (CH 2 )6 - (NH - C - (CH 2 )8 - C —
]n ¾¾¾¾¾®
Nylon 6, 10 Polymerisation
Styrene
15. (d) Acrylonitrile is the monomer used in the
preparation of orlon.
(– CH2 – CH = CH – CH2 – CH – CH2 –)n
16. (c) All other three polymers are obtained by
addition polymerisation Butadiene -
Styrene copolymer
17. (b) Vinyl alcohol, CH2=CHOH, monomer of (SBR or BUNA - S)
polyvinyl alcohol exists mainly as CH3CHO ;
hence polyvinyl alcohol is best prepared by the 19. (b)
alkaline hydrolysis of polyvinyl acetate which 20. (d) Vinylidene chloride does not form isotatic,
in turn is prepared by the polymerisation of vinyl syndiotactic and atactic-polymers. Vinylidene
acetate chloride does not contain chiral carbon atoms.
 CHAPTER
Chemistry in Everyday
30 Life
1. (b) 12. (c) We know that N-acetyl-para-aminophenol
2. (a) Amoxycillin is semisynthetic modification of (or paracetamol) is an antipyretic which can also
penicillin be used as an analgesic to relieve pains.
3. (d) 4. (c) 5. (c) 13. (b) Dilute solutions of boric acid and hydrogen
6. (d) Vitamin E is an antioxidant present in edible peroxide are weak antiseptics.
oils. 14. (b) Structurally, biodegradable detergents
7. (a) Substances used for the treatment of malaria should contain branched alkyl chain.
are antimalarials, e.g. quinine, chloroquine.
15. (c) The correct matching is as follows :
8. (a)
9. (b) Paul Ehrlich, the father of chemotherapy
defined it to injure or destroy infection caused Column I Column II
by microorganism by the use of drugs without (A) Sodium perborate Milk bleaching agent
causing any injury to the host. (B) Chlorine Disinfectant
10. (a) (C) Bithional Antiseptic
11. (b) The term “antihistamine” refers only to H1
(D) Potassium stearate Soap
antagonists, which is also known as H1-receptor
antagonists and H1-antihistamine.
 202 CHEMISTRY

CHAPTER

31 Practical Chemistry

1 8. (a) IV th group needs higher S 2– ion

1. (d) Meq of FeSO4 = 10 × =1 concentration. In presence of HCl, the
10
dissociation of H2S decreases hence produces
(Meq of FeSO4 = Meq of KMnO4)
less amount of sulphide ions due to common ion
Meq. of KMnO4 needed = 1
effect, thus HCl decreases the solubility of H2S
\ Meq of 10 mL of 0.02 M = 10 × 0.1 = 1 which is sufficient to precipitate IInd group radical.
(1 M K MnO4 = 5e– of KMnO4 in acid medium) 9. (c) Carius method of estimation of halogen: In
2. (d) HgI2 + 2KI ––® K2HgI4 this method a known weight of organic
D
HgI2 ¾¾
® Hg + I2 ­ compound is heated with fuming nitric acid in
(Violet) presence of AgNO3. Halogen forms silver halide.
3. (c) Carbon and hydrogen of the compound are
4. (b) The chemistry of the Lassaigne’s test of oxidised to CO2 and H2O.
nitrogen is % of Halogen (X)
D At. wt . of X × wt. of AgX ×100
Na + C + N ¾¾® NaCN = Mol. wt. of AgX × wt. of organic compound
From organic
compound
Let the atomic weight of the halogen (X) = x
2NaCN + FeSO 4 ¾¾
® Fe(CN) 2 + Na 2SO 4 the atomic weight of AgX = 108 + x
Substituting the value in the above equation we
Fe(CN)2 + 4NaCN ¾¾
® Na 4[Fe(CN)6 ]
get,
Sod. ferrocyanide
æ x ö 2.21 ´ 100
3Na 4 [Fe(CN) 6 ] + 4Fe3+ ¾¾
® 46.78 = ç 108 + x ÷ ´
è ø 2
Fe 4 [Fe(CN)6 ]3 + 12Na +
(Ferric ferrocyanide) 46.78 ´ 2 x
(Prussian blue) =
2.21 ´ 100 108 + x
5. (b) 3Mg + N2 ¾¾
® Mg3N2
X Y x
0.42335 =
Mg3N2 + 6H2O ¾¾ ® 3 Mg(OH)2 + 2NH3 108 + x
CuSO4 + 4NH3 ® Cu[(NH3)4] SO4 0.42335(108 + x) = x
deep blue colour 45.7218 + 0.42335x = x
6. (d) Mixture of salt, Na 2CO3, water when x = 79.3 l 80
combinedly heated in test tube gives soda extract. \ Halogen present in organic compound is
7. (c) Microcosmic salt [Na(NH4)HPO4.4H2O] is Bromine.
also used for bead test.
Practical Chemistry 203

+6 18. (a) H 2SO 4 is dibasic.

10. (a) ® Fe3+ + Cr 3+
FeCl 2 + K 2 Cr2 O 7 ¾¾ 0.1 MH 2SO 4 = 0.2NH 2SO 4
Dn = 6 Meq of H 2SO 4 taken = = 100 ´ 0.2 = 20
No. of eq. of FeCl2 Meq of H 2SO 4 neutralised byNaOH = 20 × 0.5 = 10
= No. of eq. of K2Cr2O7 Meq of H 2SO 4 neutralised by NH3 = 12 – 10 = 10
N1V1 = N2V2 % of
N1 × 10 = M × n × 25 [Q N = M × n] 1.4 ´ M eq of acid neutrialised by NH 3
N2 =
n wt. of organic compound
N1 × 10 = V(in L) ´ n f ´ 25 1.4 ´ 10
= = 46.6
0.3
1.225
294 % of nitrogen in urea = 14 ´ 2 ´ 100 = 46.6
N1 × 10 = ´ 25 60
250 ´ 10-3
19. (b) Percentage of nitrogen by Kjeldahl’s method
1.225 ´ 25
N1 = 14 Normality of acid ´ vol. of acid used
294 ´ 250 ´ 10 ´ 10-3 = ´
1000 wt. of organic compound
1.225
= Mass of organic compound = 0.5 g
10 ´ 10 ´ 10-3 ´ 294 Unused acid required = 80 mL of 0.5 M NaOH
12.25 = 80 mL of 0.5 N NaOH
N1 = = 0.25 º 40 mL of 0.5 M or 1 N H2SO4
294
Acid used for absorption of ammonia
11. (d) Na 2 [Fe(CN)5 NO] + S2- ® = (50 – 40) mL of 1 N H2SO4
= 10 mL of 1 N H2SO4
Na 4 [Fe(CN)5 NOS]
Sodium thio-nitroprusside 1.4 ´ 1 ´ 10
(violet) % of nitrogen = = 28%
0.5
12. (a) % Of sulphur 20. (b) Glycerol is purified by vaccum distillation.
32 Mass of BaSO4 formed 21. (d) Since diazo compounds may lose nitrogen
= ´ ´ 100 in the form of nitrogen gas, they sometimes do
233 Mass of substance taken
not respond Lassaigne’s test for nitrogen.
32 0.699 heat
% of S = ´ ´ 100 = 20 % 22. (b) N-containing compound ¾¾¾® N2
233 0.480
2g 0.4 g
13. (d) Yellow colour is due to the formation of
0.4 g of N2 is obtained from 2 g of compound
(NH4)3PO4.12MoO3
2
14. (d) Carboxylic acids dissolve in sodium 28 g of N2 is obtained from × 28 = 140
0.4
bicarbonate, while phenol does not. Hence molecular weight of the compound is
15. (b) 2NaI + 2NaNO2 + 4CH3COOH ¾ ¾® 140 which coincides with C6H5N2Cl (72 + 5 + 28
I2 + 2NO + 4CH3COONa + 2H2O + 35.5 = 140.5).
16. (b) K2SO4 raises b.pt. and CuSO4 acts as catalyst. 23. (b) If the organic compound also contains
17. (c) (C2H5)3N+HCl– is an ionic compound, so it nitrogen or sulphur, the Lassaigne's extract on
will form precipitate of AgCl on adding AgNO3. boiling with dil. HNO3 decomposes sodium
In 2, 4, 6-trinitro-chlorobenzene, —Cl is activated cyanide or sodium sulphide formed during fusion.
due to the presence of three —NO2 groups in NaCN + HNO3 ¾¾
® NaNO3 + HCN ­
o- and p-positions, so it will be very reactive Na 2S + 2HNO3 ¾¾
® 2NaNO 3 + H 2S ­
leading to formation of AgCl on adding HNO3 If cyanide an d sulphide ions are not
and AgNO3. decomposed, they will react with silver nitrate
and hence will interfere with the test.
 204 CHEMISTRY

NaCN + AgNO3 ¾¾
® AgCN + NaNO 3 Normality = Molarity × n
Silver
cyanide where n = Mol.mass = 98 = 2
(White ppt.) Eq.mass 49
Na 2S + 2AgNO3 ¾¾
® Ag 2S + 2NaNO3
Silver
\ Normality = 0.5 × 2 = 1 N H2SO4
sulphide Volume of acid used to neutralise NH3 = 10 cm3
(Black ppt.) Mass of organic compound taken = 0.25 g
24. (c) IV group reagent
Þ (NH4OH + NH4Cl + H2S gas) 1.4 ´ 1 ´ 10
\ %N = = 56.
0.25
25. (c) ®[Cu(NH3)4]2 +
CuSO 4 + 4NH 4OH ¾¾
29. (16.46) Given wt of compound taken (w)
Intense blue colour
_ = 0.35 g
+ SO 24 + 2 H 2 O Volume of nitrogen collected (V) = 55 ml
50 ´ 1 Room temperature (t K) = 300 K
26. (50) Eq of KMnO4 used = = 0.005
1000 ´ 10 Atmospheric pressure (P) = 715 mm
\ Eq of FAS reacted = 0.005 Aq. tension (r) = 15 mm
\ weight of FAS needed = 0.005 × 392 = 1.96 g Calculation -
1.96 Volume of N2 at NTP
% purity = ´ 100 = 50%
3.92 (P - ρ) ´ V 273
Thus percentage purity of FAS is 50% = ´ ml
t 760
27. (20) % of N in an organic compound (715 - 15) ´ 55 273
= ´ = 46.098 ml
Mass of nitrogen 300 760
= ´ 100 ..... (i)
Mass of organic compounds % of nitrogen
Now, 22400 mL of N2 at STP weigh = 28 g 28 ´ vol.of N 2 at NTP ´ 100
\ 224 mL of N2 at STP weigh =
22400 ´ wt of organic compound
28
= ´ 224 28 ´ 46.098 ´ 100
22400 = = 16.46%
On substituting the value in equation (i) we get, 22400 ´ 0.35
28 ´ 224 30. (13.33) Percentage of
%N = ´ 100 = 20%
22400 ´ 1.4 62 wt. of Mg 2 P2 O 7
28. (56) Percentage of N in a compound P= × × 100
222 wt. of compound
1.4 ´ Normality of acid ´ Volume of acid used
= 62 1.332
Mass of the substance taken = × × 100 = 13.33%
222 2.79
Given, 0.5 M H2SO4 is used.
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