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Topic-wise Solved Papers Chemistry

Some Basic Concepts of

Chemistry 1
1. In a compound C, H and N atoms are present in 7. To neutralise completely 20 mL of 0.1 M aqueous
9 : 1 : 3.5 by weight. Molecular weight of solution of phosphorous acid (H3 PO3), the
compound is 108. Molecular formula of value of 0.1 M aqueous KOH solution required
compound is [2002] is [2004]
(a) C2H6N2 (b) C3H4N (a) 40 mL (b) 20 mL
(c) C6H8N2 (d) C9H12N3. (c) 10 mL (d) 60 mL
2. With increase of temperature, which of these 8. The ammonia evolved from the treatment of 0.30
changes? [2002] g of an organic compound for the estimation of
(a) molality nitrogen was passed in 100 mL of 0.1 M
(b) weight fraction of solute sulphuric acid. The excess of acid required 20
(c) molarity
mL of 0.5 M sodium hydroxide solution for
(d) mole fraction.
complete neutralization. The organic compound
3. Number of atoms in 558.5 gram Fe (at. wt. of
is [2004]
Fe = 55.85 g mol–1) is [2002]
(a) urea (b) benzamide
(a) twice that in 60 g carbon
(b) 6.023 ´ 1022 (c) acetamide (d) thiourea
(c) half that in 8 g He 9. Two solutions of a substance (non electrolyte)
(d) 558.5 ´ 6.023 ´ 1023 are mixed in the following manner. 480 ml of 1.5
4. What volume of hydrogen gas, at 273 K and 1 M first solution + 520 ml of 1.2 M second
atm. pressure will be consumed in obtaining 21.6 solution. What is the molarity of the final
g of elemental boron (atomic mass = 10.8) from mixture ? [2005]
the reduction of boron trichloride by hydrogen? (a) 2.70 M (b) 1.344 M
[2003] (c) 1.50 M (d) 1.20 M
(a) 67.2 L (b) 44.8 L 10. If we consider that 1/6, in place of 1/12, mass of
(c) 22.4 L (d) 89.6 L carbon atom is taken to be the relative atomic
5. 25ml of a solution of barium hydroxide on mass unit, the mass of one mole of the substance
titration with a 0.1 molar solution of hydrochloric will [2005]
acid gave a litre value of 35ml. The molarity of (a) be a function of the molecular mass of the
barium hydroxide solution was substance
(a) 0.14 (b) 0.28 [2003] (b) remain unchanged
(c) 0.35 (d) 0.07 (c) increase two fold
6. 6.02 × 1020 molecules of urea are present in 100 (d) decrease twice
ml of its solution. The concentration of urea 11. How many moles of magnesium phosphate,
solution is [2004] Mg3(PO4)2 will contain 0.25 mole of oxygen
(a) 0.02 M (b) 0.01 M atoms? [2006]
(c) 0.001 M (d) 0.1 M (a) 1.25 × 10–2 (b) 2.5 × 10–2
(Avogadro constant, NA = 6.02 × 1023 mol–1) (c) 0.02 (d) 3.125 × 10–2
 EBD_7764
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C-2 Chemistry
12. Density of a 2.05M solution of acetic acid in exists as M3+ would be :
water is 1.02 g/mL. The molality of the solution (a) 7.01% (b) 4.08%[2013]
is [2006] (c) 6.05% (d) 5.08%
(a) 2.28 mol kg –1 (b) 0.44 mol kg–1 18. 3 g of activated charcoal was added to 50 mL of
(c) 1.14 mol kg –1 (d) 3.28 mol kg–1 acetic acid solution (0.06N) in a flask. After an
13. The density (in g mL–1) of a 3.60 M sulphuric hour it was filtered and the strength of the filtrate
acid solution that is 29% H 2 SO 4 was found to be 0.042 N. The amount of acetic
(molar mass = 98 g mol–1) by mass will be acid adsorbed (per gram of charcoal) is :
(a) 1.45 (b) 1.64 [2007] [JEE M 2015]
(c) 1.88 (d) 1.22 (a) 42 mg (b) 54 mg
(c) 18 mg (d) 36 mg
14. In the reaction, [2007]
19. At 300 K and 1 atm, 15 mL of a gaseous
2Al (s) + 6HCl(aq) ® hydrocarbon requires 375 mL air containing 20%
2Al3+ (aq) + 6Cl - (aq) + 3H 2 (g) O2 by volume for complete combustion. After
(a) 11.2 L H2(g) at STP is produced for every combustion the gases occupy 330 mL. Assuming
mole HCl(aq) consumed that the water formed is in liquid form and the
(b) 6 L HCl(aq) is consumed for every 3 L H2(g) volumes were measured at the same temperature
produced and pressure, the formula of the hydrocarbon
(c) 33.6 L H2 (g) is produced regardless of is: [JEE M 2016]
temperature and pressure for every mole (a) C4H8 (b) C4H10
Al that reacts (c) C3H6 (d) C3H8
(d) 67.2 H2(g) at STP is produced for every 20. The most abundant elements by mass in the
mole Al that reacts. body of a healthy human adult are :
15. The molality of a urea solution in which 0.0100 g Oxygen (61.4%) ; Carbon (22.9%), Hydrogen
of urea, [(NH2)2CO] is added to 0.3000 dm3 of (10.0%) ; and Nitrogen (2.6%). The weight which
water at STP is : [2011RS] a 75 kg person would gain if all 1H atoms are
(a) 5.55 ´ 10 -4 m (b) 33.3 m replaced by 2H atoms is [JEE M 2017]
(c) 3.33 × 10–2 m (d) 0.555 m (a) 15 kg (b) 37.5 kg
16. A gaseous hydrocarbon gives upon combustion (c) 7.5 kg (d) 10 kg
0.72 g of water and 3.08 g. of CO2. The empirical 21. 1 gram of a carbonate (M2CO3) on treatment
formula of the hydrocarbon is : [2013] with excess HCl produces 0.01186 mole of CO2.
(a) C2H4 (b) C3H4 The molar mass of M2CO3 in g mol–1 is :
(c) C6H5 (d) C7H8 [JEE M 2017]
17. Experimentally it was found that a metal oxide (a) 1186 (b) 84.3
has formula M0.98O. Metal M, present as M2+
(c) 118.6 (d) 11.86
and M3+ in its oxide. Fraction of the metal which

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(c) (c) (a) (a) (d) (b) (a) (a) (b) (d) (d) (a) (d) (a) (a)
16 17 18 19 20 21
(d) (b) (c) (d) (c) (b)
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Some Basic Concepts of Chemistry C-3

1. (c) Percentage 6. (b) Moles of urea present in 100 ml of sol.=

R.N.A Simplest ratio
6.02 ´ 1020
9 3 6.02 ´ 10 23
C 9 = 3
12 4
6.02 ´10 20 ´1000
1 \M = = 0.01M
H 1 =1 4 6.02 ´10 23 ´100
1
[ Q M = Moles of solute present in 1L of
3.5 1 solution]
N 3.5 = 1
14 4 7. (a) N1V1 = N 2 V2
Empirical formula = C3H4N (Note : H3PO3 is dibasic \ M = 2N)
(C3H4N)n = 108
20 ´ 0.2 = 0.1´ V (Thus. 0.1 M = 0.2 N)
(12 × 3 + 4 × 1 + 14)n = 108
\ V = 40 ml
(54)n = 108
8. (a) H 2SO 4 is dibasic.
108
n= =2 0.1 MH 2SO 4 = 0.2NH 2SO 4 [
54
\ molecular formula = C6 H8N2 QM = 2´ N ]
2. (c) Among all the given options molarity is Meq of H 2SO 4 taken = = 100 ´ 0.2 = 20
correct because the term molarity involve
volume which increases on increasing Meq of H 2SO 4 neutralised by
temperature. NaOH = 20 ´ 0.5 = 10
558.5 Meq of H 2SO 4 neutralised by
3. (a) Fe (no. of moles) = = 10 moles
55.85 NH3 = 20 – 10 = 10 % of
C (no. of moles) in 60 g of C = 60/12 = 5 moles. 1.4 ´ M eq of acid neutrialised by NH3
N2 =
4. (a) 2BCl3 + 3H 2 ® 2B + 6HCl wt. of organic compound

3 1.4 ´ 10
or BCl3 + H 2 ® B + 3HCl = = 46.6
2 0.3
Now, since 10.8 gm boron requires 14 ´ 2 ´ 100
hydrogen % of nitrogen in urea = = 46.6
60

=
3
´ 22.4L at N.T.P
[ Mol.wt of urea =60]
2 Similarly % of Nitrogen in Benzamide
hence 21.6 gm boron requires hydrogen 14 ´ 100
= = 11.5% [C6H5CONH2 = 121]
3 22.4 121
´ ´ 21.6 < 67.2L at N.T. P..
2 10.8 14 ´ 1 ´ 100
5. (d) 25 × N = 0.1 × 35 ; N = 0.14 Acctamide = = 23.4%
59
Ba(OH)2 is diacid base [ CH3CONH2=59]
N 14 ´ 2 ´ 100
hence N = M × 2 or M = Thiourea = = 36.8%
2 76
[NH2CSNH2 = 76]
M = 0.07 M
Hence the compound must be urea.
 EBD_7764
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C-4 Chemistry
9. (b) = 3.6 × 98 g = 352.8 g
\ 1000 ml solution has 352.8 g of H2SO4
From the molarity equation.
Given that 29 g of H2SO4 is present in =
M1V1 + M2V2 = MV
100 g of solution
Let M be the molarity of final mixture,
\ 352.8 g of H2SO4 is present in
M1V1 +M V2
2 100
M= where V = V1 + V2 = ´ 352.8 g of solution
V 29
= 1216 g of solution
480 ´ 1.5 + 520 ´ 1.2
M= = 1.344 M
480 + 520 Mass 1216
Density = =
10. (d) Relative atomic mass = Volume 1000
= 1.216 g/ml = 1.22 g/ml
Mass of one atom of the element
14. (a) 2Al(s) + 6HCl(aq) ® 2Al3+(aq) + 6Cl–
th
1/12 part of the mass of one atom of Carbon - 12 (aq) + 3H2(g)
Q 6 moles of HCl produces = 3 moles of H2
Mass of one atom of the element = 3 × 22.4 L of H2 at S.T.P
or ´ 12
mass of one atom of the C - 12 \ 1 mole of HCl produces
Now if we use 1 / 6 in place of 1 /12 the 3 ´ 22.4
formula becomes = L of H2 at S.T.P
6
Relative atomic mass = = 11.2 L of H2 at STP
15. (a) Molality = Moles of solute / Mass of
Mass of one atom of element solvent in kg
´6
Mass of one atom of carbon 0.01/ 60 0.01
Molality = = ;
\ Relative atomic mass decrease twice 0.3 60 ´ 0.3
11. (d) 1 Mole of Mg3(PO4)2 contains 8 mole of d = 1 g/ml
oxygen atoms
= 5.55 ´ 10-4 m
\ 8 mole of oxygen atoms º 1 mole of
Mg3(PO4)2 mole of Mg3(PO4)2 16. (d) Q 18 gm, H2O contains = 2 gm H
\ 0.72 gm H2O contains
1
0.25 mole of oxygen atom º ´ 0.25 mole 2
8 = ´ 0.72 gm = 0.08 gm H
18
of Mg3(PO4)2
Q 44 gm CO2 contains = 12 gm C
= 3.125 ´ 10 -2 mole of Mg3 (PO4)2 \ 3.08 gm CO2 contains
12. (a)
12
= ´ 3.08 = 0.84 gm C
æ1 M ö 44
Apply the formula d = M ç + 2 ÷
è m 1000 ø 0.84 0.08
\C: H= :
12 1
æ1 60 ö = 0.07 : 0.08 = 7 : 8
\ 1.02 = 2.05 ç + ÷
è m 1000 ø \ Empirical formula = C7H8
On solving we get, m = 2.288 mol/kg 17. (b) For one mole of the oxide
13. (d) Since molarity of solution is 3.60 M. It Moles of M = 0.98
means 3.6 moles of H2SO4 is present in its Moles of O2– = 1
1 litre solution. Let moles of M3+ = x
Mass of 3.6 moles of H2SO4 \ Moles of M2+ = 0.98– x
= Moles × Molecular mass On balancing charge
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Some Basic Concepts of Chemistry C-5
(0.98 – x) × 2 + 3x – 2 = 0 20. (c) Percentage (by mass) of elements given in
x = 0.04 the body of a healthy human adult is :-
0.04
\ % of M3+ = ´100 < 4.08% Oxygen = 61.4%, Carbon = 22.9%,
0.98
Hydrogen = 10.0% and Nitrogen = 2.6%
18. (c) Let the weight of acetic acid initially be w1
in 50 ml of 0.060 N solution. Q Total weight of person = 75 kg
Let the N = (Normality = 0.06 N)
10
0.06 = \ Mass due to 1H is = 75 ´ = 7.5 kg
Þ = 0.18 g = 180 mg. 100
After an hour, the strength of acetic acid =
0.042 N If 1H atoms are replaced by 2H atoms.
so, let the weight of acetic acid be w2 Mass gain by person would be = 7.5 kg
N=
21. (b) Given chemical eqn
0.042 =
Þ w2 = 0.126 g = 126 mg M2CO3 + 2HCl ® 2MCl + H2O + CO2
1gm 0.01186 mole
So amount of acetic acid adsorbed per 3g
= 180 – 126 mg = 54 mg from the balanced chemical eqn.
Amount of acetic acid adsorbed per g = 18 nM2CO3 = nCO2
19. (d) CxHy(g) + O2(g) ® xCO2(g) + H2O(l)
Volume of O2 used = = 75 ml 1
= 0.01186
\ From the reaction of combustion M 2 CO3
1 ml CxHy requires = 1
15 ml = \ M 2 CO3 =
0.01186
So, 4x + y = 20
Þ M = 84.3 g/mol
x= 3
y= 8
C3 H 8
 EBD_7764
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C-6 Chemistry

Structure of Atom 2
1. In a hydrogen atom, if energy of an electron in 7. The de Broglie wavelength of a tennis ball of
ground state is 13.6. ev, then that in the 2nd mass 60 g moving with a velocity of 10 metres
excited state is [2002] per second is approximately [2003]
(a) 1.51 eV (b) 3.4 eV (a) 10–31 metres (b) 10–16 metres
(c) 6.04 eV (d) 13.6 eV. (c) 10–25 metres (d) 10–33 metres
2. Uncertainty in position of a minute particle of Planck’s constant, h = 6.63 × 10–34 Js
mass 25 g in space is 10-5 m. What is the uncertainty 8. Which of the following sets of quantum numbers
in its velocity (in ms-1)? (h = 6.6 ´ 10-34 Js) is correct for an electron in 4f orbital ? [2004]
[2002] (a) n = 4, l = 3, m = + 1, s = + ½
(a) 2.1 ´ 10–34 (b) 0.5 ´ 10 –34
(b) n = 4, l = 4, m = – 4, s = – ½
(c) 2.1 ´ 10–28 (d) 0.5 ´ 10–23. (c) n = 4, l = 3, m = + 4, s = + ½
3. The number of d-electrons retained in Fe2+ (At. (d) n = 3, l = 2, m = – 2, s = + ½
no. of Fe = 26) ion is [2003] 9. Consider the ground state of Cr atom (X = 24).
(a) 4 (b) 5 The number of electrons with the azimuthal
(c) 6 (d) 3 quantum numbers, l = 1 and 2 are, respectively
4. The orbital angular momentum for an electron [2004]
h (a) 16 and 4 (b) 12 and 5
revolving in an orbit is given by l (l + 1) . .
2p (c) 12 and 4 (d) 16 and 5
This momentum for an s-electron will be given 10. The wavelength of the radiation emitted, when
by [2003] in a hydrogen atom electron falls from infinity to
h stationary state 1, would be (Rydberg constant
(a) zero (b) = 1.097×107 m–1) [2004]
2p
1 h (a) 406 nm (b) 192 nm
(c) h (d) + .
2. 2 2p (c) 91 nm (d) 9.1×10–8 nm
2p
11. Which one of the following sets of ions
5. Which one of the following groupings represents represents the collection of isoelectronic
a collection of isoelectronic species ?(At. nos. : species? [2004]
Cs : 55, Br : 35) [2003] (a) K+, Cl–, Mg2+, Sc3+
(a) N3–, F–, Na+ (b) Be, Al3+, Cl– (b) Na+, Ca2+, Sc3+, F–
(c) Ca2+, Cs+, Br (d) Na+, Ca2+, Mg2+ (c) K+, Ca2+, Sc3+, Cl–
6. In Bohr series of lines of hydrogen spectrum, (d) Na+, Mg2+, Al3+, Cl–
the third line from the red end corresponds to
(Atomic nos. : F = 9, Cl = 17, Na = 11, Mg = 12,
which one of the following inter-orbit jumps of
Al = 13, K = 19, Ca = 20, Sc = 21)
the electron for Bohr orbits in an atom of
hydrogen [2003] 12. In a multi-electron atom, which of the following
orbitals described by the three quantum
(a) 5 ® 2 (b) 4 ® 1 members will have the same energy in the
(c) 2®5 (d) 3 ® 2 absence of magnetic and electric fields? [2005]
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Structure of Atom C-7
(A) n = 1, l = 0, m = 0 (B) n = 2, l = 0, m = 0 19. The ionization enthalpy of hydrogen atom is
(C) n = 2, l = 1, m = 1 (D) n = 3, l = 2, m = 1 1.312 × 106 J mol–1. The energy required to excite
(E) n = 3, l = 2, m = 0 the electron in the atom from n = 1 to n = 2 is
(a) (D) and (E) (b) (C) and (D) [2008]
(c) (B) and (C) (d) (A) and (B) (a) 8.51 × 105 J mol–1 (b) 6.56 × 105 J mol–1
13. Of the following sets which one does NOT (c) 7.56 × 105 J mol–1 (d) 9.84 × 105 J mol–1
contain isoelectronic species? [2005] 20. Calculate the wavelength (in nanometer)
associated with a proton moving at 1.0 × 103 ms –1.
(a) BO 33 - , CO 32 - , NO 3-
(Mass of proton = 1.67 × 10–27 kg and
(b) SO32 - , CO32 - , NO3- h = 6.63 × 10–34 Js) [2009]
(a) 0.40 nm (b) 2.5 nm
(c) CN - , N 2 , C 22 -
(c) 14.0 nm (d) 0.32 nm
(d) PO 34 - , SO 24 - , ClO -4 21. In an atom, an electron is moving with a speed
14. According to Bohr's theory, the angular of 600 m/s with an accuracy of 0.005%. Certainity
momentum of an electron in 5th orbit is [2006] with which the position of the electron can be
(a) 10 h / p (b) 2.5 h / p located is ( h = 6.6 × 10–34 kg m2s–1, mass of
(c) 25 h / p (d) 1.0 h / p electron, em = 9.1 × 10–31 kg) : [2009]
15. Uncertainty in the position of an electron (mass (a) 5.10 × 10 –3 m (b) 1.92 × 10 –3 m
= 9.1 × 10–31 kg) moving with a velocity 300 ms–1, (c) 3.84 × 10 –3 m (d) 1.52 × 10 –4 m
accurate upto 0.001% will be [2006] 22. The energy required to break one mole of Cl – Cl
(a) 1.92 × 10–2 m (b) 3.84 × 10–2 m bonds in Cl 2 is 242 kJ mol –1 . The longest
(c) 19.2 × 10–2 m (d) 5.76 × 10–2 m wavelength of light capable of breaking a single
(h = 6.63 × 10–34 Js) Cl – Cl bond is (c = 3 × 108 ms–1 and NA = 6.02 ×
16. Which one of the following sets of ions 1023 mol–1). [2010]
represents a collection of isoelectronic species? (a) 594 nm (b) 640 nm
[2006] (c) 700 nm (d) 494 nm
(a) N3–, O2–, F–, S2– 23. Ionisation energy of He+ is 19.6 × 10–18 J atom–1.
(b) Li+, Na+, Mg2+, Ca2+ The energy of the first stationary state (n = 1) of
(c) K+, Cl–, Ca2+, Sc3+ Li2+ is [2010]
(d) Ba2+, Sr2+, K+, Ca2+ (a) 4.41 × 10–16 J atom–1
17. Which of the following sets of quantum numbers (b) –4.41 × 10–17 J atom–1
represents the highest energy of an atom? (c) –2.2 × 10–15 J atom–1
[2007] (d) 8.82 × 10–17 J atom–1
(a) n = 3, l = 0, m = 0, s = +1/2
24. The frequency of light emitted for the transition
(b) n = 3, l = 1, m = 1, s = +1/2 n = 4 to n = 2 of the He+ is equal to the transition
(c) n = 3, l = 2, m = 1, s = +1/2 in H atom corresponding to which of the
(d) n = 4, l = 0, m = 0, s = +1/2. following? [2011RS]
18. Which one of the following constitutes a group (a) n = 2 to n = 1 (b) n = 3 to n = 2
of the isoelectronic species? [2008] (c) n = 4 to n = 3 (d) n = 3 to n = 1
2– –
(a) C2 , O2 , CO, NO 25. The electrons identified by quantum numbers n
(b) NO+ ,C2– – and l : [2012]
2 , CN , N 2
(A) n = 4, l = 1 (B) n = 4, l = 0
(c) CN – , N 2 ,O2– 2–
2 , C2 (C) n = 3, l = 2 (D) n = 3, l = 1
(d) N 2 ,O2– , NO+ ,CO can be placed in order of increasing energy as :
 EBD_7764
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C-8 Chemistry
(a) (C) < (D) < (B) < (A) 29. Which of the following is the energy of a possible
(b) (D) < (B) < (C) < (A) excited state of hydrogen? [JEE M 2015]
(c) (B) < (D) < (A) < (C) (a) –3.4 eV (b) +6.8 eV
(d) (A) < (C) < (B) < (D) (c) +13.6 eV (d) –6.8 eV
30. A stream of electrons from a heated filaments
26. The increasing order of the ionic radii of the
was passed two charged plates kept at a
given isoelectronic species is : [2012]
potential difference V esu. If e and m are charge
– 2+ +
(a) Cl , Ca , K , S 2– (b)S , Cl , Ca2+ , K+
2– –
and mass of an electron, respectively, then the
2+ + –
(c) Ca , K , Cl , S 2– (d)K+, S2–, Ca2+, Cl– value of h/l (where l is wavelength associated
27. Energy of an electron is given by E = – 2.178 × with electron wave) is given by: [JEE M 2016]
æ Z2 ö (a) meV (b) 2meV
10-18 J ç 2 ÷ . Wavelength of light required to
èn ø (c) meV (d) 2meV
excite an electron in an hydrogen atom from level 31. The radius of the second Bohr orbit for hydrogen
n = 1 to n = 2 will be : [2013] atom is : [JEE M 2017]
(h = 6.62 × 10 –34 Js and c = 3.0 × 108 ms–1) (Plank's const. h = 6.6262 × 10–34 Js ; mass of
electron = 9.1091 × 10–31 kg ; charge of electron
(a) 1.214 × 10–7 m (b) 2.816 × 10.–7 m
e = 1.60210 × 10–19 C ; permittivity of vaccum
(c) 6.500 × 10–7 m (d) 8.500 × 10–7 m
Î0 = 8.854185 × 10–12 kg–1 m–3 A2)
28. The correct set of four quantum numbers for the
(a) 1.65Å (b) 4.76Å
valence electrons of rubidium atom (Z = 37) is:
(c) 0.529Å (d) 2.12Å
[2014]
32. The group having isoelectronic species is :
1 1 (a) O2– , F–, Na+, Mg2+ [JEE M 2017]
(a) 5, 0, 0, + (b) 5,1, 0, +
2 2 (b) O– , F–, Na, Mg+
1 1 (c) O2– , F–, Na , Mg2+
(c) 5,1,1, + (d) 5, 0,1, +
2 2 (d) O– , F–, Na+ , Mg2+

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

1. (a) 2nd excited state will be the 3rd energy level.

6.62 ´ 10 -34
13.6 \ Dv =
13.6 4 ´ 3.14 ´ 0.025 ´ 10 -5
En = 2
eV or E = eV = 1.51 eV.
n 9
= 2.1 ´ 10 -28 ms -1
2. (c) 3. (c) Fe++ (26 – 2 = 24) = 1s2 2s2 2p6 3s2 3p6 4s0
h 3d6 hence no. of d electrons retained is 6.
h Dx.m.Dv =
Dx. Dp = ; or [Two 4s electron are removed]
4p 4p
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Structure of Atom C-9

4. (a) 13. (b) Calculating number of electrons

For s-electron, l = 0 3-
BO3 ¾¾® 5 + 8 ´ 3 + 3 = 32 ü
2- ï iso-electronic
\ Orbital angular momentum = 1. CO3 ¾¾® 6 + 8 ´ 3 + 2 = 32ý species
h -
® 7 + 8 ´ 3 + 1 = 32 ï
NO3 ¾¾
0(0 + 1) = 0 þ
2p
5. (a) N3–, F– and Na+ contain 10 electrons each.
6. (a) The lines falling in the visible region 2-
SO3 ® 16 + 8 ´ 3 + 2 = 42ü
¾¾
ï
comprise Balmer series. Hence the third line 2- ï not iso-electronic
2. CO3 ¾¾® 32 ý species
from red would be n1 =2, n 2 = 5 i.e. 5 ® 2. - ï
NO3 ¾¾® 32 ïþ
h 6.6 ´ 10 -34
7. (d) l= = = 10 -33 m
mv 60 ´ 10 -3 ´10 CN
-
® 6 + 7 + 1 = 14ü
¾¾
ï
ï iso-electronic
8. (a) The possible quantum numbers for 4f 3. N 2 ¾¾
® 7 ´ 2 = 14 ý species
electron are - ï
C 2 ¾¾
® 6 ´ 2 + 2 = 14 ï
n = 4, l = 3, m = – 3, –2 –1, 0, 1 , 2 , 3 and þ
1
s=± ® 15 + 8 ´ 4 + 3 = 50 ü
PO34- ¾¾
2 ï
Of various possiblities only option (a) is 2- ï iso-electronic
4. SO 4 ¾¾
® 16 + 8 + 2 = 50 ý species
possible. - ï
ClO4 ¾¾
® 17 + 8 ´ 4 + 1 = 50ï
9. (b) Electronic configuration of Cr atom þ
(z = 24) = 1s 2 , 2s2 2p 6 ,3s 2 3p 6 3d 5 , 4s1 Hence the species in option (b) are not
iso-electronic.
when l = 1, p - subshell,
14. (b) Angular momentum of an electron in nth
Numbers of electrons = 12 orbital is given by ,
when l = 2, d - subshell,
nh
Numbers of electrons = 5 mvr =
2p
10. (c) For n = 5, we have
Angular momentum of electron
1 æ 1 1 ö÷
= Rç - 5h 2.5h
l ç n2 n2 ÷ = =
è 1 2ø
2p p
1 æ1 1 ö 15. (a) Given m = 9.1 × 10–31kg
= 1.097 ´ 10 7 ç - ÷ = 1.097 ´ 10 7 h = 6.6 × 10–34Js
l è1 ¥ ø
300 ´ .001
l = 91.15 ´ 10 -9 m » 91nm Dv = = 0.003ms–1
100
+, 2+ , 3+ , -
11. (c) 19 K 20 Ca 21Sc 17 Cl From Heisenberg's uncertainity principle
each contains 18 electrons. 6.62 ´ 10 -34
12. (a) The energy of an orbital is given by (n + l) Dx =
4 ´ 3.14 ´ 0.003 ´ 9.1 ´ 10-31
in (d) and (c). (n + l) value is (3 + 2) = 5
hence they will have same energy, since = 1.92 ´ 10 -2 m
there n values are also same.
 EBD_7764
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C-10 Chemistry
16. (c) (a) N3– = 7 + 3 = 10e–, O–– ––® 8 + 2 = 10e– DE is given by the relation,
E1 = – 1.312 × 106 J mol–1
F– = 9 + 1 = 10e–, S – – ––® 16 + 2 = 18e– \ DE = E2 – E1 = [–3.28 × 105]– [–1.312 ×
(not iso electronic) 106 ] J mol–1
(b) Li+ = 3+1= 4e–, Na+ = 11–1 = 10e–, = (–3.28 × 105 + 1.312 × 106) J mol–1
Mg++ = 12–2=10e– = 9.84 × 105 J mol–1
Ca++ = 20 – 2 = 18e– (not isoelectronic) Thus the correct answer is (d)
(c) K+ = 19 – 1= 18e–, Cl– =17 + 1 = 18e–,
h 6.63 ´ 10-34
Ca++ = 20 – 2 =18e, Sc3+ = 21–3 = 18e– 20. (a) l= =
mv 1.67 ´ 10 -27 ´ 1 ´ 103
(isoelectronic)
(d) Ba 56 – 2 = 54e, Sr++ 38–2 = 36e–
++ = 3.97 × 10–10 meter = 0.397 nanometer
21. (b) According to Heisenberg uncertainty
principle.
K+= 9–1 = 18e–, Ca++= 20–2 = 18e–
(not isoelectronic) h h
Dx.mDv = Dx =
17. (c) (a) n = 3, l = 0 means 3s-orbital and n + 4p 4 pmD v
l= 3 600 ´ 0.005
Here Dv = = 0.03
(b) n = 3, l = 1 means 3p-orbital n + l = 4 100
(c) n = 3, l = 2 means 3d-orbital n + l = 5 6.6 ´ 10-34
So, Dx =
(d) n = 4, l = 0 means 4s-orbital n + l = 4 4 ´ 3.14 ´ 9.1 ´ 10-31 ´ 0.03
Increasing order of energy among = 1.92 × 10–3 meter
these orbitals is 22. (d) Energy required to break one mole of Cl –
3s < 3p < 4s < 3d Cl bonds in Cl2
\ 3d has highest energy..
18. (b) Species having same number of electrons 242 ´ 103 hc
= =
are isoelectronic calculating the number 6.023 ´ 10 23 l
of electrons in each species given here, we
get. 6.626 ´ 10-34 ´ 3 ´ 108
=
CN– (6 + 7 + 1 = 14); N2 (7 + 7 = 14); l
O22–(8 + 8 +2 = 18) ; C22– (6 + 6 + 2 = 14);
6.626 ´ 10 -34 ´ 3 ´ 108 ´ 6.023 ´ 10 23
O2– (8 + 8 + 1 = 17) ; NO+ (7 + 8 – 1 = 14) \l=
CO (6 + 8 = 14) ; NO (7 + 8 = 15) 242 ´ 108
From the above calculation we find that all = 0.4947 × 10–6 m = 494.7 nm
the species listed in choice (b) have 14 Z2
electrons each so it is the correct answer. 23. (b) I. E = ´ 13.6 eV ...(i)
n2
19. (d) (DE), The energy required to excite an
electron in an atom of hydrogen from n = 1 I1 Z12 n22
to n = 2 is DE (difference in energy E2 and or I = 2 ´ 2 ...(ii)
2 n1 Z 2
E1)
Values of E2 and E1 are, Given I1 = – 19.6 × 10–18 , Z1 = 2,
n1 = 1 , Z2 = 3 and n2 = 1
-1.312 ´106 ´ (1)2 Substituting these values in equation (ii).
E2 =
(2)2 19.6 ´ 10 -18 4 1
– = ´
= –3.28 × 105 J mol–1 I2 1 9
 www.crackjee.xyz
Structure of Atom C-11

-18 9 æ 1 1 ö hc
or I2 = -19.6 ´ 10 ´ 27. (a) DE = 2.178 ´ 10-18 ç 2 - 2 ÷ =
4 è1 2 ø l
= – 4.41 × 10–17 J/atom 3 hc
Þ 2.178 ´ 10-18 ´ =
24. (a) For He+ 4 l
1 æ 1 1ö 6.62 ´ 10-34 ´ 3 ´ 108
v= = RH Z 2 ç - =
l è 2 2 42 ÷ø l
For H 6.62 ´ 10 -34 3 ´ 108 ´ 4
l=
2.178 ´ 10 -18 ´3
æ ö –7
= 1.214 × 10 m
1 1 1
v= = RH ç - ÷ 28. (a) The electronic configuration of Rubidium
l ç n12 n2 ÷
è 2ø (Rb = 37) is
For same frequency, 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 5s1
æ ö æ ö Since last electron enters in 5s orbital
1 1 1 1 1
z2 = ç 2 - 2 ÷ = ç 2 - 2 ÷ Hence n = 5, l = 0, m = 0, s = ±
çè 2 4 ÷ø çè n1 n2 ÷ø 2
29. (a) Total energy =
Since, z = 2
where n = 2, 3, 4 ....
1 1 1 1 Putting n = 2
\ - = -
n12 n22 12 2 2 ET =
\ n1 = 1 & n2 = 2 30. (b) As electron of charge ‘e’ is passed through
25. (b) (a) 4 p (b) 4 s ‘V’ volt, kinetic energy of electron will be
eV
(c) 3 d (d) 3 p
Wavelength of electron wave (l) =
Accroding to Bohr Bury's (n + l) l = Þ\ =
rule, increasing order of energy (D) < (B) < 31. (d) Radius of nth Bohr orbit in H-atom
(C) < (A). = 0.53 n2Å
Note : If the two orbitals have same value Radius of II Bohr orbit = 0.53 × (2)2
of (n + l) then the orbital with lower value = 2.12 Å
of n will be filled first. 32. (a) Isoelectronic species have same no. of
26. (c) Among isoelectronic species ionic radii electrons.
increases as the charge increases. ions O–2 F– Na+ Mg2+
Order of ionic radii Ca2+ < K+ < Cl– < S2– 8+2 9+1 11–1 12–2
The number of electrons remains the same No. of e– = 10 10 10 10
but nuclear charge increases with increase therefore O 2– , F – , Na + , Mg 2+ are
in the atomic number causing decrease in isoelectronic
size.
 EBD_7764
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C-12 Chemistry

3
Classification of Elements
and Periodicity in Properties
1. According to the Periodic Law of elements, the 7. In which of the following arrangements, the
variation in properties of elements is related to their order is NOT according to the property indicated
[2003] against it? [2005]
(a) nuclear masses (a) Li < Na < K < Rb :
(b) atomic numbers Increasing metallic radius
(c) nuclear neutron-proton number ratios (b) I < Br < F < Cl :
(d) atomic masses Increasing electron gain enthalpy
2. Which one of the following is an amphoteric (with negative sign)
oxide ? [2003] (c) B < C < N < O
(a) Na2O (b) SO2 Increasing first ionization enthalpy
(c) B2O3 (d) ZnO (d) Al 3+ < Mg 2+ < Na + < F -
3. Which one of the following ions has the highest Increasing ionic size
value of ionic radius ? [2004] 8. Following statements regarding the periodic
(a) O2– (b) B3+ trends of chemical reactivity of the alkali metals
(c) Li+ (d) F– and the halogens are given. Which of these
statements gives the correct picture? [2006]
4. Among Al2O3, SiO2, P2O3 and SO2 the correct
order of acid strength is [2004] (a) Chemical reactivity increases with increase
in atomic number down the group in both
(a) Al2O3 < SiO2< SO2 < P2O3
the alkali metals and halogens
(b) SiO2< SO2 < Al2O3 < P2O3
(b) In alkali metals the reactivity increases but
(c) SO2< P2O3 < SiO2 < Al2O3 in the halogens it decreases with increase
(d) Al2O3 < SiO2< P2O3 < SO2 in atomic number down the group
5. The formation of the oxide ion O (2g-) requires (c) The reactivity decreases in the alkali metals
first an exothermic and then an endothermic step but increases in the halogens with increase
as shown below [2004] in atomic number down the group
O(g) + e - = O(g)
-
DHº = -142 kJmol -1 (d) In both the alkali metals and the halogens
O - (g) + e - = O (g)
2-
DHº = 844 kJmol -1 the chemical reactivity decreases with
This is because increase in atomic number down the group
(a) O– ion will tend to resist the addition of 9. In which of the following arrangements, the
another electron sequence is not strictly according to the
(b) Oxygen has high electron affinity property written against it? [2008]
(c) Oxygen is more elecronegative (a) HF < HCl < HBr , HI : increasing acid
strength
(d) O– ion has comparatively larger size than
oxygen atom (b) NH3 < PH3 < AsH3 <SbH3 : increasing
basic strength
6. Which of the following oxides is amphoteric in
(c) B < C < O < N : increasing first ionization
character? [2005]
enthalpy
(a) SnO2 (b) SiO 2
(d) CO2 < SiO2 < SnO2 < PbO2 : increasing
(c) CO2 (d) CaO oxidising power
 www.crackjee.xyz
Classification of Elements and Periodicity in Properties C-13
10. The correct sequence which shows decreasing Ca, Ba, S, Se and Ar ? [2013]
order of the ionic radii of the elements is (a) Ca < S < Ba < Se < Ar
[2010] (b) S < Se < Ca < Ba < Ar
(a) Al3+ > Mg 2+ > Na + > F- > O2- (c) Ba < Ca < Se < S < Ar
(b) Na + > Mg 2 + > Al3+ > O 2- > F- (d) Ca < Ba < S < Se < Ar
(c) Na + > F- > Mg2 + > O2 - > Al3+ 13. The ionic radii (in Å) of N3–, O2– and F– are
(d) O2 - > F- > Na + > Mg 2 + > Al3+ respectively : [JEE M 2015]
11. The correct order of electron gain enthalpy with (a) 1.71, 1.40 and 1.36
negative sign of F, Cl, Br and I, having atomic (b) 1.71, 1.36 and 1.40
number 9, 17, 35 and 53 respectively, is : (c) 1.36, 1.40 and 1.71
[2011RS] (d) 1.36, 1.71 and 1.40
(a) F > Cl > Br > I (b) Cl > F > Br > I 14. Which of the following atoms has the highest
(c) Br > Cl > I > F (d) I > Br > Cl > F first ionization energy? [JEE M 2016]
12. Which of the following represents the correct (a) K (b) Sc
order of increasing first ionization enthalpy for (c) Rb (d) Na

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14
(b) (d) (a) (d) (a) (a) (c) (b) (b) (d) (b) (c) (a) (b)

1. (b) According to modern periodic law, the SO 2 and P 2 O 3 are acidic as their
properties of the elements are repeated after corresponding acids H2SO3 and H3PO3 are
certain regular intervals when these strong acids.
elements are arranged in order of their 5. (a) O– ion exerts a force of repulsion on the
increasing atomic numbers. incoming electron. The energy is required
2. (d) Na2O (basic), SO2 and B2O3 (acidic) and to overcome it.
ZnO is amphoteric. 6. (a) CaO is basic as it form strong base Ca(OH)2
3. (a) O– – and F– are isoelectronic. Hence have on reaction with water.
same number of shells, therefore greater CaO + H2O –––––® Ca(OH)2
the nuclear charge smaller will be the size CO2 is acidic as it dissolve in water forming
i.e. unstable carbonic acid.
O– – > F– H2O + CO2 –––––® H2CO3
further Li + and B3+ are isoelectronic. Silica (SiO2) is insoluble in water and acts
therefore as a very weak acid.
Li+ > B3+ SnO2 is amphoteric as it reacts with both
Hence the correct order of atomic size is. acid and base.
O-- > F– > Li+ > B3+ SnO2 + 2H2SO4–––––® Sn(SO4)2 + 2H2O
4. (d) As the size increases the basic nature of SnO2 + 2KOH–––––® K2SnO3 + H2O
oxides changes to acidic nature i.e., acidic 7. (c) In a period the value of ionisation potential
nature increases. increases from left to right with breaks
SO 2 > P 2 O 3 > SiO 2 > Al 2 O 3 where the atoms have some what stable
Acidic Weak Amphoteric configuration. In this case N has half filled
acidic

www.crackjee.xyz
C-14
stable orbitals. Hence has highest
ionisation energy. Thus the correct order
is
B< C< O < N
and not as given in option (c)
8. (b) The alkali metals are highly reactive because
their first ionisation potential is very low
and hence they have great tendency to
loses electron to form unipositive ion.
NOTE On moving down group- I from
Li to Cs ionisation enthalpy decreases
hence the reactivity increases. The
halogens are most reactive elements due
to their low bond dissociation energy, high
electron affinity and high enthalpy of
hydration of halide ion. However their
reactivity decreases with increase in atomic
number
9. (b) In hydrides of 15th group elements, basic
character decreases on descending the
group i.e.
NH3 > PH3 > AsH3 > SbH3.
10. (d) All the given species contains 10 e– each
i.e. isoelectronic.
For isoelectronic species anion having
high negative charge is largest in size and
the cation having high positive charge is
smallest.
EBD_7764
Chemistry
11. (b) As we move down in a group electron gain
enthalpy becomes less negative because
the size of the atom increases and the
distance of added electron from the nucleus
increases. Negative electron gain enthalpy
of F is less than Cl. This is due to the fact
that when an electron is added to F, the
added electron goes to the smaller n = 2
energy level and experiences significant
repulsion from the other electrons present
in this level. In Cl, the electron goes to the
larger n = 3 energy level and consequently
occupies a larger region of space leading
to much less electron–electron repulsion.
So the correct order is
Cl > F > Br > I.
12. (c) On moving down a group size increases
hence ionisation enthalpy decreases,
hence Se < S and Ba < Ca. Further, Ar being
an inert gas has maximum IE.
13. (a) For isoelectronic species, size of anion in-
creases as negative charge increases. Thus
the correct order is
14. (b) Alkali metals have the lowest ionization
energy in each period on the other hand Sc
is a d - block element.
Transition metals have smaller atomic radii
and higher nuclear charge leading to high
ionisation energy.
 www.crackjee.xyz
Chemical Bonding and Molecular Structure C-15

4
Chemical Bonding and
Molecular Structure
1. In which of the following species the interatomic 7. The pair of species having identical shapes for
bond angle is 109° 28’? [2002] molecules of both species is [2003]
(a) NH3, (BF4) –1 +
(b) (NH4) , BF3 (a) XeF2, CO2 (b) BF3, PCl3
(c) NH3, BF4 (d) (NH2)–1, BF3. (c) PF5, IF5 (d) CF4, SF4
2. Which of the following are arranged in an 8. The correct order of bond angles (smallest first)
increasing order of their bond strengths? [2002] in H2S, NH3, BF3 and SiH4 is [2004]
(a) O2– < O2 < O2+ <O22– (a) H2S < NH3 < SiH4 < BF3
(b) O22– < O2– < O2 <O2+ (b) NH3 < H2S < SiH4 < BF3
(c) O2– < O22– < O2 <O2+ (c) H2S < SiH4 < NH3 < BF3
(d) O2+ < O2 < O2– <O22– (d) H2S < NH3 < BF3 < SiH4
3. Hybridisation of the underline atom changes in: 9. The bond order in NO is 2.5 while that in NO+ is 3.
[2002] Which of the following statements is true for
these two species ? [2004]
(a) AlH3 changes to AlH -4
(a) Bond length in NO+ is equal to that in NO
(b) H 2 O changes to H3O+ (b) Bond length in NO is greater than in NO+
(c) Bond length in NO+ is greater than in NO
(c) NH 3 changes to NH +4 (d) Bond length is unpredictable
(d) in all cases 10. The states of hybridization of boron and oxygen
4. An ether is more volatile than an alcohol having atoms in boric acid (H3BO3) are respectively
the same molecular formula. This is due to [2004]
[2003] (a) sp3 and sp2 (b) sp2 and sp 3
(a) alcohols having resonance structures (c) sp2 and sp2 (d) sp3 and sp3
(b) inter-molecular hydrogen bonding in ethers 11. Which one of the following has the regular
(c) inter-molecular hydrogen bonding in tetrahedral structure ? [2004]
alcohols (a) BF4- (b) SF4
(d) dipolar character of ethers
5. Which one of the following pairs of molecules (c) XeF4 (d) [ Ni(CN) 4 ]2 -
will have permanent dipole moments for both
(Atomic nos. : B = 5, S = 16, Ni =28, Xe = 54)
members ? [2003]
12. The maximum number of 90º angles between
(a) NO2 and CO2 (b) NO2 and O3
bond pair-bond pair of electrons is observed in
(c) SiF4 and CO2 (d) SiF4 and NO2 [2004]
6. Which one of the following compounds has the (a) dsp2 hybridization
smallest bond angle in its molecule ? [2003]
(b) sp3d hybridization
(a) OH2 (b) SH2
(c) dsp3 hybridization
(c) NH3 (d) SO2
(d) sp3d2 hybridization
 EBD_7764
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C-16 Chemistry
13. Lattice energy of an ionic compound depends 21. Which one of the following pairs of species
upon [2005] have the same bond order? [2008]
(a) Charge on the ion and size of the ion (a) CN– and NO+ (b) CN– and CN+
(b) Packing of ions only (c) O–2 and CN– (d) NO+ and CN+
(c) Size of the ion only 22. The bond dissociation energy of B – F in BF3 is
(d) Charge on the ion only 646 kJ mol–1 whereas that of C – F in CF4 is 515
14. Which of the following molecules/ions does not kJ mol–1. The correct reason for higher B – F
bond dissociation energy as compared to that of
contain unpaired electrons? [2006]
C – F is [2008]
+
(a) N2 (b) O2 (a) stronger s bond between B and F in BF3 as
compared to that between C and F in CF4.
(c) O 22 - (d) B2
(b) significant pp – pp interaction between B
15. In which of the following molecules/ions are all and F in BF3 whereas there is no possibility
the bonds not equal? [2006] of such interaction between C and F in CF4.
(a) XeF4 (b) BF4 – (c) lower degree of pp – pp interaction between
(c) SF4 (d) SiF4 B and F in BF3 than that between C and F
16. The decreasing values of bond angles from NH3 in CF4.
(106º) to SbH3 (101º) down group-15 of the (d) smaller size of B– atom as compared to that
periodic table is due to [2006] of C– atom.
(a) decreasing lp-bp repulsion 23. Using MO theory, predict which of the following
(b) decreasing electronegativity species has the shortest bond length? [2008]
(c) increasing bp-bp repulsion (a) O +2 (b) O 2–
(d) increasing p-orbital character in sp3 (d) O 2+
(c) O 2–
2 2
17. Which of the following species exhibits the
24. The number of types of bonds between two
diamagnetic behaviour? [2007]
carbon atoms in calcium carbide is : [2011RS]
(a) NO (b) O2 2–
(a) One sigma, One pi (b) Two sigma, one pi
(c) O2+ (d) O2.
(c) Two sigma, two pi (d) One sigma, two pi
18. The charge/size ratio of a cation determines its
25. Ortho-Nitrophenol is less soluble in water than
polarizing power. Which one of the following
p- and m- Nitrophenols because : [2012]
sequences represents the increasing order of
the polarizing power of the cationic species, K+, (a) o-Nitrophenol is more volatile steam than
Ca2+, Mg2+, Be2+? [2007] those of m- and p-isomers.
(a) Ca2+ < Mg2+ < Be+ < K+ (b) o-Nitrophenol shows intramolecular
H-bonding
(b) Mg2+ < Be2+ < K+ < Ca2+
(c) o-Nitrophenol shows intermolecular
(c) Be2+ < K+ < Ca2+ < Mg2+
H-bonding
(d) K+ < Ca2+ < Mg2+ < Be2+.
(d) Melting point of o-Nitrophenol is lower
19. In which of the following ionization processes, than those of m- and p-isomers.
the bond order has increased and the magnetic
26. In which of the following pairs the two species
behaviour has changed? [2007]
are not isostructural ? [2012]
(a) N 2 ® N2 + (b) C2 ® C2 + - +
(a) CO23 - and NO3 (b) PCl 4 and SiCl4
(c) NO ® NO + (d) O 2 ® O 2 + .
20. Which of the following hydrogen bonds is the (c) PF5 and BrF5 (d) AlF63 - and SF6
strongest? [2007] 27. Which one of the following molecules is
(a) O – H - - - F (b) O – H - - - H expected to exhibit diamagnetic behaviour ?
(c) F – H - - - F (d) O – H - - - O. [2013]
 www.crackjee.xyz
Chemical Bonding and Molecular Structure C-17
(a) C2 (b) N2 (a) It is diamagnetic in gaseous state
(c) O2 (d) S2 (b) It is neutral oxide
28. Which of the following is the wrong statement (c) It combines with oxygen to form nitrogen
[2013] dioxide
(a) ONCl and ONO– are not isoelectronic. (d) It’s bond order is 2.5
(b) O3 molecule is bent 31. The species in which the N atom is in a state of
(c) Ozone is violet-black in solid state sp hybridization is : [JEE M 2016]
(d) Ozone is diamagnetic gas. (a) NO 3- (b) NO 2
29. In which of the following pairs of molecules/
ions, both the species are not likely to exist ? (c) NO +2 (d) NO 2-
[2013] 32. Which of the following species is not
+ 2 - - 2-
(a) H 2 , He 2 (b) H 2 , He 2 paramagnetic ? [JEE M 2017]
(c) H 22 + , He2 (d) H -2 , He 22 + (a) NO (b) CO
30. Which one of the following properties is not (c) O2 (d) B2
shown by NO? [2014]

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

1. (a) In NH3 and BF4- the hybridisation is sp3 1

Bond order = (8 –6 ) = 1
2
and the bond angle is almost 109º 28'.
2. (b) O2+ (15) = KK s 2s2, s* 2s2, s 2px2 , NOTE As we know that as the bond order

{p2py2 = p2p2z , {p* 2 p1y =p2p0z decreases, stability also decreases and
hence the bond strength also decreases.
1 5 Hence the correct order of their increasing
Bond order = (8–3) = = 2.5
2 2 bond strength is
O2 (16) = KK s 2s2, s* 2s2, s 2px2,
O 22 - < O2– < O2 < O2+
{ p2py2 = p2pz2,{ p* 2py1 = p* 2pz1
3. (a)
1
Bond order = (8 – 4) = 2
2 é æ No. of electronsö
O2– (17) = KK s 2s2, s* 2s2, s 2px2, 1 êç ÷+
{p2py2 = p2pz2,{p* 2py2 = p* 2pz1 Hybridisation =
2 ê ç in valence ÷
ê è shell of atom ø
1 ë
Bond order = (8 – 5) = 1.5
2 æ No.of monovalentö æ charge on ö
– ç +
O22– (18) = KK s 2s2 s* 2s2 s2px2, çè atoms around it ÷ø è cation ÷ø
{p2py2 = p 2pz2,{p* 2py2 = p* 2pz2
 EBD_7764
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C-18 Chemistry
9. (b) Now since bond order of NO+ given (3) is
æ charge on ö higher than that of NO (2.5). Thus bond
çè anion ÷ø length of NO+ will be shorter.
(a) For AlH3, 10. (b) H 3
O sp
Hybridisation of Al atom = 1 [ 3 + 3 - 0 + 0]
2
= 3 = sp2
For AlH4–, B sp
2

Hybridisation of Al atom = 1 [ 3 + 4 - 0 + 1]
2
= 4 = sp3
sp3 O O
H
(b) For H2O, sp3
Hybridisation of O atom H
1
= [ 6 + 2 - 0 + 0] = 4 = sp3
2
For H3O+, Hybridisation of O atom
11. (a) XeF4 (sp3d 2 square planar),

1 [ Ni(CN) 4 ]2 - (dsp2 square planar ),

=
2
[ 6 + 3 - 1 + 0] = 4 = sp3
BF4- (sp3 tetrahedral), SF4 (sp3d see saw
(c) For NH3
shaped)
Hybridisation of N atom
12. (d)
1
= [ 5 + 3 - 0 + 0] = 4 = sp3
2 M
For NH +4 , Hybridisation of N atom

1
=
2
[ 5 + 4 - 1 + 0] = 4 = sp3
Thus hybridisation changes only in
option (a).
4. (c) In ether, there is no H-bonding while
alcohols have intermolecular H-bonding
5. (b) Both NO2 and O3 have angular shape and dsp2 hybridisation sp 3 d or dsp 3
hybridisation
hence will have net dipole moment.
Number of 90° angle Number of 90°
6. (b) In H2S, due to low electronegativity of
angle
sulphur the L.P. - L. P. repulsion is more
between bonds = 4 between bonds = 6
than B. P. - B. P. repulsion and hence the
bond angle is minimum.
SO 2 H 2 O H 2S NH3
Bond angle 119.5° 104.5° 92.5° 106.5°
7. (a) Both XeF2 and CO2 have a linear structure.
F — Xe — F O=C=O
8. (a) The order of bond angles sp3d2 hybridisation
BF3 > SiH 4 > NH 3 > H 2S Number of 90° angle
120º 109º 28¢ 107 º 92.5º between bonds = 12
 www.crackjee.xyz
Chemical Bonding and Molecular Structure C-19
13. (a) The value of lattice energy depends on the more unpaired electrons as in
charges present on the two ions and the O2 ® s1s2 , s*1s 2 , s2 s2 , s* 2s 2 , s2 px2 ,
distance between them.
14. (c) The distribution of electrons in MOs is as {p 2 p 2y = p 2 pz2 ,
follows :
{ p* 2 p1y = p* 2 p1z - 2 unpaired electrons
N 2 + (electr ons 13) s 2 s *2 s 2 s *2
p2 s1 p* s*
p2 p* O+2 ® s1s 2 , s*1s 2 , s2s 2 , s* 2s 2 , s2 p 2,
x

O2 (electrons 16) s2 s*2 s2 s*2 s2 p2 { p 2 p 2y = p 2 p z2 {p *

2 p1y = p * 2 pz0 - 1 unpaired electron
p2
unpaired electron
p*1 s*
p*1 NO ® s1s 2 , s*1s 2 , s 2 s 2 , s* 2 s 2 , s2 p 2 ,
x
2
O22– (electrons 18) s2 s*2 s2 s*2 s2 p 2
p p 2 p z2 , {p* 2 p1y = p* 2 p 0z - 1 unpaired electron
p* s* 18. (d) Smaller the size and higher the charge more
p* will be polarising power of cation. Since
1 the order of the size of cation is
B2 (electrons 10) s2 s*2 s2 s*2 p1
p K + > Ca ++ > Mg ++ > Be++ . So the
Only O22– does not contain any unpaired correct order of polarising power is
electron. K+ < Ca2+ < Mg2+ < Be2+
15. (d) In SF4 the hybridisation is sp3d and the 19. (c) (a) N2 : bond order 3, paramagnetic
shape of molecule is N2– : bond order, 2.5, paramagnetic
F (b) C2 : bond order 2, diamagnetic
F C2+ : bond order 1.5, paramagnetic
S (c) NO : bond order 2.5, paramagnetic
NO+ : bond order 3, diamagnetic
F (d) O2 : bond order 2, paramagnetic
F
16. (b) The bond angle decreases on moving down O2+ : bond order 2.5, paramagnetic
the group due to decrease in bond pair- 20. (c) NOTE Greater the difference between
bond pair repulsion.
NH3 PH3 ASH3 SbH3 BiH3 electro-negativity of bonded atoms,
107º 94º 92º 91º 90º stronger will be bond. Since F is most
electronegative hence F – H ...... F is the
NOTE This can also be explained by the strongest bond.
fact that as the size of central atom increases 21. (a) For any species to have same bond order
sp3 hybrid orbital becomes more distinct we can expect them to have same number
with increasing size of central atom i.e. pure of electrons. Calculating the number of
p- orbitals are utilized in M–H bonding electrons in various species.
17. (b) Diamagnetic species have no unpaired O2– (8 + 8 + 1 = 17) ; CN - (6 + 7 + 1 = 14)
electrons
NO+(7 + 8 – 1= 14); CN+ (6 + 7 –1 = 12)
2 We find CN– and NO+ both have 14
O 2 2- Þ s1s2, s*1s2, s2s2, s*2s2, s 2 px ,
{p2py2 = p2pz2, {p*2py2 = p*2pz2 electrons so they have same bond order.
Whereas paramagnetic species has one or Correct answer is (a).
 EBD_7764
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C-20 Chemistry
22. (b) NOTE The delocalised pp - pp {p 2p2y = p 2pz2 } s 2 p2x
bonding between filled p-orbital of F and Thus M.O. configuration suggests that it
vacant p-orbital of B leads to shortening contains one s & 2p bonds.
of B–F bond length which results in higher 25. (b) Compounds involved in chelation become
bond dissociation energy of the B–F bond. non-polar. Consequently such compounds
are soluble in non-polar solvents like ether,
benzene etc. and are only sparingly soluble
in water whereas meta and para isomers
F are more soluble in water & less soluble in
B F non-polar solvents.
F H
O O
Å
Vacant Filled N
2p-orbital 2p -orbital O intra-molecular H-bonding

F F 26. (c) PF5 trigonal bipyramidal

+
B=F B–F
+
F
F F F
+1/3
F P
+
F F F
+1/3
B–F B F F
+1/3
F F BrF5 square pyramidal (distorted)
23. (d) Bond order
F
No.of bonding electrons - No.of antibonding electrons F F
=
2 Br
10 - 5 F F
+
Bond order in O2 = = 2.5
2
27. (a, b) The molecular orbital structures of C2 and
- 10 - 7
Bond order in O 2 = = 1.5 N2 are
2
10 - 8
Bond order in O 22 - = =1 N2 = s1s2 s *1s2 s2s2 s *2s 2 s2 px2p2 py2p2 pz2
2
10 - 4
Bond order in O 22 + = =3
2 C2 = s1s 2 s *1s 2 s 2s 2 s * 2s 2 p2 py 2 p 2 Pz2
1 Both N2 and C2 have paired electrons,
Since Bond order µ hence they are diamagnetic.
Bond length
28. All options are correct,
\ Bond length is shortest in O 22 + .
24. (d) Calcium carbide exists as Ca2+ and C22–.
(a) ONCl = 8 + 7 + 17 = 32e - ü not
- - ý isoelectronic
According to the molecular orbital model, ONO = 8 + 7 + 8 + 1 = 24e þ
C 2 2– should have molecular orbital ..
configuration : (b) 7 8Å O 1.278A°
1. 2 The central atom is sp 2
s1s2 s *1s2 s 2s2 s *2s2 O 116.8° O hybridized with one lone pair.
 www.crackjee.xyz
Chemical Bonding and Molecular Structure C-21
(c) It is a pale blue gas. At – 249.7°, it forms violet NO+2 = i.e. sp hybridisation
black crystals. NO–2 = i.e. sp2 hybridisation
NO–3 = i.e. sp2 hybridisation
(d) It is diamagnetic in nature due to absence of The lewis structure of NO2 shows a bent mo-
unpaired electrons. lecular geometry with trigonal planar electron
29. (c) H2+ 0
2 = s1s s*1s
0 pair geometry hence the hybridization will be
sp 2
1
Bond order for H2+
2 =
(0 - 0) = 0 32. (b)
2
He2 = s1s2s*1s2 1. NO ® one unpaired electron is present in p*
molecular orbit hence paramagnetic.
1
Bond order for He2 = (2 - 2) = 0 2 *2 2 *2 2 2 2
2 2. CO ® s1s , s1s , s2s , s2s , p2p x , p2p y , s2pz
so both H22+ and He2 does not exist.
30. (a) Nitric oxide is paramagnetic in the gaseous no unpaired electron hence diamagnetic.
state because of the presence of one 2 *2 2 *2 2 2 2 *1 *1
3. O2® s1s , s1s , s2s , s2s , s2pz , p2px , p2p y , p2p x , p2p y
unpaired electron in its outermost shell.
The electronic configuration of NO is two unpaired electron hence paramagnetic.
s12s s1*2s s 22 s s*2 2 2
2s s2 pz p2 px = p22 p y p*1 2 *2 2 *2 1 1
2 px 4. B2 ® s1s , s1s , s2s , s2s , p2p x , p2p y
31. (c) Hybridization (H) = [no. of valence electrons
of central atom + no. of Monovalent atoms at- B2 contains two unpaired electrons hence
tached to it + (–ve charge if any) – (+ve charge paramagnetic
if any)]
 EBD_7764
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C-22 Chemistry

States of Matter
5
1. For an ideal gas, number of moles per litre in 7. Which one of the following statements is NOT
terms of its pressure P, gas constant R and true about the effect of an increase in temperature
temperature T is [2002] on the distribution of molecular speeds in a gas?
(a) PT/R (b) PRT [2005]
(c) P/RT (d) RT/P. (a) The area under the distribution curve
2. Value of gas constant R is [2002] remains the same as under the lower
(a) 0.082 litre atm temperature
(b) 0.987 cal mol–1 K–1 (b) The distribution becomes broader
(c) 8.3 J mol–1 K–1 (c) The fraction of the molecules with the most
probable speed increases
(d) 83 erg mol–1 K–1.
(d) The most probable speed increases
3. Kinetic theory of gases proves [2002]
8. If 10–4 dm3 of water is introduced into a 1.0 dm3
(a) only Boyle’s law
flask at 300 K, how many moles of water are in
(b) only Charles’ law the vapour ph ase when equilibrium is
(c) only Avogadro’s law established ? [2010]
(d) all of these. (Given : Vapour pressure of H2O at 300 K is 3170
4. According to the kinetic theory of gases, in an Pa; R = 8.314 J K–1 mol–1)
ideal gas, between two successive collisions a (a) 5.56× 10–3 mol (b) 1.53 × 10–2 mol
gas molecule travels [2003] (c) 4.46 × 10 mol (d) 1.27 × 10–3 mol
–2
(a) in a wavy path 9. When r, P and M represent rate of diffusion,
(b) in a straight line path pressure and molecular mass, respectively, then
(c) with an accelerated velocity
the ratio of the rates of diffusion (rA / rB ) of
(d) in a circular path
two gases A and B, is given as [2011RS]
5. As the temperature is raised from 20ºC to 40ºC,
the average kinetic energy of neon atoms (a) ( PA / PB ) ( M B / M A )1/ 2
changes by a factor of which of the following ? (b) ( PA / PB )1/ 2 ( M B / M A )
[2004]
(c) ( PA / PB ) ( M A / M B )1/ 2
(a) 313 (b) (313 / 293)
293 (d) ( PA / PB )1/ 2 ( M A / M B )
(c) 1 (d) 2 10. The molecular velocity of any gas is : [2011RS]
2
(a) inversely proportional to absolute
6. In van der Waals equation of state of the gas temperature.
law, the constant ‘b’ is a measure of [2004] (b) directly proportional to squar e of
(a) volume occupied by the molecules temperature.
(b) intermolecular attraction (c) directly proportional to square root of
(c) intermolecular repulsions temperature.
(d) intermolecular collisions per unit volume (d) inversely proportional to the square root
 www.crackjee.xyz
States of Matter C-23
of temperature. 14. The ratio of masses of oxygen and nitrogen in a
11. The compressibility factor for a real gas at high particular gaseous mixture is 1 : 4. The ratio of
pressure is : [2012] number of their molecule is: [2014]
RT (a) 1 : 4 (b) 7 : 32
(a) 1 + (b) 1 (c) 1 : 8 (d) 3 : 16
pb
15. The intermolecular interaction that is dependent
pb pb on the inverse cube of distance between the
(c) 1 + (d) 1 – molecules is : [JEE M 2015]
RT RT
12. For gaseous state, if most probable speed is (a) London force
denoted by C*, average speed by C and mean (b) hydrogen bond
square speed by C, then for a large number of (c) ion - ion interaction
molecules the ratios of these speeds are: (d) ion - dipole interaction
[2013] 16. Two closed bulbs of equal volume (V) contain-
ing an ideal gas initially at pressure pi and tem-
(a) C* : C : C = 1.225 : 1.128 : 1
perature T1 are connected through a narrow
(b) C* : C : C = 1.128 : 1.225 : 1
tube of negligible volume as shown in the figure
(c) C* : C : C = 1 : 1.128 : 1.225 below. The temperature of one of the bulbs is
(d) C* : C : C = 1 : 1.225 : 1.128 then raised to T2. The final pressure pf is :
13. If Z is a compressibility factor, van der Waals [JEE M 2016]
equation at low pressure can be written as:
[2014] æ T ö æ T T ö
(a) 2 pi ç 2 ÷ (b) 2 pi ç 1 2 ÷
è T1 + T2 ø è T1 + T2 ø
RT a
(a) Z = 1+ (b) Z =1-
Pb VRT æ T T ö æ T1 ö
(c) pi ç 1 2 ÷ (d) 2 pi ç ÷
Pb Pb è T1 + T2 ø è T1 + T2 ø
(c) Z = 1- (d) Z = 1+
RT RT

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(c) (c) (d) (b) (a) (a) (c) (d) (a) (c) (c) (c) (b) (b) (b)
16
(a)

1. (c) PV = nRT (number of moles = n/V) with the walls of the container and between
\ n/V = P/RT.. two successive collisions molecules travel
2. (c) Value of gas constant in a straight line path but show haphazard
( R ) = 0.0821L atm K–1 mol–1 motion due to collisions.
= 8.314 × 107 ergs K–1mol–1 3
= 8.314JK–1mol–1 = 1.987 cal K–1 mol–1 K ´ 313
K .E of neon at 40 °C 313
3. (d) Kinetic theory of gases proves all the given 5. (a) = 2 =
gas laws. K.E of neon at 20°C 3 293
K ´ 293
4. (b) According to kinetic theory the gas 2
molecules are in a state of constant rapid 6. (a) In van der waals equation ‘b’ is for volume
motion in all possible directions colloiding correction
in a random manner with one another and 7. (c) Distribution of molecular velocities at two
different temperature is given shown below.
 EBD_7764
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C-24 Chemistry
Most probable 8RT
Fraction of molecules velocity Average Speed (C) =
pM
300 K 3RT
Root mean square velocity (C) =
M
600 K
2RT 8RT 3RT
V C*: C : C = : :
M pM M
Molecular velocity
4 3
NOTE At higher temperature more = 1: : = 1:1.128 :1.225
p 2
molecules have higher velocities and less PV
molecules have lower velocities. 13. (b) Compressibility factor ( Z ) =
As evident from fig. thus it is clear that RT
(For one mole of real gas)
With the increase in temperature the most van der Waals equation
probable velocity increase butthe fraction a
of such molecules decreases. (P + )(V - b ) = RT
8. (d) From the ideal gas equation : V2
At low pressure, volume is very large and
PV = nRT
hence correction term b can be neglected
PV 3170 ´ 10-3 in comparison to very large volume of V.
or n = = = 1.27 × 10–3
RT 8.314 ´ 300 i.e. V - b » V
P æ a ö
9. (a) r µ
m çè P + 2 ÷ø V = RT
V
rA PA M B a
= PV + = RT
rB PB M A V
10. (c) The different type of molecular velocities a
possessed by gas molecules are PV = RT -
V
2RT PV a
(i) Most probable velocity (a) = = 1-
M RT VRT
2RT a
(ii) Average velocity v = Hence, Z = 1 -
M VRT
(iii) Root mean square velocity in all three w
3RT
14. (b) Number of moles of O 2 =
cases v = 32
M 4w w
In all the above cases Number of moles of N 2 = =
28 7
Velocity × T
a
\ Ratio = w : w = 7 : 32
æ a ö 32 7
11. (c) çè P + 2 ÷ø (V - b) = RT at high pressure 2
V V 15. (b) Hydrogen bond is a type of strong
can be neglected electrostatic dipole-dipole interaction and
PV – Pb = RT and PV = RT + Pb dependent on the inverse cube of distance
PV Pb between the molecular ion-dipole
= 1+ interaction.
RT RT 16. (a) For a given mass of an ideal gas, the
Pb volume and amount (moles) of the gas are
Z = 1+ ; Z > 1 at high pressure
RT directly proportional if the temperature and
pressure are constant. i.e
2RT Hence in the given case.
12. (c) Most probable speed (C*) = Initial moles and final moles are equal
M
(nT)i = (nT)f
 www.crackjee.xyz
Thermodynamics C-25

Thermodynamics
6
1. If an endothermic reaction is non-spontaneous change for the reaction
at freezing point of water and becomes feasible H 2 C = CH 2 (g) + H 2 (g) ® H 3C — CH 3 (g) a t
at its boiling point, then [2002] 298 K will be [2003]
(a) DH is –ve, DS is +ve (a) – 250 kJ (b) + 125 kJ
(b) DH and DS both are +ve (c) – 125 kJ (d) + 250 kJ
(c) DH and DS both are –ve 7. In an irreversible process taking place at constant
(d) DH is +ve, DS is -ve T and P and in which only pressure-volume work
2. A heat engine abosrbs heat Q1 at temperature is being done, the change in Gibbs free energy
T1 and heat Q2 at temperature T2. Work done (dG) and change in entropy (dS), satisfy the criteria
by the engine is J (Q1 + Q2). This data [2002] [2003]
(a) violates 1st law of thermodynamics (a) (dS)V, E > 0, (dG)T, P < 0
(b) violates 1st law of themodynamics if Q1 is –ve (b) (dS)V, E = 0, (dG)T, P = 0
(c) (dS)V, E = 0, (dG)T, P > 0
(c) violates 1st law of thermodynamics of Q2 is –ve
(d) (dS)V, E < 0, (dG)T, P < 0
(d) does not violate 1st law of themodynamics.
8. The correct relationship between free energy
3. For the reactions, [2002] change in a reaction and the corresponding
2C + O2 ® 2 CO2 ; DH = -393 J equilibrium constant Kc is [2003]
2Zn + O2 ® 2ZnO ; DH = -412 J (a) – DG = RT ln Kc (b) DGº = RT ln Kc
(a) carbon can oxidise Zn (c) – DGº = RT ln Kc (d) DG = RT ln Kc
(b) oxidation of carbon is not feasible 9. The enthalpy change for a reaction does not
(c) oxidation of Zn is not feasible depend upon [2003]
(d) Zn can oxidise carbon. (a) use of different reactants for the same
4. The heat required to raise the temperature of product
body by 1 K is called [2002] (b) the nature of intermediate reaction steps
(a) specific heat (b) thermal capacity (c) the differences in initial or final
(c) water equivalent (d) none of these. temperatures of involved substances
5. The internal energy change when a system goes (d) the physical states of reactants and
products
from state A to B is 40 kJ/mole. If the system goes
10. An ideal gas expands in volume from 1×10–3 to
from A to B by a reversible path and returns to
1 × 10–2 m3 at 300 K against a constant pressure
state A by an irreversible path what would be the
of 1×105 Nm–2. The work done is [2004]
net change in internal energy ? [2003]
(a) 270 kJ (b) – 900 kJ
(a) > 40 kJ (b) < 40 kJ
(c) – 900 (d) 900 kJ
(c) Zero (d) 40 kJ
11. The enthalpies of combustion of carbon and
6. If at 298 K the bond energies of C — H, C — C, carbon monoxide are – 393.5 and – 283 kJ mol–1
C = C and H — H bonds are respectively 414, respectively. The enthalpy of formation of
347, 615 and 435 kJ mol–1, the value of enthalpy carbon monoxide per mole is [2004]
 EBD_7764
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C-26 Chemistry
(a) – 676.5 kJ (b) 676.5 kJ Cl2(g) = 2Cl(g), 242.3 kJ mol–1
(c) 110.5 kJ (d) – 110.5 kJ I2(g) = 2I(g), 151.0 kJ mol–1
12. Consider the reaction : N 2 + 3H 2 ® 2 NH 3 ICl(g) = I(g) + Cl(g), 211.3 kJ mol–1
carried out at constant temperature and I2(s) = I2(g), 62.76 kJ mol–1
pressure. If DH and DU are the enthalpy and Given that the standard states for iodine and
chlorine are I2 (s) and Cl 2 (g), the standard
internal energy changes for the reaction, which
enthalpy of formation for ICl(g) is : [2006]
of the following expressions is true ? [2005] –1
(a) +16.8 kJ mol (b) +244.8 kJ mol–1
(a) DH > DU (b) DH < DU
(c) –14.6 kJ mol–1 (d) –16.8 kJ mol–1
(c) DH = DU (d) DH = 0
17. (DH – DU) for the formation of carbon monoxide
13. If the bond dissociation energies of XY,
(CO) from its elements at 298 K is [2006]
X 2 and Y2 (all diatomic molecules) are in the (R = 8.314 J K–1 mol–1)
ratio of 1 : 1 : 0.5 and DHf for the formation of XY (a) –2477.57 J mol–1 (b) 2477.57 J mol–1
is – 200 kJ mole -1 . The bond dissociation (c) –1238.78 J mol–1 (d) 1238.78 J mol–1
energy of X 2 will be [2005] 18. In conversion of lime-stone to lime,
CaCO3(s) ® CaO(s) + CO2(g) the values of
-1
(a) 400 kJ mol (b) 300 kJ mol -1
DH° and DS° are + 179.1 kJ mol-1 and 160.2 J/K
-1 -1 respectively at 298 K and 1 bar. Assuming that
(c) 200 kJ mol (d) 100 kJ mol
14. An ideal gas is allowed to expand both reversibly DH° and DS° do not change with temperature,
and irreversibly in an isolated system. If Ti is temperature above which conversion of
the initial temperature and T f is the final limestone to lime will be spontaneous is[2007]
temperature, which of the following statements (a) 1118 K (b) 1008 K
is correct? [2006] (c) 1200 K (d) 845 K.
(a) (Tf)rev = (Tf)irrev 19. Assuming that water vapour is an ideal gas, the
(b) Tf = Ti for both reversible and irreversible
processes internal energy change (DU) when 1 mol of
(c) (Tf)irrev > (Tf)rev water is vapourised at 1 bar pressure and 100°C,
(d) Tf > Ti for reversible process but Tf = Ti (given : molar enthalpy of vapourisation of water
for irreversible process at 1 bar and 373 K = 41 kJ mol–1 and R = 8.3 J
15. The standard enthalpy of formation (DfHº) at mol–1 K–1) will be [2007]
298 K for methane, CH4 (g) is –74.8 kJ mol–1. (a) 41.00 kJ mol–1 (b) 4.100 kJ mol–1
The additional information required to determine (c) 3.7904 kJ mol–1 (d) 37.904 kJ mol–1
the average energy for C – H bond formation 20. Identify the correct statement regarding a
would be [2006] spontaneous process: [2007]
(a) the first four ionization energies of carbon (a) Lowering of energy in the process is the
and electron gain enthalpy of hydrogen only criterion for spontaneity.
(b) the dissociation energy of hydrogen (b) For a spontaneous process in an isolated
molecule, H2 system, the change in entropy is positive.
(c) the dissociation energy of H2 and enthalpy (c) Endothermic processes are never
of sublimation of carbon spontaneous.
(d) latent heat of vapourization of methane (d) Exothermic processes are always
16. The enthalpy changes for the following spontaneous.
processes are listed below : [2006] 21. Oxidising power of chlorine in aqueous solution
 www.crackjee.xyz
Thermodynamics C-27
can be determined by the parameters indicated 26. The value of enthalpy change (DH) for the
below: reaction
1
D H Q C2 H5OH(l) + 3O2 (g) ®
1 2 diss D eg HQ
Cl2 (g) ¾¾¾¾¾ ® Cl(g) ¾¾¾¾ ® Cl– (g)
2 2CO 2 (g) + 3H 2O(l)
D Q
H at 27° C is – 1366.5 k J mol–1. The value of internal
Hyd
¾¾¾¾ ® Cl– (aq) energy change for the above reaction at this
(using the data, temperature will be : [2011RS]
–1
D diss H Cl = 240 kJ mol , (a) – 1369.0 kJ (b) – 1364.0 kJ
2
–1
(c) – 1361.5 kJ (d) – 1371.5 kJ
D eg H Cl = –349 kJ mol , 27. Consider the reaction :
–1
D hyd H Cl – = –381 kJ mol ), will be [2008] 4NO2 (g) + O 2 (g) ® 2N 2 O5 (g),
DrH = – 111 kJ.
(a) + 152 kJ mol–1 (b) – 610 kJ mol–1
If N2O5(s) is formed instead of N2O5(g) in the
(c) – 850 kJ mol–1 (d) + 120 kJ mol–1
above reaction, the DrH value will be :
22. Standard entropy of X2, Y2 and X Y3 are 60, 40
(given, DH of sublimation for N2O5 is 54 kJ
and 50 J K–1 mol –1 , respectively. For the
mol–1) [2011RS]
reaction,
(a) + 54 kJ (b) + 219 kJ
1 3 (c) – 219 J (d) – 165 kJ
X 2 + Y2 ® XY3 , DH = –30kJ , to be at
2 2 28. The incorrect expression among the following
equilibrium, the temperature will be [2008]
is: [2012]
(a) 1250 K (b) 500 K
(c) 750 K (d) 1000 K DGsystem
(a) = -T
23. On the basis of the following thermochemical DStotal
+
data : (Δ f G°H (aq) = 0) [2009] (b) In isothermal process,
+ –
H 2 O(l ) ® H (aq) + OH (aq); DH = 57.32kJ V
wreversible = –nRT ln f
1 Vi
H2 (g)+ O2 (g) ¾¾ ® H2 O(l); ΔH=–286.20kJ
2
The value of enthalpy of formation of OH– ion DHº -TDSº
(c) ln K =
at 25° C is: RT
(a) –228.88 kJ (b) +228.88 kJ (d) K = e–DGº/RT
(c) –343.52 kJ (d) –22.88 kJ 29. A piston filled with 0.04 mol of an ideal gas
24. The standard enthalpy of formation of NH3 expands reversibly from 50.0 mL to 375 mL at a
is – 46.0 kJ mol–1. If the enthalpy of formation constant temperature of 37.0ºC. As it does so, it
of H2 from its atoms is – 436 kJ mol–1 and that of
absorbs 208 J of heat. The values of q and w for
N2 is – 712 kJ mol–1, the average bond enthalpy
the process will be: [2013]
of N – H bond in NH3 is [2010]
(R = 8.314 J/mol K) (ln 7.5 = 2.01)
(a) – 964 kJ mol–1 (b) + 352 kJ mol–1
(c) + 1056 kJ mol–1 (d) – 1102 kJ mol–1 (a) q = + 208 J, w = – 208 J
25. For a particular reversible reaction at (b) q = – 208 J, w = – 208 J
temperature T, DH and DS were found to be both (c) q = – 208 J, w = + 208 J
+ve. If Te is the temperature at equilibrium, the (d) q = + 208 J, w = + 208 J
reaction would be spontaneous when 30. For complete combustion of ethanol,
(a) Te > T (b) T > Te [2010] C2 H5 OH ( l ) + 3O2 ( g ) ¾¾
® 2CO2 ( g ) + 3H 2 O ( l ) ,
(c) Te is 5 times T (d) T = Te
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C-28 Chemistry
the amount of heat produced as measured in 32. The heats of combustion of carbon and carbon
bomb calorimeter, is 1364.47 kJ mol–1 at 25ºC. monoxide are –393.5 and –283.5 kJ mol–1,
respectively. The heat of formation (in kJ) of
Assuming ideality the enthalpy of combustion, carbon monoxide per mole is : [JEE M 2016]
DcH, for the reaction will be: (a) –676.5 (b) – 110.5
(R = 8.314 kJ mol–1) [2014] (c) 110.5 (d) 676.5
33. DU is equal to [JEE M 2017]
(a) -1366.95 kJ mol-1
(a) Isochoric work (b) Isobaric work
(b) -1361.95 kJ mol-1 (c) Adiabatic work (d) Isothermal work
34. Given [JEE M 2017]
(c) -1460.95 kJ mol-1
C(graphite) + O2(g) ® CO2(g) ;
(d) -1350.50 kJ mol-1 DrH° = –393.5 kJ mol–1
31. The following reaction is performed at 298 K.
[JEE M 2015] 1
H2 (g) + O (g) ® H2O(l) ; DrH° = –285.8 kJ
2NO(g) + O2(g) 2NO2(g) 2 2
The standard free energy of formation of NO(g) mol–1
is 86.6 kj/mol at 298 K. What is the standard free CO2(g) + 2H2O(l) ® CH4(g) + 2O2(g);
energy of formation of NO2(g) at 298 K? DrH° = + 890.3 kJ mol–1
(Kp = 1.6 × 1012) Based on the above thermochemical equations,
(a) 86600 – the value of DrH° at 298 K for the reaction
(b) 0.5[2 × 86,600 – R(298) ln(1.6 × 1012)] C(graphite) + 2H2(g) ® CH4(g) will be :
(c) R(298) ln(1.6 × 1012) – 86600 (a) + 74.8 kJ mol–1 (b) + 144.0 kJ mol–1
(d) 86600 + R(298) ln(1.6 × l012) (c) – 74.8 kJ mol–1 (d) – 144.0 kJ mol–1

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

1. (b) DG = DH – TDS 2. (a) According to first law of thermodynamics

Since DG = DH – TDS for an endothermic
reaction,
DH = +ve and at low temperature D S = + ve
Hence DG = (+) DH – T ( + )DS
and if T D S < DH (at low temp)
DG = +ve (non spontaneous)
But at high temperature, reaction becomes
spontaneous i.e. DG = –ve.
because at higher temperature TDS > DH.
energy can n either be created n or
destroyed although it can be converted
from one form to another.
NOTE Carnot cycle is based upon this
principle but during the conversion of heat
into work some mechanical energy is
always converted to other form of energy
hence this data violates 1st law of
thermodynamics.
 www.crackjee.xyz
Thermodynamics C-29
3. (d) DH negative shows that the reaction is 13. (N) X 2 + Y2 ¾¾® 2 XY , DH = 2(–200).
spontaneous. Higher negative value for Zn Let x be the bond dissociation energy of
shows that the reaction is more feasible. X2. Then
4. (b) The heat required to raise the temperature
of body by 1K is called thermal capacity or DH = -400 = x x - x + x y - y - 2x x - y
heat capacity. = x + 0.5 x – 2 x = -0.5 x
5. (c) For a cyclic process the net change in the
internal energy is zero because the change 400
or x = = 800 kJ mol -1
in internal energy does not depend on the 0.5
path. (In the question paper, this option was not
reversible path mentioned. So the answer has been marked ‘N’)
14. (c) NOTE In a reversible process the work
A B done is greater than in irreversible process.
Hence the heat absorbed in reversible
process would be greater than in the latter
irreversible path case. So
Tf (rev.) < Tf (irr.)
6. (c) CH2 = CH2 (g) + H2 (g) ® CH3 - CH3 15. (c) The standard enthalpy of formation of CH4
Enthalpy change = Bond energy of is given by the equation :
reactants – Bond energy of products. C (s ) + 2 H 2 (g ) ¾
¾® CH 4 (g )
D H = 1(C = C) + 4 (C – H) + 1 (H- H) - 1 (C - C) Hence, dissociation energy of hydrogen
- 6 (C - H) and enthalpy of sublimation of carbon is
= 1 (C = C) + 1 ( H – H) – 1 (C – C) – 2 (C– H) required.
= 615 + 435 – 347 – 2 × 414 = 1050 – 1175 = 16. (a) I 2 (s) + Cl 2 (g) ¾¾
® 2ICl(g)
–125 kJ.
DA = [DHI2(s) ®I2(g) + DHI–I + DHCl–Cl] –
7. (a) For spontaneous reaction, dS > 0 and dG
[DHI – Cl]
should be negative i.e. < 0.
= 151.0 + 242.3 + 62.76 –2 × 211.3 = 33.46
8. (c) DGº = – RT lnKc or – DGº = RT lnKc
33.46
9. (b) Enthalpy change for a reaction does not DH of ( ICl ) = = 16.73 kJ / mol
depend upon the nature of intermediate 2
reaction steps. 1
17. (d) For the reaction, C (s ) + O 2 (g ) ¾ ¾® CO
10. (c) w = –PDV = – 10–5 (1 ´ 10 –2 –1´ 10–3) 2
= – 900 J DH = DU + DnRT or DH – DU = DnRT
1 1
11. (d) (i) C + O2 CO2, DH = –393.5 kJmol–1 Dn = 1 - = ;
2 2
1 1
(ii) CO+ O 2 CO2, DH = –283.0 DH – DU = ´ 8.314 ´ 298
2 2
kJmol–1 = 1238.78 J mol–1
Operating (i) - (ii), we have 18. (a) DG° = DH° – TDS°
For a spontaneous reaction DG° < 0
1
C + O2 ® CO DH = -110.5 kJmol -1 DH °
2 or DH° – TDS° < 0 Þ T >
12. (b) DH = DU + DnRT for DS°
3
179.3 ´ 10
Þ T> > 1117.9K » 1118K
N 2 + 3H 2 ¾ ¾® 2 NH 3 160.2
Dng = 2 – 4 = – 2 19. (d) Given DH = 41 kJ mol–1 = 41000 J mol–1
\ D H = D U - 2 RT or D U T = 100°C = 273 + 100 = 373 K
n=1
= D H+ 2R T \ D U > D H
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C-30 Chemistry
DU = DH – DnRT = 41000 – (2 × 8.314 × 373)
DH r = DH°f (H + .aq)+DH°f (OH – .aq)–
= 37898.88 J mol–1 ; 37.9 kJmol–1
20. (b) Spontaneity of reaction depends on DH°f (H2 O, l)
tendency to acquire minimum energy state
and maximum randomness. For a 57.32 = 0 + DH°f (OH – , aq) – DH°f (H 2 O, l) …(iii)
spontaneous process in an isolated system For reaction (ii)
the change in entropy is positive. DH r = DH°f (H 2 O, l) –
21. (b) The energy involved in the conversion of
1
1 DH°f (H 2 , g) – DH°f (O2 , g )
Cl2 (g) to Cl–1 (aq) is given by 2
2
1 –286.20 = DH°f (H 2 O, l)
DH = D diss H (–)
Cl2
+ D eg H (–) (–)
Cl + D hyl H Cl On replacing this value in equ. (iii) we have
2
Substituting various values from given
57.32 = DH°f (OH – , aq) – (–286.20)
data, we get
DH°f = –286.20 + 57.32
DH = æç ´ 240 ö÷ + (–349) + (–381) kJmol –1
1
è2 ø = –228.88 kJ
= (120 – 349 – 381) kJ mol–1 = – 610 kJ mol–1
i.e., the correct answer is (b) 24. (b) N 2 + 3H 2 ¾¾ ® 2NH 3 DH = 2 ´ -46.0
22. (c) For a reaction to be at equilibrium DG = 0. kJ mol–1
Since DG = DH – TDS so at equilibrium Let x be the bond enthalpy of N – H bond
then
DH – TDS = 0
[Note : Enthalpy of formation or bond
or DH = TDS formation enthalpy is given which is
For the reaction negative but the given reaction involves
1 3 bond breaking hence values should be
X 2 + Y2 ¾¾ ® XY3 ; DH = –30kJ
2 2 taken as positive.]
(given) DH = S Bond energies of products – S Bond
Calculating DS for the above reaction, we energies of reactants
get 2 × – 46 = 712 + 3 × (436) – 6x
é1 3 ù – 92 = 2020 – 6x
DS = 50 - ê ´ 60 + ´ 40ú JK -1 6x = 2020 + 92
ë2 2 û
=50 – (30 + 60) JK–1 = – 40 JK–1 6x = 2112
x = + 352 kJ/mol
At equilibrium, TDS = DH
25. (b) At equilibrium DG = 0
[Q DG = 0] Hence, DG = DH – TeDS = 0
\ DH
\ DH = TeDS or Te =
T ´ (–40) = –30 ´ 1000 [Q 1kJ = 1000J] DS
For a spontaneous reaction
–30 ´1000
or T= or 750 K DG must be negative which is possible only
–40 if DH < TDS
23. (a) Given, for reaction
® H + (aq.) + OH – (aq.);
(i)H2O (l) ¾¾ or T > DH ; Te < T
DS
DH r = 57.32 kJ 26. (b) C2 H5OH(l) + 3O 2 (g)
1
(ii) H 2 ( g ) + O 2 ( g ) ¾¾ ® H 2 O(l); ® 2CO 2 (g) + 3H 2O(l)
2 Dng = 2 - 3 = -1
DH r = –286.20 kJ
DU = DH - Dng RT
For reaction (i)
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Thermodynamics C-31
= -1366.5 - (-1) Given equation,
2NO(g) + O2 (g) 2NO2(g)
8.314
= -1366.5 - (1) ´ ´ 300 \ 2DG°NO2 – 2DG°NO = – R(298) ln (1.6 × 1012)
103
= – 1366.5 + 0.8314 × 3 = – 1364 kJ 2DG°NO2 – 2 × 86600 = – R(298) ln (1.6 × 1012)
27. (d) 2DG°NO2 = 2 × 86600 – R(298) ln (1.6 × 1012)
4NO 2 (g) + O 2 (g) ® 2N 2 O 5 (g), D rH = – 111 kJ DG°NO2 = [2 × 86600 – R(298) ln (1.6 × 1012]

– 54
= 0.5 [2 × 86600 – R (298) ln (1.6 × 1012)]
D H' 32. (b) Given
2N 2 O5 (s) C(s) + O2(g) ® CO2(g); DH= –393.5 kJ mol–1 …(i)
– 111 – 54 = D H' CO(g)+ O2(g) ® CO2(g); DH= –283.5 kJ mol–1…(ii)
D H' = – 165 kJ \ Heat of formation of CO = eqn(i) – eqn (ii)
28. (c) DG° = DH° – TDS° = –393.5 – (–283.5)
– RT lnK = DH° – TDS° = –110 kJ
DH° - TDS° 33. (c) From 1st law of thermodynamics
lnK = -
RT DU = q + w
29. (a) Process is isothermal reversible expansion, For adiabatic process :
hence q=0
DU = 0, therefore q = – w.
\ DU = w
Since q = + 208 J, w = – 208 J
34. (c) Given
30. (a) C 2 H 5 OH(l ) + 3O 2 ( g ) ¾¾
®
CO2(g) + 2H2O(l) ® CH4(g) + 2O2(g);
2CO2 ( g ) + 3H2O(l)
DrH° = 890.3...(i)
Bomb calorimeter gives DU of the reaction
C(graphite) + O2 (g) ® CO2(g) ;
Given, DU = –1364.47 kJ mol–1
Dng = – 1 DrH° = – 393.5 kJ mol–1 ...(ii)
DH = DU + DngRT = 1
H2(g) + O2(g) ® H2O(l);
1 ´ 8.314 ´ 298 2
-1364.47 - DrH° = – 285.8 kJ mol–1 ...(iii)
1000
= – 1366.93 kJ mol–1 D r H° = å (D r H°) products – å (Df H°)Reactants
31. (b) DG°NO(g) = 86.6k J/mol = 86600 J/mol 890.3 = é1´ ( D f H °)CH + 2 ´ 0 ù – [1´ ( -393.5 ) + 2 ( –285.8 ) ]
ë 4 û
= x J/mol
12 ( D f H °) CH = 890.3 – 965.1 = –74.8 kJ / mol
T = 298, KP = 1.6 × 10 4
DG° = – RT ln K
P
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7
C-32 Chemistry

Equilibrium
7
1. 1 M NaCl and 1 M HCl are present in an aqueous 8. For the reaction equilibrium [2003]
solution. The solution is [2002] N2O4 (g) 2 NO2 (g)
(a) not a buffer solution with pH < 7 the concentrations of N 2 O 4 and NO 2 at
(b) not a buffer solution with pH > 7 equilibrium are 4.8 × 10–2 and 1.2 × 10–2 mol L–1
(c) a buffer solution with pH < 7 respectively. The value of Kc for the reaction is
(d) a buffer solution with pH > 7. (a) 3 × 10–1 mol L–1 (b) 3 × 10–3 mol L–1
2. Species acting as both Bronsted acid and base (c) 3 × 103 mol L–1 (d) 3.3 × 102 mol L–1
is [2002] 9. Consider the reaction equilibrium [2003]
(a) (HSO4) –1 (b) Na2CO3 2 SO2 (g) + O2(g) 2 SO3 (g) ; DHº = –198 kJ
(c) NH3 (d) OH–1. On the basis of Le Chatelier’s principle, the
3. Let the solubility of an aqueous solution of condition favourable for the forward reaction is
Mg(OH)2 be x then its Ksp is [2002] (a) increasing temperature as well as pressure
(a) 4x 3 (b) 108x 5
(b) lowering the temperature and increasing the
(c) 27x4 (d) 9x. pressure
4. Change in volume of the system does not alter (c) any value of temperature and pressure
which of the following equilibria? [2002] (d) lowering of temperature as well as pressure
(a) N2 (g) + O2 (g) 2NO (g) 10. When rain is accompanied by a thunderstorm,
(b) PCl5 (g) PCl3 (g) + Cl2 (g) the collected rain water will have a pH value
(c) N2 (g) + 3H2 (g) 2NH3 (g) [2003]
(d) SO2Cl2 (g) SO2 (g) + Cl2 (g). (a) slightly higher than that when the
5. For the reactionCO (g) + (1/2) O2 (g) = CO2 (g), thunderstorm is not there
Kp / Kc is [2002] (b) unin fluenced by occurrence of
(a) RT (b) (RT) –1 thunderstorm
(c) (RT)–1/2 (d) (RT)1/2 (c) which depends on the amount of dust in
6. Which one of the following statements is not air
true? [2003] (d) slightly lower than that of rain water without
(a) pH + pOH = 14 for all aqueous solutions thunderstorm.
(b) The pH of 1 × 10–8 M HCl is 8
11. The conjugate base of H 2 PO -4 is [2004]
(c) 96,500 coulombs of electricity when passed
through a CuSO4 solution deposits 1 gram (a) H3PO4 (b) P2O5
equivalent of copper at the cathode
(c) PO 34- (d) HPO 24 -
(d) The conjugate base of H 2 PO -4 is HPO 24-
7. The solubility in water of a sparingly soluble 12. What is the equilibrium expression for the reaction
salt AB2 is 1.0 × 10–5 mol L–1. Its solubility P4 (s) + 5O2 (g) P4 O10 (s) ? [2004]
product number will be [2003]
(a) 4 × 10–10 (b) 1 × 10–15 (a) Kc = [O 2 ]5
(c) 1 × 10–10 (d) 4 × 10–15
 www.crackjee.xyz
Equilibrium C-33

(b) Kc = [P4O10 ] / 5[P4 ][O2 ] 18. The exothermic formation of CIF3 is represented
by the equation :
(c) Kc = [P4 O10 ]/[P4 ][O 2 ]5 Cl2 (g) + 3F2 (g) 2ClF3 (g) ;

(d) Kc = 1/[O 2 ]5 Δ H = – 329 kJ

13. For the reaction, Which of the following will increase the quantity
of CIF3 in an equilibrium mixture of
Kp Cl 2 , F2 and ClF3 ? [2005]
CO(g) + Cl 2 (g) COCl2 (g) the Kc
(a) Adding F2
is equal to [2004] (b) Increasing the volume of the container
(a) RT (b) RT (c) Removing Cl2
(d) Increasing the temperature
(c) 1 (d) 1.0
RT 19. For the reaction : [2005]
14. The equilibrium constant for the reaction 2NO2(g) 2NO (g ) + O 2(g ) ,
N 2 (g) + O 2 (g) 2NO2 (g) at temperature
(K c = 1.8 ´ 10- 6 at 184°C) (R = 0.0831 kJ/
T is 4×10–4. The value of Kc for the reaction
(mol. K))
1 1
NO2 (g) N 2 (g) + O2 (g) at the same When K p and K c are compared at 184°C, it is
2 2
found that
temperature is [2004]
–4
(a) Whether Kp is greater than, less than or
(a) 4 × 10 (b) 50 equal to Kc depends upon the total gas
(c) 2.5 × 102 (d) 0.02 pressure
15. The molar solubility (in mol L–1) of a sparingly (b) Kp = Kc
soluble salt MX4 is ‘s’. The corresponding (c) Kp is less than Kc
solubility product is Ksp. ‘s’ is given in term of
(d) Kp is greater than Kc
Ksp by the relation : [2004]
20. Hydrogen ion concentration in mol/L in a
(a) s = (256 K sp )1/ 5 (b) s = (128 K sp )1/ 4 solution of pH = 5.4 will be : [2005]
(a) 3.98 ´ 10 -6 (b) 3.68 ´ 10 -6
1/ 4 1/ 5
(c) s = ( K sp /128) (d) s = ( K sp / 256)
(c) 3.88 ´ 106 (d) 3.98 ´ 108
16. If a is the degree of dissociation of Na 2SO 4 , 21. What is the conjugate base of OH - ? [2005]
the Vant Hoff’s factor (i) used for calculating
(a) O2- (b) O -
the molecular mass is
(c) H2O (d) O 2
(a) 1 – 2 a (b) 1 + 2 a [2005]
(c) 1 – a (d) 1 + a 22. An amount of solid NH 4 HS is placed in a flask
17. The solubility product of a salt having general already containing ammonia gas at a certain
temperature and 0.50 atm pressure. Ammonium
formula MX 2 , in water is : 4 × 10 -12 . The hydrogen sulphide decomposes to yield
concentration of M 2+ ions in the aqueous NH 3 and H 2S gases in the flask. When the
solution of the salt is [2005] decomposition reaction reaches equilibrium, the
total pressure in the flask rises to 0.84 atm? The
(a) 4.0 ´ 10 -10 M (b) 1.6 ´ 10 -4 M
equilibrium constant for NH 4 HS decomposition
-4 -6
(c) 1.0 ´ 10 M (d) 2.0 ´ 10 M at this temperature is [2005]
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C-34 Chemistry
(a) 0.11 (b) 0.17 stant Ksp of AgIO3 at a given temperature is
(c) 0.18 (d) 0.30 1.0 × 10–8, what is the mass of AgIO3 contained
23. Phosphorus pentachloride dissociates as in 100 ml of its saturated saolution? [2007]
follows, in a closed reaction vessel [2006] (a) 1.0 × 10– 4 g (b) 28.3 × 10–2 g
PCl5(g) PCl3(g) + Cl2(g) (c) 2.83 × 10–3 g (d) 1.0 × 10–7 g.
29. The equilibrium constants K p and K p2 for the
If total pressure at equilibrium of the reaction 1
mixture is P and degree of dissociation of PCl5 is reactions X ƒ2Y and Z ƒ P + Q,
x, the partial pressure of PCl3 will be respectively are in the ratio of 1 : 9. If the degree
of dissociation of X and Z be equal then the
æ x ö æ x ö
(a) çè ÷P (b) ç
è 1 - x ÷ø
P ratio of total pressures at these equilibria is
x - 1ø
[2008]
æ x ö æ 2x ö (a) 1: 36 (b) 1 : 1
(c) çè ÷P (d) ç
è 1 - x ÷ø
P
x + 1ø (c) 1 : 3 (d) 1 : 9
24. The equilibrium constant for the reaction 30. For the following three reactions a, b and c,
1 equilibrium constants are given: [2008]
SO3(g) SO 2 (g ) + O 2 (g)
2 (i) CO(g) ∗ H 2O(g) ƒ CO 2 (g) ∗ H 2 (g); K1
is Kc = 4.9 × 10–2. The value of Kc for the reaction (ii) CH4 (g) ∗ H2O(g) ƒ CO(g) ∗ 3H2 (g); K 2
2SO2(g) + O2(g) 2SO3(g)
(iii) CH4 (g) + 2H2O(g) ƒ CO2 (g) + 4H2 (g);K3
will be [2006]
(a) 9.8 × 10–2 (b) 4.9 × 10–2 (a) K1 K 2 = K3 (b) K 2 K3 = K1
(c) 416 (c) 2.40 × 10–3
(c) K3 = K1 K2 (d) K3 .K 23 = K12
25. Given the data at 25ºC
31. Four species are listed below: [2008]
Ag + I - ¾
¾® AgI + e - E º = 0.152 V – +
i. HCO3 ii. H3 O
¾® Ag+ + e -
Ag ¾ Eº = -0.800 V
What is the value of log Ksp for AgI? (2.303 RT/ iii. HSO4– iv. HSO3F
F = 0.059 V) [2006] Which one of the following is the correct
(a) –37.83 (b) –16.13 sequence of their acid strength?
(c) –8.12 (d) +8.612 (a) iv < ii < iii < i (b) ii < iii < i < iv
26. The first and second dissociation constants of (c) i < iii < ii < iv (d) iii < i < iv < ii
an acid H2A are 1.0 × 10–5 and 5.0 × 10–10 respec- 32. The pKa of a weak acid, HA, is 4.80. The pKb of
tively. The overall dissociation constant of the a weak base, BOH, is 4.78. The pH of an aqueous
acid will be [2007] solution of the correspondng salt, BA, will be
(a) 0.2 × 105 (b) 5.0 × 10–5 [2008]
(c) 5.0 × 1015 (d) 5.0 × 10–15. (a) 9.58 (b) 4.79
27. The pKa of a weak acid (HA) is 4.5. The pOH of (c) 7.01 (d) 9.22
an aqueous buffer solution of HA in which 50% 33. Solid Ba(NO3)2 is gradually dissolved in a 1.0 ×
of the acid is ionized is [2007] 10– 4 M Na2CO3 solution. At what concentration
(a) 7.0 (b) 4.5 of Ba2+ will a precipitate begin to form? (KSP for
for BaCO3 = 5.1 × 10–9) [2009]
(c) 2.5 (d) 9.5
28. In a saturated solution of the sparingly soluble (a) 5.1 × 10 –5 M (b) 8.1 × 10 –8 M
strong electrolyte AgIO3 (molecular mass = 283) (c) 8.1 × 10 –7 M (d) 4.1 × 10 –5 M
ˆˆ†
the equilibrium which sets in is AgIO3 (s) ‡ˆˆ 34. Three reactions involving H2PO4– are given
below : [2010]
Ag + (aq) + IO3-(aq) . If the solubility product con-
(i) H3PO4 + H2O® H3O+ + H2PO4–
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Equilibrium C-35
(ii) H2PO4– + H2O ® HPO42– + H3O+ 1 1
(iii) H2PO4– + OH– ® H3PO4 + O2– NO( g) ® N2 ( g ) + O 2 ( g ) at the same
2 2
In which of the above does H 2 PO-4 act as an temperature is:
acid ? (a) 0.02 (b) 2.5 × 102
(a) (ii) only (b) (i) and (ii) (c) 4 × 10–4 (d) 50.0
(c) (iii) only (d) (i) only 41. The pH of a 0.1 molar solution of the acid HQ is
35. In aqueous solution the ionization constants for 3. The value of the ionization constant, Ka of the
carbonic acid are acid is : [2012]
K1 = 4.2 × 10–7 and K2 = 4.8 × 10–11. (a) 3 × 10–1 (b) 1 × 10–3
Select the correct statement for a saturated 0.034 (c) 1 × 10–5 (d) 1 × 10–7
M solution of the carbonic acid. [2010] 42. How many litres of water must be added to 1
2 -
(a) The concentration of CO3 is 0.034 M. litre an aqueous solution of HCl with a pH of 1
(b) The concentration of CO32 - is greater than to create an aqueous solution with pH of 2 ?
that of HCO3- . [2013]
(c) The concentrations of H+ and HCO3- are (a) 0.1 L (b) 0.9 L
approximately equal. (c) 2.0 L (d) 9.0 L
(d) The concentration of H+ is double that of
CO32 - .
1 ˆˆˆˆˆˆ
†
43. For the reaction SO 2(g ) + O 2(g ) ‡ˆˆˆˆˆSO 3(g ) , if
2
36. Solubility product of silver bromide is 5.0 × 10– x
13. The quantity of potassium bromide (molar K P = KC ( RT ) where the symbols have usual
mass taken as 120 g mol–1) to be added to 1 litre meaning then the value of x is (assuming
of 0.05 M solution of silver nitrate to start the ideality): [2014]
1
precipitation of AgBr is [2010] (a) –1 (b) -
2
(a) 1.2 × 10–10 g (b) 1.2 × 10–9 g 1
(c) 6.2 × 10–5 g (d) 5.0 × 10–8 g (c) (d) 1
2
37. At 25°C, the solubility product of Mg(OH)2 is
1.0 × 10–11. At which pH, will Mg2+ ions start 44. The standard Gibbs energy change at 300 K for
precipitating in the form of Mg(OH)2 from a the reaction 2A B + C is 2494.2 J. At a given time,
solution of 0.001 M Mg2+ ions? [2010] the composition of the reaction mixture is [A] =,
(a) 9 (b) 10 [B] = 2 and [C] = . The reaction proceeds in the :
(c) 11 (d) 8 [R = 8.314 J/K/mol, e = 2.718] [JEE M 2015]
38. An acid HA ionises as (a) forward direction because Q < Kc
ˆˆ† H + + A -1
HA ‡ˆˆ (b) reverse direction because Q < Kc
The pH of 1.0 M solution is 5. Its dissociation (c) forward direction because Q > Kc
constant would be : [2011RS] (d) reverse direction because Q > Kc
(a) 5 (b) 5 ´ 10 -8 45. The equilibrium constant at 298 K for a reaction
(c) 1 ´ 10-5 (d) 1 ´ 10-10 A +B C+D is 100. If the initial concentration of
39. The Ksp for Cr(OH)3 is 1.6 × 10–30. The solubility all the four species were 1 M each, then equilib-
of this compound in water is : [2011RS] rium concentration of D (in mol L–1) will be :
(a) 4 1.6 ´ 10 -30 [JEE M 2016]
(a) 1.818 (b) 1.182
(b) 4 1.6 ´ 10 -30 / 27 (c) 0.182 (d) 0.818
(c) 1.6 ´ 10-30/ 27
46. pKa of a weak acid (HA) and pKb of a weak base
(d) 2 1.6 ´ 10 -30 (BOH) are 3.2 and 3.4, respectively. The pH of
40. The equilibrium constant (Kc) for the reaction their salt (AB) solution is [JEE M 2017]
N2(g) + O2(g) ® 2NO(g) at temperature T is (a) 7.2 (b) 6.9
4 × 10–4. The value of Kc for the reaction [2012]
(c) 7.0 (d) 1.0
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C-36 Chemistry
Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(a) (a) (a) (a) (c) (b) (d) (b) (b) (d) (d) (d) (c) (b) (d)
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
(b) (c) (a) (d) (a) (a) (a) (c) (c) (b) (d) (d) (c) (a) (c)
31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
(c) (c) (a) (a) (i) (c) (b) (b) (d) (b) (d) (c) (d) (b) (d) (a)
46
(b)

\ pH = – log [H+] = –log 11×10–8

1. (a) NOTE A buffer is a solution of weak
= –[log11 + 8 log 10]
acid and its salt with strong base and vice
= –[1.0414 – 8] = 6.9586
versa.
HCl is strong acid and NaCl is its salt with 7. (d) ˆˆ† A∗2 ∗ 2B,
AB2 ‡ˆˆ
strong base. pH is less than 7 due to HCl. [A] = 1.0 × 10–5, [B] = [2.0 × 10–5] ,
2. (a) (HSO4)– can accept and donate a proton Ksp = [B]2 [A] = [2 × 10–5]2 [1.0 × 10–5] = 4 × 10–15
(HSO4)– + H+ ® H2SO4 (acting as base)
(HSO4)– – H+ ® SO42–. (acting as acid) [NO2 ]2 [1.2 ´ 10 -2 ]2
8. (b) Kc = =
3. (a) Mg(OH)2 ® [Mg2+] + 2[OH–] [N 2O 4 ] [4.8 ´ 10 -2 ]
x 2x = 3 ´ 10–3 mol/L
Ksp = [Mg] [OH]2 = [x][2x]2 = x.4x2 = 4x3. 9. (b) Due to exothermicity of reaction low or
4. (a) In this reaction the ratio of number of moles optimum temperature will be required. Since
of reactants to products is same i.e. 2 : 2, 3 moles are changing to 2 moles.
hence change in volume will not alter the \ High pressure will be required.
number of moles. 10. (d) The rain water after thunderstorm contains
dissolved acid and therefore the pH is less
5. (c) K p = K c (RT)Dn ;
than rain water without thunderstorm.
æ 1ö 3 1 11. (d) NOTE Conjugate acid-base differ by H+
Dn = 1 - ç 1 + ÷ = 1 - = - .
è 2ø 2 2 +
–H
Kp H 2 PO 4 HPO 4
-1/ 2
\ K = (RT) Acid conjugate
ugate base
c 12. (d) For P4 (s) + 5O 2 (g) P4O10 (s)
6. (b) pH of an acidic solution should be less than
7. The reason is that from H2O. [H+] = 10– 1
7M which cannot be neglected in Kc = . The solids have
(O 2 ) 5
comparison to 10 –8M. The pH can be
calculated as. concentration unity
from acid, [H+] = 10–8M. 13. (c) K p = K c (RT) Dn ;
from H2O, [H+] = 10–7M Here D n = 1– 2 = –1
\ Total [H+] = 10–8 + 10–7 Kp 1
= 10–8 (1 + 10) = 11× 10–8 \ =
K c RT
 www.crackjee.xyz
Equilibrium C-37

[ NO]2 1
14. (b) Kc = = 4 ´10 - 4 5.4 = log
[ N 2 ][O 2 ] [H + ]
On solving, [H+] = 3.98 × 10–6
[N 2 ]1/ 2 [O 2 ]1/ 2 1 21. (a) Conjugate acid-base pair differ by only one
K ¢c = =
[NO] Kc proton.

1 OH - ¾
¾® H + + O 2 - Conjugate base
= = 50
4 ´ 10 -4 of OH– is O2–
22. (a) NH 4 HS(s ) NH 3(g ) + H 2 S(g )
15. (d) MX4 M 4+ + 4X -
S 4S start 0 .5 atm 0 atm
At equib. 0 .5 + x atm x atm.
Ksp = [s] [4s]4 = 256 s5
Then 0.5 + x + x = 2x + 0.5 = 0.84 (given)
1/ 5
æ Ksp ö Þ x = 0.17 atm.
\s = ç ÷
è 256 ø
p NH3 = 0.5 + 0.17 = 0.67 atm
+ -–
16. (b) Na 2SO 4 2Na + SO 4
2a
; p H 2S = 0.17 atm
1- a a
2
1 - a + 2a + a K= pNH 3 ´ pH 2S = 0.67 ´ 0.17 atm
Vant. Hoff’s factor i = = 1 + 2a
1 = 0.1139 = 0.11
17. (c)
MX 2 M + + + 2X -
s 2s 23. (c) PCl5(g) PCl3(g) + Cl2(g)
Where s is the solubility of MX2
1–x x x
then Ksp = 4s3; s × (2s)2 = 4×10–12
Total moles after dissociation
= 4s3; s = 1 × 10–4
1–x+x +x =1+x
\ [M++] = s = 1[M++] = 1.0 × 10– 4
18. (a) The reaction given is an exothermic reaction p = mole fraction of
PCl 3
thus accordingly to Lechatalier’s principle æ x ö
lowering of temperature, addition of F2 and PCl3 × Total pressure = ç ÷P
è1+ x ø
or Cl2 favour the for ward direction and
hence the production of ClF3 . 1
24. (c) SO3(g) SO 2 (g ) + O 2 (g)
19. (d) For the reaction:- 2

ˆˆ
†
2NO 2 (g) ‡ˆˆ 2NO(g) + O 2 (g) [SO 2 ] [O2 ]½
Kc = = 4.9 ´ 10-2 ;
Given Kc = 1.8 × 10–6 at 184 ºC [SO3 ]
R = 0.0831 kj/mol. k On taking the square of the above reaction
Kp= 1.8 × 10–6 × 0.0831 × 457 = 6.836 × 10–
6
[SO 2 ]2 [O 2 ]
[ Q 184°C = (273 + 184) = 457 k, = 24.01´10 - 4
[SO 3 ]2
Dn = (2 + 1, –1) = 1]
Hence it is clear that Kp > Kc now K'C for 2SO2(g) + O2(g) 2SO3
1
20. (a) pH = –log [H+] = log [SO 3 ]2 1
[H + ] = = = 416
2
[SO 2 ] [O 2 ] 24.01´10 - 4
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C-38 Chemistry
+ -
25. (b) (i) Ag ¾
¾® Ag + e E º = - 0.800 V \ s = K sp = 1´10-8
(ii) Ag + I - ¾
¾® AgI + e - E º = 0 .152 V = 1.0 × 10–4 mol/lit = 1.0 × 10–4 × 283 g/lit
From (i) and (ii) we have, (Q Molecular mass of Ag IO3 = 283)
¾® Ag + + I - E º = -0.952 V
AgI ¾
1.0 ´10-4 ´ 283 ´100
= gm /100ml
0.059 1000
Eocell = log K
n = 2.83 × 10–3 gm/ 100 ml
0.059 29. (a) Let the initial moles of X be ‘a’ and that of
\ –0.952 = log [Ag+] [I–] Z be ‘b’ then for the given reactions, we
1
[ Q k = [Ag+][I–]]
X
  2Y
0.952 have  
or - = log K sp or –16.13 = log
0.059 Initial a moles 0
Ksp At equi. a(1 – a) 2aa
(moles)
26. (d) ˆˆ† H∗ ∗ HA,
H 2 A ‡ˆˆ
Total no. of moles = a (1 – a) + 2aa
+ - = a – aa + 2aa
\ K = 1.0 × 10–5 = [H ][HA ] (Given) = a (1 + a)
1
[H 2 A] Dn
(n y ) 2 æ PT ö
HA- ¾¾
® H+ + A-- Now, K P1 = ´ç 1 ÷
nx ç ån ÷
è ø
[H + ][A -- ] (Given)
\ K 2 = 5.0 ´ 10 -10 = (2aa)2 .PT1
[HA - ] or, K P1 =
[a(1 - a)][a(1 + a)]
[H + ]2 [A 2 - ]
K= = K1 ´ K2
[H 2 A] 
Z P + Q
= (1.0 × 10–5) × (5 × 10–10) = 5 × 10–15 

é salt ù Initial b moles 0 0

27. (d) For acidic buffer pH = pKa + log ê ú At equi. b(1 – a) ba ba
ë acid û
(moles)
éA- ù Total no . of moles = b(1 – a) + ba + ba
pH = pK + log ë û
or a
[ HA ] = b – ba + ba + ba
= b(1 + a)
Given pKa = 4.5 and acid is 50% ionised.
[HA] = [A–] (when acid is 50% ionised) Dn
nQ ´ nP é PT ù
\ pH = pKa + log 1 Now K P = ´ê 2 ú
ë ån û
2 nz
\ pH = pKa = 4.5
pOH = 14 – pH = 14 – 4.5 = 9.5 (ba)(ba).PT2
28. (c) Let s = solubility or K P2 =
[b(1 - a)][b(1 + a)]
ˆˆ† Ag ∗ ∗ IO3,
AgIO3 ‡ˆˆ
s s
K P1 4a 2 .PT1 (1 - a )2 4PT1
Ksp = [Ag+] [IO3–] = s × s = s2 = ´ =
or
Given Ksp = 1 × 10–8 K P2 (1 - a 2 ) PT2 .a 2 PT2
 www.crackjee.xyz
Equilibrium C-39

PT1 1 é K P1 1 ù [HCO3- ][H3O + ] x´ x

= êQ = given ú K1 = =
or [H 2CO3 ] 0.034 - x
PT2 9 êë K P2 9 úû
PT1
1
= x2
or PT2 36 or 1 : 36 Þ 4.2 ≥10,7 ; Þ x < 1.195≥10,4
0.034
i.e., (a) is the correct answer.
As H 2 CO 3 is a weak acid so the
30. (c) Reaction (c) can be obtained by adding
concentration of
reactions (a) and (b) therefore K3 = K1. K2
H2CO3 will remain 0.034 as 0.034 >> x.
Hence (c) is the correct answer.
31. (c) The correct order of acidic strength of the x = [H+] = [ HCO3- ] = 1.195 × 10–4
given species in
Now, HCO3– (aq ) ∗ H 2O(l ) ƒ CO32– ( aq ) ∗ H3O∗ ( aq )
HSO3 F > H 3 O + > HSO 4 - > HCO3- x, y y y
(iv) (ii) (iii) (i)
As HCO3- is again a weak acid (weaker
or (i) < (iii) < (ii) < (iv)
It corresponds to choice (c) which is correct than H2CO3) with x >> y.
answer. [CO32– ][H3O+ ] y ´ (x + y)
32. (c) In aqueous solution BA(salt) hydrolyses K2 = =
[HCO3– ] ( x - y)
to give + +
Note : [H3O ] = H from first step (x) and
BA + H2O BOH + HA
from second step (y) = (x + y)
Base acid [As x > > y so x + y ; x and x – y ; x]
Now pH is given by
y≥ x
1 1 1 So, K 2 ; =y
pH = pKw + pKa - pKb x
2 2 2
substituting given values, we get Þ K 2 = 4.8 ´ 10-11 = y = [CO32 - ]
1 So the concentration of [H+] ; [ HCO3– ]=
pH = (14 + 4.80 - 4.78) = 7.01
2
concentrations obtained from the first
33. (a) Na 2 CO3 ¾¾
® 2Na + + CO32- step. As the dissociation will be very low
1 ´10-4 M 1´10-4 M 1´10-4 M
in second step so there will be no change
in these concentrations.
K SP(BaCO3 ) = [Ba 2+ ][CO 32– ] Thus the final concentrations are
5.1 ´ 10 -9 [H + ] = [ HCO3- ] = 1.195 × 10 –4 &
[Ba 2+ ] = = 5.1 ´ 10 -5 M
1 ´ 10 -4 [CO23 - ] = 4.8 ´ 10 -11
34. ® H3O + + H 2 PO4-
(a) (i) H3PO4 + H 2O4 ¾¾
acid1 base2 acid 2 base1 36. (b) ˆˆ† Ag∗ ∗ Br,
AgBr ‡ˆˆ
Ksp = [Ag+] [Br–]
-
® HPO4-- + H 3O +
(ii) H 2PO4 + H 2O ¾¾ For precipitation to occur
acid1 base 2 base1 acid2 Ionic product > Solubility product
H 2PO 4- + OH - ¾¾
® H3PO4 + O -- K sp 5≥10,13
(iii) acid 2 base2 [Br, ] < < < 10,11
[Ag∗ ]
base1 acid1
0.05
Hence only in (ii) reaction H2PO4– is acting
as an acid. i.e., precipitation just starts when 10–11
moles of KBr is added to 1l AgNO 3
35. (c) H 2 CO3 (aq )∗ H2 O(l ) ƒ HCO3– (aq) ∗ H3O+ (aq)
0.034, x x x
solution
\ Number of moles of Br – needed from
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C-40 Chemistry
KBr = 10–11 M2 = 0.01 V2 = ?
\ Mass of KBr = 10–11 × 120 = 1.2 × 10–9 g From
M1V1 = M2V2
37. (b) Mg(OH)2 ‡ˆˆˆˆ† Mg∗∗ ∗ 2OH, 0.1 × 1 = 0.01 × V2
Ksp = [Mg++][OH–]2 V2 = 10 litres
1.0 × 10–11 = 10–3 × [OH–]2 \ Volume of water added = 10 – 1 = 9 litres
1
10,11 ˆˆ† SO3 (g)
SO2 (g) ∗ O2 (g) ‡ˆˆ
[OH, ] < < 10,4
43. (b)
2
10,3
\ pOH = 4 K P = KC ( RT ) x
\ pH + pOH = 14 where x = Dng = number of gaseous
\ pH = 10
38. (d) pH = 5 means moles in product
[H+] = 10–5 – number of gaseous moles in reactant
ˆˆ† H + + A -1
HA ‡ˆˆ æ 1ö 3 1
= 1 - ç1 + ÷ = 1 - = -
t=0 c 0 0 è 2ø 2 2
teq c (1 – a) ca ca 44. (d) DG° = 2494.2J
2A B + C.
[H+ ][A- ] (ca)2 [H+ ]2 R = 8.314 J/K/mol.
Ka = = = e = 2.718
[HA] c (1– a) c - [H+ ] [A] = , [B] = 2, [C] =
But, [H+] << C Q= =4
\ Ka = (10–5)2 = 10–10 DG° = – 2.303 RT log KC.
2494.2 J = – 2.303 × (8.314 J/K/mol) × (300K)
39. (b) ˆˆ† Cr 3+ (aq.) + 3OH - (aq.)
Cr(OH)3 (s) ‡ˆˆ logKC
Þ log KC = –
27 S 4 = K sp Þ log KC = – 0.4341
1/ 4 1/ 4 KC = 0.37
æ K sp ö æ 1.6 ´ 10-30 ö Q > KC.
S =ç ÷ =ç ÷
è 27 ø 27 45. (a) Given,
è ø
A + B C + D
40. (d) For the reaction No. of moles initially 1 1 1 1
N2 + O2 ¾¾ ® 2NO K = 4 × 10–4 At equilibrium 1–a 1–a 1+a
Hence for the reaction 1+a
\ Kc = = 100
1 1 \ = 10
NO ¾¾
® N2 + O2
2 2 On solving
1 1 a = 0.81
K'= = = 50 [D]At eq = 1 + a = 1 + 0.81 = 1.81
K 4×10 – 4 46. (b) Given
pKa (HA) = 3.2
[H + ]
41. (c) H+ = C a ; a = pKb (BOH) = 3.4
C The salt (AB) given is a salt is of weak acid
and weak base. Hence the pH can be
10 –3
or a = = 10-2 calculated by the formula
0.1 1 1
\ pH = 7 + pK a – pK b
Ka = C a 2 = 0.1´ 10-2 ´10-2 = 10–5 2 2
1 1
42. (d) Q pH = 1 ; H+ = 10–1 = 0.1 M = 7 + (3.2) – (3.4)
2 2
pH = 2 ; H+ = 10–2 = 0.01 M = 6.9
\ M1 = 0.1 V1 = 1
 www.crackjee.xyz

8
Redox Reactions

1. Which of the following is a redox reaction?

Z
[2002] X Mn 2+ + 2Y CO 2 + H2 O
(a) NaCl + KNO3 ® NaNO3 + KCl 2
(b) CaC2O4 + 2HCl ® CaCl2 + H2C2O4 values of X, Y and Z respectively are
(c) Mg(OH)2 + 2NH4Cl ® MgCl2 +2NH4OH [Online May 12, 2012; 2013 Offline]
(d) Zn + 2AgCN ® 2Ag + Zn(CN)2. (a) 2, 5, 16 (b) 8, 2, 5
2. Several blocks of magnesium are fixed to the (c) 5, 2, 16 (d) 5, 8, 4
bottom of a ship to [2003] 5. The molecular formula of a commercial resin used
(a) make the ship lighter for exchanging ions in water softening is
(b) prevent action of water and salt C8H7SO3– Na+ (Mol. wt. 206. What would be
(c) prevent puncturing by under-sea rocks the maximum uptake of Ca2 + ions by the resin
(d) keep away the sharks when expressed in mole per gram resin?
3. Which of the following chemical reactions depict [JEE M 2015]
the oxidizing beahviour of H2SO4?
2 1
[2006] (a) (b)
(a) NaCl + H 2 SO 4 ¾¾® NaHSO 4 + HCl 309 412
(b) 2PCl5 + H 2SO 4 ¾¾ ® 1 1
(c) (d)
2POCl3 + 2HCl + SO 2 Cl2 103 206
(c) 2 HI + H 2 SO 4 ¾
¾® I 2 + SO 2 + 2 H 2 O 6. Which of the following reactions is an example
of a redox reaction? [JEE M 2017]
(d) Ca(OH) 2 + H 2SO 4 ¾¾ ®
(a) XeF4 + O2F2 ® XeF6 + O2
CaSO 4 + 2H 2 O (b) XeF2 + PF5 ® [XeF]+ PF6–
4. In the following balanced reaction, (c) XeF6 + H2O ® XeOF4 + 2HF
X MnO4- + Y C2 O24 - + Z H + (d) XeF6 + 2H2O ® XeO2F2 + 4HF

Answer Key
1 2 3 4 5 6
(d) (b) (c) (a) (b) (a)

2. (b) Magnesium provides cathodic protection

0 +1 –2e - 0 +2 and prevent rusting or corrosion.
1. (d) Zn + 2Ag CN ¾ ¾ ¾® Ag + Zn (CN)2
+ 2e - +6 +4
3. (c) 2HI -1 + H 2SO 4 ¾¾® I 02 + SO2 + 2H 2 O
The oxidation state shows a change only
in this reaction oxidation number of S is
in (d)
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C-42 Chemistry
decreasing from + 6 to +4 hence undergoing On balancing
reduction and for HI oxidation Number of I
is increasing from –1 to 0 hence C2 O 4– – ¾¾
® 2CO 2 + 2e – .... (iv)
underegoing oxidation therefore H2SO4 is On multiplying eqn. (ii) by 5 and (iv) by
acting as oxidising agent. 2 and then adding we get
4. (a) X MnO 4– + Y C2 O 2–
4 +ZH
+ 2MnO 4– + 5C2 O4– – + 16H + ¾¾®
Z 2Mn ++ + 10CO2 + 8H 2 O
X Mn 2 + + 2Y CO 2 + H 2O
2 5. (b) 2 mole of water softner require 1 mole of
First half reaction Ca2+ ion
So, 1 mole of water softner require mole of
® Mn + +
MnO4– ¾¾ .... (i) Ca2+ ion
On balancing Thus, will be maximum uptake
6. (a) In the reaction
MnO4– + 8H + + 5e – ¾¾
® Mn ++ + 4H 2O
Oxidation
.... (ii) +4 +1 +6 0
Second half reaction XeF4 + O2F2 ® XeF6 + O2
Reduction
C2 O 4– – ¾¾
® 2CO 2 .... (iii)
 www.crackjee.xyz
Hydrogen C-43

9
Hydrogen

1. Which of the following species is diamagnetic 5. In which of the following reactions H2O2 acts
in nature? as a reducing agent? [2014]
(a) H -2 (b) H +2 [2005] (a) H 2 O 2 + 2H + + 2e - ® 2H 2 O
+
(c) H 2 (d) He 2 (b) H 2 O 2 + 2e - ® O2 + 2H +
2. Which of the following statements in relation to (c) H 2 O 2 + 2e - ® 2OH -
the hydrogen atom is correct ? [2005]
(d) H 2 O 2 + 2OH - - 2e - ® O2 + 2H 2 O
(a) 3s, 3p and 3d orbitals all have the same
energy 6. From the following statements regarding H2O2,
(b) 3s and 3p orbitals are of lower energy than choose the incorrect statement : [JEE M 2015]
3d orbital (a) It has to be stored in plastic or wax lined
(c) 3p orbital is lower in energy than 3d orbital glass bottles in dark
(d) 3s orbital is lower in energy than 3p orbital (b) It has to be kept away from dust
3. In context with the industrial preparation of (c) It can act only as an oxidizing agent
hydrogen from water gas (CO + H2), which of (d) It decomposes on exposure to light
the following is the correct statement? [2008] 7. Which one of the following statements about
(a) CO and H2, are fractionally separated using water is FALSE ? [JEE M 2016]
differences in their densities (a) There is extensive intramolecular hydrogen
(b) CO is removed by absorption in aqueous bonding in the condensed phase.
Cu2Cl2 solution (b) Ice formed by heavy water sinks in normal
(c) H2 is removed through occlusion with pd water.
(c) Water is oxidized to oxygen during
(d) CO is oxidised to CO2 with steam in the
photosynthesis.
presen ce of a catalyst followed by
(d) Water can act both as an acid and as a
absorption of of CO2 in alkali
base.
4. Very pure hydrogen (99.9) can be made by which 8. The concentration of fluoride, lead, nitrate and
of the following processes ? [2012] iron in a water sample from an underground lake
(a) Reaction of methane with steam was found to be 1000 ppb, 40 ppb, 100 ppm and
(b) Mixing natural hydrocarbons of high 0.2 ppm, respectively. This water is unsuitable
molecular weight for drinking due to high concentration of :
(c) Electrolysis of water [JEE M 2016]
(d) Reaction of salts like hydrides with water (a) Nitrate (b) Iron
(c) Fluoride (d) Lead

Answer Key
1 2 3 4 5 6 7 8
(c) (a) (d) (d) (d) (c) (a) (a)
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C-44 Chemistry

1. (c) 4. (d) Very pure hydrogen can be prepared by

the action of water on sodium hydride.
A diamagnetic substance contains no
unpaired electron. NaH + H2O ¾¾ ® NaOH + H2
H2 is diamagnetic as it contains all paired (very pure Hydrogen)
electrons 5. (d) The reducing agent loses electron during
redox reaction i.e. oxidises itself.
H 2 = sb2 , H 2+ = s1b , H 2- = sb2 , s*1 +
a ; He 2 = sb2 , s*1
a
(diamagnetic) (paramagnetic) (paramagnetic) (paramagnetic) -1
(paramagnetic) -2
(a) H 2O 2 + 2H + + 2e - ¾¾
® 2H 2 O (Re d.)
= sb2 , H +2 = s1b , H 2- = sb2 , s*1 +
a ; He2 = sb2 , s*1
a
magnetic) (paramagnetic) (paramagnetic) (paramagnetic) (paramagnetic) -1 0
(b) ® O 2 + 2H + + 2e- (Ox.)
H 2O 2 ¾¾
2. (a) NOTE In one electron species, such as
H-atom, the energy of orbital depends only -1 -2
on the principal quantum number, n. (c) H 2O 2 + 2e - ¾¾
® 2 OH - (Re d.)
Hence answer (d)
i.e. is < 2s = 2p < 3s = 3p = 3d < 4s 0
= 4p Þ 4d = 4g (d) H 2O 2-1 + 2OH - ¾¾
® O 2 + H 2O + 2e- (Ox.)
3. (d) On the industrial scale hydrogen is
prepared from water gas according to 6. (c) has oxidizing and reducing properties both.
following reaction sequence 7. (a) There is extensive intermolecular
catalyst hydrogen bonding in the condensed
CO + H 2 + H 2 O ¾¾¾¾
® CO2 + 2H 2
1424 3 { phase instead of intramolecular
water gas (steam) H-bonding.
2NaOH
8. (a) The maximum limit of nitrate in drinking
¾¾¾¾
® Na 2 CO3 + H 2 O water is 50 ppm. Excess nitrate in drinking
(alkali)
water can cause disease such as
From the above it is clear that CO is first
methemoglobinemia (‘blue baby’
oxidised to CO2 which is then absorbed in
syndrome).
NaOH.
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The s-Block Elements C-45

10
The s-Block Elements

1. KO2 (potassium super oxide) is used in oxygen (a) hydration energies of cations
cylinders in space and submarines because it (b) inter-ionic attraction
[2002] (c) entropy of solution formation
(a) absorbs CO2 and increases O2 content (d) lattice energies of solids
(b) eliminates moisture 7. Which one of the following processes will
(c) absorbs CO2 produce hard water ? [2003]
(d) produces ozone. (a) Saturation of water with MgCO3
2. The metallic sodium disolves in liquid ammonia (b) Saturation of water with CaSO4
to form a deep blue coloured solution. The deep
(c) Addition of Na2SO4 to water
blue colour is due to formation of: [2002]
(d) Saturation of water with CaCO3
(a) solvated electron, e(NH3 )-x
8. One mole of magnesium nitride on the reaction
(b) solvated atomic sodium, Na(NH3)y
with an excess of water gives : [2004]
(c) (Na+ + Na–)
(a) two moles of ammonia
(d) NaNH2 + H2
(b) one mole of nitric acid
3. A metal M readily forms its sulphate MSO4 which
(c) one mole of ammonia
is water-soluble. It forms its oxide MO which
becomes inert on heating. It forms an insoluble (d) two moles of nitric acid
hyroxide M(OH)2 which is soluble in NaOH 9. Based on lattice energy and other
solution. Then M is [2002] considerations which one of the following alkali
(a) Mg (b) Ba metal chlorides is expected to have the highest
(c) Ca (d) Be. melting point ? [2005]
4. In curing cement plasters water is sprinkled from (a) RbCl (b) KCl
time to time. This helps in [2003] (c) NaCl (d) LiCl
(a) developing interlocking needle-like crystals 10. The ionic mobility of alkali metal ions in aqueous
of hydrated silicates solution is maximum for [2006]
(b) hydrating sand and gravel mixed with (a) Li + (b) Na +

cement (c) K+ (d) Rb+

(c) converting sand into silicic acid 11. The products obtained on heating LiNO2 will
(d) keeping it cool be : [2011RS]
5. The substance not likely to contain CaCO3 is
(a) Li 2 O + NO2 + O2 (b) Li 3 N + O 2
(a) calcined gypsum (b) sea shells [2003]
(c) dolomite (d) a marble statue (c) Li 2 O + NO + O 2 (d) LiNO3 + O2
6. The solubilities of carbonates decrease down 12. What is the best description of the change that
the magnesium group due to a decrease in occurs when Na2O(s) is dissolved in water ?
[2003] [2011RS]
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C-46 Chemistry
(a) Oxide ion accepts sharing in a pair of 16. Which one of the following alkaline earth metal
electrons sulphates has its hydration enthalpy greater
(b) Oxide ion donates a pair of electrons than its lattice enthalpy ? [JEE M 2015]
(c) Oxidation number of oxygen increases (a) BaSO4 (b) SrSO4
(d) Oxidation number of sodium decreases (c) CaSO4 (d) BeSO4
13. Which of the following on thermal 17. The main oxides formed on combustion of Li,
decomposition yields a basic as well as acidic Na and K in excess of air are, respectively:
oxide ? [2012] [JEE M 2016]
(a) NaNO3 (b) KClO3 (a) Li2O2, Na2O2 and KO2
(c) CaCO3 (d) NH4NO3 (b) Li2O, Na2O2 and KO2
14. The first ionisation potential of Na is 5.1 eV. The (c) Li2O, Na2O and KO2
value of electron gain enthalpy of Na+ will be
(d) LiO2, Na2O2 and K2O
[2013]
(a) – 2.55 eV (b) – 5.1 eV 18. Both lithium and magnesium display several
similar properties due to the diagonal
(c) – 10.2 eV (d) + 2.55 eV
relationship; however, the one which is incorrect
- is : [JEE M 2017]
15. Stability of the species Li 2 , Li 2 and
(a) Both form basic carbonates
Li +2 increases in the order of : [2013]
(b) Both form soluble bicarbonates
(a) Li 2 < Li 2+ < Li 2- (b) Li -2 < Li +2 < Li 2 (c) Both form nitrides
(d) Nitrates of both Li and Mg yield NO2 and
(c) Li 2 < Li 2- < Li 2+ (d) Li -2 < Li 2 < Li 2+
O2 on heating

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

1. (a) 2KO2 + 2 H2O ® 2 KOH + H2O2 + O2 . It is ammoniated electron which is

KO2 is used as an oxidising agent. It is used
as air purifier in space capsules. Submarines
and breathing masks as it produces oxygen
and remove carbon dioxide.
2. (a) The alkali metals dissolve in liquid ammonia
without evolution of hydrogen. The metal
loses electrons and combine with ammonia
molecule.
M––® M+ (in liquid ammonia)
+ e– (ammoniated)
M + (x + y) NH3 ®[M(NH3)x]+ + e–(NH3)y
Solvated electron
responsible for colour.
3. (d) Sulphate of alkaline earth metal are
sparingly soluble or almost not soluble in
water whereas BeSO4 is soluble in water
due to high degree of solvation. Be(OH)2
is insoluble in water but soluble in NaOH.
BeO + 2NaOH––––––––® Na2BeO2 + H2O
4. (a) Setting of cement is exothermic process
which develops interlocking crystals of
hydrated silicates
5. (a) Gypsum is CaSO4.2H2O
 www.crackjee.xyz
The s-Block Elements C-47
6. (a) As we move down the group, the lattice
energies of car bonates remain ® Na + + e -
14. (b) Q For Na ¾¾ IE1 = 5.1 eV
approximately the same. However the
\ For Na + + e - ¾¾
® Na EF = -5.1 eV
hydration energies of the metal cation
decreases from Be++ to Ba++, hence the (because the reaction is reverse)
solubilities of carbonates of the alkaline 15. (b) Li2 = s1s2 s*1s2 s2s2
earth metal decrease down the group 1
mainly due to decreasing hydration \ Bond order = (4 - 2) = 1
2
energies of the cations from Be++ to Ba++. Li2+ = s1s2 s*1s2 s2s1
7. (b) Permanent hardness of water is due to
chlorides and sulphates of calcium and 1
B.O. = (3 - 2) = 0.5
magnesium i.e CaCl2, CaSO4, MgCl2 and 2
MgSO4. Li2 = s1s2 s*1s2s2s2s*2s1
–

8. (a) Mg3N2+ 6H2O 3Mg(OH ) 2 + 2 NH 3 1

9. (c) LiCl has partly covalent character. Other
halides are ionic in nature. Lattice energy
decreases with increase of ionic radius of
cation, anion being the same. Larger is the
lattice energy, the higher will be m. pt. hence
NaCl will have highest lattice energy.
10. (d) Smaller the size of cation higher is its
hydration energy and greater is its ionic 16.
mobility hence the correct order is
Li+ < Na+ < K+ < Rb+
11. (a) 4LiNO3 ® 2Li 2 O + 4NO2 + O2
12. (b) O 2 - (base) + H 2 O(acid) ® OH - (C.B.) +
OH - (C.A.) 17.
O2– acts as Lewis base.
13. (c) Calcium carbonate on thermal
decomposition gives CaO (Basic oxide) and
CO2 (Acidic oxide) 18. (a) Mg can form basic carbonate like
B.O. = (4 - 3) = 0.5
2
The bond order of Li2+ and Li2– is same but
Li2+ is more stable than Li2– because Li2+ is
smaller in size and has 2 electrons in
antibonding orbitals whereas Li2– has 3
electrons in antibonding orbitals. Hence Li2+
is more stable than Li2–.
(d) In alkaline earth metals, ionic size increases
down the group. The lattice energy remains
constant because sulphate ion is so large, so
that small change in cationic size does not make
any difference. On moving down the group the
degree of hydration of metal ions decreases very
much leading to decrease in solubility.
(b) On heating with excess of air Li, Na and K forms
following oxides
4 Li + O2 2Li2O Lithium monoxide
2Na + O2 Na2O2 Sodium peroxide
K + O2 KO2 Potassium superoxide

CaCO 3
D
CaO + CO 2­ 3MgCO3 . Mg(OH)2 . 3H2O ¯
Basic oxide Acidic oxide While Li can form only carbonate (Li2CO3)
not basic carbonate.
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C-48 Chemistry

11
The p-Block Elements
(Group-13 and 14)
1. Alum helps in purifying water by [2002] (a) forming covalent halides
(a) forming Si complex with clay partiles (b) forming polymeric hydrides
(b) sulphate part which combines with the dirt (c) exhibiting maximum covalency in compounds
and removes it (d) exhibiting amphoteric nature in their oxides
(c) coagulaing the mud particles 6. Aluminium chloride exists as dimer, Al2Cl6 in
(d) making mud water soluble. solid state as well as in solution of non-polar
2. Graphite is a soft solid lubricant extremely solvents such as benzene. When dissolved in
difficult to melt. The reason for this anomalous water, it gives [2004]
behaviour is that graphite [2003]
(a) [Al(OH) 6 ]3- + 3HCl
(a) is an allotropic form of diamond
(b) has molecules of variable molecular masses (b) [Al(H 2 O) 6 ]3+ + 3Cl -
like polymers
(c) has carbon atoms arranged in large plates (c) Al 3+ + 3Cl -
of rings of strongly bound carbon atoms
(d) Al 2 O3 + 6HCl
with weak interplate bonds
(d) is a non-crystalline substance 7. Heating an aqueous solution of aluminium
chloride to dryness will give [2005]
3. Glass is a [2003]
(a) super-cooled liquid (a) Al(OH)Cl 2 (b) Al 2O 3
(b) gel
(c) Al 2 Cl 6 (d) AlCl3
(c) polymeric mixture
(d) micro-crystalline solid 8. In silicon dioxide [2005]
4. For making good quality mirrors, plates of float (a) there are double bonds between silicon and
glass are used. These are obtained by floating oxygen atoms
molten glass over a liquid metal which does not (b) silicon atom is bonded to two oxygen
solidify before glass. The metal used can be atoms
[2003] (c) each silicon atom is surrounded by two
(a) tin (b) sodium oxygen atoms and each oxygen atom is
(c) magnesium (d) mercury bonded to two silicon atoms
5. Beryllium and aluminium exhibit many properties (d) each silicon atom is surrounded by four
which are similar. But, the two elements differ in
oxygen atoms and each oxygen atom is
[2004]
bonded to two silicon atoms.
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The p-Block Elements (Group-13 and 14) C-49

9. The structure of diborane ( B2 H 6 ) contains 11. Among the following substituted silanes the
one which will give rise to cross linked silicone
[2005]
polymer on hydrolysis is [2008]
(a) four 2c-2e bonds and four 3c-2e bonds
(a) R4Si (b) R2SiCl2
(b) two 2c-2e bonds and two 3c-3e bonds (c) RSiCl3 (d) R3SiCl
(c) two 2c-2e bonds and four 3c-2e bonds
12. In view of the sings of D r G ° for the following
(d) four 2c-2e bonds and two 3c-2e bonds
reactions :
10. Which one of the following is the correct
statement? [2008] PbO 2 + Pb ® 2PbO, DrG° < 0

(a) Boric acid is a protonic acid SnO 2 + Sn ® 2SnO, D r G° > 0

(b) Beryllium exhibits coordination number of
which oxidation states are more characteristics
six
for lead and tin ? [2011RS]
(c) Chlorides of both beryllium and aluminium
(a) For lead + 2, for tin + 2
have bridged chloride structures in solid
(b) For lead + 4, for tin + 4
phase
(c) For lead + 2, for tin + 4
(d) B2 H 6 .2NH 3 is known as ‘inorganic
(d) For lead + 4, for tin + 2
benzene’

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12
(c) (c) (a) (d) (c) (b) (b) (d) (d) (c) (c) (c)

1. (c) Alum furnishes Al3+ ions which bring about
coagulation of negatively charged clay
particles, bacteria etc.
2. (c) In graphite, carbon is sp2 hybridized. Each
carbon is thus linked to three other carbon
atoms forming hexagonal rings. Since only
three electrons of each carbon are used in
making hexagonal ring, fourth electron of
each carbon is free to move. This makes
graphite a good conductors of heat and
electricity.
Further graphite has a two dimensional sheet
like structure. These various sheets are held
together by weak van der Waal’s force of
attraction. due to these weak forces of
attraction, one layer can slip over the other.
This makes graphite soft and a good
lubricating agent.
3. (a) Glass is a translucent or transparent
amorphous supercooled solid solution or
we can say super cooled liquid of silicates
and borats having a general formula R2O.
MO . 6 SiO2. where R = Na or K and M = Ca,
Ba, Zn or Pb.
4. (d) It is mercury because it exists as liquid at
room temperature.
5. (c) The maximum valency of beryllium is +2
while that of aluminium is +3.
6. ˆˆ†
(b) Al2Cl6 + 12H2O ‡ˆˆ
2[Al(H2O)6]3+ + 6 C1-
7. (b) The solution of aluminium chloride in water
is acidic due to hydrolysis.
AlCl3 + 3H2O –––––® Al(OH)3 + 3HCl.
On heating it till dryness Al(OH)3 is
converted into Al2O3
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C-50 Chemistry
acid so (a) is incorrect statement.
Al(OH)3 ¾¾ D Al O + 3H O
® 2 3 2 The coordination number exhibited by
8. (d) In SiO2 (quartz), each of O-atom is shared beryllium is 4 and not 6 so statement (b) is
between two SiO44– tetrahedra. incorrect.
Both BeCl 2 and AlCl 3 exhibit bridged
structures in solid state so (c) is correct
statement.
11. (c) The cross linked polymers will be formed
by RSiCl3
OH
|
3nH 2O
9. (d) In diborane structure B2H6 there are two nRSiCl3 ¾¾¾¾ ® nR - Si - OH ¾¾
®
-3nHCl |
2c-2e bonds and two 3c–2e bonds (see
OH
structure of diborane).
Structure of B 2H6 :
| |
O O
Hb | |
R - Si - O - Si
Ht •• Ht | |
O O
B B | |
R - Si - O - Si - R
| |
Ht •• Ht
O O
Hb | |
(Cross linked polymer)
10. (c) The correct formula of inorganic benzene
is B3N3H6 so (d) is incorrect statement
12. (c) Negative D r G° value indicates that + 2
OH oxidation state is more stable for Pb2+. Also
|
Boric acid (H3BO3 or B - OH ) is a lewis it is supported by inert pair effect that + 2
| oxidation state is more stable for Pb and +
OH 4 oxidation state is more stable for Sn.
i.e. Sn++ < Pb++, Sn4+ > Pb4+
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Organic Chemistry-Some Basic Principles & Techniques C-51

12
Organic Chemistry-Some
Basic Principles & Techniques
1. Arrangement of (CH3)3 – C –, (CH3)2 – CH –, 2-methyl-3-butanol
CH3 – CH2 – when attached to benzyl or an
O
unsaturated group in increasing order of ||
inductive effect is [2002] (d) CH 3 – C H – C – CH 2 – CH 3 ® 2-methyl-
|
(a) (CH3)3 –C – < (CH3)2 – CH – < CH3 – CH2 – CH3
(b) CH3 –CH2– < (CH3)2– CH – < (CH3)3 – C – 3-pentanone
(c) (CH3)2 – CH– <(CH3)3 –C –< CH3 –CH2 – 6. The IUPAC name of CH3COCH(CH3)2 is[2003]
(d) (CH3)3 – C– < CH3 –CH2 –<(CH3)2 –CH – (a) 2-methyl-3-butanone
2. A similarity between optical and geometrical (b) 4-methylisopropyl ketone
isomerism is that [2002] (c) 3-methyl-2-butanone
(a) each forms equal number of isomers for a (d) Isopropylmethyl ketone
given compound 7. In which of the following species is the
(b) if in a compound one is present then so is underlined carbon having sp3 hybridisation?
the other [2002]
(c) both are included in stereoisomerism (a) CH3 COOH (b) CH3 CH2 OH
(d) they have no similarity. (c) CH3 COCH3 (d) CH2 = CH –CH3
3. Which of th e following does n ot show 8. Racemic mixture is formed by mixing two [2002]
geometrical isomerism? [2002] (a) isomeric compounds
(a) 1,2-dichloro-1-pentene (b) chiral compounds
(b) 1,3-dichloro-2-pentene (c) meso compounds
(c) 1,1-dichloro-1-pentene (d) enantiomers with chiral carbon.
(d) 1,4-dichloro-2-pentene 9. Following types of compounds (as I, II) [2002]
4. The functional group, which is found in amino CH3 CH === CHCH3 CH3 CHOH
acid is [2002] |
(a) – COOH group (b) – NH2 group CH 2CH3
(c) – CH3 group (d) both (a) and (b). are studied in terms of isomerism in:
5. Which of the following compounds has wrong (a) chain isomerism
IUPAC name? [2002] (b) position isomerism
(c) conformers
(a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl
(d) stereoisomerism
butanoate
10. The reaction: [2002]
(b) CH 3 - C H - CH 2 - CHO ® H 2O
| (CH3)3C – Br ¾¾¾® (CH3)3 – C –OH
CH (a) elimination reaction
3-methyl-butanal (b) substitution reaction
(c) free radical reaction
(c) CH 3 - C H - C H - CH 3 ®
| | (d) displacement reaction.
OH CH 3
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C-52 Chemistry
11. In the anion HCOO– the two carbon-oxygen 17. Amongst the following compounds, th e
bonds are found to be of equal length. what is optically active alkane having lowest molecular
the reason for it ? [2003] mass is [2004]
(a) The C = O bond is weaker than the C — O
bond H
|
(b) The anion HCOO– has two resonating (a) CH 3 - C - <
structures |
(c) The anion is obtained by removal of a C 2 H5
proton from the acid molecule CH3
(d) Electronic orbitals of carbon atom are |
hybridised (b) CH 3 - CH 2 - C H - CH 3
12. The general formula CnH2nO2 could be for open
(c) CH 3 - CH 2 - CH 2 - CH 3
chain [2003]
(a) carboxylic acids (b) diols (d) CH 3 - CH 2 - C º CH
(c) dialdehydes (d) diketones 18. Consider the acidity of the carboxylic acids :
13. Among the following four structures I to IV,
(a) PhCOOH
[2003]
(b) o-NO2C6H4COOH
CH3 O CH3
| || | (c) p-NO2C6H4COOH
C 2 H 5 - CH - C3H 7 , CH 3 - C - C H - C 2 H 5 ,
(d) m-NO2C6H4COOH
( I)
( II ) Which of the following order is correct? [2004]
H (a) 2 > 4 > 1 > 3 (b) 2 > 4 > 3 > 1
| Å CH3
H- C |
C2 H5 - CH- C2H5 (c) 1 > 2 > 3 > 4 (d) 2 > 3 > 4 > 1
|
H , 19. Which of the following is the strongest base ?
( III ) ( IV ) [2004]
it is true that
(a) only I and II are chiral compounds (a)
(b) only III is a chiral compound
(c) only II and IV are chiral compounds
(d) all four are chiral compounds (b) NHCH3
14. The IUPAC name of the compound is
(c) NH2
HO
(a) 3, 3-dimethyl - 1- cyclohexanol [2004] (d) CH2NH2
(b) 1, 1-dimethyl-3-hydroxy cyclohexane
(c) 3, 3-dimethyl-1-hydroxy cyclohexane 20. Which of the following compounds is not chiral?
(d) 1, 1-dimethyl-3-cyclohexanol (a) 1-chloro-2-methyl pentane [2004]
15. Which one of the following does not have sp2 (b) 2-chloropentane
hybridized carbon ? [2004] (c) 1-chloropentane
(a) Acetonitrile (b) Acetic acid (d) 3-chloro-2-methyl pentane
(c) Acetone (d) Acetamide 21. Due to the presence of an unpaired electron,
16. Which of the following will have a mesoisomer free radicals are: [2005]
also? [2004] (a) cations
(a) 2, 3- Dichloropentane (b) anions
(b) 2, 3-Dichlorobutane
(c) chemically inactive
(c) 2-Chlorobutane
(d) chemically reactive
(d) 2-Hydroxypropanoic acid
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Organic Chemistry-Some Basic Principles & Techniques C-53
22. The decreasing order of nucleophilicity among • • •
(b) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H <
the nucleophiles [2005] •
(C6H5)3 C
(A) CH 3C - O - • • •
(c) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H <
||
•
O (C6H5)3 C
• • •
(B) CH 3 O - (d) (C6H5)3 C < (C6H5)2 C H < (CH3)3 C <
•
(CH3)2 C H
(C) CN -
27. CH 3 Br + Nu - ¾
¾® CH 3 - Nu + Br -
O The decreasing order of the rate of the above
||
(D) H 3C S – O – is reaction with nucleophiles (Nu–) A to D is
|| [2006]
O
[Nu = (A) PhO , (B) AcO , (C) HO–, (D)
– – –

(a) (C), (B), (A), (D) (b) (B), (C), (A), (D) CH3O–]
(c) (D), (C), (B), (A) (d) (A), (B), (C), (D) (a) A > B > C > D (b) B > D > C > A
23. The reaction [2004, 2005] (c) D > C > A > B (d) D > C > B > A
O

Me
||

||

R–C + Nu R–C +X D
28.
X Nu Å
is fastest when X is N Me
OH
(a) OCOR (b) OC 2 H 5 n-Bu Et
The alkene formed as a major product in the
(c) NH 2 (d) Cl above elimination reaction is [2006]
24. Which types of isomerism is shown by 2, 3- Me Me
dichlorobutane? (a) (b)
(a) Structural (b) Geometric [2005]
(c) Optical (d) Diastereo
(c) Me (d) CH2 = CH2
25. The IUPAC name of the compound shown below
29. Increasing order of stability among the three
is : main conformations (i.e. Eclipse, Anti, Gauche)
Cl of 2-fluoroethanol is [2006]
(a) Eclipse, Anti, Gauche
(b) Anti, Gauche, Eclipse
Br (c) Eclipse, Gauche, Anti
(a) 3-bromo-1-chlorocyclohexene [2006]
(d) Gauche, Eclipse, Anti
(b) 1-bromo-3-chlorocyclohexene
(c) 2-bromo-6-chlorocyclohex-1-ene
30. The IUPAC name of is
(d) 6-bromo-2-chlorocyclohexene
26. The increasing order of stability of the following
(a) 3-ethyl-4-4-dimethylheptane [2007]
free radicals is [2006]
•
(b) 1, 1-diethyl-2,2-dimethylpentane
• •
(a) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (c) 4, 4-dimethyl-5,5-diethylpentane
•
(CH3)2 C H (d) 5, 5-diethyl-4,4-dimethylpentane.
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C-54 Chemistry
31. Which of the following molecules is expected to 36. The correct decreasing order of priority for the
rotate the plane of plane-polarised light? [2007] functional groups of organic compounds in the
IUPAC system of nomenclature is [2008]
COOH CHO (a) – COOH, – SO3H, – CONH2, – CHO
(b) – SO3H, – COOH,– CONH2, – CHO
(a) H2N H (b) HO H
(c) – CHO, – COOH, – SO3H, – CONH2
H (d) – CONH2, – CHO, – SO3H, – COOH
CHOH
2
37. The IUPAC name of neopentane is [2009]
(c)
(a) 2, 2 dimethylpropane
SH (b) 2 methylpropane
H2N NH2 (c) 2, 2 dimethylbutane
(d) H H (d) 2- methylbutane
Ph Ph 38. Arrange the carbanions, [2009]
32. Presence of a nitro group in a benzene ring
(CH3 )3 C , C Cl3 , (CH3 ) 2 C H , C6 H5 CH 2
[2007]
(a) deactivates the ring towards electrophilic in order of their decreasing stability :
substitution (a) (CH3 ) 2 C H > CCl3 > C6 H5 C H2 > (CH3 )3 C
(b) activates the ring towards electrophilic
substitution (b) C Cl3 > C6 H5 CH 2 > (CH 3 )2 CH > (CH3 )3 C
(c) renders the ring basic (c) (CH3 )3 C > (CH3 )2 CH > C6 H 5 CH 2 > C Cl3
(d) deactivates the ring towards nucleophilic (d) C6 H5 CH 2 > C Cl3 > (CH3 )3 C > (CH 3 ) 2 CH
substitution.
33. Which one of the following conformations of 39. The alkene that exhibits geometrical isomerism is:
cyclohexane is chiral? [2007] (a) 2- methyl propene [2009]
(a) Boat (b) Twist boat (b) 2-butene
(c) Rigid (d) Chair. (c) 2- methyl -2- butene
34. The absolute configuration of [2008] (d) propene
HO2C CO2H 40. The number of stereoisomers possible for a
compound of the molecular formula
OH CH3 – CH = CH – CH(OH) – Me is: [2009]
HO H H (b) 2 (c) 4
(a) S, S (b) R, R
(d) 6 (d) 3
(b) R, S (c) S, R
41. The correct order of increasing basicity of the
35. The electrophile, E Å attacks the benzene ring given conjugate bases (R = CH3) is [2010]
to generate the intermediate s-complex. Of the (a) RCOO < HC º C < R < NH 2
following, which s-complex is lowest energy?
[2008] (b) R < HC º C < RCOO < NH 2
NO2
(c) RCOO < NH 2 < HC º C < R
H
+ E (d) RCOO < HC º C < NH 2 < R
(a) (b) +
42. Out of the following, the alkene that exhibits
H E optical isomerism is [2010]
NO2 NO2 (a) 3-methyl-2-pentene
H
(b) 4-methyl-1-pentene
(c) + E (d) + H (c) 3-methyl-1-pentene
E (d) 2-methyl-2-pentene
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Organic Chemistry-Some Basic Principles & Techniques C-55
43. The change in the optical rotation of freshly 48. Which of the following compounds will exhibit
prepared solution of glucose is known as: geometrical isomerism ? [JEE M 2015]
[2011RS] (a) 2 - Phenyl -1 - butene
(a) racemisation (b) specific rotation (b) 1, 1 - Diphenyl - 1 - propene
(c) mutarotation (d) tautomerism (c) 1 - Phenyl - 2 - butene
44. The non aromatic compound among the
(d) 3 - Phenyl -1 - butene
following is : [2011RS]
49. In Carius method of estimation of halogens, 250
mg of an organic compound gave 141 mg of AgBr.
(a) (b) The percentage of bromine in the compound is :
S [JEE M 2015]
(at. mass Ag =108; Br = 80)
(a) 48 (b) 60
(c) (d)
(c) 24 (d) 36
– 50. The absolute configuration of [JEE M 2016]
CO2H
45. A solution of ( – ) – 1 – chloro –1– phenylethane
in toluene racemises slowly in the presence of a H OH
small amount of SbCl5, due to the formation of :
H Cl
[2013]
(a) carbanion (b) carbene CH3
(c) carbocation (d) free radical is :
46. The order of stability of the following (a) (2S, 3S) (b) (2R, 3R)
carbocations : [2013] (c) (2R, 3S) (d) (2S, 3R)
Å 51. The hottest region of Bunsen flame shown in
CH 2
the figure below is : [JEE M 2016]
Å Å region 4
CH 2 = CH - C H 2 ; CH3 - CH 2 - CH 2 ; is :
I II region 3
III
(a) III > II > I (b) II > III > I region 2
(c) I > II > III (d) III > I > II
region 1
47. For which of the following molecule significant
m ¹ 0?
Cl CN
(a) region 3 (b) region 4
(i) (ii) [2014] (c) region 1 (d) region 2
52. Which of the following molecules is least
Cl CN resonance stabilized? [JEE M 2017]
OH SH
(a) (b)
O
(iii) (iv)

OH SH (c) (d)
(a) Only (i) (b) (i) and (ii) N O
(c) Only (iii) (d) (iii) and (iv)
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C-56 Chemistry
Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(b) (c) (c) (d) (c) (c) (b) (d) (d) (b) (d) (a) (a) (a) (a)
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
(b) (a) (d) (d) (c) (d) (a) (d) (c) (a) (b) (c) (b) (a) (a)
31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
(b) (a) (b) (b) (b) (a) (a) (b) (b) (b) (d) (c) (c) (d) (c)
46 47 48 49 50 51 52
(d) (d) (c) (c) (d) (d) (d)

1. (b) –CH3 group has +I effect, as number of 5. (c) The correct name is 3 - methylbut - 2 - ol
–CH3 group increases, the inductive effect
O CH 3
increases. 1 2| | 3| 4
Therefore the correct order is 6. (c) C H3 - C - C H - C H 3 ;
CH3– CH2– < (CH3)2 – CH– < (CH3)3 C – 3- methyl-2-butanone
2. (c) Sterioisomerism involve those isomers 7. (b) In molecules (a), (c) and (d), the carbon
which contain same ligands in their atom has a multiple bond, only (b) has sp3
co-ordination spheres but differ in the hybridization.
arrangement of these ligands in space. 8. (d) A mixtur e of equal amount of two
Stereo-isomerism is of two type geomerical enantiomers is called a racemic mixture. A
isomerism and optical isomerism. In racemic mixture does not rotate plane–
geomerical isomerism ligands occupy polarized light. They are optically inactive
different positions around the central metal because for every molecule in a racemic
atom or ion. mixture that rotate plane of polarized light
in one direction, there is a mirror image
NOTE In optical isomerism isomers molecule that rotates the plane in opposite
have same formula but differ in their ability direction.
to rotate directions of the plane of 9. (d)
polarised light.
Stereoisomerism is of two types i.e.,
Cl geometrical isomerism and optical
3. (c) C = CH - CH 2 - CH 2 CH3 does isomerism
Cl Both the structures shows sterioisomerism.
not show geometrical isomerism due to Structure I shows geometrical isomerism
presence of two similar Cl atoms on the as it contains two different atoms(H) and
same C-atom. Geometrical isomerism is groups (CH3 ) attached to each carbon
shown by compounds in which the groups/ containing double bond.
atoms attached to C = C are different. H3C CH3 H CH3
C=C C=C
H H H3C H
4. (d) Amino acids contain – NH2 and – COOH
Cis butene Trans butene
NH 2 Structure II shows optical isomerism as it
groups e.g Glycine CH 2
COOH
contains a chiral carbon (attached to four
different group) atom.
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Organic Chemistry-Some Basic Principles & Techniques C-57

CH3 H3C O
sp3 sp sp3 ||
H
*
C OH OH C H CH3 - C º N ; CH3 - C - NH 2
sp 2
Acetonitrile Acetamide
CH2CH3 H3CH2C
butyl alcohol (Two enantiomers) 16. (b) NOTE The compounds containing two

10. (b) The hydrolysis of t-butyl bromide is an similar assymmetric C-atoms have plane of
example of SN1 reaction. The reaction symmetry and exist in Meso form.
consists of two steps. CH3
CH3 CH3 H Cl
Slow step
(i) CH3 C Br ¾¾¾¾ ¾® CH3 C+ :Br plane of symmetry
H Cl
CH3 CH3
CH3
CH3 CH3
Meso 2, 3 dichlorobutane
+ Fast step
(ii) CH3 C+ OH – ¾¾¾¾® CH3 C OH 17. (a) Only 2- cylcopropyl butane has a chiral
|

|
|

CH3 centre.
CH3
11. –
(d) HCOO exists in following resonating H
structures *
CH3 – C – chiral centre
O OΠ
|| | C2H5
H , C, O, « H , C < O 18. (d) In aromatic acids presence of electron
Hence in it both the carbon oxygen bonds withdrawing substituent e.g. –NO 2
are found equal. disperses the negative charge of the anion
12. (a) CnH2nO2 is general formula for carboxylic and stablises it and hence increases the
acid acidity of the parent benzoic acid.
13. (a) CH3
Further o-isomer will have higher acidity
O CH3 Chiral
Carbon than corresponding m and p isomers. Since
C2H5 C* C3H7 CH3 C C* C2H5
nitro group at p-position have more
H Chiral H
(I) carbon pronounced electron withdrawing than
(II)
–NO 2 group at m-position hence the
H CH3 correct order is the one given above.
|
|
H — C* C2H5 — C — C2H5
| Achiral
H Carbon | Achiral COOH COOH
H carbon
(III) (IV)

<
NO2

COOH COOH
14. (a) 1 3 IUPAC name –
2 NO2
HO < <
3, 3-Dimethyl -1 cyclohexanol
NO2
O O
sp 3 || sp 3 sp3 ||
15. (a) H3 C - C - CH 3 ; CH3 - C - OH ; 19. (d) Lone pair of electrons present on the
sp 2 sp2 nitrogen of benzyl amine is not involved
Acetone Acetic acid
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C-58 Chemistry
in resonance. Cl
20. (c) 1-chloropentane is not chiral while others 1
are chiral in nature 6 2
25. (a)
ClCl ClCl 5 3 Br
| | | | | | | | | | | | | | | | | | | | 4
- -CC
– –CC - -CC
- -CC
- -CC
; ; C-C-C C
-C- -CC
- -CC
-C-, -,
| | | | | | | | | | | |* |* | | | | | | 3-bromo-1chlorocyclohexene
1- chloropentane 2 - chloropentane
26. (b) The order of stability of free radicals
• •
| | (C6 H 5 ) 3 C > (C 6 H 5 ) 2 C H > (CH 3 ) 3
- Cl - C - –C – Cl
| | | | | | | | | | • •
- C – C – C– C– C – C– C – C – C – C – C > (CH3 ) 2 CH
| |* | | | | | |* | |
1-chloro-2-methyl 3-chloro-2-methyl The stabilisation of first two is due to
pentane pentane resonance and last two is due to inductive
21. (d) Free radicals are electrically neutral, effect.
unstable and very reactive on account of 27. (c)
the presence of odd electrons.
The stronger the acid, the weaker the
22. (a) In moving down a group, the basicity and conjugate base formed.
nucleophilicity are inversely related, i.e.
The acid character follows the order :
nucleophilicity increases while basicity
decreases. In going from left to right across CH3COOH > C6H5OH > H2O > CH3OH
a period, the basicity and nucleophilicity The basic character will follow the order
are directly related. Both of the CH3COO– < C6H5O– < O–H < CH3O–
characteristics decrease as the 28. (b) Hofmann's rule : When theoretically more
electronegativity of the atom bearing lone than one type of alkenes are possible in
pair of electrons increases. If the eliminations reaction, the alkene containing
nucleophilic centre of two or more species least alkylated double bond is formed as
is same, nucleophilicity parallels basicity, major product. Hence
i.e. more basic the species, stronger is its
Me Me
nucleophilicity. D
Hence based on the above facts, the +
OH N Me
correct order of nucleophilicity will be n-Bu |
O Et
– – –
H3C S— O– > CN > CH3O > CH3 C– O It is less stearically b-hydrogen is
O O removed
(D) (C) (B) (A)
H
29. (a) H H
O
||
23. (d) R - C - X ; when X is Cl the C–X bond is d–
H F
more polar and ionic which leaves the
d+
compound more reactive for nucleophilic O–H
substitution reaction.
Due to hydrogen bonding between H & F
Cl Cl gauche conformation is most stable hence
24. (c) CH3 CH3 . 2, 3-dichloro butane will the correct order is
H H
exhibit optical isomerism due to the Eclipse, Anti, Gauche
presence of two asymmetric carbon atom.
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Organic Chemistry-Some Basic Principles & Techniques C-59

CH3 O O
7 6 5 4| 3 2 1 || ||
30. (a) CH3 - CH 2 - CH 2 - C - CH - CH 2 - CH3 –COOH > –SO3 H > – C - NH 2 > - C - H
| |
CH3 CH 2 37. (a) CH3
| |
1 3 2
CH3 H3C- C - CH3
3- ethyl - 4,4 -dimethyl heptane |
CH3
31. (b) NOTE The organic compounds which Neopentane
have chiral carbon atom (a carbon atom or 2, 2- Dimethylpropane
attached to four different group or atoms
38. (b)
and do not have plane of symmetry rotate
plane polarised light. Cl
– – – –
CHO C Cl > C6H5CH2 > (CH3)2 CH > (CH3)3C
| Cl
HO - C*- H (* is asymmetric carbon) –ve charge –M effect +I effect of CH3 group
| highly dispersed delocalises intensifies the –ve charge
–ve charge
CH 2 OH due to – I effect

32. (a) Nitro group is electron withdrawing group, 39. (b) H3C CH3 H3C H
so it deactivates the ring towards C=C C=C
electrophilic substitution.
H H H CH3
33. (b) Chiral conformation will not have plane of
symmetry. Since twist boat does not have *
40. (b) CH 3 – CH = CH – CHCH 3
plane of symmetry it is chiral. |
OH
4 1 exhibits both geometrical as well as optical
isomerism.
cis - R cis - S
3 6
trans - R trans - S
41. (d) The correct order of basicity is
RCOO - < CH º C - < NH 2 - < R -
5 2
42. (c) For a compound to show optical isomerism,
34. (b) The absolute configuration is (R, R)
presence of chiral carbon atom is a
(using priority rules to get the absolute necessary condition.
configuration)
So the correct answer is (b) H
35. (b) In option (b) the complex formed is with |
benzene where as in other cases it is formed H 2 C < HC — C* — CH 2 , CH3
with nitrobenzene with –NO2 group in |
different position (o-, m-, p-). The complex CH3
formed with nitrobenzene in any position 3- methyl-1-pentene
of –NO2 group is less stable than the 43. (c) When either of the two forms of glucose is
complex formed with benzene so the correct dissolved in water there is change in
answer is (b) rotation till the equilibrium value of + 52.5º.
NOTE The most stable complex has This is known as mutarotation
a–D(+)Glucose Equilibrium Mixture
lowest energy.
+111.5º +52.5º
36. (a) The correct order of priority for the given
b–D–(+)Glucose
functional group is +111.5º +19.5º
 EBD_7764
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C-60 Chemistry
H H H
44. (d) sp3 Carbon |
48. (c) H3C — C = CH — CH 2
|
Ph
Cyclopentadiene does not obey Huckel's 1- Phenyl-2-butene the two groups around
Rule, as it has sp3 carbon in the ring. each of the doubly bonded carbon
45. (c) Carbocations are planar hence can be attacked Because, all are different. This compound
on either side to form racemic mixture. can show cis-and trans-isomerism.
SbCl
Å 49. (c) Mass of substance = 250 mg = 0.250 g
Cl - CH- CH3 ¾¾¾¾ 5 ® Ph - C H - CH + SbCl- ¾¾
®
Toluene 3 6 Mass of AgBr = 141 mg = 0.141 g
| (carbocation) 1 mole of AgBr = 1 g atom of Br
Ph 188 g of AgBr = 80 g of Br
(- )
\ 188 g of AgBr contain bromine = 80 g
Ph - CH - CH3 + SbCl5 0.141 g of AgBr contain bromine =
| 80
Cl ´ 0.141
(d+l) mixture 188
This much amount of bromine present in
46. (d) Higher stability of allyl and aryl substituted
0.250 g of organic compound
methyl carbocation is due to dispersal of
\ % of bromine = = 24%
positive charge due to resonance
50. (d) CO2H
+ +
CH 2 = CH - C H 2 ¬¾® CH 2 - CH = CH 2 H 1 OH
Resonating structures of allyl carbocation
2
+
CH2 CH2 CH2 CH2 H Cl
Å Å CH3
At (1),
Å 3 1
S
Resonating structures of benzyl carbocation
whereas in alkyl carbocations dispersal of posi- 4 1 2 3
tive charge on different hydrogen atoms is due
to hyperconjugation. Hence the correct order of
stability will be 2 4
Å
CH2 It is ‘S’configurated
At. (2),
Å Å 2 1
> CH 2 = CH - C H 2 > CH3 - CH 2 - CH 2 R
Allyl, I Propyl, II
Benzyl, III 4 1 3 2
H
O O 3 4
47. (d)
H 51. (d) Region 2 (blue flame) will be the hottest region
H of Bunsen flame shown in given figure
S S O
H
In both the molecules the bond moments 52. (d) is nonaromatic and hence least
are not canceling with each other and hence
the molecules has a resultant dipole and
hence the molecule is polar. reasonance stabilized whereas other three
are aromatic.
 www.crackjee.xyz
Hydrocarbons C-61

13
Hydrocarbons

1. Which of these will not react with acetylene? 8. Of the five isomeric hexanes, the isomer which
[2002] can give two monochlorinated compounds is
(a) NaOH (b) ammonical AgNO3 [2005]
(c) Na (d) HCl. (a) 2-methylpentane
2. What is the product when acetylene reacts with (b) 2, 2-dimethylbutane
hypochlorous acid? [2002] (c) 2, 3-dimethylbutane
(a) CH3COCl (b) ClCH2CHO (d) n-hexane
(c) Cl2CHCHO (d) ClCH2COOH. 9. The compound formed as a result of oxidation
3. On mixing a certain alkane with chlorine and of ethyl benzene by KMnO4 is [2007]
irradiating it with ultraviolet light, it forms only (a) benzyl alcohol (b) benzophenone
one monochloroalkane. This alkane could be
[2003] (c) acetophenone (d) benzoic acid.
(a) pentane (b) isopentane 10. Which of the following reactions will yield
(c) neopentane (d) propane 2, 2-dibromopropane? [2007]
4. Butene-1 may be converted to butane by (a) CH3 – CH = CH2 + HBr ®
reaction with [2003] (b) CH3 – C º CH + 2HBr ®
(a) Sn – HCl (b) Zn – Hg (c) CH3CH = CHBr + HBr ®
(c) Pd/H2 (d) Zn – HCl (d) CH º CH + 2HBr ®
5. Which one of the following has the minimum 11. The reaction of toluene with Cl2 in presence of
boiling point? [2004] FeCl3 gives predominantly [2007]
(a) 1 - Butene (b) 1 - Butyne (a) m-chlorobenzene
(c) n- Butane (d) isobutane (b) benzoyl chloride
6. 2-Methylbutane on reacting with bromine in the (c) benzyl chloride
presence of sunlight gives mainly [2005] (d) o- and p-chlorotoluene.
(a) 1-bromo-3-methylbutane 12. Toluene is nitrated and the resulting product is
(b) 2-bromo-3-methylbutane reduced with tin and hydrochloric acid. The
(c) 2-bromo-2-methylbutane product so obtained is diazotised and then
(d) 1-bromo-2-methylbutane heated wth cuprous bromide. The reaction
7. Reaction of one molecule of HBr with one mixture so formed contains [2008]
molecule of 1, 3-butadiene at 40°C gives (a) mixture of o- and p-bromotoluenes
predominantly [2005] (b) mixture of o- and p-dibromobenzenes
(a) 1-bromo-2-butene under kinetically (c) mixture of o- and p-bromoanilines
controlled conditions
(d) mixture of o- and m-bromotoluenes
(b) 3-bromobutene under thermodynamically
controlled conditions 13. In the following sequence of reactions, the
(c) 1-bromo-2-butene under thermodyna- alkene affords the compound ‘B’
mically controlled conditions CH 3 - CH = CH - CH 3 ¾¾3¾
O
® A ¾¾¾
H O
2 ® B.
(d) 3-bromobutene under kinetically controlled Zn
conditions The compound B is [2008]
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C-62 Chemistry
(a) C H3CH2CHO (b) C H3COCH3 CH3
(c) C H3CH2COCH3 (d) C H3CHO CH3
14. The hydrocarbon which can react with sodium (a) (b) H3C
in liquid ammonia is [2008]
CH3
(a) CH 3CH 2 CH 2 C º CCH 2CH 2 CH3
CH3
(b) CH 3CH 2C º CH CH3
(c) CH 3CH = CHCH3
(c) CH3 (d)
(d) CH 3CH 2C º CCH 2CH3
CH3
15. The treatment of CH3MgX with CH 3C º C - H
produces [2008] 21. The product of the reaction given below is:
(a) CH 3 - CH = CH 2
1. NBS/hv
(b) CH 3C º C - CH3 X
H H 2. H 2O/K 2CO3
| |
(c) CH 3 - C = C - CH3
[JEE M 2016]
(d) CH4
16. One mole of a symmetrical alkene on ozonolysis O CO2H
gives two moles of an aldehyde having a
molecular mass of 44 u. The alkene is [2010]
(a) (b)
(a) propene (b) 1-butene
(c) 2-butene (d) ethene
17. Ozonolysis of an organic compound 'A' produces
OH
acetone and propionaldhyde in equimolar
mixture. Identify 'A' from the following
compounds: [2011RS] (c) (d)
(a) 1 – Pentene
(b) 2 – Pentene 22. The reaction of propene with HOCl (Cl2 + H2O)
(c) 2 – Methyl – 2 – pentene
proceeds through the intermediate:
(d) 2 – Methyl – 1 – pentene
[JEE M 2016]
18. Which branched chain isomer of the
hydrocarbon with molecular mass 72u gives only (a) CH 3 – CH ( OH ) - CH 2+
one isomer of mono substituted alkyl halide ?
[2012] (b) CH3 – CHCl - CH 2+
(a) Tertiary butyl chloride
(b) Neopentane (c) CH3 – CH + - CH 2 – OH
(c) Isohexane
(d) Neohexane (d) CH3 – CH + - CH 2 – Cl
19. 2-Hexyne gives trans-2-Hexene on treatment
with : [2012] 23. 3-Methyl-pent-2-ene on reaction with HBr in
(a) Pt/H2 (b) Li / NH3 presence of peroxide forms an addition product.
(c) Pd/BaSO4 (d) Li AlH4 The number of possible stereoisomers for the
20. Which compound would give 5 - keto - 2 - product is : [JEE M 2017]
methylhexanal upon ozonolysis ? (a) Six (b) Zero
[JEE M 2015] (c) Two (d) Four
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Hydrocarbons C-63

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(a) (c) (c) (c) (d) (c) (c) (c) (d) (b) (d) (a) (d) (b) (d)
16 17 18 19 20 21 22 23
(c) (c) (b) (b) (d) (d) (d) (d)

1. (a) Acetylene reacts with the other three as: boiling points than the corrosponding
alkanes.
CH 2 Thus B.pt. follows the order
Na
CH º CNa CH º CH +HCl
liq. NH 3
CHCl alkynes > alkene > alkanes (straight chain)
CH3 > branched chain alkanes.
+HCl
CH3
CHCl CHCl2 |
Br
[AgNO3+NH4OH] 6. (c) CH3 - CH - CH2 - CH3 ¾¾®
¾2
CH º CH sun light
CH3
[AgNO +NH OH] |
AgCº CAg + NH4NO3 CH3 - C - CH2CH3
white ppt. |
Br
CHOH 2-bromo-2-methylbutane
2. (c) CH º CH + HOCl ¾¾
® ||
Ease of replacement of H-atom 3° > 2° > 1°.
CHCl
7. (c) CH2 = CH – CH = CH2CH2 + HBr
Br
HOCl é
CH (OH ) 2 ù CHO
- H 2O
¾¾¾®ê | ú ¾¾ ¾ ¾® |
CH2 = CH – CH – CH3
ëê CHCl 2 ûú CHCl 2
dichloroacetaldehyde At –80°C the product is
1, 2-addition
3. (c) In neopentane all the H atoms are same (1º).
CH2 – CH = CH – CH3
CH3
| Br
CH 3 - C - CH 3 At 40°C the product is
| 1, 4-addition
CH3
CH3 CH3
4. (c) Alkenes combine with hydrogen under | |
pressure and in presence of a catalyst (Ni, 8. (c) CH 3 - C H - C H - CH 3 . Since it contains
Pt or Pd) and form alkanes. only two types of H-atoms hence it will
H 2 / Pd give only two mono chlorinated
Butene - 1 ¾¾¾¾® Butane
CH3 CH3
5. (d) NOTE Among isomeric alkanes, the | |
straight chain isomer has higher boiling compounds viz. Cl.CH 2 - C H - C H - CH 3
1-chloro -2,3 -dimethyl butane
point than the branched chain isomer. The
CH 3 CH 3
greater the branching of the chain, the | |
lower is the boiling point. Further due to CH 3 - C - C H - CH 3
the presence of p electrons, these moleculs |
and Cl
are slightly polar and hence have higher 2 -chloro - 2,3-dimethyl butane
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C-64 Chemistry
9. (d) When alkyl benzene are oxidised with alkaline
KMnO4, (strong oxidising agent) the entire CH3
alkyl group is oxidised to –COOH group (HNO3+ HSO)
2 4
regardless of length of side chain.
CH2CH3
( O ), KMnO4 / OH-
¾¾¾¾¾¾¾¾ ® CH3 CH3
Ethyl benzene (HNO + HSO)
NO2
COOH +

NO2
Benzoic aicd
o- p-
10. (b) The reaction follows Markownikoff rule on reduction with Sn/HCl they will form
which states that when unsymmetrical corresponding anilines in which –NO2 group
reagent adds across unsymmetrical double
changes to –NH2. The mixture now contains
or triple bond the negative part adds to
carbon atom having lesser number of CH3 CH3
hydrogen atoms. NH2
CH3 - C º CH + HBr ® and . These anilines

Br NH2
HBr |
CH3 - C = CH 2 ¾¾¾
® CH3 - C - CH3 when diazotized and then treated with CuBr
| | forms o-, p- bromotoluenes.
Br Br
13. (d) Completing the sequence of given reactions,
2, 2-
dibromo-propane O
CH 3 – CH = CH - CH 3 ¾¾3¾
®
11. (d) FeCl3 is Lewis acid. In presence of FeCl3 side
chain hydrogen atoms of toluene are
O
substituted.
CH3 Zn / H O
CH3 CH3– CH CH – CH3 ¾¾¾¾®
2
Cl
FeCl3
+ Cl2 ¾¾¾® + O O
Toluene o-chloro toluene ‘A’
(ozonide)
CH3

2CH3CHO+ H 2 O + ZnO
Cl 'B '
p-chloro toluene Thus ‘B’ is CH3CHO
Hence (d) is correct answer.
CH3
14. (b) Alkynes having terminal –C º H react with
Na in liquid ammonia to yield H2 gas of the
12. (a) NOTE Toluene ( ) contains –
given compounds CH3CH2C º CH can react
with Na in liquid NH3 so the correct answer
CH3 group which is o-, p- directing group so is (b).
on nitration of toluene the –NO2 group will
Na in
occupy o-, p- positions. CH3CH 2 C º CH ¾¾¾¾¾
®
liquid NH3
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Hydrocarbons C-65
19. (b) Anti addition of hydrogen atoms to the triple
1
CH3 CH 2 C º C – Na + + H 2 (g) bond occurs when alkynes are reduced with
2 sodium (or lithium) metal in ammonia,
15. (d) Writing the reaction we get ethylamine, or alcohol at low temperatures.
This reaction called, a dissolving metal
CH 3 MgX + CH 3 – C º C – H ¾¾
®
reduction, produces an (E)- or trans-alkene.
CH3 – C º CMgX + CH 4 (g) Sodium in liq. NH3 is used as a source of
So we find that CH4 is produced in this electrons in the reduction of an alkyne to a
trans alkene.
reaction.
16. (c) The given molecular formula suggests that CH3 CH2 CH2 C C CH3
2-Hexyne
the aldehyde formed will be acetaldehyde
Li/NH 3
hence the alkene will be CH3 CH2 CH2 H
Birch reduction
CH3CH = CH CH3 C C
H CH3
2- butene
Trans-2-Hexene
O3 H O 20. (d) When 1, 3-dimethylcyclopentene is heated with
¾¾® H
ozone and then with zinc and acetic acid,
C C
oxidative cleavage leads to keto - aldehyde.
O O
CH3 CH3
O
1O - 78° C
Zn / H 2O 2CH3CHO + H 2O 2 ¾ ¾ ¾3¾ ¾ ¾ ¾
® O C–H
¾¾¾¾® 2 - Zn- CH 3 COOH
17. (c) From the products formed it is clear that
the compound has 5 carbon atoms with a CH3 CH3
double bond and methyl group on 2 nd
carbon atom.
O O
CH3 || ||
| CH3 — C— CH 2 — CH 2 — CH— C— H
CH3 - C = CH - CH 2 - CH3 |
CH3
O / Zn, H O
¾¾¾¾¾¾
3 2 ® 5- keto – 2 – methylhexanal
21. (d) N – bromosuccinimide results into bromination
(2–Methyl–2–pentene) at allylic and benzylic positions
(A)

CH3 O
| NBS/hv
CH3 - C = O + CH3 - CH 2 - C

Acetone Propionaldehyde
18. (b)
More stable
CH3
Cl2/hv Br HO
H 2O/K 2CO 3
H3C C CH3 monohalogenation
single product NBS

CH3
neopentane
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C-66 Chemistry
22. (d)

CH2 – CH – CH3 CH3 CH3

Å Cl More stable intermediate
CH2 = CH – CH3 + Cl – H Br Br H
Å
CH2 – CH – CH3
H CH3 H3C H
Cl

Å C2H5 C2H5
CH2 – CH – CH3 OH CH2 – CH – CH3 (I) (II)
Cl Cl OH
23. (d) If two chirality centres are created as a CH3 CH3
result of an addition reaction four
stereoisomers can be obtained as products. Br H H Br

CH3 CH3 H CH3 H3C H

HBr
C = C ¾¾ ¾®
– H2 O
H C2H5 C2H5 C2H5
cis-3, methyl pent-2-ene
(III) (IV)
Br CH3
| |
CH3 – CH – CH – CH2 – CH3
* *
2, Bromo, 3-methyl pentane
(2 chiral centre)
 www.crackjee.xyz
Environmental Chemistry C-67

14
Environmental
Chemistry
1. The smog is essentially caused by the presence (c) Ozone absorbs infrared radiation.
of [2004] (d) Oxides of nitrogen in the atmosphere can
(a) Oxides of sulphur and nitrogen cause the depletion of ozone layer.
(b) O2 and N2 (c) O2 and O3 4. What is DDT among the following ? [2012]
(d) O3 and N2 (a) Greenhouse gas
2. Identify the wrong statement in the following: (b) A fertilizer
[2008] (c) Biodegradable pollutant
(a) Chlorofluorocarbons are responsible for (d) Non-biodegradable pollutant
ozone layer depletion 5. The gas leaked from a storage tank of the Union
(b) Greenhouse effect is responsible for global Carbide plant in Bhopal gas tragedy was: [2013]
warming (a) Methyl isocyanate
(c) Ozone layer does not permit infrared (b) Methylamine
radiation from the sun to reach the earth (c) Ammonia
(d) Acid rain is mostly because of oxides of (d) Phosgene
nitrogen and sulphur 6. A water sample has ppm level concentration of
3. Identify the incorrect statement from the following anions [2017]
following : [2011RS] – 2– –
F = 10; SO4 = 100; NO3 = 50
(a) Ozone absorbs the intense ultraviolet the anion/anions that make/makes the water
radiation of the sun. sample unsuitable for drinking is/are :
(b) Depletion of ozone layer is because of its (a) only NO3– (b) both SO42– and NO3–
chemical reactions with chlorofluoro –
alkanes. (c) only F (d) only SO42–

Answer Key
1 2 3 4 5 6
(a) (c) (c) (d) (a) (c)

1. (a) Photochemical smog is caused by oxides N2O + h u ¾ ¾® NO + N

of sulphur and nitrogen. reactive nitric oxide
2. (c) NOTE Ozone layer acts as a shield and NO + O 3 ¾ ¾® NO 2 + O 2
does not allow ultraviolet radiation from O3 + h u ¾ ¾® O 2 + O
sun to reach earth. It does not prevent infra-
red radiation from sun to reach earth. NO 2 + O ¾ ¾® NO + O 2
Thus option (c) is wrong statement and so 2 O3 + h u ¾ ¾® 3 O 2 (Net reaction)
it is the correct answer. The presence of oxides of nitrogen increase
3. (c) The ozone layer, existing between 20 to the decomposition of O 3 .
35 km above the earth’s surface, shield the
earth from the harmful U. V. radiations from 4. (d) DDT is a non-biodegradable pollutant.
5. (a)
the sun. 6. (c) Above 2 ppm concentration of F – in
Depletion of ozone is caused by oxides of drinking water cause brown mottling of
nitrogen teeth.
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C-68 Chemistry

15
The Solid State

1. Na and Mg crystallize in BCC and FCC type

20 3 24 3
crystals respectively, then the number of atoms (c) pr (d) pr
of Na and Mg present in the unit cell of their 3 3
respective crystal is [2002] 6. In a compound, atoms of element Y form ccp
(a) 4 and 2 (b) 9 and 14 lattice and those of element X occupy 2/3rd of
(c) 14 and 9 (d) 2 and 4. tetrahedral voids. The formula of the compound
will be [2008]
2. How many unit cells are present in a cube-
shaped ideal crystal of NaCl of mass 1.00 g ? (a) X4 Y3 (b) X2 Y3
[2003] (c) X2 Y (d) X3 Y4
[Atomic masses : Na = 23, Cl = 35.5] 7. Copper crystallises in fcc with a unit cell length
(a) 5.14 × 1021 unit cells of 361 pm. What is the radius of copper atom?
[2009]
(b) 1.28 × 1021 unit cells
(a) 127 pm (b) 157 pm
(c) 1.71 × 1021 unit cells
(c) 181 pm (d) 108 pm
(d) 2.57 × 1021 unit cells
8. The edge length of a face centered cubic cell of
3. What type of crystal defect is indicated in the
an ionic substance is 508 pm. If the radius of the
diagram below ? [2004]
cation is 110 pm, the radius of the anion is
Na + Cl - Na + Cl - Na + Cl - (a) 288 pm (b) 398 pm [2010]
Cl– c Cl– Na+ c Na+ (c) 618 pm (d) 144 pm
Na+Cl– c Cl– Na+ Cl– 9. Percentages of free space in cubic close packed
Cl– Na+ Cl–Na+ c Na+ structure and in body centered packed structure
(a) Interstitial defect are respectively [2010]
(a) 30% and 26% (b) 26% and 32%
(b) Schottky defect
(c) 32% and 48% (d) 48% and 26%
(c) Frenkel defect
10. Copper crystallises in fcc lattice with a unit cell
(d) Frenkel and Schottky defects
edge of 361 pm. The radius of copper atom is :
4. An ionic compound has a unit cell consisting of [2011RS]
A ions at the corners of a cube and B ions on the
(a) 108 pm (b) 128 pm
centres of the faces of the cube. The empirical
(c) 157 pm (d) 181 pm
formula for this compound would be [2005]
11. Lithium forms body centred cubic structure. The
(a) A 3B (b) AB3 length of the side of its unit cell is 351 pm. Atomic
radius of the lithium will be : [2012]
(c) A 2B (d) AB
(a) 75 pm (b) 300 pm
5. Total volume of atoms present in a face-centred (c) 240 pm (d) 152 pm
cubic unit cell of a metal is (r is atomic radius)
12. Which of the following exists as covalent
[2006]
crystals in the solid state ? [2013]
12 3 16 3 (a) Iodine (b) Silicon
(a) pr (b) pr
3 3 (c) Sulphur (d) Phosphorus
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The Solid State C-69
13. CsCl crystallises in body centered cubic lattice. (c) It contains Cs3+ and I– ions.
If ‘a’ is its edge length then which of the (d) It contains Cs+, I– and lattice I2 molecule.
following expressions is correct? [2014] 15. Sodium metal crystallizes in a body centred cubic
(a) r +r = 3a lattice with a unit cell edge of 4.29Å. The radius
Cs + Cl -
of sodium atom is approximately : [JEE M 2015]
3a (a) 5.72Å (b) 0.93Å
(b) r +r =
Cs + Cl - 2 (c) 1.86Å (d) 3.22Å
16. A metal crystallises in a face centred cubic
3 structure. If the edge length of its unit cell is 'a',
(c) r +r = a
Cs + Cl - 2 the closest approach between two atoms in
metallic crystal will be : [JEE M 2017]
(d) r +r = 3a
Cs + Cl - (a) 2a (b) 2 2 a
14. The correct statement for the molecule, CsI3 is:
(a) It is a covalent molecule. [2014] a
(c) 2a (d)
2
(b) It contains Cs+ and I3- ions.

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(d) (d) (b) (b) (b) (a) (a) (d) (b) (b) (d) (b) (c) (b) (c)
16
(d)

1. (d) In bcc - points are at corners and one in the

centre of the unit cell. 1.0 ´ 6.02 ´10 23
\ units cells = = 2.57 × 1021
Number of atoms per unit cell 58.5 ´ 4
unit cells.
1
= 8´ +1 = 2 . 3. (b) When equal number of cations and anions
8 are missing from their regular lattice positions,
In fcc - points are at the corners and also we have schottky defect.
centre of the six faces of each cell. This type of defects are more common in
Number of atoms per unit cell ionic compounds with high co-ordination
1 1 number and where the size of positive and
= 8´ + 6 ´ = 4 . negative ions are almost equal e.g. NaCl
8 2
KCl etc.
2. (d) Since in NaCl type of structure 4 formula 4. (b) Number of A ions in the unit cell.
units form a cell. Number of formulas in
1
1. 0 ´8 = 1
=
cube shaped crystals = ´ 6.02 ´ 10 23 8
58.5 Number of B ions in the unit cell
No. of unit cells present in a cubic crystal 1
´6 = 3
=
3
P ´ a ´ NA m ´ NA 2
= = Hence empirical formula of the compound
M´Z M´Z = AB3
 EBD_7764
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C-70 Chemistry
5. (b) The face centered cubic unit cell contains
11. (d) For BCC structure 3 a = 4r
4 atom
4 16 3 3
\ Total volume of atoms = 4 ´ pr 3 = pr 3 r= a = ´ 351 = 152 pm.
3 3 4 4
6. (a) From the given data, we have 12. (b)
Number of Y atoms in a unit cell = 4
Number of X atoms in a unit cell 13. (c)
Cl – Cl –
2 16
= 8´ = Cl –
3 3 Cl
From the above we get the formula of the
compound as X16 / 3Y4 or X 4 Y3 Cs+

7. (a) For fcc unit cell, 4r = 2a

Cl – Cl
2 ´ 361 Cl –
r= = 127 pm Cl –
4
8. (d) For an Fcc crystal
Relation between radius of cation, anion
edge length and edge length of the cube
rcation + ranion =
2
2r + 2r = 3a
Cs + Cl-
508
110 + ranion = 3a
2 r +r =
Cs + Cl-
2
ranion = 254 – 110 = 144 pm
9. (b) Packing fraction is defined as the ratio of 14. (b) CsI3 dissociates as CsI3 ® Cs+ + I3–
the volume of the unit cell that is occupied 15. (c) In bcc the atoms touch along body
by the spheres to the volume of the unit diagonal
cell. \ 2r + 2r = 3a
P.F. for ccp and bcc are 0.74 and 0.68
respectively. 3a 3 ´ 4.29
\ r= = = 1.857Å
So, the free space in ccp and bcc are 26% 4 4
& 32% respectively.
16. (d) For a FCC unit cell
10. (b) fcc lattice
a = 361 pm 2a
r=
a 2 = 4r 4

361 ´ 2 2a a
r= = 127.6 » 128pm \ closest distance (2r) = =
4 4 2
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Solutions C-71

16
Solutions

1. Freezing point of an aqueous solution is 6. Which one of the following aqueous solutions
(–0.186)°C. Elevation of boiling point of the same will exihibit highest boiling point ? [2004]
solution is Kb = 0.512°C,Kf = 1.86°C, find the (a) 0.015 M urea (b) 0.01 M KNO3
increase in boiling point. [2002] (c) 0.01 M Na2SO4 (d) 0.015 M glucose
(a) 0.186°C (b) 0.0512°C 7. For which of the following parameters the
(c) 0.092°C (d) 0.2372°C. structural isomers C2 H5 OH and CH3 OCH3
2. In mixture A and B components show -ve would be expected to have the same
deviation as values?(Assume ideal behaviour) [2004]
(a) D Vmix > 0 [2002] (a) Boiling points
(b) D Hmix < 0 (b) Vapour pressure at the same temperature
(c) A – B interaction is weaker than A – A and B (c) Heat of vaporization
– B interaction (d) Gaseous densities at the same temperature
(d) A – B interaction is stronger than A – A and and pressure
B – B interaction. 8. Which of the following liquid pairs shows a
3. If liquids A and B form an ideal solution [2003] positive deviation from Raoult’s law ? [2004]
(a) the entropy of mixing is zero (a) Water - nitric acid
(b) the free energy of mixing is zero (b) Benzene - methanol
(c) the free energy as well as the entropy of (c) Water - hydrochloric acid
mixing are each zero (d) Acetone - chloroform
(d) the enthalpy of mixing is zero 9. Which one of the following statements is FALSE?
4. In a 0.2 molal aqueous solution of a weak acid [2004]
HX the degree of ionization is 0.3. Taking kf for (a) The correct order of osmotic pressure for
water as 1.85, the freezing point of the solution 0.01 M aqueous solution of each
will be nearest to [2003] compound is
(a) – 0.360º C (b) – 0.260º C BaCl 2 > KCl > CH 3COOH > sucrose
(c) + 0.480º C (d) – 0.480º C (b) The osmotic pressure (p) of a solution is
5. A pressure cooker reduces cooking time for food given by the equation p = MRT, where M is
because [2003] the molarity of the solution
(a) boiling point of water involved in cooking (c) Raoult’s law states that the vapour pressure
is increased of a component over a solution is
(b) the higher pressure inside the cooker proportional to its mole fraction
crushes the food material (d) Two sucrose solutions of same molality
(c) cooking involves chemical changes helped prepared in different solvents will have the
by a rise in temperature same freezing point depression
(d) heat is more evenly distributed in the 10. Benzene and toluene form nearly ideal solution.
cooking space At 20°C, the vapour pressure of benzene is 75
torr and that of toluene is 22 torr. The partial
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C-72 Chemistry
vapour pressure of benzene at 20°C for a (a) 210.0 g mol–1 (b) 90.0 g mol–1
solution containing 78 g of benzene and 46 g of (c) 115.0 g mol–1 (d) 105.0 g mol–1.
toluene in torr is [2005] 17. At 80° C, the vapour pressure of pure liquid ‘A’
(a) 53.5 (b) 37.5 is 520 mm Hg and that of pure liquid ‘B’ is 1000
(c) 25 (d) 50 mm Hg. If a mixture solution of ‘A’ and ‘B’ boils
11. Equimolar solutions in the same solvent have at 80° C and 1 atm pressure, the amount of ‘A’ in
[2005] the mixture is (1 atm = 760 mm Hg) [2008]
(a) Different boiling and different freezing (a) 52 mol percent (b) 34 mol percent
points (c) 48 mol percent (d) 50 mol percent
(b) Same boiling and same freezing points 18. The vapour pressure of water at 20° C is 17.5
(c) Same freezing point but different boiling mm Hg. If 18 g of glucose (C6 H12 O 6) is added
points to 178.2 g of water at 20° C, the vapour pressure
(d) Same boiling point but different freezing of the resulting solution will be [2008]
points (a) 17.325 mm Hg (b) 15.750 mm Hg
12. Among the following mixtures, dipole-dipole as (c) 16.500 mm Hg (d) 17.500 mm Hg
the major interaction, is present in [2006] 19. A binary liquid solution is prepared by mixing n-
(a) KCl and water heptane and ethanol. Which one of the following
(b) benzene and carbon tetrachloride statements is correct regarding the behaviour
(c) benzene and ethanol of the solution? [2009]
(d) acetonitrile and acetone (a) The solution is non-ideal, showing – ve
deviation from Raoult’s Law.
13. 18 g of glucose (C6H12O6) is added to 178.2 g of
water. The vapour pressure of water for this (b) The solution is non-ideal, showing + ve
aqueous solution at 100ºC is [2006] deviation from Raoult’s Law.
(a) 76.00 Torr (b) 752.40 Torr (c) n-heptane shows + ve deviation while
ethanol shows – ve deviation from Raoult’s
(c) 759.00 Torr (d) 7.60 Torr
Law.
14. A mixture of ethyl alcohol and propyl alcohol
(d) The solution formed is an ideal solution.
has a vapour pressure of 290 mm at 300 K. The
vapour pressure of propyl alcohol is 200 mm. If 20. Two liquids X and Y form an ideal solution. At
the mole fraction of ethyl alcohol is 300 K, vapour pressure of the solution
0.6, its vapour pressure (in mm) at the same containing 1 mol of X and 3 mol of Y is 550 mmHg.
temperature will be [2007] At the same temperature, if 1 mol of Y is further
added to this solution, vapour pressure of the
(a) 360 (b) 350
solution increases by 10 mmHg. Vapour pressure
(c) 300 (d) 700
( in mmHg) of X and Y in their pure states will be,
15. Equal masses of methane and oxygen are mixed respectively: [2009]
in an empty container at 25°C. The fraction of
(a) 300 and 400 (b) 400 and 600
the total pressure exerted by oxygen is [2007]
(c) 500 and 600 (d) 200 and 300
(a) 1/2 (b) 2/3
21. If sodium sulphate is considered to be
1 273 completely dissociated into cations and anions
(c) ´ (d) 1/3.
3 298 in aqueous solution, the change in freezing point
of water (DTf), when 0.01 mol of sodium sulphate
16. A 5.25% solution of a substance is isotonic with a
is dissolved in 1 kg of water, is (Kf = 1.86 K kg
1.5% solution of urea (molar mass = 60 g mol–1) in
mol–1) [2010]
the same solvent. If the densities of both the
solutions are assumed to be equal to 1.0 g cm–3, (a) 0.372 K (b) 0.0558 K
molar mass of the substance will be [2007] (c) 0.0744 K (d) 0.0186 K
 www.crackjee.xyz
Solutions C-73
22. On mixing, heptane and octane form an ideal (a) 0.875 M (b) 1.00 M
solution. At 373 K, the vapour pressures of the (c) 1.75 M (d) 0.975 M
two liquid components (heptane and octane) are 27. Consider separate solutions of 0.500 M
105 kPa and 45 kPa respectively. Vapour pressure C2H5OH(aq), 0.100 M Mg3 (PO4)2 (aq), 0.250
of the solution obtained by mixing 25.0 g of M KBr(aq) and 0.125 M
heptane and 35 g of octane will be
Na3PO4(aq) at 25°C. Which statement is true
(molar mass of heptane = 100 g mol–1 and of about these solutions, assuming all salts to be
octane = 114 g mol–1) [2010] strong electrolytes? [2014]
(a) 72.0 kPa (b) 36.1 kPa (a) They all have the same osmotic pressure.
(c) 96.2 kPa (d) 144.5 kPa
(b) 0.100 M Mg3(PO4)2(aq) has the highest
23. A 5% solution of cane sugar (molar mass 342) is osmotic pressure.
isotonic with 1% of a solution of an unknown
(c) 0.125 M Na3 PO 4 (aq) has the highest
solute. The molar mass of unknown solute in g/
osmotic pressure.
mol is : [2011RS]
(d) 0.500 M C2 H5OH(aq) has the highest
(a) 171.2 (b) 68.4
osmotic pressure.
(c) 34.2 (d) 136.2
28. The vapour pressure of acetone at 20°C is 185
24. The density of a solution prepared by dissolving torr. When 1.2 g of a non-volatile substance was
120 g of urea (mol. mass = 60 u) in 1000 g of dissolved in 100 g of acetone at 20°C, its vapour
water is 1.15 g/mL. The molarity of this solution pressure was 183 torr. The molar mass (g mol–1)
is : [2012] of the substance is : [JEE M 2015]
(a) 0.50 M (b) 1.78 M (a) 128 (b) 488
(c) 1.02 M (d) 2.05 M
(c) 32 (d) 64
25. Kf for water is 1.86 K kg mol–1. If your automobile
radiator holds 1.0 kg of water, how many grams 29. The freezing point of benzene decreases by
of ethylene glycol (C2H6O2) must you add to 0.45°C when 0.2g of acetic acid is added to 20 g
get the freezing point of the solution lowered to of benzene. If acetic acid associates to form a
–2.8ºC ? [2012] dimer in benzene, percentage association of
(a) 72 g (b) 93 g acetic acid in benzene will be : [JEE M 2017]
(c) 39 g (d) 27 g (Kf for benzene = 5.12 K kg mol –1)
26. The molarity of a solution obtained by mixing (a) 64.6% (b) 80.4%
750 mL of 0.5(M) HCl with 250 mL of 2(M) HCl will (c) 74.6% (d) 94.6%
be : [2013]
Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(b) (d) (d) (d) (a) (c) (d) (b) (d) (d) (d) (d) (b) (b) (d)
16 17 18 19 20 21 22 23 24 25 26 27 28 29
(a) (d) (a) (b) (b) (b) (a) (b) (d) (b) (a) (a) (d) (d)

WB DTb K b DTb
1. (b) DTb = K b ´1000 ; = =
M B ´ WA DTf Kf -0.186

WB 0.512
DTf = K f ´1000 ; = = 0.0512°C.
M B ´ WA 1.86
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C-74 Chemistry
2. (d) In solution containing A and B component between ethanol molecules which weaken
showing negative deviation A–A and B–B intermolecular forces. This results in
interactions are weaker than that of A–B increase in vapour pressure.
interactions. For such solutions. 9. (d) DTf = K f ´ m ´ i . Since Kf has different
DH = –ve and DV = –ve
values for different solvents, hence even
3. (d) When A and B form an ideal solution,
DHmix = 0 if the m is the same DTf will be different
4. (d) DTf = Kf × m × i ; 10. (d) Given, Vapour pressure of benzene = 75
DTf = 1.85 × 0.2 × 1.3 = 0.480º C torr
\ Tf = 0 – 0.480ºC = – 0.480ºC Vapour pressure of benezene = 22 torr
+ mass of benzene in = 78g
( HX H + X - , i = 1.3) 78
1- 0.3 0. 3 0.3
hence moles of benzene = = 1mole
5. (a) NOTE On increasing pressure, the 78
(mol.wt of benzene = 78)
temperature is also increased. Thus in mass of toluence in solution = 46g
pressure cooker due to increase in pressure
46
the b.p. of water increases. hence moles of toluene = = 0.5 mole
6. (c) Q DTb° = Tb – Tbº 92
Where Tb = b.pt of solution now partial pressure of benezene
Tb° = b.pt of solvent or Tb = Tb° + DTb 1 1
= Pºb. Xb = 75 × = 50 torr = 75 ×
NOTE Elevation in boiling point is a 1 + 0.5 1.5
colligative property, which depends upon 2
the no. of particles.Thus greater the = 75 × = 50
3
number of particles, greater is it elevation
and hence greater will be its boiling point. 11. (d) Equimolar solutions of normal solutes in
the same solvent will have the same b. pts
Na2SO4 2Na + SO4 and same f. pts.
Since Na2SO4 has maximum number of d+ d-
particles (3) hence has maximum boiling 12. (d) Acetonitrile ( CH 3 - C º N ) and acetone
point. d+
7. (d) Gaseous densities of ethanol and dimethyl (CH3)
d–
ether would be same at same temperature C = O both are polar
and pressure. The heat of vaporisation, V.P. d–
and b.pts will differ due to (CH3)
H-bonding in ethanol. molecules, hence
dipole-dipole interaction exist between
8. (b) NOTE Positive deviations are shown
them. Between KCl and water ion-dipole
by such solutions in which solvent- interaction is found and in Benzene ethanol
solvent and solute-solute interactions are and Benzene–Carbon tetra chloride
stronger than the solvent interactions. In dispersion force is present
such solution, the intcractions among
molecules becomes weaker. Therefore their 13. (b) Moles of glucose = 18 = 0.1
escaping tendency increases which results 180
in the increase in their partial vapour Moles of water = 1 78 .2
= 9.9
pressures. 18
In a solutions of benzene and methanol Total moles = 0.1 + 9.9 = 10
there exists inter molecular H– bonding.
p H 2O = Mole fraction × Total pressure
9.9
= ´ 760
10
In this solution benzene molecules come = 752.4 Torr
 www.crackjee.xyz
Solutions C-75

14. (b) PAo = ? , Given PBo

= 200mm , xA = 0.6, or 760 = 520X A + 1000 - 1000X A
xB = 1 – 0.6 = 0.4, P = 290 or 480X A = 240
P = PA + PB = PAo x A + PBo x B 240 1
or X A = = or 50 mol. percent
Þ 290 = PAo × 0.6 + 200 × 0.4 480 2
\ PAo
i.e., The correct answer is (d)
= 350 mm
15. (d) Let the mass of methane and oxygen = m 18. (a) NOTE On addition of glucose to water,,
gm. vapour pressure of water will decrease. The
Mole fraction of O2 vapour pressure of a solution of glucose
in water can be calculated using the relation
Moles of O2
=
Moles of O 2 + Moles of CH 4 Po - Ps Moles of glucose in solution
=
Ps moles of water in solution
m / 32 m / 32 1
= = =
m / 32 + m /16 3m / 32 3 17.5 - Ps 18/180
or = [Q Po = 17.5 ]
Partial pressure of O2 = Total pressure × Ps 178.2/18
1 1
mole fraction of O2 , PO2 = P × = P
3 3 or 17.5 – Ps = 0.1 ´ Ps or Ps = 17.325 mm Hg.
9.9
16. (a) Hence (a) is correct answer.
Osmotic pressure ( p ) of isotonic solutions 19. (b) For this solution intermolecular interactions
between n-heptane and ethanol aare
are equal. For solution of unknown weaker than n-heptane - n-heptane &
substance (p = CRT) ethanol-ethanol interactions hence the
5.25 / M solution of n-heptane and ethanol is non-
C1 = ideal and shows positive deviation from
V
Raoult’s law.
For solution of urea, C2 (concentration) =
20. (b) Ptotal = PA° X A + PB° X B
1.5 / 60
1 3
V 550 = PA° ´ + PB° ´
Given, p1 = p2 4 4
Q p = CRT PA° + 3PB° = 550 ´ 4 ...(i)
\ C1RT = C2RT or C1 = C2 In second case
5.25 / M 1.8 / 60 1 4
or = Ptotal = PA° ´ + PB° ´
V V 5 5
\ M = 210 g/mol
17. (d) At 1 atmospheric pressure the boiling point PA° + 4PB° = 560 ´ 5 ...(ii)
of mixture is 80°C. Subtract (i) from (ii)
At boiling point the vapour pressure of
mixture, PT = 1 atmosphere = 760 mm Hg. \ PB° = 560 ´ 5 - 550 ´ 4 = 600
Using the relation, Q PA° = 400
PT = PAo X A + PBo X B , we get 21. (b) Sodium sulphate dissociates as
PT = 520X A + 1000(1 - X A ) ® 2Na + + SO -4 -
Na 2SO 4 (s) ¾¾
hence van’t hoff factor i = 3
{Q PAo = 520mm Hg ,
Now D T f = i k f .m
PBo = 1000 mm Hg , X A + X B = 1 } = 3 × 1.86 × 0.01 = 0.0558 K
 EBD_7764
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C-76 Chemistry
22. (a) PTotal = = P° A x A + P° B X B M V + M 2V2
M= 1 1 where V = total volume
V
= P°Heptane X Heptane + P°Octane X Octane 750 ´ 0.5 + 250 ´ 2
=
25 /100 35 /114 1000
= 105 ´ 25 35 + 45 ´ 25 35 = 0.875 M
+ + 27. (a) p = i CRT
100 114 100 114 p
C2 H5 OH = 1´ 0.500 ´ R ´ T = 0.5 RT
0.25 0.3
= 105 ´ + 45 ´ p
Mg3 (PO 4 )2
0.25 + 0.3 0.25 + 0.3
105 ´ 0.25 45 ´ 0.3 26.25 + 13.5
= 5 ´ 0.100 ´ R ´ T = 0.5 RT
= + =
0.55 0.55 0.55 pKBr = 2 ´ 0.250 ´ R ´ T = 0.5 RT
= 72 kPa p Na PO = 4 ´ 0.125 ´ RT = 0.5 RT
3 4
23. (b) For isotonic solutions Since the osmotic pressure of all the given
p1 = p 2 solutions is equal. Hence all are isotonic
solution.
C1 = C2 28. (d) Using relation,
5 / 342 1/ M p° - ps w 2 M1
= =
0.1 0.1 ps w1M 2
5 1 where w1, M1 = mass in g and mol. mass of
= solvent
342 M
w2, M2 = mass in g and mol. mass of
342 solute
Þ M = = 68.4 gm/mol
5 Let M2 = x
moles of solute p° = 185 torr
24. (d) Molarity =
volume of solution(l) ps = 183 torr
Mass of solution = 1000 + 120 = 1120 185 - 183
=
M M 1120 183
d = ;v = = mL (Mol. mass of acetone = 58)
v d 1.15
x = 64
120 ´ 1.15 \ Molar mass of substance = 64
= ´ 1000 = 2.05 M
60 ´ 1120 29. (d) In benzene
25. (b) DTf = i × Kf × m 2CH3COOH ƒ (CH3COOH)2
Given DTf = 2.8, Kf = 1.86 K kg mol–1 i = 1 1–a a/2
(ethylene glygol is a non- electrolyte) i = 1 – a + a/2 = 1 – a/2
Here a is degree of association
wt. of solvent = 1 kg
DTf = iKfm
Let of wt of solute = x
Mol. wt of ethylene glycol = 62 æ 0.2 ö
çè ÷
æ aö 60 ø
x 0.45 = ç1 – ÷ (5.12)
2.8 = 1 × 1.86 × è 2ø 20
62 ´ 1 1000
2.8 ´ 62 a
or x = = 93 gm 1– = 0.527
1.86 2
26. (a) From molarity equation : a = 0.945
M1V1 + M2V2 = M × V % degree of association = 94.6%
 www.crackjee.xyz
Electrochemistry C-77

Electrochemistry
17
1. Conductivity (unit Siemen’s S) is directly (a) 29.5 × 10–2 (b) 10
proportional to area of the vessel and the (c) 1 × 1010 (d) 1 × 10–10
concentration of the solution in it and is 7. Standard reduction electrode potentials of three
inversely proportional to the length of the metals A, B & C are respectively + 0.5 V, – 3.0 V &
vessel then the unit of the constant of –1.2 V. The reducing powers of these metals are
proportionality is [2003]
(a) Sm mol–1 (b) Sm2 mol–1 [2002] (a) A > B > C (b) C > B > A
(c) S–2m2 mol (d) S2m2 mol–2. (c) A > C > B (d) B > C > A
2. EMF of a cell in terms of reduction potential of 8. When during electrolysis of a solution of AgNO3
its left and right electrodes is [2002] 9650 coulombs of charge pass through the
(a) E = Eleft - Eright (b) E = Eleft + Eright electroplating bath, the mass of silver deposited
(c) E = Eright - Eleft (d) E = – (Eright + Eleft). on the cathode will be [2003]
3. What will be the emf for the given cell [2002] (a) 10.8 g (b) 21.6 g
Pt | H2 (P1) | H+ (aq) | | H2 (P2) | Pt (c) 108 g (d) 1.08 g
RT P2 9. For the redox reaction : [2003]
RT P
(a) log e 1 (b) 2 F loge P Zn (s) + Cu 2 + (0.1 M ) ® Zn 2 + (1 M ) + Cu (s)
F P2 2
RT P º
taking place in a cell, E cell is 1.10 volt. Ecell for
(c) log e 2 (d) none of these.
F P1
the cell will be æç 2.303 ö
RT
4. Which of the following reaction is possible at = 0.0591÷ [2003]
anode? [2002] è F ø
(a) 2 Cr + 7H2O ® Cr2O7 + 14H
3+ 2– + (a) 1.80 volt (b) 1.07 volt
(b) F2 ® 2F – (c) 0.82 volt (d) 2.14 volt
10. In a hydrogen-oxygen fuel cell, combustion of
(c) (1/2) O2 + 2H+ ® H2O
hydrogen occurs to [2004]
(d) none of these. (a) produce high purity water
5. When the sample of copper with zinc impurity is (b) create potential difference between two
to be purified by electrolysis, the appropriate electrodes
electrodes are [2002] (c) generate heat
Cathode Anode (d) remove adsorbed oxygen from elctrode
(a) pure zinc pure copper surfaces
(b) impure sample pure copper 11. Consider the following Eº values
(c) impure zinc impure sample Eº = +0.77 V ; E º = -0.14 V
(d) pure copper impure sample. Fe3 + / Fe 2 + Sn 2 + / Sn

6. For a cell reaction involving a two-electron Under standard conditions the potential for the
change, the standard e.m.f. of the cell is found reaction
to be 0.295 V at 25ºC. The equilibrium constant
of the reaction at 25ºC will be [2003] Sn(s) + 2Fe3+ (aq) ® 2Fe 2+ (aq) + Sn 2+ (aq) is
 EBD_7764
www.crackjee.xyz
C-78 Chemistry
(a) 0.91 V (b) 1.40 V [2004] To prepare 5.12 kg of aluminium metal by this
(c) 1.68 V (d) 0.63 V method we require [2005]
12. The standard e.m.f. of a cell involving one
(a) 5.49 × 101 C of electricity
electron change is found to be 0.591 V at 25ºC.
The equilibrium constant of the reaction is (b) 5.49 × 10 4 C of electricity
(F = 96,500 C mol–1; R = 8.314 JK–1 mol–1)
(a) 1.0 × 1010 (b) 1.0 × 105 [2004] (c) 1.83 × 10 7 C of electricity
(c) 1.0 × 10 1 (d) 1.0 × 1030
(d) 5.49 × 10 7 C of electricity
13. The limiting molar conductivities Lº for NaCl,
Electrolyte: KCl KNO 3 HCl NaOAc NaCl
KBr and KCl are 126, 152 and 150 S cm2 mol–1 19.
2 –1
L ¥ (S cm mol ) : 149.9 145 426.2 91 126.5
respectively. The Lº for NaBr is [2004]
(a) 278 S cm2 mol–1 (b) 176 S cm2 mol–1 ¥
Calculate L HOAc using appropriate molar
(c) 128 S cm2 mol–1 (d) 302 S cm2 mol–1 conductances of the electrolytes listed above
14. In a cell that utilises the reaction at infinite dilution in H 2 O at 25°C [2005]
Zn(s) + 2H + (aq) ® Zn 2+ (aq) + H 2 (g)
addition of H2SO4 to cathode compartment, will (a) 217.5 (b) 390.7
[2004] (c) 552.7 (d) 517.2
(a) increase the E and shift equilibrium to the o o
20. The molar conductivities L NaOAc and L HCl
right
at infinite dilution in water at 25ºC are 91.0 and
(b) lower the E and shift equilibrium to the right
426.2 S cm2/mol respectively. To calculate
(c) lower the E and shift equlibrium to the left
o
(d) increase the E and shift equilibrium to the left L HOAc , the additional value required is [2006]
15. The E º 3+ 2 + values for Cr, Mn, Fe and Co o o
M /M (a) L NaOH (b) L NaCl
are – 0.41, + 1.57, + 0.77 and + 1.97V respectively. o
o
For which one of these metals the change in (c) LH O (d) L KCl
2
oxidation state from +2 to +3 is easiest?
21. Resistance of a conductivity cell filled with a
(a) Fe (b) Mn [2004]
solution of an electrolyte of concentration 0.1
(c) Cr (d) Co M is 100 W. The conductivity of this solution is
16. For a spontaneous reaction the D G, equilibrium 1.29 S m–1. Resistance of the same cell when
filled with 0.2 M of the same solution is 520 W.
constant (K) and E oCell will be respectively
The molar conductivity of 0.2 M solution of
[2005] electrolyte will be [2006]
(a) –ve, >1, –ve (b) –ve, <1, –ve (a) 1.24 × 10–4 S m2 mol–1
(c) +ve, >1, –ve (d) –ve, >1, +ve (b) 12.4 × 10–4 S m2 mol–1
17. The highest electrical conductivity of the (c) 124 × 10–4 S m2 mol–1
following aqueous solutions is of [2005]
(d) 1240 × 10–4 S m2 mol–1
(a) 0.1 M difluoroacetic acid
22. The equivalent conductances of two strong elec-
(b) 0.1 M fluoroacetic acid trolytes at infinite dilution in H2O (where ions
(c) 0.1 M chloroacetic acid move freely through a solution) at 25°C are given
(d) 0.1 M acetic acid below : [2007]
18. Aluminium oxide may be electrolysed at 1000°C
LoCH3COONa = 91.0 S cm 2 / equiv.
to furnish aluminium metal (At. Mass = 27 amu;
1 Faraday = 96,500 Coulombs). The cathode L o HCl = 426.2 S cm 2 / equiv.
reaction is– Al 3+ + 3e- ® Al ° What additional information/ quantity one needs
 www.crackjee.xyz
Electrochemistry C-79
(a) 0.385 V (b) 0.770 V
to calculate Lo of an aqueous solution of acetic
(c) –0.270 V (d) –0.072 V
acid?
27. The Gibbs energy for the decomposition of
(a) Lo of chloroacetic acid (ClCH2COOH) Al2O3 at 500°C is as follows :
(b) Lo of NaCl 2 4
Al2 O3 ® Al + O2 , D r G = + 966 kJ mol -1
3 3
(c) L o of CH3COOK
(d) the limiting equivalent coductance of The potential difference needed for electrolytic
reduction of Al2O3 at 500°C is at least [2010]
H + (l° ). (a) 4.5 V (b) 3.0 V
H+
23. The cell, (c) 2.5 V (d) 5.0 V
Zn | Zn 2+ (1 M) || Cu 2+ (1 M) | Cu (E°cell = 1.10 V)
28. The correct order of E ° 2 + values with
M /M
was allowed to be completely discharged at 298 negative sign for the four successive elements
K. The relative concentration of Zn 2+ to Cu2+ Cr, Mn, Fe and Co is [2010]
(a) Mn > Cr > Fe > Co (b) Cr < Fe > Mn > Co
æ [Zn 2+ ] ö
ç ÷ (c) Fe > Mn > Cr > Co (d) Cr > Mn > Fe > Co
ç [Cu 2+ ] ÷ is [2007]
è ø 29. Resistance of 0.2 M solution of an electrolyte is
(a) 9.65 × 104 (b) antilog (24.08) 50 W. The specific conductance of the solution
is 1.3 S m–1. If resistance of the 0.4 M solution
(c) 37.3 (d) 1037.3.
of the same electrolyte is 260 W, its molar
24. Given Eº = –0.72 V, Eº
Cr 3+ / Cr Fe2 + / Fe conductivity is : [2011RS]
–4
(a) 6.25 × 10 S m mol 2 –1
= – 0.42 V. The potential
for the cell (b) 625 × 10–4 S m2 mol–1
Cr|Cr3+ (0.1M)|| Fe2 + (0.01 M)| Fe is [2008] (c) 62.5 S m2 mol–1
(a) 0.26 V (b) 0.336 V (d) 6250 S m2 mol–1
(c) – 0.339 (d) 0.26 V 30. The standard reduction potentials for Zn2+/Zn,
25. In a fuel cell methanol is used as fuel and oxygen Ni2+/Ni and Fe2+/Fe are –0.76,–0.23 and –0.44 V
gas is used as an oxidizer. The reaction is respectively.

CH 3OH(l ) + 3/2O 2 (g) ¾¾

® The reaction X +Y 2 + ¾¾ ® X 2+ + Y will be
spontaneous when : [2012]
CO2 (g) + 2H 2O(l ) (a) X = Ni, Y = Fe (b) X = Ni, Y = Zn
At 298 K standard Gibb’s energies of formation (c) X= Fe, Y = Zn (d) X= Zn, Y = Ni
for CH3OH(l), H2O(l) and and CO2 (g) are –166.2 31. Given :
–237.2 and –394.4 kJ mol–1 respectively. If
standard enthalpy of combustion of methonal Eo 3+ = -0.74 V; Eo - = 1.51 V
Cr / Cr MnO 4 / Mn 2+
is – 726 kJ mol–1, efficiency of the fuel cell will
be: [2009] Eo 2 - 3+ = 1.33 V; Eo = 1.36 V
Cr O / Cr
2 7 Cl / Cl-
(a) 87% (b) 90%
Based on the data given above, strongest
(c) 97% (d) 80%
oxidising agent will be : [2013]
26. Given:
(a) Cl (b) Cr3+
E° 3+ = –0.036V,
Fe / Fe (c) Mn 2+ (d) MnO4 –
E° = –0.439 V 32. Four successive members of the first row
Fe 2+ / Fe
The value of standard electrode potential for transition elements are listed below with atomic
the change, numbers. Which one of them is expected to have

Fe3+ (aq) + e – ¾¾
® Fe 2+ (aq) will be: [2009]
the highest Eo 3+ 2+ value ? [2013]
M /M
 EBD_7764
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C-80 Chemistry

( )
(a) Cr(Z = 24) (b) Mn(Z = 25)
(c) Fe(Z = 26) (d) Co(Z = 27) 2 Mn3+ + e - ® Mn 2+ ; E o = +1.51V
33. Resistance of 0.2 M solution of an electrolyte is
50 W. The specific conductance of the solution The Eo for 3Mn 2 + ® Mn + 2Mn 3+ will be:
is 1.4 S m–1. The resistance of 0.5 M solution of [2014]
the same electrolyte is 280 W. The molar (a) –2.69 V; the reaction will not occur
conductivity of 0.5 M solution of the electrolyte (b) –2.69 V; the reaction will occur
in S m2 mol–1 is: [2014] (c) –0.33 V; the reaction will not occur
(a) 5 × 10–4 (b) 5 × 10–3 (d) –0.33 V; the reaction will occur
(c) 5 × 103 (d) 5 × 102 36. Two Faraday of electricity is passed through a
34. The equivalent conductance of NaCl at solution of CuSO 4 . The mass of copper
concentration C and at infinite dilution are lC deposited at the cathode is
(at. mass of Cu = 63.5 amu) [JEE M 2015]
and l¥ , respectively. The correct relationship (a) 2g (b) 127 g
between lC and l¥ is given as: (c) 0 g (d) 63.5 g
(Where the constant B is positive) [2014] 37. Given [JEE M 2017]
(a) lC = l ¥ + ( B ) C Eo
Cl /Cl –
= 1.36V, E o 3 +
Cr / Cr
= –0.74V,
2
(b) lC = l ¥ - ( B ) C E o
= 1.33V, Eo = 1.51V.
Cr /O2– /Cr3+ – /Mn 2 +
MnO4
2 7
(c) lC = l¥ - ( B ) C
Among the following, the strongest reducing
(d) lC = l¥ + ( B ) C agent is
(a) Cr (b) Mn 2+
35. Given below are the half-cell reactions:
(c) Cr3+ (d) Cl–
Mn 2 + + 2e - ® Mn ; E o = -1.18V

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(b) (c) (b) (a) (d) (c) (d) (a) (b) (b) (a) (a) (c) (a) (c)
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
(d) (a) (d) (b) (b) (b) (b) (d) (d) (c) (b) (c) (a) (a) (d)
31 32 33 34 35 36 37
(d) (d) (a) (c) (a) (d) (a)

3. (b) Oxidation half call:-

area ´ conc km 2 mol
1. (b) given S µ = H2(g) ––––––– ®– 2H+(1M) + 2e–
l m ´ m3 P1
\k = Sm2 mol-1 Reduction half cell
2H+ (1M) + 2e– ––––––– ®
– H2(g)
2. (c) Ecell = Reduction potential of cathode
P2
(right)
The net cell reaction
– reduction potential of anode (left)
H2(g) ––––––– ®– H2(g)
= Eright – Eleft.
P1 P2
 www.crackjee.xyz
Electrochemistry C-81
E ºcell = 0.00 V n=2
11. (a) Fe3+ + e - ® Fe2+ DG° = -1´ F ´ 0.77
RT
\ Ecell = Eºcell – logeK
nF
Sn 2+ + 2e - ® Sn(s) DG° = -2 ´ F(-0.14)
RT P
=0– log e 2
nF P1 for Sn(s) + 2Fe3+ (aq) ®
RT P2 2Fe 2 + (aq) + Sn 2 + (aq)
or Ecell = log e P
2F 1 \ Standar d potential for the given
reaction
4. (a) 2Cr 3+ + 7 H 2 O ® Cr2 O 72 - + 14H +
O.S. of Cr changes from +3 to +6 by loss of or E ocell = E o + Eo
electrons. At anode oxidation takes place. Sn / Sn 2 + Fe3+ / Fe 2 +
5. (d) Pure metal always deposits at cathode. = 0.14 + 0.77 = 0.91 V
6. (c) The equilibrium constant is related to the 0.059
standard emf of cell by the expression 12. (a) E°cell = Eocell – log K c
n
n 2
log K = Eº cell ´ = 0.295 ´ 0.0591
0.059 0.059 or 0 = 0.591 – log K c
1
590
log K = = 10 or K = 1 × 1010 or log K c =
0.591
= 10 or Kc = 1 ´ 1010
59 0.0591
7. (d) A B C
+0.5C –3.0V –1.2V 13. (c) L º NaCl = l° Na + + lCl - ....(i)

NOTE The higher the negative value of L° KBr = l°K + + l°Br - ....(ii)
reduction potential, the more is the
reducing power. L° KCl = l°K + + lCl- ....(iii)
Hence B > C > A. operating (i) + (ii) - (iii)
8. (a) When 96500 coulomb of electricity is
passed through the electroplating bath the L° NaBr = l° Na + + l º Br –
amount of Ag deposited = 108g
= 126 + 152 - 150 = 128 S cm 2 mol -1
\ when 9650 coulomb of electricity is
passed deposited Ag. 14. (a) Zn(s) + 2H + + (aq) Zn 2+ (aq) + H 2 (g)
108
= ´ 9650 = 10.8 g 0.059 [Zn 2 + ][H 2 ]
96500 E cell = E °cell - log
2 [H + ]2
0.059 [Cu +2 ] Addition of H2SO4 will increase [H+]and
9. (b) E cell = E º cell + log
n [ Zn + 2 ] Ecell will also increase and the equilibrium
will shift towards RHS
0.059 15. (c) The given values show that Cr has
= 1.10 + log[0.1]
2 maximum oxidation potental, therefore its
= 1.10 - 0.0295 = 1.07 V oxidation will be easiest. (Change the sign
to get the oxidation values)
10. (b) In H 2 - O 2 fuel cell, the combustion of
H2 occurs to create potential difference 16. (d) NOTE For spontaneous reaction DG
between the two electrodes should be negative. Equilibrium constant
should be more than one
 EBD_7764
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C-82 Chemistry
(DG = – 2.303 RT log Kc, If Kc = 1 then m (molar conductivity) = ?
DG = 0; If Kc < 1 m = k × V (k can be calculated as
1 æ1ö
then DG = +ve). Again DG = - nFE ocell . k= now
R çè a ÷ø
E ocell must be +ve to have DG –ve. cell constant is known.)
Hence,
17. (a) Thus difluoro acetic acid being strongest
1 1000
acid will furnish maximum number of ions m= ´ 129 ´ ´ 10 -6 m 3
showing highest electrical conductivity. 520 0.2
The decreasing acidic strength of the = 12.4 ×10–4 Sm2 mol–1
carboxylic acids given is
22. (b) NOTE According to Kohlrausch’s law,,
difluoro acetic acid > fluoro acetic acid
> chloro acetic acid > acetic acid. molar conductivity of weak electrolyte
18. (d) 1 mole of e– = 1F = 96500 C acetic acid (CH3COOH) can be calculated
as follows:
27g of Al is deposited by 3 × 96500 C
5120 g of Al will be deposited by (
L oCH3COOH = L oCH3COONa + L oHCl - L oNaCl )
=
3 ´ 96500 ´ 5120
= 5.49 ´ 10 7 C \ Value of L o NaCl should also be known
27
for calculating value of LoCH 3COOH .
23. (d) E cell = 0; when cell is completely
mFz
q=
We know, Q discharged.
M
5120 ´ 96500 ´ 3 æ é Zn 2 + ù ö
0.059
q=
\Q = 5.49 ´ 107 C Ecell = E°cell - log ç ë û÷
27 ç + ÷
2 ç é Cu ù ÷
2
èë ûø
19. (b) L¥
HCl = 426.2 (i)
æ é Zn 2 + ù ö
L¥
AcONa = 91.0 (ii) 0.059
or 0 = 1.1 - log ç ë û÷
2 ç é 2+ ù ÷
ç Cu ÷
L¥
NaCl = 126.5 (iii) èë ûø
æ é Zn 2+ ù ö
¥
L AcOH = (i) + (ii) - (iii) log ç ë û ÷ = 2 ´1.1 = 37.3
ç é 2+ ù ÷ 0.059
ç Cu ÷
= [426.2 + 91.0 - 126.5] = 390.7 èë ûø

20. (b) o
L CH is given by the following æ é Zn 2 + ù ö
3COOH çë û ÷ = 1037.3
\ ç 2+ ù ÷
equation é
ç Cu ÷
èë ûø
LoCH COOH
3 (o
= L CH
3COONa )(
+ L oHCl - L oNaCl ) 24. (d) From the given representation of the cell,
o
Ecell can be found as follows.
Hence L NaCl is required.
0.059 [Cr3+ ]
2
1ælö Ecell = Eo - Eo - log
21. (b) R = 100 W , k = ç ÷ , Fe 2+
/ Fe Cr 3+
/ Cr 6 [Fe2+ ]3
R è aø
l [Nernst -Equ.]
(cell constant) = 1.29 × 100m–1
a 0.059 (0.1)2
Given, R = 520W, C = 0.2 M, = –0.42 – (–0.72) - log
6 (0.01)3
 www.crackjee.xyz
Electrochemistry C-83
0.059 0.1´ 0.1 \ The potential difference needed for the
= –0.42 + 0.72 - log reduction = 2.5 V.
6 0.01´ 0.01´ 0.01
0.059 10-2 0.059 28. (a) The value of E o for given metal ions
= 0.3 - log = 0.3 - ´4 M 2∗ M
6 -6 6
10 are
= 0.30 – 0.0393 = 0.26 V Eo < ,1.18 V,
Hence option (d) is correct answer. Mn 2∗ Mn

3 Eo < ,0.9 V,
25. (c) CH3OH (l) + O (g) ® CO2 (g) + 2H2O Cr 2∗ Cr
2 2
(l) Eo < ,0.44 V and
Fe 2∗ Fe
DG r = DG f (CO 2 , g) + 2DG f (H 2 O, l) -
Eo < ,0.28 V.
3 Co 2∗ Co
DG f (CH3OH, l ) – DG f (O2 ,g)
2 The correct order of E o 2∗ values
= – 394.4 + 2 (–237.2) – (–166.2) – 0 M M
= – 394.4 – 474.4 + 166.2 = – 702.6 k J without considering negative sign would
be
702.6
% efficiency = ´ 100 = 97% Mn2+ > Cr2+ > Fe2+ > Co2+.
726
26. (b) Given 1 l
29. (a) k= ´
R A
Fe3+ + 3e - ® Fe ,
1 l
E° 3+ = –0.036 V … (i) 1.3 = ´
Fe / Fe 50 A
Fe 2 + + 2e - ® Fe , l
= 65m-1
E° = –0.439V … (ii) A
Fe 2+ / Fe
we have to calculate k ´ 1000
L=
molarity
Fe3+ + e - ® Fe2 + , DG = ? [molarity is in moles/litre but 1000 is used
To obtain this equation subtract equ (ii) to convert liter into cm3]
from (i) we get
æ 1 ö
çè ´ 65 m -1 ÷ ´ 1000 cm 3
Fe3+ + e – ® Fe 2 + … (iii) 260 ø
=
As we know that DG = –nFE 0.4 moles
Thus for reaction (iii) 650 m -1 1
DG = DG1 - DG = ´ m3
260 ´ 4 mol 1000
– nFE° = – nFE1 – (–nFE2) = 6.25 × 10–4 S m2 mol–1
–nFE° = nFE2 – nFE1 30. (d) For a spontaneous reaction DG must be –ve
–1FE° = 2× 0.439F – 3 × 0.036 F
Since DG = – nFE°
–1 FE° = 0.770 F
\ E° = – 0.770V Hence for DG to be -ve DE° has to be
positive. Which is possible when X = Zn,
O -- > F- > Na + > Mg ++ > Al3+ Y = Ni
27. (c) DG = – nFE Zn + Ni++ ¾¾
® Zn++ + Ni
ΧG 966´10 3
E° + E°
or E < < < ,2.5 V Zn / Zn +2 Ni 2+ / Ni
,nF 4´96500
 EBD_7764
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C-84 Chemistry
= 0.76 + (– 0.23) = + 0.53 (positive)
2.5 ´ 10-3 ´ 1000
31. (d) Higher the value of standard reduction =
potential, stronger is the oxidising agent, 0.5
hence MnO4– is the strongest oxidising = 5 S cm2 mol–1 = 5 × 10–4 S m2 mol–1
agent. 34. (c) According to Debye Huckle onsager
equation,
E° = – 0.41 V E°Fe3+ / Fe 2 + = +
32. (d) Cr 3+ / Cr 2 +
lC = l¥ - B C
0.77 V
35. (a) (a)
E ° 3+ = + 1.57 V,,
Mn / Mn 2 +
Mn 2+ + 2e- ® Mn; E o = -1.18V ; ...(i)
E° = + 1.97 V
Co3+ / Co 2 +
33. (a) Given for 0.2 M solution (b) Mn 3+ + e ® Mn 2+ ; E o = -1.51V ; ...(ii)
R = 50 W Now multiplying equation (ii) by two and
k = 1.4 S m–1 = 1.4 × 10–2 S cm–1 subtracting from equation (i)
l 1 l 3Mn 2+ ® Mn + + 2Mn 3+ ;
Now, R = r = ´
a k a
l E o = EOx. + ERed.
-2
Þ = R ´ k = 50 ´1.4 ´ 10
a = – 1.18 + (– 1.51) = – 2.69 V
For 0.5 M solution (–ve value of EMF (i.e. DG = +ve) shows
R = 280 W that the reaction is non-spontaneous)
k =? 36. (d) Cu 2+ + 2e – ¾¾
® Cu
l
= 50 ´ 1.4 ´ 10-2 2F i.e. 2 × 96500 C deposit Cu = 1 mol = 63.5g
a
37. (a) E° – / Mn 2 + = 1.51V
l 1 l MnO 4
Þ R=r = ´
a k a E° = 1.36V
Cl2 /Cl –
1
Þ k= ´ 50 ´ 1.4 ´ 10 -2
280 E° = 1.33V
Cr2 O72 - /Cr3+
1
= ´ 70 ´ 10-2
280 E° = – 0.74
Cr3+ / Cr
= 2.5 × 10–3 S cm–1
Since Cr 3+ is having least reducing
k ´1000
Now, L m = potential, so Cr is the best reducing agent.
M
 www.crackjee.xyz
Chemical Kinetics C-85

Chemical Kinetics
18
1. Units of rate constant of first and zero order 6. The half-life of a radioactive isotope is three
reactions in terms of molarity M unit are hours. If the initial mass of the isotope were 256
respectively [2002] g, the mass of it remaining undecayed after 18
(a) sec–1 , Msec–1 (b) sec–1, M hours would be [2003]
(c) Msec–1 , sec–1 (d) M, sec–1. (a) 8.0 g (b) 12.0 g
2. For the reaction A + 2B ® C, rate is given by (c) 16.0 g (d) 4.0 g
R = [A] [B]2 then the order of the reaction is 7. In respect of the equation k = Ae - E a / RT in
chemical kinetics, which one of the following
[2002]
statements is correct ? [2003]
(a) 3 (b) 6
(a) A is adsorption factor
(c) 5 (d) 7.
(b) Ea is energy of activation
3. The differential rate law for the reaction (c) R is Rydberg’s constant
H2 + I2 ® 2HI is [2002] (d) k is equilibrium constant
d[ H 2 ] d[ I 2 ] d[ HI ] 8. For the reaction system : [2003]
(a) - =- =- 2NO(g) + O 2 (g) ® 2 NO 2 (g) volume is
dt dt dt
suddenly reduced to half its value by increasing
d[H 2 ] d[I 2 ] 1 d[Hl ] the pressure on it. If the reaction is of first order
(b) = = with respect to O2 and second order with respect
dt dt 2 dt
to NO, the rate of reaction will
1 d[H 2 ] 1 d[I 2 ] d[Hl] (a) diminish to one-eighth of its initial value
(c) = =-
2 dt 2 dt dt (b) increase to eight times of its initial value
(c) increase to four times of its initial value
d[H 2 ] d[I 2 ] d[HI]
(d) -2 = -2 = (d) diminish to one-fourth of its initial value
dt dt dt 9. In a first order reaction, the concentration of the
4. If half-life of a substance is 5 yrs, then the total reactant, decreases from 0.8 M to 0.4 M is 15
amount of substance left after 15 years, when minutes. The time taken for the concentration to
initial amount is 64 grams is [2002] change from 0.1 M to 0.025 M is [2004]
(a) 16 grams (b) 2 grams (a) 7.5 minutes (b) 15 minutes
(c) 32 grams (d) 8 grams. (c) 30 minutes (d) 60 minutes
5. The integrated rate equation is [2002] 10. The rate equation for the reaction 2A + B ® C is
Rt = log C0 - logCt. found to be: rate = k[A][B]. The correct statement
The straight line graph is obtained by plotting in relation to this reaction is that the [2004]
(a) rate of formation of C is twice the rate of
1 disappearance of A
(a) time vs logCt (b) vs C
time t
(b) t1 / 2 is a constant
1 1 (c) unit of k must be s–1
(c) time vs Ct (d) vs (d) value of k is independent of the initial
time Ct
concentrations of A and B
 EBD_7764
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C-86 Chemistry
11. The half-life of a radioisotope is four hours. If the 16. A reaction was found to be second order with
initial mass of the isotope was 200 g, the mass respect to the concentration of carbon monoxide.
remaining after 24 hours undecayed is [2004] If the concentration of carbon monoxide is
(a) 3.125 g (b) 2.084 g doubled, with everything else kept the same,
(c) 1.042 g (d) 4.167 g the rate of reaction will [2006]
12. A reaction involving two different reactants (a) increase by a factor of 4
can never be [2005] (b) double
(a) bimolecular reaction (c) remain unchanged
(b) second order reaction
(c) first order reaction (d) triple
(d) unimolecular reaction 17. Rate of a reaction can be expressed by Arrhenius
equation as : [2006]
13. A schematic plot of ln K eq versus inverse of
k = A e–E/RT
temperature for a reaction is shown below [2005]
In this equation, E represents
6.0 (a) the total energy of the reacting molecules
at a temperature, T
ln Keq

(b) the fraction of molecules with energy

greater than the activation energy of the
reaction
2.0
1.5 ´ 10 - 3 1 (K -1 ) 2.0 ´ 10 - 3
(c) the energy above which all the colliding
T molecules will react
The reaction must be (d) the energy below which all the colliding
(a) highly spontaneous at ordinary temperature molecules will react
(b) one with negligible enthalpy change 18. The following mechanism has been proposed
(c) endothermic for the reaction of NO with Br 2 to form NOBr :
(d) exothermic NO(g) + Br2(g) NOBr2(g)
14. t 1 can be taken as the time taken for the NOBr 2 (g ) + NO (g ) ¾
¾® 2 NOBr ( g )
4
If the second step is the rate determining step,
3 the order of the reaction with respect to NO(g)
concentration of a reactant to drop to of its
4 is [2006]
initial value. If the rate constant for a first order (a) 3 (b) 2
t1 (c) 1 (d) 0
reaction is K, the can be written as 19. The energies of activation for forward and reverse
4
reactions for A2 + B2 ƒ 2AB are 180 kJ mol–1
(a) 0.75/K (b) 0.69/K [2005]
and 200 kJ mol–1 respectively. The presence of a
(c) 0.29/K (d) 0.10/K
catalyst lowers the activation energy of both
15. Consider an endothermic reaction X ® Y with
(forward and reverse) reactions by 100 kJ mol–1.
the activation energies E b and E f for the The enthalpy change of the reaction
backward and forward reactions, respectively. (A2 + B2 ® 2AB) in the presence of a catalyst
In general [2005] will be (in kJ mol–1) [2007]
(a) there is no definite relation between (a) 20 (b) 300
E b and E f (c) 120 (d) 280
(b) E b = Ef 20. Consider the reaction, 2A + B ® products.
When concentration of B alone was doubled,
(c) E b > Ef the half-life did not change. When the
concentration of A alone was doubled, the rate
(d) Eb < Ef
 www.crackjee.xyz
Chemical Kinetics C-87
increased by two times. The unit of rate constant 26. A reactant (A) froms two products : [2011RS]
for this reaction is [2007] k
A ¾¾
1 ® B, Activation Energy Ea
(a) s – 1 (b) L mol–1 s–1 k
1
(c) no unit (d) mol L–1 s–1. A ¾¾®
2
C, Activation Energy Ea2
21. A radioactive element gets spilled over the floor If Ea2 = 2 Ea1, then k1 and k2 are related as :
of a room. Its half-life period is 30 days. If the (a) k2 = k1e Ea1 / RT (b) k2 = k1e Ea2 / RT
initial velocity is ten times the permissible value,
after how many days will it be safe to enter the (c) k1 = Ak2e Ea1 / RT (d) k1 = 2k2e Ea2 / RT
room? [2007] 27. For a first order reaction (A) ® products the
(a) 100 days (b) 1000 days concentration of A changes from 0.1 M to 0.025
(c) 300 days (d) 10 days. M in 40 minutes.
The rate of reaction when the concentration of
1 A is 0.01 M is : [2012]
22. For a reaction A ® 2B, rate of disappearance
2 (a) 1.73 × 10–5 M/min (b) 3.47 × 10–4 M/min
of ‘A’ is related to the rate of appearance of ‘B’ (c) 3.47 × 10–5 M/min (d) 1.73 × 10–4 M/min
by the expression [2008] 28. The rate of a reaction doubles when its
d[A] 1 d[B] d[A] 1 d[B] temperature changes from 300 K to 310 K.
(a) – = (b) – = Activation energy of such a reaction will be : (R
dt 2 dt dt 4 dt = 8.314 JK–1 mol–1 and log 2 = 0.301) [2013]
d[A ] d[B] d[A] d[B] (a) 53.6 kJ mol –1 (b) 48.6 kJ mol–1
(c) – = (d) – =4 –1
dt dt dt dt (c) 58.5 kJ mol (d) 60.5 kJ mol–1
23. The half life period of a first order chemical 29. For the non - stoichiometric reaction
reaction is 6.93 minutes. The time required for 2A + B ® C + D, the following kinetic data
the completion of 99% of the chemical reaction were obtained in three separate experiments, all
will be (log 2 = 0.301) [2009] at 298 K.
(a) 23.03 minutes (b) 46.06 minutes
(c) 460.6 minutes (d) 230.03 minutes Initial Initial In itial rate of
Con centration Concentration formation of C
24. The time for half life period of a certain reaction –1 –1
A ¾¾ ® Products is 1 hour. When the initial (A ) (B ) (mol L s )
concentration of the reactant ‘A’, is 2.0 mol L–1, 0.1 M 0.1 M 1.2 × 10
–3

how much time does it take for its concentration 0.1 M 0.2 M 1.2 × 10 –3
to come from 0.50 to 0.25 mol L–1 if it is a zero –3
order reaction ? [2010] 0.2 M 0.1 M 2.4 × 10
(a) 4 h (b) 0.5 h
(c) 0.25 h (d) 1 h The rate law for the formation of C is: [2014]
25. Consider the reaction : dc dc
= k [ A][ B ] = k [ A] [ B ]
2

Cl 2 (aq) + H 2S(aq) ® (a) (b)

dt dt
S(s) + 2H + (aq) + 2Cl - (aq)
dc dc
The rate equation for this reaction is = k [ A][ B ] = k [ A]
2
(c) (d)
rate = k[Cl 2 ][H 2S] dt dt
Which of these mechanisms is/are consistent 30. Higher order (>3) reactions are rare due to :
with this rate equation? [2010] [JEE M 2015]
+ - +
A. Cl 2 + H 2S ® H + Cl + Cl + HS (slow) -
(a) shifting of equilibrium towards reactants
Cl + + HS- ® H + + Cl- + S (fast) due to elastic collisions
(b) loss of active species on collision
B. H 2S ƒ H + + HS- (fast equilibrium) (c) low probability of simultaneous collision
Cl 2 + HS- ® 2Cl - + H + + S (Slow) of all the reacting species
(a) B only (b) Both A and B (d) increase in entropy and activation energy
(c) Neither A nor B (d) A only as more molecules are involved
 EBD_7764
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C-88 Chemistry
31. Decomposition of H2O2 follows a first order 32. Two reactions R1 and R2 have identical pre-
reaction. In fifty minutes the concentration of exponential factors. Activation energy of R1
H2O2 decreases from 0.5 to 0.125 M in one such
exceeds that of R2 by 10 kJ mol–1. If k1 and k2
decomposition. When the concentration of
are rate constants for reactions R1 and R2
H2O2 reaches 0.05 M, the rate of formation of
O2 will be: [JEE M 2016] respectively at 300 K, then ln(k2/k1) is equal to :
–1
(a) 2.66 L min at STP (R = 8.314 J mol–1K–1) [JEE M 2017]
(b) 1.34 × 10–2 mol min–1 (a) 8 (b) 12
(c) 6.96 × 10–2 mol min–1 (c) 6 (d) 4
(d) 6.93 × 10–4 mol min–1

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

1. (a) For a zero order reaction.

2d [ H 2 ] 2d [ I2 ] d [ HI]
rate =k[A]º i.e. rate = k or – =- =
hence unit of k = M.sec–1 dt dt dt
For a first order reaction. 4. (d) t1/2 = 5 years, T = 15 years hence total num-
rate = k [A] ber of half life periods = 15 = 3 .
k = M.sec–1/M = sec–1 5
2. (a) NOTE Order is the sum of the power of \ Amount left = 64 = 8g
the concentrations terms in rate law ( 2) 3
expression. 5. (a) Rt = log Co – log Ct
Hence the order of reaction is = 1 + 2 = 3 It is clear from the equation that if we plot a
graph between log Ct and time, a straight
1 d [ HI]
3. (d) rate of appearance of HI = k
2 dt line with a slope equal to – and
2.303
-d éë H 2 ùû intercept equal to log [Ao] will be obtained.
rate of formation of H2 =
dt 6. (d) t1/2 = 3hrs. T = 18 hours
Q T = n ´ t1/ 2
-d [ I 2 ]
rate of formation of I2 = 18
dt
\n= =6
3
-d [ H 2 ] d [ I2 ] 1 d [ HI] Initial mass (C0) = 256 g
hence =- =
dt dt 2 dt
 www.crackjee.xyz
Chemical Kinetics C-89

C0 256 256 2.303 1 2.303 4

\ Cn = = = = 4g. 14. (c) t1/ 4 = log = log
n 6 64 K 3/ 4 K 3
2 ( 2)

7. (b) In equation k = Ae - E a / RT ; 2.303

A = Frequency factor = (log 4 - log 3)
K
k = velocity constant, R = gas constant
and Ea = energy of activation 2.303
= (2 log 2 - log 3)
8. (b) r = k [O2][NO]2. When the volume is K
reduced to 1/2, the conc. will double 2.303 0.29
\ New rate = k [2O2][2 NO]2 = 8 k [O2][NO]2 = (2 ´ 0.301 - 0.4771) =
K K
The new rate increases to eight times of its 15. (d) Enthalpy of reaction (DH) = Ea – Ea
initial. (f) (b)
9. (c) As the concentration of reactant for an endothermic reaction DH = +Ve
decreases from 0.8 to 0.4 in 15 minutes hence for DH to be negative
Ea < Ea
(b) (f)
hence the t1 / 2 is 15 minutes. To fall the
16. (a) Since the reaction is 2nd order w.r.t CO.
concentration from 0.1 to 0.025 we need Thus, rate law is given as.
two half lives i.e., 30 minutes. r = k [CO]2
10. (d) The velocity constant depends on Let initial concentration of CO is a i.e. [CO]
temperature only. It is independent of =a
concentration of reactants. \ r1 = k (a)2 = ka2
n when concentration becomes doubled,
æ 1ö
11. (a) Nt = N 0 ç ÷ where n is number of half i.e.[CO] = 2a
è 2ø
\ r2 = k (2a)2 = 4ka2 \ r2 = 4r1
life periods. So, the rate of reaction becomes 4 times.
Total time 24 17. (c) In Arrhenius equation k = A e–E/RT, E is the
n= = =6 energy of activation, which is required by
half life 4
the colliding molecules to react resulting
6 in the formation of products.
æ 1ö
\ N t = 200 ç ÷ = 3.125g . 18. (b) (i) NO(g) + Br2(g) NOBr2(g)
è 2ø
12. (d) The molecularity of a reaction is the number (ii) NOBr2 (g ) + NO (g ) ¾
¾® 2 NOBr ( g )
of reactant molecules taking part in a single Rate law equation = k[NOBr2] [NO]
step of the reaction. But NOBr2 is intermediate and must not
appear in the rate law equation
NOTE The reaction involving two
[NOBr2 ]
different reactant can never be unimolecular. from Ist step K C =
13. (d) The graph show that reaction is [NO] [Br2 ]
exothermic. \ [NOBr2] = KC [NO] [Br2]
\ Rate law equation = k . KC [NO]2 [Br2]
-DH
log k = +1 hence order of reaction is 2 w.r.t. NO.
RT
19. (a) DH R = E f - E b = 180 – 200 = – 20 kJ/mol
For exothermic reaction DH < 0
The nearest correct answer given in
1 choices may be obtained by neglecting
\ log k Vs would be negative straight sign.
T
line with positive slope.
 EBD_7764
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C-90 Chemistry
0.693 0.693 2.303 ´ 2
20. (b) For a first order reaction t1/ 2 = i.e. =
K 6.93 t
t = 46.06 min
for a first order reaction t1/ 2 does not
24. (c) For the reaction
depend up on the concentration. From the A ® Product
given data, we can say that order of
given t1/ 2 = 1 hour
reaction with respect to B = 1 because
change in concentration of B does not for a zero order reaction
change half life.
tcompletion =
[ A0 ] = initial conc.
Order of reaction with respect to A = 1 k rate constant
because rate of reaction doubles when
concentration of B is doubled keeping \ t1 / 2 =
[ A0 ]
concentration of A constant. 2k
\ Order of reaction = 1 + 1 = 2 and units of
second order reaction are L mol–1 sec–1. or k =
[ A0 ] =
2
= 1 mol lit –1 hr–1
21. (a) Suppose activity of safe working = A 2 t1/ 2 2 ´1
Given A0 = 10A Further for a zero order reaction
0.693 0.693 dx change in concentration
l= = k= =
t1/ 2 30 dt time
0.50 - 0.25
2.303 A 2.303 10A 1=
t½ = log 0 = log time
l A 0.693 / 30 A
\ time = 0.25 hr.
2.303 ´ 30 25. (d) Since the slow step is the rate determining
= ´ log10 = 100 days.
0.693 step hence if we consider option (1) we
find
22. (b) The rates of reactions for the reaction
Rate = k [ Cl2 ][ H 2S]
1
A ¾¾ ® 2B Now if we consider option (2) we find
2
Rate = k [ Cl2 ] éë HS ùû
can be written either as -
...(1)
d From equation (i)
-2 [A] with respect to ‘A’’
dt
é H + ù éHS- ù
1 d ë ûë û
or [B] with respect to ‘B’ k=
2 dt H 2S
From the above, we have
- k [ H 2 S]
d 1 d or éë HS ùû =
–2 [A] = [B] H+
dt 2 dt Substituting this value in equation (1) we
d 1 d find
or – [A] = [B]
dt 4 dt
Rate = k [ Cl2 ] K
[ H 2S] = k ' [ Cl2 ][ H 2S]
i.e., correct answer is (b) H+éH+ ù
23. (b) For first order reaction, ë û
hence only , mechanism (1) is consistent
2.303 100
k= log with the given rate equation.
t 100 - 99
26. (c) k1 = A1e - Ea1 / RT .........(i)
0.693 2.303 100
= log
6.93 t 1 k2 = A2 e- Ea2 / RT ........(ii)
 www.crackjee.xyz
Chemical Kinetics C-91
On dividing eqn (i) from eqn. (ii) We find, x = 1
k1 A d [C ]
= 1 ( Ea1 - Ea1 ) / RT Hence = k[ A]1 [ B ]0
k 2 A2 dt
........(iii) 30. (c) Reactions of higher order (>3) are very rare due
to very less chances of many molecules to
Given Ea2 = 2 Ea1 undergo effective collisions.
On substituting this value in eqn. (iii) 1
31. (d) H2O2(aq) ® H2O(aq) + O (g)
Ea / RT 2 2
k1 = k 2 A ´ e 1
For a first order reaction
27. (b) For a first order reaction
2.303 a
2.0303 a 2.303 0.1 k= log
k= log = log t (a - x)
t a-x 40 0.025 Given a = 0.5, (a – x) = 0.125, t = 50 min
2.303 2.303 ´ 0.6020 2.303 0.5
= log 4 = \ k= log
40 40 50 0.125
= 2.78 ´ 10–2 min–1
= 3.47 ´ 10 –2 r = k[H2O2] = 2.78 ´ 10–2 ´ 0.05
R = k (A)1 = 3.47 × 10–2 × 0.01 = 1.386 ´ 10–3 mol min–1
= 3.47 × 10–4 Now
28. (a) Activation energy can be calculated from d [ H 2 O2 ] d [ H2 O] 2d [ O2 ]
the equation - = =
dt dt dt
log k2 - Ea æ 1 1 ö
= - 2d [ O2 ] d [ H 2 O2 ]
log k1 2.303 R çè T2 T1 ÷ø \ = -
dt dt

Given
k2
= 2 ; T2 = 310 K ; T1 = 300 K d [ O2 ] 1 d[H 2 O 2 ]
k1 \ = ´
dt 2 dt

= log 2 =
- Ea æ 1
-
1 ö 1.386 ´10-3
ç ÷ = = 6.93 ´ 10–4 mol min–1
2.303 ´ 8.314 è 310 300 ø 2
Ea = 53598.6 J/mol = 53.6 kJ/mol. 32. (d) From arrhenius equation,
d [C ] – Ea
29. (d) Let rate of reaction = = k[A]x [B]y k = A.e RT
t
Now from the given data –E a /RT
so, k1 = A.e 1 .....(1)
1.2 × 10 – 3 = k [0.1]x[0.1]y .....(i)
1.2 × 10 – 3 = k [0.1]x[0.2]y .....(ii) –E a / RT
k 2 = A.e 2 .....(2)
2.4 × 10 – 3 = k [0.2]x[0.1]y .....(iii)
Dividing equation (i) by (ii) On dividing equation (2) (1)
-3 x y
1.2 ´10 k[0.1] [0.1]
Þ = (E a – Ea )
-3
1.2 ´10 k [0.1]x [0.2] y k 1 2
Þ 2 =e RT
We find, y = 0 k1
Now dividing equation (i) by (iii)
æ k ö Ea – Ea 2 10, 000
1.2 ´10-3 k[0.1]x [0.1] y ln ç 2 ÷ = 1 = =4
Þ = è k1 ø RT 8.314 ´ 300
2.4 ´10 -3 k [0.2] x [0.1] y
 EBD_7764
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C-92 Chemistry

19
Surface Chemistry

1. The formation of gas at the surface of tungsten (b) Mixing the sols has no effect
due to adsorption is the reaction of order [2002] (c) Sodium sulphate solution causes
(a) 0 (b) 1 coagulation in both sols
(c) 2 (d) insufficient data. (d) Magnesium chloride solution coagulates,
the gold sol more readily than the iron (III)
2. Which one of the following characteristics is
hydroxide sol
not correct for physical adsorption ? [2003] 6. In Langmuir's model of adsorption of a gas on a
(a) Adsorption increases with increase in solid surface [2006]
temperature (a) the mass of gas striking a given area of
(b) Adsorption is spontaneous surface is proportional to the pressure of
(c) Both enthalpy and entropy of adsorption the gas
are negative (b) the mass of gas striking a given area of
(d) Adsorption on solids is reversible surface is independent of the pressure of
3. Identify the correct statement regarding enzymes the gas
[2004] (c) the rate of dissociation of adsorbed
(a) Enzymes are specific biological catalysts molecules from the surface does not
that cannot be poisoned depend on the surface covered
(d) the adsorption at a single site on the surface
(b) Enzymes are normally heterogeneous
may involve multiple molecules at the same
catalysts that are very specific in their
time
action
7. Gold numbers of protective colloids A, B, C and D
(c) Enzymes are specific biological catalysts
are 0.50, 0.01, 0.10 amd 0.005, respectively. the
that can normally function at very high
correct order of their protective powers is [2008]
temperatures (T~1000K) (a) D < A < C < B (b) C < B < D < A
(d) Enzymes are specific biological catalysts (c) A < C < B < D (d) B < D < A < C
that possess well-defined active sites 8. Which of the following statements is incorrect
4. The volume of a colloidal particle, VC as regarding physissorptions? [2009]
compared to the volume of a solute particle in a (a) More easily liquefiable gases are adsorbed
readily.
true solution VS , could be [2005]
(b) Under high pressure it results into multi
VC ~ 10 3 VC ~ - 3 molecular layer on adsorbent surface.
(a) - (b) - 10
VS VS (c) Enthalpy of adsorption ( DH adsorption) is
VC VC ~ low and positive.
(c) ~ 10 23
- (d) -1 (d) It occurs because of van der Waal’s forces.
VS VS 9. According to Freundlich adsorption isotherm
5. The disperse phase in colloidal iron (III) which of the following is correct? [2012]
hydroxide and colloidal gold is positively and x
negatively charged, respectively. Which of the (a) µ p0
m
following statements is NOT correct ? [2005]
x
(a) Coagulation in both sols can be brought (b) µ p1
about by electrophoresis m
 www.crackjee.xyz
Surface Chemistry C-93
x 12. The Tyndall effect is observed only when
(c) µ p1/n following conditions are satisfied: [JEE M 2017]
m
(d) All the above are correct for different (i) The diameter of the dispersed particles is
ranges of pressure much smaller than the wavelength of the
10. The coagulating power of electrolytes having light used.
ions Na+, Al3+ and Ba2+ for arsenic sulphide sol
increases in the order : [2013] (ii) The diameter of the dispersed particle is
(a) Al3+ < Ba2+ < Na+ (b) Na+ < Ba2+ < Al3+ not much smaller than the wavelength of
(c) Ba2+ < Na+ < Al3+ (d) Al3+ < Na+ < Ba2+ the light used.
11. For a linear plot of log (x/m) versus log p in a (iii) The refractive indices of the dispersed
Freundlich adsorption isotherm, which of the phase and dispersion medium are almost
following statements is correct? (k and n are
constants) [JEE M 2016] similar in magnitude.
(a) Only 1 n appears as the slope. (iv) The refractive indices of the dispersed
phase and dispersion medium differ
(b) log (1 n ) appears as the intercept. greatly in magnitude.
(c) Both k and 1 n appear in the slope term. (a) (i) and (iv) (b) (ii) and (iv)
(d) 1 n appears as the intercept. (c) (i) and (iii) (d) (ii) and (iii)

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12
(b) (a) (d) (a) (b) (a) (c) (c) (d) (c) (a) (b)

1. (b) It is zero order reaction 5. (b) When oppositely charged sols are mixed
their charges are neutralised. Both sols may
[ NOTE Adsorption of gas on metal sur--
be partially or completely precipitated.
face is of zero order] 6. (a) According to Langmuir's Model of
2. (a) As adsorption is an exothermic process. adsorption of a gas on a soild surface the
\ Rise in temperature will decrease adsorption mass of gas adsorbed(x)per gram of the
(according to Le-chatelier principle). adsorbent (m) is directly proportional to
3. (d) Enzymes are very specific biological the pressure of the gas (p) at constant
catalysts possessing well - defined active temperature i.e.
sites x
4. (a) Particle size of colloidal particle = 1mµ to µp
m
100 mµ 7. (c) For a protective colloid µ lesser the value
(suppose 10 mµ) of gold number better is the protective
power.
4 3 4 3
Vc = pr Vc = p(10) Thus the correct order of protective power
3 = 3 of A, B, C and D is
Particle size of true solution particle = 1mm Þ (A) < (C) < (B) < (D)
Gold number 0.50 0.10 0.01 0.005
4 3 Vc 3
Vs = p(1) hence now = 10 Hence (c) is the correct answer
3 Vs
 EBD_7764
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C-94 Chemistry
8. (c) Adsorption is an exothermic process, 11. (a) According to Freundlich adsorption isotherm
hence DH will always be negative x 1
9. (d) The Freundlich adsorption isotherm is log = log K + log P
m n
mathematically represented as
Thus if a graph is plotted between log(x/m) and
x log P, a straight line will be obtained
= kP1/n
m n
1/
at high pressure 1/n = 0. Hence, x / m µ =
pe
P° s lo

log x/m
at low pressure 1/n = 1 Hence, x/m µ P¢

Intercept = log K
10. (c) According to Hardy Schulze rule, greater
the charge on cation, greater is its log P
coagulating power for negatively charged The slope of the line is equal to 1/n and the
sol (As2S3), hence the correct order of intercept on log x/m axis will correspond to log
coagulating power : Na+ < Ba2+ < Al3+ K.
12. (b)
 www.crackjee.xyz
General Principles and Processes of Isolation of Elements C-95

20
General Principles and
Processes of Isolation of Elements
1. Aluminium is extracted by the electrolysis of 6. Which method of purification is represented by
[2002] the following equation ? [2012]
(a) bauxite
523K
(b) alumina Ti(s) + 2I 2 (g) ¾¾¾®
(c) alumina mixed with molten cryolite
1700K
(d) molten cryolite. TiI 4 (g) ¾¾¾¾
® Ti(s) + 2I 2 (g)
2. The metal extracted by leaching with a cyanide
(a) Zone refining (b) Cupellation
is [2002]
(a) Mg (b) Ag (c) Polling (d) Van Arkel
(c) Cu (d) Na. 7. The metal that cannot be obtained by
3. Which one of the following ores is best electrolysis of an aqueous solution of its salts
concentrated by froth-flotation method? [2004] is: [2014]
(a) Galena (b) Cassiterite (a) Ag (b) Ca
(c) Magnetite (d) Malachite (c) Cu (d) Cr
4. During the process of electrolytic refining of
copper, some metals present as impurity settle 8. In the context of the Hall - Heroult process for
as ‘anode mud’. These are [2005] the extraction of Al, which of the following
(a) Fe and Ni (b) Ag and Au statements is false ? [JEE M 2015]
(c) Pb and Zn (d) Sn and Ag 3+
(a) Al is reduced at the cathode to form Al
5. Which of the following factors is of no (b) Na3AlF6 serves as the electrolyte
significance for roasting sulphide ores to the (c) CO and CO2 are produced in this process
oxides and not subjecting the sulphide ores to
(d) Al2O3 is mixed with CaF2 which lowers the
carbon reduction directly? [2008]
(a) Metal sulphides are thermodynamically melting point of the mixture and brings
more stable than CS2 conductivity
(b) CO2 is thermodynamically more stable than 9. Which one of the following ores is best
CS2 concentrated by froth floatation method?
(c) Metal sulphides are less stable than the [JEEM 2016]
corresponding oxides (a) Galena (b) Malachite
(d) CO2 is more volatile than CS2 (c) Magnetite (d) Siderite

Answer Key
1 2 3 4 5 6 7 8 9
(c) (b) (c) (b) (c) (d) (b) (b) (a)

www.crackjee.xyz
C-96
1. (c) Pure aluminium can be obtained by
electrolysis of a mixture containing alumina,
crayolite and fluorspar in the ratio 20 : 24 :
20. The fusion temperature of this mixture
is 900ºC and it is a good conductor of
electricity.
2. (b) Silver ore forms a soluble complex with
NaCN from which silver is precipitated
using scrap zinc.
Zn
Ag 2 S + 2 NaCN ® Na[Ag (CN ) 2 ] ¾¾®
Na 2 [ Zn (CN ) 4 ] + Ag ¯
sodargento-cynanide
(soluble)
3. (c) NOTE Galena is PbS and thus purified
by froth floatation method.
Froath floatation method is used to
concentrate sulphide ores. This method is
based on th e preferential wetting
properties with the froathing agent and
water.
4. (b) During the process of electrolytic refining
Ag and Au are obtained as anode mud.
5. (c) NOTE The reduction of metal sulphides
by car bon reduction process is not
spontaneous because DG for such a
process is positive. The reduction of metal
oxide by carbon reduction process is
spontaneous as DG for such a process is
negative.
EBD_7764
Chemistry
From this we find that on thermodynamic
considerations CO2 is more stable than CS2
and the metal sulphides are more stable
than corresponding oxides.
In view of above the factor listed in choice
(c) is incorrect and so is of no significance.
Hence the correct answer is (c)
6. (d) Van Arkel is a method in which heat
treatment is used to purify metal in this
process metals are converted into other
metal compound for loosly coupled like as
iodine to make metal iodide which are easily
decomposed and give pure metal.
The process is known as Van Arkel
method.
7. (b) On electrolysis of aqueous solution of
s-block elements H2 gas discharge at
cathode.
1
At cathode: H 2O + e- ® H 2 + OH -
2
8. (b) In the metallurgy of aluminium, purified Al2O3
is mixed with Na3AlF6 or CaF2 which lowers
the melting point of the mix and brings
conductivity.
9. (a) Froth floatation method is mainly applicable
for sulphide ores.
(1) Malachite ore : Cu(OH)2 . CuCO3
(2) Magnetite ore : Fe3O4
(3) Siderite ore : FeCO3
(4) Galena ore : PbS (Sulphide Ore)
 www.crackjee.xyz

The p-Block Elements

(Group 15, 16, 17 & 18)
21
1. In XeF2, XeF4, XeF6 the number of lone pairs on solution which appears like a cloudy smoke.
Xe are respectively [2002] (c) due to strong affin ity for water,
(a) 2, 3, 1 (b) 1, 2, 3 concentrated hydrochloric acid pulls
(c) 4, 1, 2 (d) 3, 2, 1. moisture of air towards itself. This moisture
2. In case of nitrogen, NCl3 is possible but not forms droplets of water and hence the
NCl5 while in case of phosphorous, PCl 3 as well cloud.
as PCl5 are possible. It is due to [2002] (d) concentrated hydrochloric acid emits
(a) availability of vacant d orbitals in P but not strongly smelling HCl gas all the time.
in N 7. Which one of the following substances has the
(b) lower electronegativity of P than N highest proton affinity ? [2003]
(c) lower tendency of H-bond formation in P (a) H2S (b) NH3
than N (c) PH3 (d) H2O
(d) occurrence of P in solid while N in gaseous 8. Which among the following factors is the most
state at room temperature. important in making fluorine the strongest
3. Number of sigma bonds in P4O10 is [2002] oxidizing halogen ? [2004]
(a) 6 (b) 7 (a) Hydration enthalpy
(c) 17 (d) 16. (b) Ionization enthalpy
4. Oxidation number of Cl in CaOCl2 (bleaching (c) Electron affinity
power) is: [2002] (d) Bond dissociation energy
(a) zero, since it contains Cl2 9. Excess of KI reacts with CuSO4 solution and
(b) – 1, since it contains Cl – then Na2S2O3 solution is added to it. Which of
(c) + 1, since it contains ClO– the statements is incorrect for this reaction ?
(d) + 1 and – 1 since it contains ClO– and Cl– [2004]
5. What may be expected to happen when (a) Na2S2O3 is oxidised
phosphine gas is mixed with chlorine gas ? (b) CuI2 is formed
[2003] (c) Cu2I2 is formed
(a) PCl3 and HCl are formed and the mixture (d) Evolved I2 is reduced
warms up 10. Which one of the following statement regarding
(b) PCl5 and HCl are formed and the mixture helium is incorrect ? [2004]
cools down (a) It is used to produce and sustain powerful
(c) PH3 . Cl2 is formed with warming up superconducting magnets
(d) The mixture only cools down (b) It is used as a cryogenic agent for carrying
6. Concentrated hydrochloric acid when kept in out experiments at low temperatures
open air sometimes produces a cloud of white (c) It is used to fill gas balloons instead of
fumes. The explanation for it is that [2003] hydrogen because it is lighter and non-
(a) oxygen in air reacts with the emitted HCl inflammable
gas to form a cloud of chlorine gas (d) It is used in gas-cooled nuclear reactors
(b) strong affinity of HCl gas for moisture in air 11. The number of hydrogen atom(s) attached to
results in forming of droplets of liquid phosphorus atom in hypophosphorous acid is
[2005]
 EBD_7764
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C-98 Chemistry
(a) three (b) one 19. Which of the following has maximum number of
(c) two (d) zero lone pairs associated with Xe ? [2011RS]
12. The correct order of the thermal stability of (a) XeF4 (b) XeF6
hydrogen halides (H–X) is [2005] (c) XeF2 (d) XeO3
(a) HI > HCl < HF > HBr 20. The molecule having smallest bond angle is :
(b) HCl< HF > HBr < HI [2012]
(c) HF > HCl < HBr > HI (a) NCl3 (b) AsCl3
(c) SbCl3 (d) PCl3
(d) HI < HBr > HCl < HF
21. Which among the following is the most reactive ?
13. Which of the following statements is true?
[JEE M 2015]
[2006]
(a) I2 (b) IC1
(a) HClO4 is a weaker acid than HClO3
(c) Cl2 (d) Br2
(b) HNO3 is a stronger acid than HNO2
22. Assertion: Nitrogen and oxygen are the main
(c) H3PO3 is a stronger acid than H2SO3 components in the atmosphere but these do not
(d) In aqueous medium HF is a stronger acid react to form oxides of nitrogen.
than HCl Reason: The reaction between nitrogen and
14. The increasing order of the first ionization oxygen requires high temperature.
enthalpies of the elements B, P, S and F (Lowest [JEE M 2015]
first) is [2006] (a) The assertion is incorrect, but the reason
(a) B < P < S < F (b) B < S < P < F is correct
(c) F < S < P < B (d) P < S < B < F (b) Both the assertion and reason are incorrect
15. What products are expected from the (c) Both assertion and reason are correct, and
disproportionation reaction of hypochlorous the reason is the correct explanation for
acid? [2006] the assertion
(a) HCl and Cl2O (b) HCl and HClO3 (d) Both assertion and reason are correct, but
(c) HClO3 and Cl2O (d) HClO2 and HClO4 the reason is not the correct explanation
16. Identify the incorrect statement among the fol- for the assertion
lowing. [2007] 23. Which one has the highest boiling point ?
(a) Br 2 reacts with hot and strong NaOH [JEE M 2015]
solution to give NaBr and H2O. (a) Kr (b) Xe
(b) Ozone reacts with SO2 to give SO3. (c) He (d) Ne
(c) Silicon reacts with NaOH(aq) in the pres- 24. The pair in which phosphorous atoms have a
ence of air to give Na2SiO3 and H2O. formal oxidation state of + 3 is : [JEE M 2016]
(a) Orthophosphorous and hypophosphoric
(d) Cl2 reacts with excess of NH3 to give N2
acids
and HCl. (b) Pyrophosphorous and pyrophosphoric
17. Regular use of the following fertilizers increases acids
the acidity of soil? [2007] (c) Orthophosphorous and
(a) Ammonium sulphate pyrophosphorous acids
(b) Potassium nitrate (d) Pyrophosphorous and hypophosphoric
(c) Urea acids
25. The reaction of zinc with dilute and
(d) Superphosphate of lime.
concentrated nitric acid, respectively, produces:
18. Which one of the following reactions of xenon [2016]
compounds is not feasible? [2009] (a) NO and N2O (b) NO2 and N2O
(a) 3Xe F4 + 6H 2 O ¾¾ ® (c) N2O and NO2 (d) NO2 and NO
2 Xe + Xe O3 +12HF +1.5O 2 26. The products obtained when chlorine gas reacts
(b) 2Xe F2 + 2H 2 O ¾¾
® 2 Xe + 4HF + O 2 with cold and dilute aqueous NaOH are :
[2017]
(c) Xe F6 + RbF ¾¾
® Rb[Xe F7 ] –
(a) ClO and ClO3 – (b) ClO2 and ClO3–
–
(d) Xe O3 + 6HF ¾¾® Xe F6 + 3H 2 O –
(c) Cl and ClO – (d) Cl– and ClO2–
 www.crackjee.xyz
The p-Block Elements (Group 15, 16, 17 & 18) C-99

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

1. (d) In the formation of XeF 2 , sp 3 d are available. Hence phosphorous can from
hybridisation occurs which gives the pentahalides also but nitrogen can not form
molecule a trigonal bipyramidal structure. pentahalide due to absence of d-orbitals
F
O
••

••
Xe ||
5s 5p 5d
Ground state P
••
configuration F O O
3. (d)
O
O P P O
||

||
Excited state
O
configuration O P
In the formation of XeF 4 , sp 3 d 2 || O
hybridization occurs which gives the O
molecule an octahedral structure.
F F 4. (d) CaOCl2 –– or it can also be written as
Ca (OCl) Cl
xe x1 x2
Excited state config.
F F hence oxidation no of Cl in OCl– is
–2 + x2 = –1
In the formation of XeF 6 , sp 3 d 3
hybridization occurs which gives the
x2 = 2–1 = +1
molecule a pentagonal bipyramidal
structure. now oxidation no. of another Cl is –1 as it
F is present as Cl–.
F 5. (d) On mixing phosphine with chlorine gas PCl5
F and HCl forms. The mixture cools down.
xe
PH3 + 4Cl2 –––––® PCl5 + 3HCl
6. (a) 4HCl + O2 ® 2Cl2 + 2H2O
F F
air cloud of white fumes
F . .
2. (a) 2 2 3 2 2 6 2 3
7N = 1s 2s 2p ; 15P = 1s 2s 2p 3s 3p 7. (b) Among the given compounds, the N H 3 is
NOTE In phosphorous the 3d- orbitals most basic. Hence has highest proton af-
finity
 EBD_7764
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C-100 Chemistry
8. (d) The fluorine has low dissociation energy atom having fully or half filled stable
of F - F bond and reaction of atomic fluorine orbitals.
is exothermic in nature In this case P has a stable half filled
-1
electronic configuration hence its ionisation
0
9. (b) 4 KI +2CuSO4 ® I 2 + Cu 2 I 2 + 2 K 2SO 4 enthalapy is greater in comparision to S.
Hence the correct order is B < S < P<F.
0 2+ +2.5 -1 15. (b) During disproportionation same compound
I 2 + 2Na 2 S2 O3 ® Na 2 S4 O6 + 2 NaI undergo simultaneous oxidation and
In this CuI2 is not formed. reduction.
10. (c) Helium is heavier than hydrogen although Oxidation
it is non-inflammable redution
- + -1 +5
3HO Cl ¾ ¾® 2HCl+ HClO 3
H
| 16. (d) Chlorine reacts with excess of ammonia to
11. (c) Hypophosphorous acid H - O - P ® O produce ammonium chloride and nitrogen.
|
H 17. (a) (NH4)2SO4 + 2H2O¾¾ ® 2H2SO4 + NH4OH
H2SO4 is strong acid and increases the
Two H-atoms are attached to P atom.
acidity of soil.
12. (c) The H–X bond strength decreases from HF 18. (d) The products of the concerned reaction
to HI. i.e. HF > HCl > HBr > HI. Thus HF is react each other forming back the reactants.
most stable while HI is least stable. This is
XeF6 + 3H 2 O ¾¾ ® XeO3 + 6HF .
evident from their decomposition reaction:
HF and HCl are stable upto 1473K, HBr
decreases slightly and HI dissociates F
considerably at 713K. The decreasing
stability of the hydrogen halide is also
reflected in the values of dissociation
energy of the H–X bond 19. (c) XeF2 : Xe

H-F H - Cl H - Br H-I
135kcal mol-1 103kcal mol -1 87kcal mol-1 71kcal mol -1

+5 +3
F
13. (b) The HNO3 is stronger than HNO 2 . The 3l p
more the oxidation state of N, the more is
the acid character.
14. (b) The correct order of ionisation enthalpies F F
is
F>P>S>B Xe

NOTE On moving along a period XeF4 : F F

ionization enthalapy increases from left to
right and decreases from top to bottom in a 2l p
group. But this trend breaks up in case of
 www.crackjee.xyz
The p-Block Elements (Group 15, 16, 17 & 18) C-101
21. (b) ICl Order of reactivity of halogens
Cl2 > Br2 > I2
F But, the interhalogen compounds are
generally more reactive than halogens
(except F2), since the bond between two
dissimilar electronegative elements is
weaker than the bond between two similar
F
atoms i.e, X – X
F Xe
22. (c) Nitrogen and oxgen in air do not react to
XeF6 : F F form oxides of nitrogen in atmosphere be-
F cause the reaction between nitrogen and
oxygen requires high temperature.
1l p 23. (b) Xe. As we move down the group, the
melting and boiling points show a regular
increase due to corresponding increase in
the magnitude of their van der waal forces
of attraction as the size of the atom increases.
24. (c) Phosphorous acid contain P in +3 oxidation
state.
Xe Acid Formula Oxidation
state of
XeO3 : O O Phosphorus
O
Pyrophosphorous acid H4P2O 5 +3
1l p Pyrophosphoric acid H4P2O 7 +5
Orthophosphorous acid H3PO 3 +3
Hence XeF2 has maximum no. of lone pairs Hypophosphoric acid H4P2O 6 +4
25. (c) Reaction of Zn with dil. HNO3
of electrons.
4Zn + 10HNO 3(dil) 4Zn(NO 3) 2 +
20. (c) All the members form volatile halides of 5H2O + N2O
the type (Zn reacts differently with very
AX3. All halides are pyramidal in shape. dilute HNO3)
The bond angle decreases on moving Reaction of Zn with conc. HNO3
down the group due to decrease in bond Zn + 4HNO 3 (conc.) Zn(NO 3) 2 +
2H2O + 2NO2
pair-bond pair repulsion.
26. (c) Cl2 + NaOH ® NaCl + NaClO + H2O
NCl3 PCl3 AsCl3
[cold and dilute]
107° 94° 92°
 EBD_7764
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C-102 Chemistry

The d-and f-Block Elements

22
1. Most common oxidation states of Ce (cerium) (a) In acidic solutions protons coordinate with
are [2002]
ammonia molecules forming NH +4 ions and
(a) +2, +3 (b) +2, +4
NH3 molecules are not available
(c) +3, +4 (d) +3, +5.
(b) In alkaline solutions insoluble Cu(OH)2 is
2. Arrange Ce+3, La+3, Pm+3 and Yb+3 in increasing
precipitated which is soluble in excess of
order of their ionic radii. [2002]
+3 +3 +3 +3
any alkali
(a) Yb < Pm < Ce < La
(c) Copper hydroxide is an amphoteric
(b) Ce+3 < Yb+3 < Pm+3 < La+3 substance
(c) Yb+3 < Pm+3 < La+3 < Ce+3 (d) In acidic solutions hydration protects
(d) Pm+3 < La+3 < Ce+3 < Yb+3. copper ions
3. Which of the following ions has the maximum 8. A red solid is insoluble in water. However it
magnetic moment? [2002] becomes soluble if some KI is added to water.
(a) Mn +2 (b) Fe+2 Heating the red solid in a test tube results in
(c) Ti+2 (d) Cr+2. liberation of some violet coloured fumes and
4. The most stable ion is [2002] droplets of a metal appear on the cooler parts of
the test tube. The red solid is [2003]
(a) [Fe(OH)3]3- (b) [Fe(Cl)6]3-
(a) HgI2 (b) HgO
(c) [Fe(CN)6]3- (d) [Fe(H2O)6]3+. (c) Pb3O4 (d) (NH4)2Cr2O7
5. When KMnO4 acts as an oxidising agent and 9. A reduction in atomic size with increase in atomic
ultimately forms [MnO4]–2, MnO2, Mn2O3, Mn+2 number is a characteristic of elements of
then the number of electrons transferred in each [2003]
case respectively is [2002] (a) d-block (b) f-block
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (c) radioactive series (d) high atomic masses
10. What would happen when a solution of
(c) 1, 3, 4, 5 (d) 3, 5, 7, 1.
potassium chromate is treated with an excess of
6. The radius of La3+ (Atomic number of La = 57) is dilute nitric acid? [2003]
1.06Å. Which one of the following given values
will be closest to the radius of Lu3+ (Atomic (a) Cr2 O 72- and H2O are formed
number of Lu = 71) ? [2003]
(b) CrO 24- is reduced to +3 state of Cr
(a) 1.40 Å (b) 1.06 Å
(c) 0.85 Å (d) 1.60 Å (c) CrO 24- is oxidized to +7 state of Cr
7. Ammonia forms the complex ion [Cu(NH3)4]2+ (d) Cr3+ and Cr2O 72- are formed
with copper ions in alkaline solutions but not in 11. Which one of the following nitrates will leave
acidic solutions. What is the reason for it ? behind a metal on strong heating ? [2003]
[2003]
 www.crackjee.xyz
The d-and f-Block Elements C-103
(a) Copper nitrate (b) Manganese nitrate 17. Heating mixture of Cu2O and Cu2S will give
(c) Silver nitrate (d) Ferric nitrate [2005]
12. Of the following outer electronic configurations (a) Cu2SO3 (b) CuO + CuS
of atoms, the highest oxidation state is achieved (c) Cu + SO3 (d) Cu + SO2
by which one of them ? [2004] 18. The oxidation state of chromium in the final
(a) (n – 1)d3 ns2 (b) (n – 1)d5 ns1 product formed by the reaction between Kl and
(c) (n – 1)d8 ns2 (d) (n – 1)d5 ns2 acidified potassium dichromate solution is:
13. The soldiers of Napolean army while at Alps [2005]
during freezing winter suffered a serious problem
(a) + 3 (b) + 2
as regards to the tin buttons of their uniforms.
White metallic tin buttons got converted to grey (c) + 6 (d) + 4
power. This transformation is related to 19. Calomel (Hg 2Cl 2 ) on reaction with ammonium
[2004] hydroxide gives [2005]
(a) a change in the partial pressure of oxygen
(a) HgO
in the air
(b) a change in the crystalline structure of tin (b) Hg 2O
(c) an interaction with nitrogen of the air at
(c) NH 2 – Hg – Hg – Cl
very low temperature
(d) an interaction with water vapour contained (d) Hg NH 2 Cl
in the humid air
20. The lanthanide contraction is responsible for
14. Among the properties (a) reducing (b) oxidising
the fact that [2005]
(c) complexing, the set of properties shown by
(a) Zr and Zn have the same oxidation state
CN– ion towards metal species is [2004]
(a) c, a (b) b, c (b) Zr and Hf have about the same radius
(c) a, b (d) a, b, c (c) Zr and Nb have similar oxidation state
15. Cerium (Z = 58) is an important member of the (d) Zr and Y have about the same radius
lanthanoids. Which of the following statements 21. The value of the ‘spin only’ magnetic moment
about cerium is incorrect? [2004] for one of the following configurations is 2.84
(a) The +4 oxidation state of cerium is not BM. The correct one is [2005]
known in solutions
(b) The +3 oxidation state of cerium is more (a) d 5 (in strong ligand field)
stable than the +4 oxidation state (b) d 3 (in weak as well as in strong fields)
(c) The common oxidation states of cerium are
+3 and +4 (c) d 4 (in weak ligand fields)
(d) Cerium (IV) acts as an oxidizing agent
16. The correct order of magnetic moments (spin (d) d 4 (in strong ligand fields)
only values in B.M.) anong is [2004] 22. Which of the following factors may be regarded
as the main cause of lanthanide contraction?
(a) [Fe(CN ) 6 ]4 - > [MnCl 4 ]2 - > [CoCl 4 ]2 - [2005]
(a) Greater shielding of 5d electrons by 4f
(b) [MnCl 4 ]2- > [Fe(CN ) 6 ]4 - > [CoCl 4 ]2 -
electrons
(b) Poorer shielding of 5d electrons by 4f
(c) [MnCl 4 ]2- > [CoCl 4 ]2 - > [Fe(CN ) 6 ]4 -
electrons
(d) [Fe(CN ) 6 ]4 - > [CoCl 4 ]2 - > [MnCl 4 ]2 - (c) Effective shielding of one of 4f electrons
by another in the subshell
(Atomic nos. : Mn = 25, Fe = 26, Co = 27) (d) Poor shielding of one of 4f electron by
another in the subshell

www.crackjee.xyz
C-104
23. A metal, M forms chlorides in its +2 and +4
oxidation states. Which of the following
statements about these chlorides is
correct? [2006]
(a) MCl2 is more ionic than MCl4
(b) MCl2 is more easily hydrolysed than MCl4
(c) MCl2 is more volatile than MCl4
(d) MCl2 is more soluble in anhydrous ethanol
than MCl4
24. Lanthanoid contraction is caused due to
[2006]
(a) the same effective nuclear charge from Ce
to Lu
(b) the imperfect shielding on outer electrons
by 4f electrons from the nuclear charge
(c) the appreciable shielding on outer
electrons by 4f electrons from the nuclear
charge
(d) the appreciable shielding on outer
electrons by 5d electrons from the nuclear
charge
25. The "spin-only" magnetic moment [in units of
Bohr magneton, (µB )] of Ni 2+ in aqueous
solution would be (At. No. Ni = 28) [2006]
(a) 6 (b) 1.73
(c) 2.84 (d) 4.90
26. The stability of dihalides of Si, Ge, Sn and Pb
increases steadily in the sequence [2007]
(a) PbX 2 << SnX 2 << GeX 2 << SiX 2
(b) GeX2 << SiX2 << SnX2 << PbX2
(c) SiX2 << GeX2 << PbX2 << SnX2
(d) SiX2 << GeX2 << SnX2 << PbX2.
27. Identify the incorrect statement among the
following: [2007]
(a) 4f and 5f orbitals are equally shielded.
(b) d-Block elements show irregular and erratic
chemical properties among themselves.
(c) La and Lu have partially filled d-orbitals
and no other partially filled orbitals.
(d) The chemistry of various lanthanoids is
very similar.
28. The actinoids exhibit more number of oxidation
states in general than the lanthanoids. This is
because [2007]
EBD_7764
Chemistry
(a) the 5f orbitals extend further from the
nucleus than the 4f orbitals
(b) the 5f orbitals are more buried than the 4f
orbitals
(c) there is a similarity between 4f and 5f
orbitals in their angular part of the wave
function
(d) the actinoids are more reactive than the
lanthanoids.
29. Larger number of oxidation states are exhibited
by the actinoids than those by the lanthanoids,
the main reason being [2008]
(a) 4f orbitals more diffused than the 5f orbitals
(b) leasser energy difference between 5f and
6d than between 4f and 5d orbitals
(c) more energy difference between 5f and 6d
than between 4f and 5d orbitals
(d) more reactive nature of the actionids than
the lanthanoids
30. Amount of oxalic acid present in a solution can
be determined by its titration with KMnO4
solution in the presence of H2SO4.The titration
gives unsatisfactory result when carried out in
the presence of HCl, because HCl [2008]
(a) gets oxidised by oxalic acid to chlorine
(b) furnishes H+ ions in addition to those from
oxalic acd
(c) reduces permanganate to Mn 2+
(d) Oxidises oxalic acid to carbon doxide and
water
31. Knowing that the chemistry of lanthanoids(Ln)
is dominated by its + 3 oxidation state, which of
the following statements is incorrect? [2009]
(a) The ionic size of Ln (III) decrease in general
with increasing atomic number
(b) Ln (III) compounds ar e generally
colourless.
(c) Ln (III) hydroxide are mainly basic in
character.
(d) Because of the large size of the Ln (III) ions
the bonding in its compounds is
predominantly ionic in character.
32. Iron exhibits +2 and + 3 oxidation states. Which
of the following statements about iron is
incorrect ? [2012]
 www.crackjee.xyz
The d-and f-Block Elements C-105
(a) Ferrous oxide is more basic in nature than +
the ferric oxide. (b) é CoCl ( NH3 ) ù + 5H +
ë 5û
(b) Ferrous compounds are relatively more
ionic than the corresponding ferric ® CO 2 + + 5NH +4 + Cl-
¾¾
compounds.
2+ 4-
(c) Ferrous compounds are less volatile than (c) é Mg ( H 2 O ) ù + ( EDTA )
ë 6û
the corresponding ferric compounds.
(d) Ferrous compounds ar e more easily 2+
® éë Mg ( EDTA ) ùû
excess NaOH + 6H 2 O
hydrolysed than the corresponding ferric ¾¾¾¾¾¾
compounds. (d) CuSO 4 + 4KCN ¾¾
®
33. Which of the following arrangements does not
represent the correct order of the property stated K 2 éëCu ( CN )4 ùû + K 2SO4
against it ? [2013]
(a) V2+ < Cr2+ < Mn2+ < Fe2+ : paramagnetic 36. Match the catalysts to the correct processes :
behaviour [JEE M 2015]
(b) Ni2+ < Co2+ < Fe2+ < Mn2+ : ionic size Catalyst Process
(c) Co3+ < Fe3+ < Cr3+ < Sc3+ : stability in (A) TiCl4 (i) Wacker process
aqueous solution (B) PdCl2 (ii) Ziegler - Natta
(d) Sc < Ti < Cr < Mn : number of oxidation polymerization
states (C) CuCl2 (iii) Contact process
34. Which series of reactions correctly represents (D) V2O5 (iv) Deacon's process
chemical reactions related to iron and its (a) (A) - (ii), (B) - (iii), (C) - (iv), (D) - (i)
compound? [2014] (b) (A) - (iii), (B) - (i), (C) - (ii), (D) - (iv)
dil. H SO H SO , O
(c) (A) - (iii), (B) - (ii), (C) - (iv), (D) - (i)
(a) Fe ¾¾¾¾¾
2 4 ® FeSO ¾¾¾¾¾
4
2 4 2®
(d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
37. The color of KMnO4 is due to : [JEE M 2015]
Fe 2 ( SO4 )3 ¾¾¾
heat
® Fe (a) L ® M charge transfer transition
O , heat dil. H SO
(b) s - s* transition
(b) Fe ¾¾¾¾
2 ® FeO ¾¾¾¾¾
2 4®
(c) M ® L charge transfer transition
heat (d) d – d transition
FeSO 4 ¾¾¾
® Fe
38. Which of the following compounds is metallic
(c) Cl , heat
Fe ¾¾¾¾®
2 FeCl3 ¾¾¾¾®
heat , air and ferromagnetic? [JEE M 2016]
(a) VO2 (b) MnO2
Zn
FeCl 2 ¾¾® Fe (c) TiO2 (d) CrO2
39. In the following reactions, ZnO is respectively
(d) O , heat CO , 600°C
Fe ¾¾¾¾
2 ® Fe3O 4 ¾¾¾¾¾
® acting as a/an: [2017]
CO , 700°C (A) ZnO + Na2O ® Na2ZnO2
FeO ¾¾¾¾¾
® Fe
(B) ZnO + CO2 ® ZnCO3
35. The equation which is balanced and represents
the correct product(s) is: [2014] (a) base and acid (b) base and base
(c) acid and acid (d) acid and base
(a) Li 2 O + 2KCl ¾¾
® 2LiCl + K 2 O

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(c) (a) (a) (c) (c) (c) (a) (a) (b) (a) (c) (d) (b) (a) (a)
16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
(c) (d) (a) (d) (b) (d) (d) (a) (b) (c) (d) (a) (a) (b) (c)
31 32 33 34 35 36 37 38 39
(b) (d) (a) (c) (b) (d) (a) (d) (d)
 EBD_7764
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C-106 Chemistry

1. (c) Common oxidation states of Ce(Cerium) are 8. (a) When KI is added to mercuric iodide it
+ 3 and + 4 disssolve in it and form complex.
2. (a) In lanthanides there is a regular decrease HgI 2 ∗ KI ® K 2 [HgI 4 ]
in the atomic radii as well as ionic radii of red, solid (so lub le)
trivalent ions as the atomic number (inso lub le)
increases from Ce to Lu. This decrease in On heating HgI2 decomposes as
size of atoms and ions is known as
HgI 2 ƒ Hg + I 2
lanthanide contraction. Although the
(violet vapours)
atomic radii do show some irregualrities but
ionic radii decreases from La to Lu. Thus 9. (b) f-block elements show a regular decrease
the correct order is. in atomic size due to lanthanide/actinide
contraction.
Yb+3 < Pm +3 < Ce +3 < La +3
10. (a) When a solution of potassium chromate is
86.8pm 97pm 102pm 103pm
treated with an excess of dilute nitric acid.
3. (a) Mn++ –5 unpaired electrons Potassium dichromate and H2O are formed.
Fe++ – 4 unpaired electrons 2K2CrO4 + 2HNO3 –® K2Cr2O7 + 2KNO3 +
Ti++ – 2 unpaired electrons H2O
Cr++ – 4 unpaired electrons Hence Cr2O7– and H2O are formed.
hence maximum no. of unpaired electron is 11. (c) AgNO3 on heating till red hot
present in Mn++.
decomposes as follows :
NOTE Magnetic moment µ number of 1
AgNO3 ® Ag + NO 2 + O2
unpaired electrons 2
4. (c) The cyano and hydroxo complexes are far 12. (d) (n–1)d5ns2 attains the maximum O.S. of + 7
more stable than those formed by halide 13. (b) Grey tin white tin
ion. This is due to the fact that CN– and
OH– are strong lewis bases (nucleophiles). Grey tin is brittle and crumbles down to
powder in very cold climate
Further [Fe(OH)5]3– is not formed. hence
most stable ion is [Fe(CN)6]3- The conversion of grey tin to white tin is
acompained by increase in volume., This
+3 +7 +6
5. (c) - 4e - -e - 2- is knwon as tin plaque or tin disease.
Mn2 O 3 ¬¾¾ ¾ [KMnO4 ] ¾ ¾¾® [MnO 4 ]
14. (a) CN– ion acts good complexing as well as
– 5e
–
– 3e
–
reducing agent.
+4
Mn
2+
MnO2 15. (a) The +4 oxidation state of cerium is also
known in solution.
1 4–
6. (c) Ionic radii µ 16. (c) [Fe (CN)6] ®
z
– no of unpaired electron = 0
z 1.06 71
Thus, 2 Þ < [MnCl4] ®
2–
z1 3+
(Ionic radii of Lu ) 57
– no of unpaired electron = 5
Þ Ionic radii of Lu3+ = 0.85 Å 2–
.. + [CoCl4] ®
7. (a) N H3 + H + (acid medium) N H4 – no of unpaired electron = 3
 www.crackjee.xyz
The d-and f-Block Elements C-107

NOTE The greater the number of

22. (d) In lanthanides, there is poorer shielding of
5d electrons by 4 f electrons resulting in
unpaired electrons, greater the magnitude greater attraction of the nucleus over 5 d
of magnetic moment. Hence the correct electrons and contraction of the atomic
order will be radii.
[MnCl4]– – > [CoCl4]– – > [Fe(CN)6]4– 23. (a) Metal atom in the lower oxidation state
17. (d) 2Cu 2 O + Cu 2S ¾¾® 6Cu + SO 2 forms the ionic bond and in the higher
self reduction. oxidation state the covalent bond. because
2- - + higher oxidation state means small size and
18. (a) Cr2O7 + 6I + 14H ¾¾
® great polarizing power and hence greater
3+ the covalent character. Hence MCl2 is more
3I2 + 7H 2O + 2 Cr
ionic than MCl4.
oxidation state of Cr is 3+.
24. (b) The configuration of Lanthanides show
19. (d) Hg 2 Cl 2 + 2NH 4OH ¾¾ ® that the additional electron enters the 4f
HgNH 2Cl +NH 4Cl + 2H 2O subshell. The shielding of one 4 f electron
20. (b) NOTE In vertical columns of transition
by another is very little or imperfect. The
imperfect shielding of f electrons is due to
elements, there is an increase in size from the shape of f orbitals which is very much
first member to second member as expected diffused. Thus as the atomic number
but from second member to third member, increases, the nuclear charge increases by
there is very small chang in size and some unity at each step. While no comparable
times sizes are same. This is due to increase in the mutual shielding effect of
lanthanide contraction this is the reason 4f occurs. This causes a contraction in the
for Zr and Hf to have same radius. size of the 4 f subshell. as a result atomic
21. (d) d 5 –––– strong ligand field and ionic radii decreases gradually from La
to Lu.
25. (c) The number of unpaired electrons in
t2g eg Ni2+(aq) = 2
m = n n + 2 = 3 = 1.73BM Water is weak ligand hence no pairing will
take place spin magnetic moment
d 3–– in weak as well as in strong field
= n(n + 2) = 2(2 + 2)

t2g eg = 8 = 2.82
26. (d) Reluctance of valence shell electrons to
m = 3(5) = 15 = 3.87 B.M. participate in bonding is called inert pair
d 4– in weak ligand field effect. The stability of lower oxidation state
(+2 for group 14 element) increases on
going down the group. So the correct order
t2g eg is
SiX2 < GeX2 < SnX2< PbX2
m = 4(8) = 24 = 4.89 27. (a) 4f orbital is nearer to nucleus as compared
d 4– in strong ligand field to 5f orbital therefore, shielding of 4 f is
more than 5f.

t2g eg 28. (a) NOTE More the distance between

nucleus and outer orbitals, lesser will be
m = 2(4) = 8 = 2.82. force of attraction on them. Distance
 EBD_7764
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C-108 Chemistry
between nucleus and 5 f orbitals is more as Co3+ / Co = + 1.97, Fe3+ / Fe = + 0.77 ;
compared to distance between 4f orbital Cr3+ / Cr2+ = – 0.41, Sc 3+ is highly stable as it
and nucleus. does not show + 2 O. S.
So actinoids exhibit more number of (d) Sc – (+ 2), (+ 3)
oxidation states in general than the Ti – (+ 2), (+ 3), (+ 4)
lanthanoids. Cr – (+ 1), (+ 2), (+ 3), (+ 4), (+ 5), (+ 6)
29. (b) NOTE The main reason for exhibiting Mn – (+ 2), (+ 3), (+ 4), (+ 5), (+ 6), (+ 7)
i.e. Sc < Ti < Cr = Mn
larger number of oxidation states by
34. (c) In equation (i) Fe2(SO4)3 and in equation
actinoids as compared to lanthanoids is
lesser energy difference between 5 f and 6d (ii) Fe2(SO4)3 on decomposing will form
orbitals as compared to that between 4f and oxide instead of Fe.
5d orbitals. The correct sequence of reactions is
In case of actinoids we can remove O ,heat CO,600°C
Fe ¾¾¾¾
2 ® Fe3 O 4 ¾¾¾¾¾ ®
electrons from 5f as also from 6 d and due
to this actinoids exhibit larger number of D
Fe2 (SO 4 )3 ¾¾
® Fe
oxidation state than lanthanoids. Thus the
correct answer is option (b) 35. (b) The complex [CoCl(NH3 )5 ]+
30. (c) The titration of oxalic acid with KMnO4 in
decomposes under acidic medium, so
presence of HCl gives unsatisfactory result
because of the fact that KMnO4 can also [CoCl(NH3 )5 ]+ + 5H + ¾¾
®
oxidise HCl along with oxalic acid. HCl on
Co 2 + + 5NH 4 + + Cl -
oxidation gives Cl 2 and HCl reduces
KMnO4 to Mn2+ thus the correct answer 36. (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
is (c). 37. (a) L ® M charge transfer spectra. KMnO4 is
31. (b) Most of the Ln3+ compounds except La3+ colored because it absorbs light in the
and Lu3+ are coloured due to the presence visible range of electromagnetic radiation.
of f-electrons. The permanganate ion is the source of
32. (d) Fe3+ is easily hydrolysed than Fe2+ due to color, as a ligand to metal, (L ® M) charge
more positive charge. transfer takes place between oxygen's p
33. (a) orbitals and the empty d-orbitals on the
(a) V = 3d 3 4s 2 ; V2+ = 3d 3 = 3 unpaired electrons metal. This charge transfer takes place
Cr = 3d 5 4s1 ; Cr2+ = 3d 4 = 4 unpaired electrons when a photon of light is absorbed, which
Mn = 3d 5 4s 2 ; Mn 2+ = 3d 5 = 5 unpaired leads to the purple color of the compound.
electrons 38. (d) Out of all the four given metallic oxides CrO2
Fe = 3d 6 4s 2 ; Fe2+ = 3d 6 = 4 unpaired electrons is attracted by magnetic field very strongly.
Hence the correct order of paramagnetic The effect persists even when the magnetic
behaviour field is removed. Thus CrO2 is metallic and
V2+ < Cr 2+ = Fe2+ < Mn2+
ferromagnetic in nature
(b) For the same oxidation state, the ionic radii
39. (d) Although ZnO is an amphoteric oxide but
generally decreases as the atomic number
in given reaction.
increases in a particular transition series. hence
the order is (A) ZnO + Na2O ® Na2ZnO2
Mn++ > Fe++ > Co++ > Ni++ acid base salt
(c) In solution, the stability of the compound (B) ZnO + CO2 ® ZnCO3
depends upon electrode potentials, SEP of the base acid salt
transitions metal ions are given as
 www.crackjee.xyz
Co-ordination Compounds C-109

Co-ordination Compounds
23
1. A square planar complex is formed by (d) the number of only anionic ligands bonded
hybridisation of which atomic orbitals? to the metal ion.
[2002] 7. Which one of the following complexes is an
outer orbital complex ? [2004]
(a) s, px , py , dyz (b) s, px , p y , d x2 - y2 3+ 4–
(a) [Co(NH3)6] (b) [Mn(CN)6]
(c) s, p x , p y , d z 2 (d) s, py , pz , dxy (c) [Fe(CN)6]4– (d) [Ni(NH3)6]2+
2. The type of isomerism present in (Atomic nos. : Mn = 25; Fe = 26; Co = 27, Ni = 28)
nitropentammine chromium (III) chloride is 8. Coordination compounds have great importance
[2002] in biological systems. In this context which of
(a) optical (b) linkage the following statements is incorrect ? [2004]
(c) ionization (d) polymerisation. (a) Cyanocobalamin is B12 and contains cobalt
3. CH3 – Mg – Br is an organo metallic compound (b) Haemoglobin is the red pigment of blood
due to [2002] and contains irons
(a) Mg – Br bond (b) C – Mg bond (c) Chlorophylls are green pigments in plants
and contain calcium
(c) C – Br bond (d) C – H bond.
(d) Carboxypeptidase - A is an exzyme and
4. One mole of the complex compound
contains zinc.
Co(NH3 ) 5 Cl 3 , gives 3 moles of ions on
dissolution in water. One mole of the same 9. Which one of the following has largest number
complex reacts with two moles of AgNO3 of isomers? [2004]
solution to yield two moles of AgCl (s). The (a) [Ir(PR 3 ) 2 H(CO)]2 +
structure of the complex is [2003]
(a) [Co(NH3)3Cl3]. 2 NH3 (b) [Co( NH 3 )5 Cl]2+
(b) [Co(NH3)4Cl2] Cl . NH3
(c) [Co(NH3)4Cl] Cl2. NH3 (c) [Ru ( NH 3 ) 4 Cl 2 ]+
(d) [Co(NH3)5Cl] Cl2
(d) [Co(en ) 2 Cl 2 ]+
5. In the coordination compound, K4[Ni(CN)4], the
oxidation state of nickel is [2003] (R = alkyl group, en = ethylenediamine)
(a) 0 (b) +1 10. The oxidation state Cr in [Cr ( NH 3 ) 4 Cl 2 ]+ is
(c) +2 (d) –1
(a) 0 (b) + 1 [2005]
6. The coordination number of a central metal atom
in a complex is determined by [2004] (c) + 2 (d) + 3
(a) the number of ligands around a metal ion 11. The IUPAC name of the coordination compound
bonded by sigma and pi-bonds both K 3[Fe(CN ) 6 ] is [2005]
(b) the number of ligands around a metal ion (a) Tripotassium hexacyanoiron (II)
bonded by pi-bonds (b) Potassium hexacyanoiron (II)
(c) the number of ligands around a metal ion (c) Potassium hexacyanoferrate (III)
bonded by sigma bonds (d) Potassium hexacyanoferrate (II)
 EBD_7764
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C-110 Chemistry
12. Which of the following compounds shows (a) 6 and 2 (b) 4 and 2
optical isomerism? [2005] (c) 4 and 3 (d) 6 and 3
(a) [Co(CN) 6 ]3 - (b) [Cr(C 2 O 4 )3 ]3 - 20. In which of the following complexes of the Co
(at. no. 27), will the magnitude of D0 be the
(c) [ ZnCl4 ]2 - (d) [Cu ( NH 3 ) 4 ]2 + hightest? [2008]
(a) [Co(CN)6] 3– (b) [Co(C2O4)3]3–
13. Which one of the following cyano complexes 3+
would exhibit the lowest value of paramagnetic (c) [Co(H2O)6] (d) [Co(NH3)6]3+
behaviour ? [2005] 21. Which of the following has an optical isomer
[2009]
(a) [Co(CN) 6 ]3 - (b) [Fe(CN) 6 ]3 - (a) [Co(en) (NH3)2] 2+

(b) [Co(H2O)4(en)]3+
(c) [Mn (CN) 6 ]3 - (d) [Cr (CN) 6 ]3 -
(c) [Co(en)2 (NH3)2]3+
(At. Nos : Cr = 24, Mn = 25, Fe = 26, Co = 27)
(d) [Co(NH3)3Cl] +
14. The IUPAC name for the complex
22. Which of the following pairs represent linkage
[Co(NO2)(NH3)5]Cl2 is : [2006]
isomers? [2009]
(a) pentaammine nitrito-N-cobalt(II) chloride
(a) [Pd(P Ph3)2(NCS)2 ] and [Pd ( P Ph3)2
(b) pentaammine nitrito-N-cobalt(III) chloride (SCN)2]
(c) nitrito-N-pentaamminecobalt(III) chloride
(b) [Co(NH3)5NO3] SO4 and
(d) nitrito-N-pentaamminecobalt(II) chloride [Co(NH3)5SO4]NO3
15. Nickel (Z = 28) combines with a uninegative (c) [PtCl2(NH3)4] Br2 and [Pt Br 2 (NH3)4] Cl2
monodentate ligand X– to form a paramagnetic
(d) [Cu(NH3)4][Pt Cl4] and [Pt(NH3)4][CuCl4]
complex [NiX4 ]2–. The number of unpaired
electron(s) in the nickel and geometry of this 23. A solution containing 2.675 g of CoCl3. 6 NH3
complex ion are, respectively : [2006] (molar mass = 267.5 g mol–1) is passed through
a cation exchanger. The chloride ions obtained
(a) one, square planar (b) two, square planar
in solution were treated with excess of AgNO3
(c) one, tetrahedral (d) two, tetrahedral
to give 4.78 g of AgCl (molar mass = 143.5 g
16. In Fe(CO)5, the Fe – C bond possesses [2006] mol–1). The formula of the complex is
(a) ionic character
(At. mass of Ag = 108 u) [2010]
(b) s-character only
(c) p-character (a) [Co(NH3 )6 ]Cl3
(d) both s and p characters (b) [CoCl2 (NH3 )4 ]Cl
17. How many EDTA (ethylenediaminetetraacetic
acid) molecules are required to make an (c) [CoCl3 (NH3 )3 ]
octahedral complex with a Ca2+ ion? [2006] (d) [CoCl(NH3 )5 ]Cl2
(a) One (b) Two
24. Which one of the following has an optical
(c) Six (d) Three
isomer? [2010]
18. Which of the following has a square planar
(a) [Zn(en) (NH3)2]2+ (b) [Co(en)3]3+
geometry? [2007]
(c) [Co(H2O)4(en)]3+ (d) [Zn(en)2]2+
(a) [PtCl4]2– (b) [CoCl4]2–
(en = ethylenediamine)
(c) [FeCl4]2– (d) [NiCl4]2–
(At. nos.: Fe = 26, Co = 27, Ni = 28, Pt = 78) 25. Which one of the following complex ions has
geometrical isomers ? [2011]
19. The coordination number and the oxidation
state of the element ‘E’ in the complex (a) [Ni(NH3)5Br]+ (b) [Co(NH3)2(en)2]3+
[E (en)2 (C2O4)]NO2 (where (en) is ethylene (c) [Cr(NH3)4(en)2]3+ (d) [Co(en)3]3+
diamine) are, respectively, [2008] (en ethylenediamine)
 www.crackjee.xyz
Co-ordination Compounds C-111
26. Which among the following will be named as (d) K3[Co(NO2)6]
dibromidobis (ethylene diamine) chromium (III) 30. The number of geometric isomers that can exist
bromide? [2012] for square planar complex [Pt (Cl) (py) (NH3)
(a) [Cr (en)3]Br3 (b) [Cr(en)2Br2]Br (NH2OH)]+ is (py = pyridine) : [JEE M 2015]
(c) [Cr(en)Br4]– (d) [Cr(en)Br2]Br (a) 4 (b) 6
27. Which of the following complex species is not (c) 2 (d) 3
expected to exhibit optical isomerism ? [2013] 31. Which one of the following complexes shows
(a) [Co(en)3]3+ optical isomerism? [JEE M 2016]
(b) [Co(en)2 Cl2]+ (a) trans [Co(en)2Cl2]Cl
(c) [Co(NH3)3 Cl3] (b) [Co(NH3)4Cl2]Cl
(d) [Co(en) (NH3)2 Cl2]+ (c) [Co(NH3)3Cl3]
28. The octahedral complex of a metal ion M3+ with (d) cis[Co(en)2Cl2]Cl
four monodentate ligands L1, L2, L3 and L4 (en = ethylenediamine)
absorb wavelengths in the region of red, green, 32. The pair having the same magnetic moment is:
yellow and blue, respectively. The increasing [At. No.: Cr = 24, Mn = 25, Fe = 26, Co = 27]
order of ligand strength of the four ligands is: [JEE M 2016]
[2014]
(a) [Mn(H2O)6] and [Cr(H2O)6]2+
2+

(a) L4 < L3 < L2 < L1 (b) [CoCl4]2– and [Fe(H2O)6]2+

(c) [Cr(H2O)6]2+ and [CoCl4]2–
(b) L1 < L3 < L2 < L4
(d) [Cr(H2O)6]2+ and [Fe(H2O)6]2+
(c) L3 < L2 < L4 < L1 33. On treatment of 100 mL of 0.1 M solution of
CoCl3 . 6H2O with excess AgNO3; 1.2 × 1022
(d) L1 < L2 < L4 < L3
ions are precipitated. The complex is : [2017]
29. Which of the following compounds is not (a) [Co(H2O)4 Cl2]Cl.2H2O
colored yellow ? [JEE M 2015]
(b) [Co(H2O)3Cl3].3H2O
(a) (NH4)3 [As(Mo3O10)4 ]
(c) [Co(H2O)6]Cl3
(b) BaCrO4
(c) Zn2[Fe(CN)6] (d) [Co(H2O)5Cl]Cl2.H2O

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

1. (b) A square planar complex is formed by

é Cr ( NH3 ) NO2 ù Cl2
hybridisation of ë 5 û
s, px, py and d 2 2 atomic orbitals It can exist in following two structures
x -y
2. (b) The chemical formula of nitropentammine éCr ( NH3 ) NO2 ù Cl2 and
chromium (III) chloride is ë 5 û
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C-112 Chemistry
nitropentammine chromium (III) chloride
[Ir(PR 3 ) 2 H(CO)]2+ , [Co(en ) 2 Cl 2 ]+
éCr ( NH3 ) ONOù Cl2 cis and trans cis and trans and
ë 5 û optical isomers
Nitropentammine chromium (III) chloride
Therefore the type of isomerism found in 10. (d) Oxidation state of Cr in [Cr ( NH 3 ) 4 Cl 2 ]+ .
this compound is linkage isomerism as nitro Let it be x, 1 × x + 4 × 0 + 2 × (–1) = 1
group is linked through N as –NO2 or Therefore x = 3.
through O as – ONO.
11. (c) K 3 [Fe (CN ) 6 ] is potassium
3. (b) Compounds that contain at least one
hexacyanoferrate (III).
carbon metal bond are known as
organ ometallic compounds. In 12. (b) C2O4 C2O 4
CH3-Mg-Br (Grignard's reagent) a bond is
present between carbon and Mg (Metal) Cr C2O 4 C2O4 Cr
hence it is an organometallic compound. C2O4
C2O4
4. (d) Co (NH3)5 Cl3 [Co(NH3)5Cl]+2 + 2Cl-
\ Structure is [Co (NH3)5 Cl] Cl2.
Non-superimposable mirror images, hence
Now [Co(NH3 )5 Cl]Cl2 + 2AgNO3 optical isomers.
® [Co(NH3 )5 Cl](NO3 )2 + 2AgCl 13. (a) No. of unpaired electron
5. (a) Let the O. No of Ni in K4[Fe(CN)6] be = x (a) Co3+ 4
then (b) Fe3+ 1
4 (+ 1) + x + (–1) × 4 = 0 (c) Mn 3+ 4
Þ 4+ x–4=0 (d) Cr3+ 3
x=0 The effective magnetic moment is given by
the number of unpaired electrons in a
6. (c) The coordination number of central metal
substance, the lesser the number of
atom in a complex is equal to number of
unpaired electrons lower is its magnetic
monovalent ligands, twice the number of
moment in Bohr – Magneton and lower
bidentate ligands and so on, around the
shall be its paramagnetism
metal ion bonded by coordinate bonds.
14. (b) [Co(NO)2(NH3)5]Cl2
Hence coordination number = no. of
pentaammine nitrito-N-cobalt (III) chloride
s bonds formed by metals with ligands
7. (d) Hybridisation 15. (d) [Ni X4]2–, the electronic configuration of
Ni2+ is
[Fe(CN)6 ]4 -,[Mn(CN) 6 ]4- ,
d 2sp3 d 2sp3

[Co(NH 3 ] 3+ ,[Ni(NH 3 ) 6 ] 2+
d 2sp 3 sp 3d 2 It contains two unpaired electrons and the
Hence [ Ni( NH3 ) 6 ] 2+
is outer orbital hybridisation is sp3 (tetrahedral).
complex. 16. (d) Due to some backbonding by sidewise
overlapping of between d-orbitals of metal
8. (c) The chlorophyll molecule plays an and p-orbital of carbon, the Fe–C bond in
important role in photosynthesis, contain Fe(CO)5 has both s and p character.
porphyrin ring and the metal Mg not Ca.
17. (a) EDTA has hexadentate four donor O atoms
9. (d) Isomers and 2 donor N atoms and for the formation
[Ru(NH 3 ) 4 Cl2 ]+ ,[Co(NH 3 )5 Cl]2 + , of octahedral complex one molecule is
cis and trans none required
 www.crackjee.xyz
Co-ordination Compounds C-113
18. (a) Complexes with dsp2 hybridisation are 24. (b) For a substance to be optical isomer
square planar. So [PtCl4]2– is square planar following conditions should be fulfiled
in shape. (a) A coordination compound which can
19. (d) In the given complex we have two bidentate rotate the plane of polarised light is
ligands said to be optically active.
(i.e en and C2O4), so coordination number (b) When the coordination compounds
of E is 6 have same formula but differ in their
(2 × 2 + 1 × 2 = 6) abilities to rotate directions of the
Let the oxidation state of E in complex be x, plane of polarised light are said to
then exhibit optical isomerism and the
[x + (–2) = 1] or x – 2 = 1 molecules are optical isomers. The
optical isomers are pair of molecules
or x = + 3, so its oxidation state is + 3
which are non-superimposable mirror
Thus option (d) is correct.
images of each other.
20. (a) In octahedral complex the magnitude of Do (c) This is due to the absence of elements
will be highest in a complex having of symmetry in the complex.
strongest ligand. Of the given ligands CN–
(d) Optical isomerism is expected in
is strongest so D o will be highest for
tetrahedral complexes of the type
[Co(CN)6]3–. Thus option (a) is correct.
Mabcd.
21. (c) H3N NH3
3+ 3+
Based on this only option (2) shows
NH3
optical isomerism
NH3
Co en Co [Co(en)3]3+

en en en

en 3+ en 3+
3+
Enantiomers of cis- éë Co(en) 2 (NH 3 ) 2 ûù
en Co Co
22. (a) The SCN– ion can coordinate through S or en
N atom giving rise to linkage isomerism
en en
M ¬ SCN thiocyanato
d–form Mirror –form
M ¬ NCS isothiocyanato.
23. (a) ® xCl-
CoCl3.6NH3 ¾¾
2.675g

xCl - + AgNO3 ¾¾
® x AgCl ¯ en Co en en
4.78g
Number of moles of the complex
2.675 'Meso' or optically inactive form
= = 0.01 moles
267.5
Number of moles of AgCl obtained Complexes of Zn++ cannot show optical
isomerism as they are tetrahedral complexes
4.78
= = 0.03 moles with plane of symmetry.
143.5
\ No. of moles of AgCl obtained [Co(H 2 O)4 (en)]3+ have two planes of
= 3 × No. of moles of complex symmetry hence it is also optically inactive.
0.03 Hence the formula of the complex is
\n= =3 [Co(NH3)6]Cl3
0.01
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C-114 Chemistry
create a complex with smaller D, which will
25. (b) 3+ absorbs light of longer l and thus lower
en
frequency. Conservely, stronger field
NH3
ligands create a larger D, absorb light of
Co shorter l and thus higher v i.e. higher
energy.
en NH3 Red < Yellow < Green < Blue
l = 650 nm 570 nm 490 nm 450 nm
cis- So order of ligand strength is
L1 < L3 < L2 < L4
NH3 3+ 29. (c)
30. (d) Square planar complexes of type M[ABCD]
form three isomers. Their position may be
obtained by fixing the position of one
en Co en ligand and placing at the trans position any
one of the remaining three ligands one by
one.
HOH2N Cl
NH3
26. (b) [Cr(en)2Br2]Br
Pt
dibromidobis(ethylenediamine) chromium
(III) Bromide.
27. (c) Octahedral coordination entities of the type py NH3
trans
Ma3b3 exhibit geometrical isomerism. The
HOH2N NH3
compound exists both as facial and meridi-
onal isomers, both contain plane of sym-
metry
Pt

NH3 NH3 py Cl
cis
Cl NH3 NH3 Cl HOH2N NH3
Co Co
NH3 Cl Cl
Cl Pt
Cl NH3
fac- mer Cl py
cis
31. (d) Optical isomerism occurs when a molecule is
28. (b) B non-super imposable with its mirror image hence
the complex
V G cis-[Co(en)2Cl2]Cl is optically active.
+ +
en en
Cl Cl

R Y CO CO

Cl
O en
Cl
en

For a given metal ion, weak field ligands Cis-d-isomer Cis-d-isomer

 www.crackjee.xyz
Co-ordination Compounds C-115
32. (d) 100 ´ 0.1
Complex Metal ion = = 0.01 mole
1000
Configuration Magnetic moment
m = n(n + 2) Moles of ions precipitated with excess of
(a) [Cr(H 2O)6 ]2+ Cr+2
1.2 ´ 1022
d4 24 AgNO3 = = 0.02 moles
(b) [Fe(H 2O)6]2+ Fe2+ 6.02 ´ 1023
d6 24 0.01 × n = 0.02
(c) [CoCl4]2– Co2+
\ n =2
d7 15
It means 2Cl– ions present in ionization
(d) [Mn(H 2O)6]2+ Mn 2+ d5 35
Since (a) and (b), each has 4 unpaired electron sphere
they will have same magnetic moment \ complex is [Co(H2O)5Cl]Cl2.H2O
33. (d) Moles of complex

Molarity ´ Volume(ml)
=
1000
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C-116 Chemistry

Haloalkanes and Haloarenes

24
1. Bottles containing C6H5I and C6 H5CH2I lost 6. Phenyl magnesium bromide reacts with methanol
their original labels. They were labelled A and B to give [2005]
for testing. A and B were separately taken in test (a) a mixture of toluene and Mg(OH)Br
tubes and boiled with NaOH solution. The end (b) a mixture of phenol and Mg(Me)Br
solution in each tube was made acidic with dilute (c) a mixture of anisole and Mg(OH)Br
HNO3 and then some AgNO3 solution was
(d) a mixture of benzene and Mg(OMe)Br
added. Substance B gave a yellow precipitate.
7. Fluorobenzene (C6H5F) can be synthesized in
Which one of the following statements is true for
the laboratory [2006]
this experiment ? [2003]
(a) by direct fluorination of benzene with F2
(a) A and C6H5CH2I
gas
(b) B and C6H5I
(b) by reacting bromobenzene with NaF
(c) Addition of HNO3 was unnecessary
solution
(d) A was C6H5I
(c) by heating phenol with HF and KF
2. The compound formed on heating
(d) from aniline by diazotisation followed by
chlorobenzene with chloral in the presence of
heating the diazonium salt with HBF4
concentrated sulphuric acid, is [2004]
8. Reaction of trans 2-phenyl-1
(a) freon (b) DDT
bromocyclopentane on reaction with alcoholic
(c) gammexene (d) hexachloroethane KOH produces [2006]
3. Tertiary alkyl halides are practically inert to (a) 1-phenylcyclopentene
substitution by S N 2 mechanism because of (b) 3-phenylcyclopentene
[2005] (c) 4-phenylcyclopentene
(a) steric hindrance (b) inductive effect (d) 2-phenylcyclopentene
(c) instability (d) insolubility 9. The structure of the major product formed in the
following reaction [2006]
4. Alkyl halides react with dialkyl copper reagents
to give [2005] CH2Cl
NaCN
(a) alkenyl halides DMF is
(b) alkanes
(c) alkyl copper halides I
(d) alkenes CH2Cl
5. Elimination of bromine from 2-bromobutane (a)
results in the formation of – [2005]
(a) Predominantly 2-butyne CN
(b) Predominantly 1-butene CH2CN
(c) Predominantly 2-butene (b)
(d) equimolar mixture of 1 and 2-butene
I
 www.crackjee.xyz
Haloalkanes and Haloarenes C-117

CH2CN
(c) CH2Br
CH2Br
CN (c) (d)
CH3
CH2Cl CH3

(d) CN 15. Among the following oxoacids, the correct

decreasing order of acid strength is: [2014]
I
(a) HOCl > HClO2 > HClO3 > HClO4
10. Which of the following is the correct order of
decreasing SN2 reactivity? [2007] (b) HClO4 > HOCl > HClO 2 > HClO3
(a) R2CH X > R3C X > RCH2 X
(c) HClO4 > HClO3 > HClO2 > HOCl
(b) RCH X > R3C X > R2CH X
(c) RCH2 X > R2CH X > R3C X (d) HClO2 > HClO 4 > HClO3 > HOCl
(d) R3C X > R2CH X > RCH2 X. 16. In SN2 reactions, the correct order of reactivity
(X is a halogen) for the following compounds: [2014]
11. The organic chloro compound, which shows
CH3Cl, CH3CH2Cl, (CH3)2CHCl and (CH3)3CCl
complete sterochemical inversion during a SN2
is:
reaction, is [2008]
(a) (C2H5)2CHCl (b) (CH3)3CCl (a) CH3 Cl > ( CH3 )2 CHCl
(c) (CH3)2 CHCl (d) CH3Cl
> CH3CH 2Cl > ( CH3 )3 CCl
12. Consider the following bromides :
Me Me (b) CH 3Cl > CH 3CH 2Cl
Me Br Me
Br Br > ( CH3 ) 2 CHCl > ( CH3 )3 CCl
(A) (B)
(c) CH3CH 2 Cl > CH3Cl
The correct order of SN1 reactivity is [2010]
(a) B > C > A (b) B > A > C > ( CH3 )2 CHCl > ( CH3 )3 CCl
(c) C > B > A (d) A > B > C
13. How many chiral compounds are possible on (d) ( CH3 )2 CHCl > CH3CH 2Cl
monochlorination of 2- methyl butane ? [2012] > CH 3Cl > ( CH3 )3 CCl
(a) 8 (b) 2
(c) 4 (d) 6 17. The major organic compound formed by the
14. Compound (A), C 8 H 9 Br, gives a white reaction of 1, 1, 1-trichloroethane with silver
precipitate when warmed with alcoholic AgNO3. powder is: [2014]
Oxidation of (A) gives an acid (B), C8H6O4. (B) (a) Acetylene (b) Ethene
easily forms anhydride on heating. Identify the (c) 2 - Butyne (d) 2 - Butene
compound (A). [2013] 18. The synthesis of alkyl fluorides is best
accomplished by : [JEE M 2015]
CH2Br C2H5 (a) Finkelstein reaction
(a) (b) (b) Swarts reaction
Br (c) Free radical fluorination
CH3 (d) Sandmeyer's reaction
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C-118 Chemistry
19. 2-chloro-2-methylpentane on reaction with 21. Which of the following , upon treatment with
sodium methoxide in methanol yields: tert-BuONa followed by addition of bromine
[JEE M 2016] water, fails to decolourize the colour of bromine?
O
CH3
(a)
(i) C2H5CH2C OCH3 Br
C6H5
CH3
(b)
(ii) C2H5CH2C = CH2 Br
O
CH3
(c)
(iii) C2H5CH = C – CH3 Br
O
CH3
(a) (iii) only (b) (i) and (ii) (d)
(c) All of these (d) (i) and (iii) Br
22. The major product obtained in the following
20. The increasing order of the reactivity of the
reaction is : [2017 ]
following halides for the SN1 reaction is
CH3CHCH2CH3 CH3CH2CH2Cl Br
|
Cl (II) H
C6H5 t-BuOK
(I)
D
p-H3CO–C6 H4–CH2Cl C6H5
(III) (a) (±)C6H5CH(OtBu)CH2C6H5
(a) (III) < (II) < (I) (b) (II) < (I) < (III) (b) C6H5CH = CHC6H5
(c) (I) < (III) < (II) (d) (II) < (III) < (I) (c) (+)C6H5CH(OtBu)CH2C6H5
(d) (–)C6H5CH(OtBu)CH2C6H5

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(d) (b) (a) (b) (c) (d) (d) (a) (b) (c) (d) (a) (c) (d) (c)
16 17 18 19 20 21 22
(b) (c) (b) (a) (b) (a) (b)

+ AgNO
1. NaOH C H ONa HNO3 /H
(d) C6H5I ¾¾ ® 6 5 ¾¾ ¾3¾® yellow ppt.
¾¾¾ ®
AgNO
Since benzyl iodide gives yellow ppt.
C6H5OH ¾¾¾¾
3
® No yellow ppt. hence this is compound B and A was
NaOH phenyl iodide (C6H5I).
C6H5CH2I ¾¾¾¾ ® C6H5CH2ONa
+ 2. (b) DDT is prepared by heating chlorbenzene
HNO3/H
¾¾¾¾¾ ® C6H5CH2OH and chloral with concentrated sulphuric
acid
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Haloalkanes and Haloarenes C-119
8. (a) The reaction is dehydrohalogenation
Br
CCl3CHO + 2 H Cl
alc. KOH
C6H5
C6H5
Cl 1-phenyl cyclopentene
H2SO4 9. (b)
CCl3CH
–H2O
CH2Cl CH2CN
NaCN
Cl ¾¾ ¾
¾®
DM F

1,1,1-trichloro–2,2 bis
(p-chlorophenyl) ethane
I I
or Nuclear substitution will not take place.
DDT
10. (c) In S N2 mechanism transition state is
pentavelent. For bulky alkyl group it will
3. (a) Due to steric hindrance tertiary alkyl halide have sterical hinderance and smaller alkyl
do not react by SN2 mechanism they react group will favour the SN2 mechanism. So
by SN1 mechanism. SN2 mechanisam is the decreasing order of reactivity of alkyl
followed in case of primary and secondary halides is
alkyl halides
RCH2X > R2CHX > R3CX
The order is
11. (d) SN2 reaction is favoured by small groups
CH3 – X > CH3– CH2X > (CH3)2 – CH.X >
on the carbon atom attached to halogen.
(CH3)3 – C–X
4. (b) In Corey House synthesis of alkanes alkyl So, the order of reactivity is
halide react with lithium dialkyl cuprate CH 3Cl > (CH 3 ) 2 CHCl > (CH 3 ) 3 CCl
R 'X + LiR 2 Cu ¾¾ ® R '- R + RCu + LiX > (C 2 H 5 ) 2 CHCl
Br
|
Alc. KOH NOTE SN2 reaction is shown to maximum extent by
5. (c) CH3 - CH - CH 2 - CH3 ¾¾¾¾¾
®
primary halides. The only primary halides
CH3 - CH = CH - CH 3 + HBr given is CH3Cl so the correct answer is
The formation of 2-butene is in accordance (d).
to Saytzeff’s rule. The more substituted 12. (a)
alkene is formed.
6. (d) CH 3OH + C 6 H 5 MgBr ¾¾ ® + –
Me Br ionisation +Br
CH 3O.MgBr + C6 H 6 Me
7. (d) A

NH2 N2Cl Me Me
ionisation Me
+ + Br –
Na NO + HCl HBF Br
¾ ¾ ¾ ¾2¾ ¾¾® ¾ ¾ ¾4 ®
0 - 5 º diazotisation B

Me
N2+BF4 F Me ionisation Me
+ Br
–
Me +
Be
D
¾¾® + BF3 + N2 C

Benzene diazonium (Balz-Schiemann Since SN1 reactions involve the formation

tetrafluoroborate reaction)
of carbocation as intermediate in the rate
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C-120 Chemistry
determining step, more is the stability of
Cl
carbocation higher will be reactivity of |
alkyl halides towards SN1 route. Now we 17. (c) 2Cl - C - CH3 + 6Ag
know that stability of carbocations follows |
the order : 3° > 2° > 1°, so SN1 reactivity Cl
should also follow the same order.
3° > 2° > 1° > Methyl (SN1 reactivity) ¾¾
® CH3C º CCH3 + 6AgCl
2 - butyne
Cl
1, 1, 1-trichloroethane
13. (c) CH2 CH CH2 CH3 18. (b) Alkyl fluorides are more conveniently
prepared by heating suitable chloro – or
CH3 bromo-alkanes with organic fluorides such
( R + S) as AsF3, SbF3, CoF2, AgF, Hg2F2 etc. This
reaction is called Swarts reaction.
Cl CH 3Br + AgF ¾¾ ® CH 3 F + AgBr

CH3 CH CH CH3 2CH3CH 2 Cl + Hg 2 F2 ¾¾

®
2CH3CH 2 F + Hg 2Cl 2
CH3
19. (a) When tert -alkyl halides are used in
(R + S)
Williamson synthesis elimination occurs
Four monochloro derivatives are chiral. rather than substitution resulting into
formation of alkene. Here alkoxide ion
CH2Br abstract one of the b-hydrogen atom along
14. (d) Alcholic with acting as a nucleophile.
AgBr¯
CH3 AgNO3
A CH3
Oxidation +– CH3OH
CH3 CH2 CH2 C CH3 + Na OCH3
COOH CO Cl
D
O
2-Chloro-2-methylpentane
COOH CO
Acid (B) Phthalic Anhydride
H CH3
15. (c) Acidic strength increases as the CH OH
CH3CH2 C C CH3 + CH3OH + NaBr
oxidation number of central atom
increases. 2-Methyl-pent-2-ene

Hence acidic strength order is

(+7) (+5) (+3) (+1)
20. (b) Since SN1 reactions involve the formation
HClO4 > HClO3 > HClO2 > HClO
of carbocation as intermediate in the rate
16. (b) Steric congestion around the carbon atom determining step, more is the stability of
undergoing the inversion process will slow carbocation higher will be the reactivity of
down the S N 2 reaction, h ence less alkyl halides towards SN1 route.
congestion faster will the reaction. So, the
order is Since stability of carbocation follows order.
CH3Cl > (CH3)CH2 – Cl > (CH3)2CH – Cl > Å
(CH3)3CCl CH3 – CH2 – CH 2
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Haloalkanes and Haloarenes C-121
Å O O
< CH3 – CH – CH2 – CH3
Å (d) tert - BuONa
¾ ¾ ¾ ¾ ¾®
< p – H3CO – C6H4 – CH 2 Br
(it decolorises bromine
solution)
Hence correct order is II < I < III
Products formed in option (2), (3) & (4)
21. (a) decolorises bromine solution due to presence
of double bond.
O O
tert - BuONa 22. (b) Elimination reaction is highly favoured if
(a) ¾¾ ¾ ¾ ¾
®
Br O-tBu
(a) Bulkier base is used
(fails to decolorise the (b) Higher temperature is used
colour of bromine) Hence in given reaction biomolecular
due to unsaturation
elimination reaction provides major
C6H5 C6H5 product.
(b) ¾¾¾¾¾
®
tert - BuONa

Br Br H
(it decolorises
bromine solution)
C6H5 t-BuOK
C6H5
O O 1, 2 elimination
(c) tert - BuONa
¾ ¾ ¾ ¾ ¾® H H
Br
(it decolorises bromine OtBu
solution)

C6H5
+ t-BuOH + Br
C6H5
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C-122 Chemistry

Alcohols, Phenols
and Ethers 25
1. During dehydration of alcohols to alkenes by
CH 3
heating with conc. H2SO4 the initiation step is
[2003]
(a)
(a) formation of carbocation CH 2 COOH
(b) elimination of water OH
(c) formation of an ester
(d) protonation of alcohol molecule CH 3
CH 2 COOH
2. Among the following compounds which can be
(b)
dehydrated very easily is [2004]
OH
CH3
|
(a) CH3 CH 2 C CH 2 CH3 CH 3
|
OH
(c)
OH CH(OH)COOH
| OH
(b) CH3CH 2 CH 2CHCH3
CH 3
(c) CH 3CH 2 CH 2 CH 2 CH 2 OH
CH(OH)COOH
(d) CH3 CH 2 CHCH 2 CH 2 OH (d)
|
CH3 OH
3. The best reagent to convert pent-3-en-2-ol into 5. HBr reacts with CH2 = CH – OCH3 under
pent-3-en-2-one is [2005] anhydrous conditions at room temperature to
(a) Pyridinium chloro-chromate give [ 2006]
(a) BrCH2 – CH2 – OCH3
(b) Chromic anhydride in glacial acetic acid
(b) H3C – CHBr – OCH3
(c) acidic dichromate
(c) CH3CHO and CH3Br
(d) Acidic permanganate
(d) BrCH2CHO and CH3OH
4. p-cresol reacts with chloroform in alkaline 6. Among the following the one that gives positive
medium to give the compound A which adds iodoform test upon reaction with I2 and NaOH
hydrogen cyanide to form, the compound B. The is [ 2006]
latter on acidic hydrolysis gives chiral carboxylic
acid. The structure of the carboxylic acid is CH3
|
[2005] (a) CH 3 - C HCH 2 OH
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Alcohols, Phenols and Ethers C-123
(b) PhCHOHCH3 11. The major product obtained on interaction of
(c) CH3CH2CH(OH)CH2CH3 phenol with sodium hydroxide and carbon
(d) C6H5CH2CH2OH dioxide is [2009]
7. The structure of the compound that gives a (a) salicylaldehyde (b) salicylic acid
tribromo derivative on treatment with bromine (c) phthalic acid (d) benzoic acid
water is [2006] 12. From amongst the following alcohols the one
CH 3 CH3 that would react fastest with conc. HCl and
anhydrous ZnCl2, is [2010]
OH
(a) (b) (a) 2-Butanol
(b) 2- Methylpropan-2-ol
(c) 2-Methylpropanol
OH
(d) 1- Butanol
CH3 CH2OH 13. The main product of the following reaction is
conc.H SO
C6 H5CH 2CH(OH)CH(CH 3 )2 ¾¾¾¾¾
2 4¾
®?
(c) (d)
OH [2010]
– +
(a) H 5C 6 H
OH O Na C=C
8. + CHCl3 + NaOH H CH(CH3)2
CHO
(b) C6H5CH2 CH3
The electrophile involved in the above reaction C=C
is [2006] H CH3

(c) H5C6CH2CH2
(a) trichloromethyl anion (CCl3) C = CH 2
H 3C
Å
(b) formyl cation (CHO) (d) C6H5 CH(CH3)2
Å
C=C
(c) dichloromethyl cation (CHCl2) H H
(d) dichlorocarbene (: CCl2) 14. Consider thiol anion (RSQ ) and alkoxy anion
9. In the following sequence of reactions,
(ROQ ) . Which of the following statements is

P +I Mg HCHO
correct ? [2011RS]
CH 3CH 2 OH ¾¾¾
2 ® A ¾¾¾® B ¾¾¾¾
®
ether
(a) RSQ is less basic but more nucleophilic
H O
C ¾¾¾
2 ®D
than ROQ
the compound D is [2007]
(b) RSQ is more basic and more nucleophilic
(a) propanal (b) butanal than ROQ
(c) n-butyl alcohol (d) n-propyl alcohol
(c) RSQ is more basic but less nucleophilic
10. Phenol, when it first reacts with concentrated
sulphuric acid and then with concentrated nitric than ROQ
acid, gives [2008]
(d) RSQ is less basic and less nucleophilic
(a) 2, 4, 6-trinitrobenzene
(b) o-nitrophenol than ROQ
(c) p-nitrophenol 15. The correct order of acid strength of the
(d) nitrobenzene following compounds : [2011RS]
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C-124 Chemistry
(A) Phenol (B) p–Cresol 19. The most suitable reagent for the conversion
(C) m–Nitrophenol (D) p–Nitrophenol of R - CH 2 - OH ® R - CHO is: [2014]
(a) D > C > A > B (b) B > D > A > C (a) KMnO4
(c) A > B > D > C (d) C > B > A > D (b) K2Cr2O7
16. Consider the following reaction : (c) CrO3
C2H5OH + H2SO4 ¾¾ ® Product (d) PCC (Pyridinium Chlorochromate)
20. Sodium phenoxide when heated with CO2 under
Among the following, which one cannot be
pressure at 125ºC yields a product which on
formed as a product under any conditions ?
acetylation produces C [2014]
[2011RS]
(a) Ethylene (b) Acetylene ONa 125° H+
+ CO 2 ¾¾¾¾
® B ¾¾¾® C
(c) Diethyl ether (d) Ethyl-hydr ogen 5 Atm Ac2O
sulphate The major product C would be
17. Arrange the following compounds in order of
decreasing acidity : [2013] OCOCH3

OH OH OH OH COOH
(a)

; ; ; ;
OH

Cl CH3 NO2 OCH3 COCH3

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

(a) II > IV > I > III (b) I > II > III > IV COCH3
(c) III > I > II > IV (d) IV > III > I > II
18. An unknown alochol is treated with the “Lucas OH
reagent” to determine whether the alcohol is
primary, secondary or tertiary. Which alcohol COOCH3
reacts fastest and by what mechanism : (c)
[2013]
(a) secondary alcohol by SN1
OCOCH3
(b) tertiary alcohol by SN1
(c) secondary alcohol by SN2
(d) tertiary alcohol by SN2 (d)
COOH

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(d) (a) (a) (c) (b) (b) (c) (d) (d) (b) (b) (b) (a) (a) (a)
16 17 18 19 20
(b) (c) (b) (d) (a)
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Alcohols, Phenols and Ethers C-125

1. (d) The dehydration of alcohol to form alkene

CH3 CH3
occurs in following three step. Step (1) is
initiation step. OH HOH
Step (1) Formation of protonated alcohol. C CN CH(OH) COOH

+ H OH H OH
+
CH3–CH2 – O –H + H CH3CH2 –– O Cyanohydrin
H
(Protonated
ethanol) 5. (b) Methyl vinyl ether under anhydrous
Step (2) Formation of carbocation condition at room temperature undergoes
addition reaction.
+ H Slow +
CH3–CH2–– O ––––––® HBr
H Ethyl
CH 2= CH - OCH3 ¾¾¾
® CH3 - CH - O - CH3
|
carbocation Br
Step (3)Elimination of a proton to form
ethene 6. (b) Only those alcohols which contain
– CHOHCH3 group undergo haloform
+ Fast + reaction. Among the given options only
H– CH 2––– CH2 CH2 = CH 2+ H
(b) contain this group, hence undergo
ethene
haloform reaction.
2. (a) 3-methyl pentan-3-ol will be dehydrated
most readily since it produces tertiary 7. (c) NOTE OH group activates the benzene
carbonium ion as intermediate. nucleus and
CH3 OH OH
|
CH3 - CH 2 - C - CH 2 - CH3 Br Br
| Br2 / H 2O
¾¾ ¾ ¾
¾®
OH CH3 CH3
Br
CH3
|
H+ 8. (d) NOTE This is Riemer-Tiemann reaction
¾¾¾
® CH3 - CH 2 - C - CH 2 - CH3
Å
and the electrophile is dichlorocarbene.
OH Cl
|
3. (a) CH3 - CH - CH = CH - CH3 ¾¾
® | ••
H – C – Cl + NaOH Cl – C – Cl + NaCl + H2O
|
O Cl
dichlorocarbene
||
CH3 - C - CH = CH - CH3 a-elimination

Pyridiminum chloro-chromate (PCC) is P +I

specific for the conversion. 9. (d) CH3CH 2 OH ¾¾¾
2 ® CH CH I
3 2
A
CH3 CH3
Mg
CHCl3 + NaOH
¾¾¾® CH3CH 2 MgI
4. (c) HCN Ether
Reimer Tiemman reaction (B)
C=O

OH OH H
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C-126 Chemistry
Mechanism
CH 2 CH3
|
HCHO
¾¾¾¾
® H - C - OMgI CH3
|
|
H Step 1 : CH3 — C — OH + H - Cl
|
(C) CH3
2 Methyl Propan-2-ol
H2 O
¾¾¾
® ∗
CH 2 CH3 ˆˆ† (CH3 )3 C — OH 2 ∗ Cl,
‡ˆˆ
|
H - C - OH ∗
| Step 2 : ˆˆ† (CH 3 )3 C∗ ∗ H 2 O
(CH3 )3 C , OH 2 ‡ˆˆ
H 3° Carbocation
(D) ∗ , ˆˆ†
n - propyl alcohol Step 3 : (CH3 )3 C ∗ Cl ‡ˆˆ (CH3 )3 C , Cl
t,Butylchloride
10. (b) Phenol on reaction with conc. H2SO4 gives 13. (a) Whenever dehydration can produce two
a mixture of o- and p- products (i.e., –SO3H different alkenes, major product is formed
group, occupies o-, p- position). At room according to Saytzeff rule i.e. more
temperature o-product is more stable, which substituted alkene (alkene having lesser
on treatment with conc. HNO3 will yield number of hydrogen atoms on the two
o-nitrophenol. doubly bonded carbon atoms) is the major
product.
OH
Such reactions which can produce two
Conc.H2SO4 or more structural isomers but one of them
in greater amounts than the other are
OH OH called regioselective ; in case a reaction
SO3H is 100% regioselective, it is termed as
Conc.H SO regiospecific.
+
In addition to being regioselective, alcohol
o- dehydrations are stereoselective (a
SO3H reaction in which a single starting
p-
At room temperature o- product is more material can yield two or more
stereoisomeric products, but gives one of
stable
them in greater amount than any other).
OH OH C6H5 ,CH2 ,CH, CH ,CH3 ¾¾¾¾¾
2 4¾
↑
Conc.H SO
SO3H NO2 | |
Conc. HNO 3 OH CH3

o- nitrophenol H H H CH(CH3)2
Hence (b) is the correct answer. C=C + C=C
C6H5 CH(CH3)2 C6H5 H
OH OH cis trans
NaOH
11. (b) CO2
(minor) (major)
COOH 14. (a) On moving down a group, the basicity &
12. (b) Tertiary alcohols react fastest with conc. nucleophilicity are inversely related, i.e.
HCl and anhydrous ZnCl2 (lucas reagent) nucleophilicity increases while basicity
as its mechanism proceeds through the decreases. i.e RSQ is more nucleophilic but
formation of stable tertiary carbocation.
less basic than ROQ . This opposite
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Alcohols, Phenols and Ethers C-127
behaviour is because of the fact that – CH3, – OCH3 decreases acidity. hence
basicity and nucleophilicity depends upon the correct order of acidity will be
different factors. Basicity is directly related OH OH OH OH
to the strength of the
H–element bond, while nucleophilicity is
indirectly related to the electronegativity > > >
of the atom to which proton is attached.
NO2 Cl CH3 OCH3
OH OH OH
III I II IV
15. (a) (–M, –I) (–I > +M) (+I, + HC ) (+ M)
18. (b) Reaction of alcohols with Lucas reagent
NO2 proceeds through carbocation formation,
CH3 SN1 mechanism.
+I –I Further 3° carbocations (from tertiary
effect effect alcohols) are highly stable thus reaction
(A) (B) (C) proceeds through SN1 mechanism.
19. (d) An excellent reagent for oxidation of 1°
OH alcohols to aldehydes is PCC.
PCC
R - CH 2 - OH ¾¾¾
® R - CHO

ONa
NO2 20. (a) + CO2 ¾¾
®
– M, – I
Sodium
effect Phenoxide
(D)
OH
Electron withdrawing substituents H SO
increases the acidity of phenols; while ¾¾¾¾
2 4®

electron releasing substituents decreases COONa

acidity. Since the + I effect is maximum in
ortho position, followed by meta and least OH
in para, thus the correct order of acidity
will COOH
D > C >A> B Salicylic acid
16. (b) (CH 3 CO) 2 O
C2 H5 - OH + H2 SO4 433K CH 2 = CH 2
ethylene
413 K
CH3 - CH 2 - O - CH2 - CH3 O
diethyl ether ||
383 K O - C - CH3
CH3CH 2 HSO4 + H 2 O
ethyl hydrogen sulphate + CH3COOH
Acetylene is not formed under any COOH
conditions. Aspirin
17. (c) Electron withdrawing substituents like (Acetyl Salicylate)
–NO2, –Cl increase the acidity of phenol
while electron releasing substituents like
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C-128 Chemistry

Aldehydes, Ketones and

Carboxylic Acids 26
Cl 2 4. When CH2 = CH — COOH is reduced with
1. ¾¾® A ¾alc.
CH3CH2COOH ¾red
KOH
¾ ¾¾® B. LiAlH4, the compound obtained will be
P [2003]
What is B? [2002] (a) CH2 = CH — CH2OH
(a) CH3CH2COCl (b) CH3CH2CHO (b) CH3 — CH2 — CH2OH
(c) CH2=CHCOOH (d) ClCH2CH2COOH. (c) CH3 — CH2 — CHO
2. On vigorous oxidation by permanganate (d) CH3 — CH2 — COOH
solution. 5. On mixing ethyl acetate with aqueous sodium
(CH3)2C = CH - CH2 - CHO gives chloride, the composition of the resultant
[2002] solution is [2004]
CH OH (a) CH3COCl+ C2H5OH + NaOH
| | (b) CH3COONa + C2H5OH
(a) CH3 - C - CH - CH 2CH 3 (c) CH3COOC2H5 + NaCl
|
CH (d) CH3Cl + C2H5COONa
6. Acetyl bromide reacts with excess of CH3MgI
CH3 followed by treatment with a saturated solution
(b)
COOH + CH3CH2COOH of NH4Cl gives [2004]
CH3 (a) 2-methyl-2propanol
CH3 (b) acetamide
(c) CH – OH + CH2CH2CH2OH (c) acetone
CH3 (d) acetyl iodide
CH3 7. Which one of the following is reduced with zinc
(d) . C = O + CH2CH2CHO and hydrochloric acid to give the corresponding
CH3 hydrocarbon? [2004]
3. Picric acid is: [2002] (a) Acetamide (b) Acetic acid
COOH (c) Ethyl acetate (d) Butan-2-one
COOH
8. Which one of the following undergoes reaction
with 50% sodium hyroxide solution to give the
(a) (b)
corresponding alcohol and acid? [2004]
NO2 OH (a) Butanal (b) Benzaldehyde
COOH (c) Phenol (d) Benzoic acid
OH 9. Among the following acids which has the lowest
O2N NO2 pK a value? [2005]
(c) (d)
NH2 (a) CH 3CH 2COOH

NO2 (b) (CH 3 ) 2 CH - COOH

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Aldehydes, Ketones and Carboxylic Acids C-129
(c) HCOOH 16. Iodoform can be prepared from all except: [2012]
(d) CH 3COOH (a) Ethyl methyl ketone
(b) Isopropyl alcohol
10. Reaction of cyclohexanone with dimethylamine (c) 3-Methyl 2-butanone
in the presence of catalytic amount of an acid
(d) Isobutyl alcohol
forms a compound if water during the reaction
17. In the given transformation, which of the
is continuously removed. The compound formed
following is the most appropriate reagent ?
is generally known [2005]
[2012]
(a) an amine (b) an imine
(c) an anemine (d) a Schiff’s base CH CH COCH3
11. The increasing order of the rate of HCN addition
to compound A – D is [2006] HO
(A) HCHO (B) CH3COCH3 Reagent
(C) PhCOCH3 (D) PhCOPh ¾¾¾¾®
(a) D < C < B < A (b) C < D < B < A CH CH CH2 CH3
(c) A < B < C < D (d) D < B < C < A
12. The correct order of increasing acid strenght of HO
the compounds [2006] Q
(A) CH3CO2H (B) MeOCH2CO2H (a) NH2 NH2 , OH (b) Zn – Hg/ HCl
Me (c) Na, Liq NH3 (d) NaBH4
(C) CF3CO2H (D) CO2H 18. An organic compound A upon reacting with NH3
Me
gives B. On heating B gives C. C in presence of
is KOH reacts with Br2 to given CH3CH2NH2. A
(a) D < A < B < C (b) A < D < B < C is : [2013]
(c) B < D < A < C (d) D < A < C < B (a) CH3COOH
13. A liquid was mixed with ethanol and a drop of (b) CH3CH2CH2COOH
concentrated H2SO4 was added. A compound
(c) CH 3 - CH - COOH
with a fruity smell was formed. The liquid was : |
[2009] CH3
(a) HCHO (b) CH3COCH3
(c) CH3COOH (d) CH3OH (d) CH3CH2COOH
14. Which of the following on heating with aqueous 19. In the reaction,
KOH, produces acetaldehyde? [2009] LiAlH
CH 3COOH ¾¾¾¾
4® A
(a) CH3CH2Cl (b) CH2ClCH2Cl
(c) CH3CHCl2 (d) CH3COCl PCl Alc.KOH
¾¾¾
5 ® B ¾¾¾¾® C,
15. In Cannizzaro reaction given below
the product C is: [2014]
Π
: ΝΓ .. (a) Acetaldehyde (b) Acetylene
2PhCHO ¾¾¾ ↑ PhCH 2 OH + PhCOΠ 2 (c) Ethylene (d) Acetyl chloride
the slowest step is : [2009]
(a) the transfer of hydride to the carbonyl 20. The correct sequence of reagents for the
group following conversion will be :
(b) the abstraction of proton from the O HO CH3
carboxylic group
(c) the deprotonation of Ph CH2OH
Π
(d) the attack of : OH at the carboxyl group HO–CH3
CHO CH3
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C-130 Chemistry
(a) [Ag(NH3)2]+ OH–, H+/CH3OH, CH3MgBr OH
(b) CH3MgBr, H+/CH3OH, [Ag(NH3)2]+ OH–
(c) CH3MgBr, [Ag(NH3)2]+ OH–, H+/CH3OH (a) CHO
(d) [Ag(NH3)2]+ OH–, CH3MgBr, H+/CH3OH
COOH
21. Sodium salt of an organic acid 'X' produces
effervescence with conc. H2SO4. 'X' reacts with OH
the acidified aqueous CaCl2 solution to give a
white precipitate which decolourises acidic (b) CHO
solution of KMnO4. 'X' is :
(a) C6H5COONa (b) HCOONa CHO
(c) CH3COONa (d) Na2C2O4
22. The major product obtained in the following
(c) CHO
reaction is :
O
COOH
O

(d) CHO
DIBAL–H
CHO

COOH

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(c) (b) (c) (a) (c) (a) (d) (b) (c) (c) (a) (a) (c) (c) (a)
16 17 18 19 20 21 22
(d) (a) (d) (c) (a) (d) (b)

1.
Cl2
(c) CH3CH2COOH ¾¾¾® CH3CHClCOOH CH2 = CH - CH 2OH
red P
5. (c) There is no reaction hence the resultant
alc.KOH mixture contains CH3 COOC2H5 + NaCl.
¾¾ ¾¾® CH 2 = CHCOOH
- HCl Acrylic acid

2. (b) Aldehydic group gets oxidised to O

||
carboxylic group. Double bond breaks and 6. (a) (i)CH MgI
CH 3 - C- Br ¾¾¾¾¾¾¾¾
3 ®
(ii)Saturated NH 4Cl
carbon gets oxidised to carboxylic group.
3. (c) 2,4,6-Trinitrophenol is also known as picric
CH3
acid. |
4. (a) LiAlH4 can reduce COOH group and not CH3 – C – OH
|
the double bond. CH3
2-methyl-2-propanol
LiAlH
CH 2 = CH - COOH ¾¾¾¾
4 ® CH
2
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Aldehydes, Ketones and Carboxylic Acids C-131
7. (d) It is Clemmensen’s reduction (Me)2CHCOOH < CH3COOH <
O MeOCH2COOH < CF3COOH
||
Zn - Hg
CH3 - C - CH 2 - CH3 ¾¾¾¾® [ NOTE Electron withdrawing groups
Conc.HCl
Butane - 2 -one increase the acid strength and electron
Zn Hg
donating groups decrease the acid
¾¾¾¾® CH3CH 2 - CH 2 CH3 strength.]
Conc.HCl
(Butane)
13. (c) Fruity smell is due to ester formation which
8. (b) This reaction is known as cannizzaro’s is formed between ethanol and acid.
reaction. In this reaction benzaldehyde in
Conc. H 2SO 4
CH3COOH + C2H5OH ¾¾¾¾¾¾
presence of 50%. NaOH undergoes ®
disproportionation reaction and form one CH3COOC2H5 + H2O
mol of Benzyl alcohol (Red. product) and
aq.KOH
14. (c) CH 3CHCl 2 ¾¾¾¾
one mole of sod. benzoate (ox. product) ® CH 3CH(OH) 2

CHO CH2OH -H O
¾¾¾¾
2 ® CH CHO
3
50% NaOH

O
+ – ||
fast
COO Na
15. (a) ˆˆˆ†
Ph – C –H + OH – ‡ˆˆˆ
+
– O
O
Ph – C – H
9. (c) pKa = –log Ka; HCOOH is the strongest Ph – C – H slow
acid and hence it has the highest Ka or
OH
lowest pKa value.
10. (c) O O–
|| |
OH Ph – C + Ph – C –H
| |
O + HN(CH3)2 N (CH3)2
OH H

–H2O
O OH
N (CH3)2 + || |
H exchange
¾¾¾¾¾¾ ® Ph – C + Ph – C –H
enamine
fast | |
O– H
11. (a) NOTE Addition of HCN to carbonyl 16. (d) Iodoform test is given by methyl ketones,
compounds is nucleophilic addition acetaldehyde and methyl secondary
reaction. The order of reactivity of carbonyl alcohols.
compounds is CH3 CH CH2 OH
Aldehydes (smaller to higher) Ketones
(smaller to higher), Then CH3
HCHO > CH3COCH3 > PhCOCH3 > PhCOPh isobutyl alcohol is a primary alcohol hence
NOTE The lower reactivity of Ketones does'nt give positive iodoform test.
17. (a) Aldehydes and ketones can be reduced to
is due to presence of two alkyl group which hydrocarbons by the action (i) of
shows +I effect. The reactivity of Ketones amalgamated zinc and concentrated
decreases as the size of alkyl group hydrochloric acid (Clemmensen reduction),
increases. or (b) of hydrazine (NH2NH2) and a strong
12. (a) The correct order of increasing acid base like NaOH, KOH or potassium tert-
strength butoxide in a high-boiling alcohol like
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C-132 Chemistry
ethylene glycol or triethylene glycol (Wolf-
Kishner reduction) O O
CH CH COCH3
[Ag(NH3)2]OH
20. (a)
Tollens reagent
HO
–
NH 2NH 2/OH
CHO CO2H
Wolf-kishner
Reduction H+/CH3OH
CH CH CH2 CH3 (esterification)

HO O
–OH group and alkene are acid-sensitive
groups so clemmensen reduction can not
be used.Acid sensitive substrate should
be reacted in the Wolf-Kishner reduction
which utilise strongly basic conditions.
C
18. (d) O OCH3
NH
3 ® B ¾¾ D Br
2 ® CH CH NH
A ¾¾¾ ® C ¾¾¾¾¾ 3 2 2 CH3MgBr
(I) II KOH,(III)

Reaction (III) is a Hofmann bromamide

reaction. Now formation of CH3CH2NH2 CH3
is possible only from a compound
CH3CH2CONH2(C) which can be obtained
from the compound CH3CH2COO– NH+4
(B).
Thus (A) should be CH3CH2COOH H3C – C – CH3
O OH
P
↑ CH3CH 2COO, NH∗ 21. (d) Na2C2O4 + H2SO4 ® Na2SO4 + CO­ +
NH3
CH3CH 2 , C, OH ¾¾¾ 4
CO2­ + H2O
(A) (B)
'x' (conc.)
Χ
¾¾↑ CH 3CH 2 CONH 2 Na2C2O4 + CaCl2 ® CaC2O4¯ + 2NaCl
(C) 'x' (white ppt.)

5CaC2O4 ¯ + 2KMnO4 + 8H2SO4

KOH Br2
(purple)
CH 3CH 2 NH 2
K2SO4 + 5CaSO4 + 2MnSO4 + 10CO2 +
8H2O
19. (c) CH3 COOH ¾¾¾¾
LiA1H
4 ® CH CH OH (colourless)
3 2
(A)
22. (b) DIBAL-H is an electrophilic reducing
PCl5 agent. It reduces both ester and carboxylic
group into an aldehyde at low temperature.
CH3CH2Cl O
(B) O OH O
Alc. KOH
H
DIBAL - H
¾ ¾ ¾ ¾®
CH2 = CH2
(C) CHO
CO2H
Hence the product (C) is ethylene.
 www.crackjee.xyz

Amines
27
1. When primary amine reacts with chloroform in (a) Curtius reaction (b) Wurtz reaction
ethanolic KOH then the product is [2002] (c) Hofmann method (d) Hinsberg method
(a) an isocyanide (b) an aldehyde 6. Amongst the following the most basic
(c) a cyanide (d) an alcohol. compound is [2005]
2. The reaction of chloroform with alcoholic KOH (a) p -nitroaniline (b) acetanilide
and p-toluidine forms [ 2003] (c) aniline (d) benzylamine
7. An organic compound having molecular mass
60 is found to contain C = 20%, H = 6.67% and
(a) H3C N2Cl
N = 46.67% while rest is oxygen. On heating it
gives NH3 alongwith a solid residue. The solid
residue give violet colour with alkaline copper
(b) H3C NHCHCl2 sulphate solution. The compound is [2005]
(a) CH 3CH 2CONH 2 (b) ( NH 2 ) 2 CO
(c) CH 3CONH 2 (d) CH 3 NCO
(c) H3C NC
8. Which one of the following is the strongest
base in aqueous solution ?
[2007]
(d) H3C CN (a) Methylamine (b) Trimethylamine
(c) Aniline (d) Dimethylamine
3. The correct order of increasing basic nature for
9. In the chemical reaction,
the bases NH3, CH3NH2 and (CH3)2NH is
[ 2003] CH3CH2NH2 + CHCl3 + 3KOH ®
(a) (CH3)2NH < NH3 < CH3NH2 (A) + (B) + 3H2O, the compounds (A) and (B)
are respectively [2007]
(b) NH3 < CH3NH2 < (CH3)2NH
(a) C2H5NC and 3KCl
(c) CH3NH2 < (CH3)2NH < NH3
(b) C2H5CN and 3KCl
(d) CH3NH2 < NH3 < (CH3)2NH
(c) CH3CH2CONH2 and 3KCl
4. Ethyl isocyanide on hydrolysis in acidic medium
generates [2003] (d) C2H5NC and K2CO3.
(a) propanoic acid and ammonium salt 10. In the chemical reactions,
(b) ethanoic acid and ammonium salt NH 2
(c) methylamine salt and ethanoic acid
(d) ethylamine salt and methanoic acid NaNO2 HBF 4
HCl, 278 K
A B
5. Which one of the following methods is neither
meant for the synthesis nor for separation of
amines? [2005]
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C-134 Chemistry
the compounds ‘A’ and ‘B’ respectively are NaNO /HCl CuCN/KCN
[2010] ¾¾¾¾¾2
0–5° C
® D ¾¾¾¾¾
D
® E + N2
(a) nitrobenzene and fluorobenzene the product E is :
(b) phenol and benzene
CN
(c) benzene diazonium chloride and
fluorobenzene
(d) nitrobenzene and chlorobenzene (a)
11. In the chemical reactions : [2011RS]
NH 2 CH3

NaNO CuCN CH3

¾¾¾¾¾ 2 ® A ¾¾¾¾® B,
HCl, 278K D

the compounds A and B respectively are : (b)

(a) Benzene diazonium chloride and
benzonitrile COOH
(b) Nitrobenzene and chlorobenzene
(c) Phenol and bromobenzene
(c)
(d) Fluorobenzene and phenol
12. A compound with molecular mass 180 is acylated
with CH3COCl to get a compound with molecular CH3
mass 390. The number of amino groups present
per molecule of the former compound is : (d) H3C CH3
[2013]
(a) 2 (b) 5 16. In the Hofmann bromamide degradation
(c) 4 (d) 6 reaction, the number of moles of NaOH and Br 2
13. On heating an aliphatic primary amine with used per mole of amine produced are :
[JEE M 2016]
chloroform and ethanolic potassium hydroxide,
the organic compound formed is: [2014] (a) Two moles of NaOH and two moles of Br 2.
(a) an alkanol (b) an alkanediol (b) Four moles of NaOH and one mole of Br 2.
(c) an alkyl cyanide (d) an alkyl isocyanide (c) One mole of NaOH and one mole of Br 2.
14. Considering the basic strength of amines in (d) Four moles of NaOH and two moles of Br 2.
aqueous solution, which one has the smallest 17. Which of the following compounds will form
pKb value? [2014] significant amount of meta product during mono-
(a) (CH3)2NH (b) CH3NH2 nitration reaction ? [2017]
(c) (CH3)3N (d) C6H5NH2 OH OCOCH3
15. In the reaction [JEE M 2015]
(a) (b)
NH2
NH2 NHCOCH3

(c) (d)
CH3
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Amines C-135

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(a) (c) (b) (d) (b) (d) (b) (d) (a) (c) (a) (b) (d) (a) (a)
16 17
(b) (c)

1. (a) C2H5NH2 + CHCl3 + 3KOH ..

CH2NH2
® C2H5N º C + 3KCl + 3HCl 6. (d) Benzylamine is most
(Ethyl isocyanide)

NH2 basic. In others the basic character is

suppressed due to Resonan ce (see
2. (c) +CHCl3+ 3KOH applications of resonance).
7. (b)
CH3
(a) (b) (c) (d)
N=C C 20% 20/12 = 1.66 1.66 / 1.66 = 1
H 6.67% 6.67 / 1 = 6.67 6.67 / 1.66 = 4.16
+3KCl+3H2 O
N 46.67% 46.67/14 = 3.33 3.33 / 1.66 = 2.02
CH3
O 26.64% 26.64 / 16 = 1.66 1.66 / 1.66 = 1.0
3. (b) The alkyl groups are electron releasing The compound is CH4N2O
group (+ I), thus increases the electron Empirical weight = 60; Mol. wt. = 60;
density around the nitrogen thereby
60
increasing the availability of the lone pair \n = =1
of electrons to proton or lewis acid and 60
making the amine more basic. Hence more
O
the no. of alkyl group more basic is the ||
amine. Therefore the correct order is Molecular formula = CH4N2O; NH 2 - C - NH 2
NH3 < CH3NH2 < (CH3)2 NH
On heating urea loses ammonia to give Biuret
4. (d) Ethyl isocyanide on hydrolysis form
primary amines. 2NH 2CONH 2 ¾¾
® H 2 NCO.NH.CONH 2 + NH 3
+ Biuret with alkaline CuSO4 gives violet colour.
H
= C + H2 O ¾¾¾
CH3CH2 N ® ®
Test for –CONH– group.
CH3CH2NH2 + HCOOH
8. (d) NOTE Aromatic amines are less basic than
Therefore it gives only one mono
chloroalkane. aliphatic amines. Among aliphatic amines the
5. (b) Wurtz reaction is for the preparation of order of basicity is 2° > 1° > 3°. The electron
hydrocarbons from alkyl halide density is decreased in 3° amine due to
crowding of alkyl group over N atom which
RX + 2 Na + XR ¾
¾® R – R + 2 NaX makes the approach and bonding by a proton
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C-136 Chemistry
relatively difficult. Therefore the basicity O
decreases. Further Phenyl group show – I P
12. (b) R - NH 2 + CH3 - C - Cl ¾¾¾®
effect, thus decreases the electron density { - HCl
on nitrogen atom and hence the basicity. Mol.Mass=16

\ dimethylamine (2° aliphatic amine) is O

P
strongest base among given choices. R - NH - C - CH3
\ The correct order of basic strength is 144244 3
Mol.mass =58
Dimethylamine > Methyl amine > Trimethyl
amine > Aniline. Now since the molecular mass increases by 42
9. (a) This is carbylamine reaction. unit as a result of the reaction of one mole of
CH3CH2NH2 + CHCl3 + 3KOH CH3COCl with one-NH2 group and the given
increase in mass is 210. Hence the number of
¾¾ ® C2H5NC + 3KCl + 3H2O –NH2 groups is = 210/42 = 5.
10. (c) Primary aromatic amines react with nitrous 13. (d) R – CH2 – NH2 + CHCl3 + 3KOH (alc)
acid to yield arene diazonium salts. Carbyl amine reaction
ArNH2 + NaNO2 + 2HX ¾¾¾ cold
® ¾¾
® R – CH2 – NC + 3KCl + 3H2O
1° Aromatic amine Alkyl isocynide
Ar—N = N+X– + NaX + 2H2O
14. (a) Arylamines are less basic than alkyl amines
Arene diazonium salt
and even ammonia. This is due to
The diazonium group can be replaced by
resonance. In aryl amines the lone pair of
fluorine by treating the diazonium salt with
electrons on N is partly shared with the
fluoroboric acid (HBF4). The precipitated
ring and is thus less available for sharing
diazonium fluoroborate is isolated, dried and
with a proton.
heated until decomposition occurs to yield
the aryl fluoride. This reaction is known as In alkylamines, the electron releasing alkyl
Balz-Schiemann reaction. group increases the electron density on
nitrogen atom and thus also increases the
Ar—N2+X– ¾¾¾®
HBF4 Ar—N2+BF4–¯ ¾¾¾
heat
® ability of amine for protonation. Hence more
Ar—F + BF3 + N2 the no. of alkyl groups higher should be
11. (a) the basicity of amine. But a slight
NH 2 N +2 Cl- discrepancy occurs in case of trimethyl
amines due to steric effect. Hence the
correct order is
NaNO2 CuCN
HCl, 278K (CH 3 )2 NH > CH3 NH 2
Diazotization Benzene diazonium > (CH3 )3 N > C6 H5 NH 2
chloride
(A) 15. (a)

C ºN + –
NH2 N = NCl CN

¾ NaNO
¾ ¾ 2¾/HCl
¾¾ ® ¾ CuCN/KCN
¾ ¾ ¾ ¾®
0 - 5° C D

Benzonitrile CH3 CH3 CH3

(B)
Sandmayer reaction
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Amines C-137
16. (b) 4 moles of NaOH and one mole of Br2 is In strongly acidic nitration medium, the
required during production of one mole amine is converted into anilinium ion
of amine during Hoffmann's bromamide (– NH3+); substitution is thus controlled
degradation reaction. not by – NH2 group but by – NH3+ group
which, because of its positive charge,
O
directs the entering group to the meta-
||
position instead of ortho, and para.
R–C–NH2 + Br2 + 4NaOH ® R–NH2 + K2CO3 + 2NaBr
+ 2H2O Å
: NH2 NH3
17. (c) Nitration takes place in presence of
concentrated
HNO3 + concentrated H2SO4 Conc. HNO
¾ Conc. 3
¾ ¾H¾SO¾®
2 4

– NH2 gp : o,p -directing – NH+3 gp : m-directing

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C-138 Chemistry

Biomolecules
28
1. RNA is different from DNA because RNA
(b) C1' and C5' respectively of the sugar
contains [2002]
(a) ribose sugar and thymine molecule
(b) ribose sugar and uracil (c) C '2 and C5' respectively of the sugar
(c) deoxyribose sugar and thymine
molecule
(d) deoxyribose sugar and uracil.
2. Complete hydrolysis of cellulose gives [2003] (d) C5' and C '2 respectively of the sugar
(a) D-ribose (b) D-glucose molecule
(c) L-glucose (d) D-fructose 8. The term anomers of glucose refers to [2006]
3. The reason for double helical structure of DNA (a) enantiomers of glucose
is operation of [2003] (b) isomers of glucose that differ in
(a) dipole-dipole interaction configuration at carbon one (C-1)
(b) hydrogen bonding (c) isomers of glucose that differ in
(c) electrostatic attractions configurations at carbons one and four
(d) van der Waals’ forces (C-1 and C-4)
4. Which base is present in RNA but not in DNA ? (d) a mixture of (D)-glucose and (L)-glucose
(a) Guanine (b) Cytosine [2004] 9. The pyrimidine bases present in DNA are [2006]
(c) Uracil (d) Thymine (a) cytosine and thymine
5. Insulin production and its action in human body (b) cytosine and uracil
are responsible for the level of diabetes. This (c) cytosine and adenine
compound belongs to which of the following (d) cytosine and guanine
categories ? [2004] 10. The secondary structure of a protein refers to
(a) An enzyme (b) A hormone [2007]
(c) A co-enzyme (d) An antibiotic (a) fixed configuration of the polypeptide
6. Which of the following is a polyamide? [2005] backbone
(a) Bakelite (b) Terylene (b) a– helical backbone
(c) Nylon-66 (d) Teflon (c) hydrophobic interactions
7. In both DNA and RNA, heterocylic base and (d) sequence of a– amino acids.
phosphate ester linkages are at – [2005] 11. a - D-(+)-glucose and b-D-(+)-glucose are [2008]
(a) C5' and C1' respectively of the sugar (a) conformers (b) epimers
(c) anomers (d) enatiomers
molecule
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Biomolecules C-139

12. The two functional groups present in a typical (a) Quinoline (b) Adenine
carbohydrate are: [2009] (c) Cytosine (d) Thymine
(a) – CHO and – COOH 18. Which of the vitamins given below is water
(b) > C = O and – OH soluble ? [2015]
(c) – OH and – CHO (a) Vitamin E (b) Vitamin K
(d) – OH and – COOH (c) Vitamin C (d) Vitamin D
13. Biuret test is not given by [2010] 19. Thiol group is present in : [2016]
(a) Cysteine (b) Methionine
(a) carbohydrates (b) polypeptides
(c) Cytosine (d) Cystine
(c) urea (d) proteins
20. Which of the following compounds will behave
14. Which of the following compounds can be
as a reducing sugar in an aqueous KOH solution?
detected by Molisch's Test ? [2012]
(a) Nitro compounds
HOH2C O CH2OH
(b) Sugars
(c) Amines (a) HO OCOCH
3
(d) Primary alcohols
15. Which one of the following statements is OH
correct? [2012]
(a) All amino acids except lysine are optically HOH2C O CH2OH
active
(b) All amino acids are optically active (b) HO
(c) All amino acids except glycine are optically
active OH
(d) All amino acids except glutamic acids are
optically active HOH2C O CH2OH
16. Synthesis of each molecule of glucose in
photosynthesis involves : [2013] (c) HO OCH
3
(a) 18 molecules of ATP
OH
(b) 10 molecules of ATP
(c) 8 molecules of ATP
(d) 6 molecules of ATP HOH2C
17. Which one of the following bases is not present O CH2OCH3
in DNA? [2014] (d) OH
OH
OH
Answer Key
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
(b) (b) (b) (c) (b) (c) (b) (b) (a) (b) (c) (c) (a) (b) (c)
16 16 17 18 19 20
(b) (a) (a) (c) (a) (a)
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C-140 Chemistry

1. (b) In RNA, the sugar is D–ribose and base is

uracil where as in DNA, the sugar is D-2
deoxyribose and the nitrogenous base is
thymine.
2. (b) Cellulose is a linear polymer of
b –D– glucose in which C1 of one glucose
unit is connected to C4 of the other through
b –D glucosidic linkage. It does not
undergo hydrolysis easily. However on
heating with dilute H2SO4 under pressure.
It does undergo hydrolysis to give only
D– glucose.
H+
(C6 H10O5 )n+nH 2O ¾¾® nC6 H12O6
D-Glucose
3. (b) DNA consists of two polynucleotide
chains, each chain forms a right handed
spiral with ten bases in one turn of the
spiral. The two chains coil to double helix
and run in opposite direction held together
by hydrogen bonding.

4. (c) RNA contains cytosine and uracil as pyrimidine bases while DNA has cytosine and thymine.
Both have the same purine bases i.e., Guanine and adenine.
5. (b) Insulin is a biochemically active peptide harmone secreted by pancreas.
6. (c) Nylon is a general name for all synthetic fibres forming polyamides.
7. (b) In DNA and RNA heterocyclic base and phosphate ester are at C 1' and C5' respectively of the sugar
molecule.

HO N
| N
5
HO – P – O – C H 2 4¢ O N
|| N
C
O C¢
H H
H | |
C3––– C2 H
| |
OH OH

8. (b) Cyclization of the open chain structure of D-(+)-glucose has created a new stereocenter at C 1 which
explains the existence of two cyclic forms of D-(+)-glucose, namely a– and b–. These two cyclic
forms are diasteromers, such diastereomers which differ only in the configuration of chiral carbon
developed on hemiacetal formation (it is C1 in glucose and C2 in fructose) are called anomers and
the hemiacetal carbon (C1 or C2) is called the anomeric carbon.
 www.crackjee.xyz
Biomolecules
9. (a) The pyrimidine bases present in DNA are
cytosine and thymine.
10. (b) The secondary structure of a protein refers
to the shape in which a long peptide chain can
exist. There are two different conformations of
the peptide linkage present in protein, these
are a-helix and b-conformation. The a-helix
always has a right handed arrangement. In
b-conformation all peptide chains are
streched out to nearly maximum extension
and then laid side by side and held together
by intermolecular hydrogen bonds. The
structure resembles the pleated folds of
drapery and therefore is known as b-pleated
sheet.
11. (c) Since a - D - (+) - glucose and
b - D - (+) glucose differ in
configuration at C – 1 atom so they are
anomers.
NOTE Anomers are those diastereomers
that differ in configuration at C – 1 atom.
i.e., (c) in the correct answer.
12. (c) NOTE Glucose is considered as a typical
carbohydrate which contains –CHO and
–OH group.
C-141
13. (a) Biuret test produces violet colour on
addition of dilute CaSO 4 to alkaline
solution of a compound containing
peptide linkage.
Polypeptides, proteins and urea have
- C- NH - (peptide) linkage while
||
O
carbohydrates have glycosidic llinkages.
So, test of carbohydtrates should be
different from that of other three.
14. (b) Molisch's Test : This is a general test for
carbohydrates. One or two drops of alcoholic
solution of a-naphthol is added to 2 ml
glucose solution. 1 ml of conc. H2SO4
solution is added carefully along the sides of
the test-tube. The formation of a violet ring
at the junction of two liquids confirms the
presence of a carbohydrate or sugar.
15. (c) With the exception of glycine all the 19 other
common amino acids have a uniquely
different functional group on the central
tetrahedral alpha carbon.
H
|
H — C — COOH
|
NH 2
glycine
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C-142 Chemistry
16. (a) 6CO2 + 12NADPH + 18ATP ® C6H12O6 + 20. (a)
12NADP + 18ADP
17. (a) DNA contains ATGC bases HOCH2 O CH2OH HOCH2 O CH2OH
O ¾¾¾¾¾Aq.KOH
So quinoline is not present in DNA. ®
HO – CH3COOK HO –
18. (c) Water-soluble vitamins dissolve in water O – C – CH3 O
and are not stored by the body. The water OH
OH OH
soluble vitamins include the vitamin B- Hemiketal
complex group and vitamin C. Ring opening
19. (a) Among 20 naturally occuring amino acids
HOCH2 OH
"Cysteine" has '– SH' or thiol functional CH2OH
group. Å vesilver
mirror
Tollen 's
¬¾¾¾ ¾
OH O
Reagent
test
Þ General formula of amino acid OH
® R–CH—COOH—NH2 (a Reducing sugar) a-hydroxy ketone
Þ Value of R = –CH2–SH in Cysteine.
 www.crackjee.xyz
Polymers C-143

Polymers
29
1. Polymer formation from monomers starts by (a) teflon (b) nylon 6, 6
[2002] (c) polystyrene (d) natural rubber
(a) condensation reaction between monomers 7. Thermosetting polymer, Bakelite is formed by
(b) coordinate reaction between monomers the reaction of phenol with : [2011RS]
(c) conversion of monomer to monomer ions (a) CH3CHO (b) HCHO
by protons (c) HCOOH (d) CH3CH2CHO
(d) hydrolysis of monomers. 8. The species which can best serve as an initiator
2. Nylon threads are made of [2003] for the cationic polymerization is : [2012]
(a) polyester polymer (a) LiAlH4 (b) HNO3
(b) polyamide polymer (c) AlCl3 (d) BaLi
(c) polyethylene polymer 9. Which one is classified as a condensation
(d) polyvinyl polymer polymer? [2014]
3. Which of the following is fully fluorinated (a) Dacron (b) Neoprene
polymer? [2005]
(a) PVC (b) Thiokol (c) Teflon (d) Acrylonitrile
(c) Teflon (d) Neoprene 10. Which polymer is used in the manufacture of
4. Bakelite is obtained from phenol by reacting with paints and lacquers ? [2015]
[2008] (a) Polypropene (b) Polyvinyl chloride
(a) (CH2OH)2 (b) CH3CHO
(c) CH3 COCH3 (d) HCHO (c) Bakelite (d) Glyptal
5. Buna-N synthetic rubber is a copolymer of : 11. Which of the following statements about low
[2009] density polythene is FALSE? [2016]
(a) H2C = CH – CH = CH2 and H5C6 – CH = CH2
(a) Its synthesis requires dioxygen or a
(b) H2C = CH – CN and H2C = CH – CHCH2 peroxide initiator as a catalyst.
(c) H2C = CH – CN and H 2 C = CH – C = CH 2
| (b) It is used in the manufacture of buckets,
C H3 dust-bins etc.
Cl (c) Its synthesis requires high pressure.
|
(d) H 2 C = CH – C = CH 2 and (d) It is a poor conductor of electricity.

H 2C = CH – CH = CH 2 12. The formation of which of the following

6. The polymer containing strong intermolecular polymers involves hydrolysis reaction?[2017]
forces e.g. hydrogen bonding, is [2010] (a) Nylon 6 (b) Bakelite
(c) Nylon 6, 6 (d) Terylene

Answer Key
1 2 3 4 5 6 7 8 9 10 11 12
(a) (b) (c) (d) (b) (b) (b) (c) (a) (d) (b) (a)
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C-144 Chemistry

1. (a) Polymerisation starts either by

condensation or addition reactions
between monomers. Condensation
polymers are formed by the combination
of monomers with the elimination of simple
molecules.Where as the addition polymers
are formed by the addition together of the
molecules of the monomer or monomers to
form a large molecule without elimination
of any thing.
2. (b) Nylon is a polyamide polymer.
3. (c) Teflon is polymer of CF2 = CF2.
4. (d) Bakelite is formed by the reaction of 5. (b) Buna – N is a copolymer of butadiene
formaldehyde (HCHO) and phenol so the (CH2 = CH – CH = CH2) and acrylonitrile
correct answer is (d). (CH2 = CHCN).
OH 6. (b) Nylon 6, 6 has amide linkage capable of
forming hydrogen bonding.
–
OH
n + n HCHO

O
OH H2N
HO + NH2
O
Adipic acid Hexamethylenediamine
H2O

H
O O
H2N N OH
NH2 + HO NH2 + HO
O O
Hexamethylenediamine Adipic acid

H2O H2O
Polymerization

H H
O O
N N
N N
O
H H
Nylon

7. (b)
8. (c) Lewis acids are the most common compounds used for initiation of cationic polymerisation. The
more popular Lewis acids are SnCl4, AlCl3, BF3 and TiCl4.
 www.crackjee.xyz
Polymers C-145
9. (a) Except Dacron all are additive polymers. dustbins, bottles, pipes etc. Low density
Terephthalic acid condenses with ethylene polythene is used for insulating electric wires
glycol to give Dacron. and in the manufacture of flexible pipes, toys,
coats, bottles etc.

HOOC COOH + 12. (a) Formation of Nylon-6 involves hydrolysis

of caprolactum, (its monomer) in initial
Terephthalic acid state.

– CH2 – CH2 – OH ¾¾
HO O ® O
Ethylene glycol
NH H 2O
H2 N(CH2)5COOH
[
CO CH 2 - CH 2 - O - ] n Caprolactam e-Amino Caproic acid

Dacron (Polyester)
O O
10. (d) Glyptal is used in the manufacture of paints
and lacquers. –(NH(CH2)5–C–NH–(CH2)5–C)–n
Polymerise
11. (b) High density polythene is used in the Nylon-6
manufacture of housewares like buckets,
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Chemistry in
Everyday Life 30
OCOCH3 4. Aspirin is known as : [2012]
COOH (a) Acetyl salicylic acid
1. The compound is used as [2002] (b) Phenyl salicylate
(c) Acetyl salicylate
(a) antiseptic (b) antibiotic (d) Methyl salicylic acid
(c) analgesic (d) pesticide. 5. Which of the following compounds is not an
2. Which of the following could act as a propellant antacid ? [2015]
for rockets? [2003] (a) Phenelzine
(a) Liquid oxygen + liquid argon (b) Ranitidine
(b) Liquid hydrogen + liquid oxygen (c) Aluminium hydroxide
(c) Liquid nitrogen + liquid oxygen (d) Cimetidine
6. Which of the following is an anionic detergent?
(d) Liquid hydrogen + liquid nitrogen [2016]
3. Which one of the following types of drugs (a) Cetyltrimethyl ammonium bromide.
reduces fever ? [2005] (b) Glyceryl oleate.
(a) Tranquiliser (b) Antibiotic (c) Sodium stearate.
(c) Antipyretic (d) Analgesic (d) Sodium lauryl sulphate.
Answer Key
1 2 3 4 5 6
(c) (b) (c) (a) (a) (d)

1. (c) The given compound is aspirin which is
antipyretic and analgesic
2. (b) Liquid hydrogen and liquid oxygen are used
as excellent fuel for rockets. H2(l) has low mass
and high enthalpy of combustion whereas
oxygen is a strong supporter of combustion.
3. (c) An antipyretic is a drug which is responsible
for lowering the temperature of the feverish
organism to normal but has no effect on
normal temperature states.
O–COCH3
COOH
4. (a) Aspirin (Acetyl salicylic acid)
5. (a) Phenelzine is an antidepressant, while
others are antacids.
6. (d) Sodium lauryl sulphate (C11H23CH2OSO–
+
3Na ) is an anionic detergent. Glyceryl
oleate is a glyceryl ester of oleic acid.
Sodium stearate (C17H35COO–Na+) is a
soap. Cetyltrimethyl ammonium bromide
é + ù -
ê CH3 (CH 2 )15 N(CH 3 )3 ú Br
ë û
is a cationic detergent.
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Analytical Chemistry C-147

Analytical Chemistry 31
1. When H2S is passed through Hg2S we get (a) Fe4[Fe(CN)6]3 (b) Na3[Fe(CN)6]
[2002] (c) Fe(CN)3 (d) Na4[Fe(CN)5NOS]
(a) HgS (b) HgS + Hg2S 5. 29.5 mg of an organic compound containing
(c) Hg2S + Hg (d) None of these. nitrogen was digested according to Kjeldahl’s
2. How do we differentiate between Fe3+ and Cr3+ method and the evolved ammonia was absorbed
in group III? [2002] in 20 mL of 0.1 M HCl solution. The excess of
(a) by taking excess of NH4OH solution the acid required 15 mL of 0.1 M NaOH solution
(b) by increasing NH4+ ion concentration for complete neutralization. The percentage of
nitrogen in the compound is [2010]
(c) by decreasing OH– ion concentration
(a) 59.0 (b) 47.4
(d) both (b) and (c)
(c) 23.7 (d) 29.5
3. Which one of the following statements is correct ?
6. For the estimation of nitrogen, 1.4 g of an organic
[2003]
compound was digested by Kjeldahl method and
(a) From a mixed precipitate of AgCl and AgI,
the evolved ammonia was absorbed in 60 mL of
ammonia solution dissolves only AgCl
(b) Ferric ions give a deep green precipitate M
sulphuric acid. The unreacted acid required
on adding potassium ferrocyanide solution 10
(c) On boiling a solution having K+, Ca2+ and
M
HCO 3- ions we get a precipitate of 20 mL of sodium hydroxide for complete
10
K2Ca(CO3)2
neutralization. The percentage of nitrogen in the
(d) Manganese salts give a violet borax bead
compound is: [2014]
test in the reducing flame
4. The compound formed in the positive test for (a) 6% (b) 10%
nitrogen with the Lassaigne solution of an (c) 3% (d) 5%
organic compound is [2004]

Answer Key
1 2 3 4 5 6
(c) (b) (a) (a) (c) (b)
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C-148 Chemistry

1. (c) When H2S is passed through Hg2S we get 5. (c) Moles of HCl taken = 20 × 0.1 × 10– 3
a mixture of mercurous sulphide and = 2 × 10–3
mercury (Hg 2S + Hg) . Moles of HCl neutralised by NaOH solution
2. (b) When we add NH4Cl, it suppresses the = 15 × 0.1 × 10–3 = 1.5 × 10–3
ionisation of NH4OH and prevents the Moles of HCl neutralised by ammonia
precipitation of higher group hydroxide in
= 2 × 10–3 – 1.5 × 10–3
gp(III).
= 0.5 × 10–3
NOTE Further ferric chloride and
1.4 ´ N ×V
chromium chloride form different colour % of nitrogen = ´ 100
w.t. of Substance
precipitates with NH4OH.
® Fe(OH)3 ¯ + 3NH4Cl
FeCl3 + 3NH4OH ––––– 1.4 ´ 0.5 ´ 10 -3
= ´ 100
reddish brown 29.5 ´ 10 -3
® Cr(OH)3 + 3NH4Cl
CrCl3 + 3NH4OH –––––
= 23.7%
Bluish green.
3. (a) Between AgCl and AgI, AgI is less soluble, 1.4 ´ meq. of acid
hence ammonia can dissolve ppt. of AgCl 6. (b) % of N =
mass of organic compound
only due to formation of complex as given
below: M
AgCl + 2NH3 ® [Ag (NH3)2]Cl meq. of H2SO4 = 60´ ´ 2 = 12
10
4. (a) Prussian blue Fe 4 [Fe(CN) 6 ]3 is formed
M
in lassaigne test for nitrogen. meq. of NaOH = 20´ = 2
10
3Na 4 [Fe(CN) 6 + 4Fe3+ ¾¾
® \ meq. of acid consumed = 12 – 2 = 10

Fe4 [Fe(CN)4 ]6 + 12Na + 1.4 ´ 10

Prussian blue \ % of N = = 10%
1.4