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Unit 2 CHEMISTRY

1. Answer (3) Replacing 1H by 2H would replace 7.5 kg with


15 kg
W1 0.01
m=   0.000555  Net gain = 7.5 kg
M1  W2 (in kg) 60  0.3
7. Answer (4)
= 5.55 × 10–4 m
2. Answer (3) Element Relative Relative Simplest whole
mass mole number ratio
3. Answer (1) 6
C 6 = 0.5 1
12
The molarity of a solution obtained by mixing
1
750 mL of 0.5 M HCl with 250 mL of 2 M HCl is H 1 =1 2
1
given by
So, X = 1, Y = 2
750  0.5  250  2
Molarity   0.875 M Equation for combustion of CXHY
1000
⎛ Y⎞ Y
4. Answer (1) C XHY  ⎜ X  ⎟ O2  XCO2  H2 O
⎝ 4⎠ 2
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
So, volume of O2 required for the combustion of ⎛ Y⎞
Oxygen atoms required = 2 ⎜ X  ⎟
1 mL hydrocarbon = 5 mL. ⎝ 4⎠

So, volume of O 2 requierd for the combustion As per information,


of 15 mL of hydrocarbon = 75 mL (i.e., 20% of
⎛ Y⎞
375 mL air) 2 ⎜ X  ⎟  2Z
⎝ 4⎠
NOTE : But for this, the total volume of gases after
combustion should be 345 mL, rather than 330 mL.
⎛ 2⎞
 ⎜1  ⎟  Z
5. Answer (4) ⎝ 4⎠
M2CO3 + 2HCl  2MCl + H2O + CO2  Z = 1.5
nM2CO3  nCO2 Molecule can be written
CXHYOZ
1
 0.01186 C1H2O3/2
MM2CO3
 C2H4O3
1 8. Answer (1)
MM2CO3 =
0.01186
h h
= 84.3 g/mol = 
p mv
6. Answer (1)

10 6.63  1034
 75 = 7.5 kg or  = 0.4 nm
1.67  1027  103
Mass of hydrogen =
100

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34 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

9. Answer (2) 13. Answer (1)

h 14. Answer (1)


p  x 
4 E1  2.178 1018 J
h
x 
4   m V ⎛ 1⎞
E2  2.178 1018 ⎜ ⎟ J
⎝4⎠
6.6  1034  100
=
4  3.14  9.1 1031  600  0.005 hc 3
 E2  E1  2.178  1018
= 1.92 × 10–3 m  4

10. Answer (1)


6.62 1034  3 108  4
 18
 1.214 107 m
hc 2.178  3 10
E
 15. Answer (2)

242 103 Na(g) Na  (g)  e, HIE  5.1 eV


E J / atom
6.023 1023
Na  (g)  e Na(g), Heg  5.1 eV
3 34 8
242 10 6.6 10  3 10
 23
 16. Answer (1)
6.023 10 
37  1s22s22p63s23p63d104s24p65s1
26 23
19.8 10  6.023 10
  0.494 106 So last electron enters 5s orbital
242 103
1
= 494 nm Hence n = 5, l = 0, ml = 0, ms  
2
11. Answer (3)
17. Answer (3)
2
EHe ZHe  Energy of excited state is negative and correspond
 2 to n > 1.
ELi2 ZLi2

–13.6
19.6 10 18 4 n=
 Eexcited state
ELi2 9

–13.6
9 = = 4 =2
ELi2  19.6 1018 –3.4
4
18. Answer (3)
= 4.41 × 10–17 J/atom
Kinetic energy of electron is = e × V
 Energy of orbit of Li+2 is –4.41 × 10–17 J/atom
As per de-Broglie's equation
12. Answer (3)
h h
1 ⎡1 1⎤  
 RHZ2 ⎢ 2 – 2 ⎥ 2mEk 2meV
 ⎣⎢ n1 n2 ⎦⎥
h
  2meV
2⎡ 1 1⎤ ⎡ 1 1 ⎤ 
 (1) ⎢ 2 – 2 ⎥  (2)2 ⎢ 2 – ⎥
⎣⎢ n1 n2 ⎦⎥ ⎣ (2) (4)2 ⎦
19. Answer (2)

1 1
– 2 
3 n2
r = a0 = 0.529 ×4
n12 n2 4 Z
 n1 = 1, n2 = 2 = 2.12 Å

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 35
20. Answer (1) 2 2 2 2 2 2 2
N2: 1s  *1s 2s  * 2s 2p x 2p y 2pz
Na+ > Li+ > Mg2+ > Be2+
21. Answer (1) 2 2 2 2 2 2 2 1 1
O2: 1s  *1s 2s  * 2s 2pz 2p x 2p y  *2p x  *2py
2– – + 2+ 3+
O > F > Na > Mg > Al
2 2 2 2 2
S2: 1s  *1s 2s  * 2s 2p 2 22p  *2p
z 2p
2 2
 *2p y
x y x
Decreasing ionic radii with increasing effective
nuclear charge for isoelectronic species.  *22pz 3s
2 2
 *3s 2
3p 2 2  *13px  *13py
z 3p x 3p y

22. Answer (4) So, C2 and N2 are diamagnetic.


Fact. 34. Answer (3)
23. Answer (2)
Bond order of each of H22 and He2 is zero.
24. Answer (2)
The coagulating power of cation to cause 35. Answer (2)
coagulation of arsenic sulphide sol increases with 2
Li2 : 1s *2 2
1s Bond order = 1
the increase of valency of the cation. 1s

25. Answer (3)


Li2 : 1s
2 *2 1
1s 2s Bond order = 0.5
The increasing order of first ionisation enthalphy of
the given elements is Ba < Ca < Se < S < Ar .
Li2 : 1s
2 *2 2 *1
1s 2s 2s Bond order = 0.5
26. Answer (3)
Radius of N3–, O2– and F– follow order Li2 is less stable than Li2 because the incoming
N3– > O2– > F– electron goes to antibonding molecular orbital.

As per inequality only option (3) is correct 36. Answer (4)


that is 1.71 Å, 1.40 Å and 1.36 Å
27. Answer (3) Cl CN
Sc is d-block element having high Zeff hence high
ionisation enthalpy. (a) (b)
28. Answer (3)
Cl CN
Mg2+, Na+, O2– and F– all have 10 electrons each.
=0 =0
29. Answer (4)
H H
Higher is the bond order, shorter is the bond length. O S
Bond order of O22 is 3.0

30. Answer (3) (c) (d)


Ksp = [Mg+2] [OH–]2 O H S H
1 × 10–11 = 0.001 × [OH–]2
0 0
 [OH–] = 10–4 M
pOH = 4, pH = 10 37. Answer (4)

31. Answer (2) Molecule/ion Hybridization

32. Answer (1) NO2– sp2


33. Answer (1, 2)
NO3– sp2
The electronic configuration of the given diatomic
molecules is NO2 sp2
2 2 2 2 2 2
C2: 1s *1s 2s *2s 2px 2py NO2 sp

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36 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

38. Answer (4) 43. Answer (3)


CO has 14 electrons (even)  it is diamagnetic
P
NO has 15e–(odd)  it is paramagnetic and has ∵ r
M
1 unpaired electron in 2p molecular orbital.
B2 has 10e– (even) but still paramagnetic and has rA PA MB
two unpaired electrons in 2p x and 2p y 
rB PB MA
(s-p mixing).
O2 has 16 e– (even) but still paramagnetic and has 44. Answer (1)
two unpaired electrons in *2p x and *2p y All molecular speed is directly proportional to
molecular orbitals.
square root of temperature.
39. Answer (4)
45. Answer (2)
Electronic configuration Bond order 46. Answer (3)*
2–1
He2  *  0.5 The ratio of most probable speed (C*), average
1s2 1s1 2
2–1 speed (C) and root mean square speed (C) is
H2–  *  0.5
1s2 1s1 2 given by
2–2
H2–
2  * 0 8
1s2 1s2 2 C* :C:C  2 : : 3
2–0 
He22  1
1s2 2
 1: 1.128 : 1.225
Molecule having zero bond order will not be a viable
molecule. *(Note: root mean square speed has been wrongly
written in the question as mean square speed).
40. Answer (3)
47. Answer (2)
KCl – Ionic bond between K+ and Cl–
PH3 – Covalent bond between P and H PV
Compressibility factor (Z) 
RT
O2 – Covalent bond between O atoms
B2H6–Covalent bond between B and H atoms (For one mole of real gas)

H2SO4 – Covalent bond between S and O and also van der Waal equation
between O and H.
a
Compound having no covalent bonds is KCl only. (P  )(V  b)  RT
V2
41. Answer (3)
At low pressure
Structure of I3–
V b  V

I ⎛ a ⎞
⎜ P  2 ⎟ V  RT
⎝ V ⎠
I
a
PV   RT
V
I
a
Number of lone pairs in I3 is 9. PV  RT 
V
42. Answer (1)
PV a
PV = nRT  1
RT VRT
3170 × 10–3 = n × 8.314 × 300

31.7 103 a
n=  1.27 103 So, Z  1
8.314  3 VRT

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 37
48. Answer (2) We know, efficiency of a fuel cell,
Let the mass of O2 = x
G
  100
Mass of N2 = 4x H

x –702.6
Number of moles of O2  =  100
32 –726

4x x  97%
Number of moles of N2  =
28 7
53. Answer (3)
x x G = H – TS
 Ratio  : = 7 : 32
32 7 For equilibrium G = 0
49. Answer (4) For spontaneous reaction, G < 0
H-bond is one of the dipole-dipole interaction and  T > Te
dependent on inverse cube of distance between the
54. Answer (3)
molecules.
50. Answer (2) 1 3
N2  H2 NH3
No. of moles initially = no. of moles finally. 2 2

pi  V pi V pf V pf V HNH3  46 kJ
   
RT1 RT1 RT1 RT2
1 3
NH3  N2  H2
2pi ⎛1 1⎞ 2 2
  pf ⎜  ⎟
T1 ⎝ T1 T2 ⎠
1 3
46  3HNH   712   436
2pi ⎛ T1T2 ⎞ 2 2
 ⎜ ⎟  pf
T1 ⎝ T1  T2 ⎠ HNH  352 kJ / mol
55. Answer (1)
⎛ T2 ⎞
 p f  2pi ⎜ ⎟ rH = –111 – (2 × 54)
⎝ T1  T2 ⎠
= –219 kJ
51. Answer (1) 56. Answer (1)
I. H2O(l)  H+(aq) + OH–(aq); H = 57.32 kJ From the data, it is clear that Pb+2 is more stable
than Pb+4 and Sn+2 is less stable than Sn+ 4.
1
II. H2(g) + O (g)  H2O(l); H = –286.20 kJ 57. Answer (4)
2 2
H = E + ngRT
Adding I & II we get,
–1366.5 = E + (–1 × 8.314 × 300 × 10–3)
1
H2(g) + O (g)  H+(aq) + OH–(aq) E = –1364 kJ
2 2
58. Answer (2)
H = 57.32 – 286.2
59. Answer (1)
= –228.88 kJ
For isothermal reversible expansion of an ideal gas,
52. Answer (3) the work done is given by
3 375
CH3OH(l) + O (g)  CO2(g) + 2H2O(l) Wrev  0.04  8.314  310ln
2 2 50
Greaction = Gproducts – Greactant
 –207.22  208 J
= [–394.4 – 2 × 237.2] – [–166.2]
q  –Wrev  208J
= –702.6 kJ
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38 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

60. Answer (1) By applying the operation


C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l) (i) + 2 × (ii) + (iii), we get
Bomb calorimeter gives U of the reaction C(graphite) + 2H2(g)  CH4(g);
So, as per question rH° = –393.5 –285.8 × 2 + 890.3
U = –1364.47 kJ mol–1 = –74.8 kJ mol–1
ng = –1 64. Answer (1)
H = U + ngRT For adiabatic process, q = 0
 As per 1st law of thermodynamics,
1 8.314  298
 1364.47 
1000 U = W

= –1366.93 kJ mol–1 65. Answer (4)

61. Answer (4) 15


C6H6 (l)  O2 (g)  6CO2 (g)  3H2O(l)
2


2NO(g) + O2(g) 
 2NO2(g)
15 3
n g  6  
2 2
G  
reaction
 
 ⎡⎢ G


⎥product
formation ⎦ H = U + ngRT
 
 ⎡⎢ G


formation ⎥
⎦reactant ⎛ 3⎞ 3
= 3263.9  ⎜  ⎟  8.314  298  10
⎝ 2⎠
⇒ RT ln K P  2   G 

NO 2
2  G 

NO
= –3263.9 + (–3.71)
⇒  G 

NO 2
2  G 

NO
 RT ln K P = –3267.6 kJ mol–1
66. Answer (1)
2  86600  R  298ln K P
⇒ G  

NO 2

2 [ CO32 ] = 10–4 M

2  86600  R  298 ln1.6 1012 Ksp [BaCO3] = [Ba2+] [ CO32 ]



2
K sp 5.1 109
 0.5 ⎡⎣2  86,600  R  298ln1.6 10 ⎦ 12 ⎤  [Ba2+] = = = 5.1 × 10–5 M
[CO32 ] 104
62. Answer (3) 67. Answer (4)
Since K2 < < K1
CO2(g) H = – 393.5 kJ mol
–1
C(s) + O2(g)
1  Conc. of H+ and HCO 3 are approximately
CO(g) + O2(g) CO2(g) H = – 283.5 kJ mol –1

– – 2 – + same.

1 68. Answer (3)


CO(g) H = – 110.5 kJ mol
–1
C(s) + O (g)
2 2 [Ag+] = 0.05, [Br–] = x M

63. Answer (1) Ksp = [Ag+] [Br–]

C(graphite) + O2(g)  CO2(g); 5 × 10–13 = 0.05 × x

rH° = –393.5 kJ mol–1 ...(i) x = 10–11 M


 Solubility of KBr is (120 × 10–11) or 1.2 × 10–9 g/L
1
H2 (g)  O2 (g)  H2O(l); 69. Answer (2)
2
O O
rH° = –285.8 kJ mol–1 ...(ii)
O – P – O – H + O–H O – P – O +H – O – H
CO2(g) + 2H2O(l)  CH4(g) + 2O2(g);
O–H H OH H
rH° = 890.3 kJ mol–1 ...(iii)
Acid Base

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 39
70. Answer (3) 77. Answer (2)
Ksp = [Mg+2] [OH–]2


 B + C, G° = 2494.2 J
2A 
1 × 10–11 = 0.001 × [OH–]2
 [OH–] = 10–4 M As we know G° = –2.303 RT logKC
pOH = 4, pH = 10  2494.2 = –2.303 × 8.314 × 300 log KC
71. Answer (4)  –0.434 = log KC
 KC = anti log (–0.434)


 3
 Cr  3OH
Cr(OH)3   KC = 0.367

– 1 1
K sp  (Cr 3 )(OH)3 Now  A   , B  2 and C 
2 2
Ksp = 27S4
⎛ ⎞ 1
–30 CB ⎜⎝ 2 ⎟⎠
 2
K sp 1.6 10 Now QC   4
S= 4 4
27 27 A 2 ⎛ 1 ⎞2
⎜2⎟
⎝ ⎠
72. Answer (2)
as QC > KC, hence reaction will shift in backward
[H ]  K a .C
direction.

10 –pH  K a .C 78. Answer (2)

A BCD
10 –5  K a .C
Initially : 1 1 11 [D]eq = 1.818 M
(10–5)2 = Ka.C
Q=1
10–10 Q < keq
Ka 
C  Equilibrium is forward shifted.
Ka = 1 × 10–10 C=1M A BCD
73. Answer (2)
Equilibrium : 1–x 1–x 1+x 1+x
74. Answer (3)
(1  x)2
75. Answer (4)  102
(1  x)2
[H+] of the given HCl solution = 0.1 M
Let x litre of water be added to 1 litre of the given 1 x
HCl solution to get pH = 2 or [H+] = 10–2 M  = 10
1 x

0.1  1 + x = 10 – 10x
 0.01⇒ x  9 litre
1 x  11x = 9
76. Answer (2)
9
 x= = 0.818
1 11
SO2 (g)  O2 (g)  SO3 (g)
2 So, equilibrium concentration of 'D' = 1.818 M.
KP = KC(RT)x 79. Answer (4)

x = n g = no. of gaseous moles in product 1


pH = 7 +
2
 pK a – pKb 
– no. of gaseous moles in reactant
1
⎛ 1⎞ 3 1 = 7+  3.2 – 3.4
2
= 1 ⎜1 ⎟  1 
⎝ 2⎠ 2 2 = 6.9
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40 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

80. Answer (1) 83. Answer (2)


H CH3COOK + H2O  CH3COOH + KOH
⎛A ⎞  RT
Equilibrium constant K  ⎜ f ⎟e Basic
⎝ Ab ⎠
FeCl3 – Acidic solution
⎛ A ⎞ H ⎛ 1 ⎞ Al(CN)3 – Salt of weak acid and weak base
ln K  ln ⎜ f ⎟  ⎜ ⎟
⎝ Ab ⎠ R ⎝ T ⎠ Pb(CH3COO)2 – Salt of weak acid and weak base
y = C + m x CH3COOK is salt of weak acid and strong base.
Comparing with equation of straight line, Hence solution of CH3COOK is basic.
H 84. Answer (3)
Slope =
R The pH range of methyl orange is
Since, reaction is exothermic, H° = –ve, therefore, 3.9 4.5
Pinkish red Yellow
slope = +ve.
Weak base is having pH greater than 7. When
ln K methyl orange is added to weak base solution, the
A solution becomes yellow. This solution is titrated by
strong acid and at the end point pH will be less
B 1 than 3.1. Therefore solution becomes pinkish red.
(0, 0) T(K)
85. Answer (4)
K2Cr2O7 Oxidation Number of Cr = 6

0.75  0.6  294


Hence, option (1) is correct. Weight of K2Cr2O7 =  22.05 g
6
81. Answer (2)
86. Answer (3)
In presence of external H+,


  2 2MnO4  5C2O24  16H  2Mn2  10CO2  8H2O
 2H  S , K a 1  K a2  K eq
H2S 
87. Answer (1)
H  S 

2
2
  1 107  1.2  1013 a 361
H2S r=   127.6 pm
2 2 2 2
0.22 S2  88. Answer (1)
 1.2  10 20
0.1
a
[S2–] = 3 × 10–20 In fcc crystal, R  r 
2
82. Answer (3) 508
 110  r   254
2
[50  1]
Final concentration of [SO4– –] = = 0.1 M r = 144 pm
[500]
89. Answer (3)
Ksp of BaSO4,
Packing fractions of fcc and bcc lattices are 74%
[Ba2+][SO42–] = 1 × 10–10 and 68%

10 10  Vacancies are 26% and 32%


[Ba2+][0.1] = = 10–9 M
0.1 90. Answer (4)

Concentration of Ba2+ in final solution = 10–9 M 2 a 1.414  361


r   128 pm
Concentration of Ba2+ in the original solution. 4 4
M1V1 = M2V2 91. Answer (3)

M1 (500 – 50) = 10–9 (500) 92. Answer (2)

M1 = 1.11 × 10–9 M Silicon is a covalent crystal in which silicon atoms


are covalently bonded to give three dimensional
So, option (3) is correct. network.
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93. Answer (2) 98. Answer (1)
Let the number of moles of M3+ be x and that of Ethanol has H-Bonding, n-heptane tries to break
M2+ is (0.98 – x) the H-bonds of ethanol, hence, V.P. increases.
3x Such a solution shows positive deviation from
Number of moles of oxide ions = 0.98  x  1 Raoult's Law.
2
or, x = 0.04 99. Answer (2)
Percentage of M3+ = 4.08% Let V. P. of pure X = x

94. Answer (3) and V. P. of pure Y = y

– Cl— 1 3
Cl Then, x + y = 550 ...(i)
Cl


4 4
Cl
1 4
+ and x + y = 560 ...(ii)
Cs 5 5
Solving (i) and (ii), we get

Cl –
Cl
— Cl x = 400 mm
Cl
and y = 600 mm
2rCl  2rCs  3 a 100. Answer (3)
Tf = i Kfm
3a
rCl  rCs  i for Na2SO4 is 3(100% ionisation)
2
95. Answer (1) 0.01
Tf = 3 × 1.86 ×
Edge length of BCC is 4.29 Å. 1

In BCC, Tf = 0.0558 K


101. Answer (2)
4
edge length = r
3 P  XAPAo  XBPBo
4 25
4.29  r nheptane   0.25
3 100
4.29 35
r 3  1.86 Å noctane =  0.307
4 114
96. Answer (2) 0.25 0.307
P 105   45
In FCC, one of the face is like 0.25  0.307 0.25  0.307
By ABC, = 47.127 + 24.84 = 71.96
2a2 = 16r2 A  72 kPa

1 2 102. Answer (4)


 r2  a
8 a For isotonic solution
1 = 2
1
 r a
2 2 C B C1 = C2

a W1 W2

Distance of closest approach = 2r = M1V1 M 2 V2
2
97. Answer (3) 5 1
=
342 100 M2 100
In Frenkel defect, cation is dislocated from its
normal lattice site to an interstitial site. M2 = 68.4

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103. Answer (1)


  CH3COOH2


2CH3 COOH 
104. Answer (1) 1–  
2
  i CRT

 i  1–
C2H5OH  1 0.500  R  T  0.5RT 2


Mg3 (PO4 )2  5  0.100  R  T  0.5RT  0.527 = 1 –
2
KBr  2  0.250  R  T  0.5 RT 
 = 0.473
2
Na3PO4  4  0.125  RT  0.5RT
  = 0.946
105. Answer (2)
 % association = 94.6%
Vapour pressure of pure acetone P°A  185 torr
108. Answer (2)
Vapour pressure of solution, PS = 183 torr
o o
3+ E =? 2+ E = – 0.439 V
Molar mass of solvent, MA = 58 g/mole Fe Fe Fe
(1) (2)
Eo = – 0.036 V
P°A  PS nB (3)
as we know 
PS nA
Go1 + Go2 = Go3
185  183 WB MA  – n1Eo1 – n2Eo2 = – n3Eo3
⇒  
183 MB WA
 – Eo + 2 × 0.439 = +3 × 0.036

2 1.2 58  Eo = +0.77 V
⇒  
183 MB 100 109. Answer (4)

1.2 58 2 4
⇒ MB   183 Al2O3  Al  O2
2 100 3 3

 63.68 g/mole G = 966 kJ/mol

106. Answer (2)  4e– are involved


 G = – nFE
18
pº –ps n 18 966 × 103 = –4 × 96500 × E
 solute  180 
ps nsolvent 178.2 17.82
966
18 E V  2.5V
4  965
At normal boiling point of water V.P. = pº = 760
 2.5 V potential difference is required
torr
110. Answer (3)
760 – ps 18
  Case-I
ps 1782
1 1
or, 1800 ps = 760 × 1782 G  S (S = Siemen)
R 50
ps = 752.4 torr
107. Answer (2) K = G × cell constant

0.2 / 60 K 1.3 S m –1
0.45 = i(5.12)  1000 Cell constant    50
20 G 1S

 i = 0.527 = 65 m–1

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Case-II 1000
Now, m 
K M
M 
Molarity 2.5 103 1000
=
G  cell constant 0.5
M 
Molarity = 5 S cm2 mol–1
= 5 × 10–4 S m2 mol–1
1 S  65 m–1
 1  = 10–3 m3
260 0.4 mol litre –1 114. Answer (3)
According to Debye-Huckel-Onsager equation,
1 S  65 m–1

260 0.4 mol  1000 m3 C     A C
= 6.25 × 10–4 S m2 mol–1 Here A = B
111. Answer (3)
 C     B C
112. Answer (4)
Of the given values of standard reduction potential, 115. Answer (2)
On electrolysis only in case of Ca2+ salt aqueous
the value of EMnO4 /Mn2 is highest. Therefore,
solution H2 gas discharge at Cathode.
MnO4 is the strongest reducing agent. Case of Cr
113. Answer (1) At cathode : Cr3+ + 2e–  Cr
For 0.2 M solution So, Cr is deposited.
R = 50  Case of Ag
 = 1.4 S m–1 = 1.4 × 10–2 S cm–1 At cathode : Ag+ + e–  Ag
1 1 So, Ag is deposited.
    cm
 1.4 10 2 Case of Cu

Now, R   l At cathode : Cu2+ + 2e–  Cu


a Case of Ca2+
l R
   50 1.4 102 1
a  At cathode : H2O + e–  H + OH–
2 2
For 0.5 M solution
116. Answer (1)
R = 280 
(1) Mn2+ + 2e  Mn; E° = –1.18V ;
=?

l G1  2F( 1.18)  2.36F


 50 1.4 102
a (2) Mn3+ + e  Mn2+ ; E° = +1.51 V;
l
 R G2  F(1.51)  1.51F
a
1 1 l (1) – 2 × (2)
  
 R a 3Mn2+  Mn + 2Mn3+ ;

1 G3  G1  2G2


 =  50 1.4 102
280
= [2.36 – 2(–1.51)] F
1
=  70 102 = (2.36 + 3.02) F
280
= 2.5 × 10–3 S cm–1 = 5.38 F

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But G3  2FE 2.303 ⎛ 1 ⎞


  6.93 log ⎜
⎝ 0.01⎟⎠
t =
 5.38F = –2FE° 2.303  0.301
 E° = –2.69 V = 46.05 minutes
As E° value is negative reaction is non 122. Answer (1)
spontaneous.
Rate depends only on slow step
117. Answer (2)
123. Answer (4)
Cu+2 + 2e  Cu
So, 2 F charge deposite 1 mol of Cu. Mass a 2
K  1
deposited = 63.5 g. 2t 1 2 1
2
118. Answer (3)
Galvanisation is coating a layer of Zn. C0  Ct 0.5  0.25
t   0.25 h
119. Answer (3) K 1
124. Answer (1)
For Cr3+ , E°Cr 3+ /Cr O2– = – 1.33 V
2 7
*Most appropriate option is (1). Answer should be
For Cl–, E°Cl– /Cl = – 1.36 V k1  k 2 e
Ea1 /RT
.
2

For Cr, E°Cr/Cr 3 = 0.74 V k1  Ae


–Ea1 /RT
,k 2  Ae
–Ea2 /RT

For Mn2 , E°Mn2 /MnO – = – 1.51 V Ea1 2Ea1


4
lnk1  lnk 2  
Positive E° is for Cr, hence it is strongest reducing RT RT
agent.
k1 E /RT
120. Answer (3)  e a1
k2
B2H6 + 3O2  B2O3 + 3H2O
27.66 of B2H6 = 1 mole of B2H6 which requires Ea1 /RT
k1  k 2 e
three moles of oxygen (O2) for complete burning
125. Answer (1)
6H2O  6H2+ 3O2 (On electrolysis)
126. Answer (1)
Number of faradays = 12 = Amount of charge
12 × 96500 = i × t k2 Ea ⎡ 1 1 ⎤
log  ⎢  ⎥
12 × 96500 = 100 × t k1 2.303R ⎣ T1 T2 ⎦

12  96500
t second Ea ⎡ 1 1 ⎤
log2  
2.303  8.314 ⎣ 300 310 ⎥⎦

100

12  96500
t hour 0.301 2.303  8.314  300  310
100  3600 Ea 
10
t = 3.2 hours
121. Answer (2)
 53600 Jmol1 or 53.6 kJmol1
127. Answer (4)
ln 2
t1/2 =
k 2A  B  C  D
2.303  0.301 1d[A] d[B]
 k= Rate of Reaction = 
6.93 2 dt dt
2.303 ⎛ a ⎞ d[C] d[D]
log ⎜  
⎝ a – 0.99a ⎟⎠
Also, t =
k dt dt
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Let rate of Reaction = k[A]x[B]y
k Ea – Ea2
ln 2 = 1
d[C] k1 RT
Or,  k[A]x [B]y
dt
Now from table, 10  103
= 4
1.2 × 10–3 = k [0.1]x[0.1]y ...(i) 8.314  300

1.2 × 10–3 = k [0.1]x[0.2]y ...(ii) 131. Answer (1)


2.4 × 10–3 = k [0.2]x[0.1]y ...(iii) Assume the order of reaction with respect to
Dividing equation (i) by (ii) acetaldehyde is x.
Condition-1 :
1.2 103 k[0.1]x [0.1]y
⇒  Rate = k[CH3CHO]x
1.2 103 k[0.1]x [0.2]y
1 = k[363 × 0.95]x
y
⎡ 1⎤ 1 = k[344.85]x ...(i)
⇒ 1 ⎢ ⎥
⎣2⎦ Condition-2 :
0.5 = k[363 × 0.67]x
⇒ y 0
0.5 = k[243.21]x ...(ii)
Now Dividing equation (i) by (iii)
Divide equation (i) by (ii),
1.2 103 k[0.1]x [0.1]y x
⇒  1 ⎛ 344.85 ⎞
2.4 103 k[0.2]x [0.1]y ⎜ ⎟ ⇒ 2  (1.414)x
0.5 ⎝ 243.21 ⎠

⎡ 1⎤ ⎡ 1⎤
1 x  x=2
⇒ ⎢2⎥  ⎢2⎥ 132. Answer (3)
⎣ ⎦ ⎣ ⎦
Physisorption is an exothermic process with H 
⇒ x 1 –20 kJ/mol
133. Answer (4)
d[C]
Hence  k[A]1[B]0 . 134. Answer (1)
dt
Number of moles of acetic acid adsorbed
128. Answer (1)
Higher order greater than 3 for reaction is rare ⎛ 50 50 ⎞
 ⎜ 0.06   0.042 
because there is low probability of simultaneous ⎝ 1000 1000 ⎟⎠
collision of all the reacting species.
129. Answer (1) 0.9
 moles
1000
0.693
Rate = K[H2O2] =  0.05  Weight of acetic acid adsorbed = 0.9 × 60 mg
25
= 54 mg
1 0.693
Rate of formation of H2O2 =   0.05
2 25 Hence, the amount of acetic acid adsorbed per g

= 6.93 × 10–4 mol min–1 54


of charcoal = mg
3
130. Answer (2)
= 18 mg
–Ea /RT
k1 = Ae 1 Hence, option (1) is correct.
–Ea /RT 135. Answer (2)
k2 = Ae 2

According to Freundlich adsorption isother :


1
k2 
Ea – Ea
e RT 1 2  x
1

k1 =  k  Pn
m
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x 1 O
 log  logP  logk H H
m n
y = m·x + C O
H H H H
1 O
O
= n H
pe
slo H H
x O
log m
H
 intercept = logk (in ice)

log P 142. Answer (2)


136. Answer (4) Calcium carbide CaC2
For Tyndall effect refractive index of dispersion
C  C carbide ion (C22–)
phase and dispersion medium must differ
significantly. Secondly, size of dispersed phase = 1 + 2
should not differ much from wavelength used. 143. Answer (4)
137. Answer (2) –2 +
O H O H
138. Answer (4)
144. Answer (3)
The reducing agent oxidises itself.
4LiNO3  2Li2O + 4NO2 + O2
(a) H2O21  2H  2e  2H2O2 145. Answer (2)
0 146. Answer (2)
(b) H O1  2e O  2H
2 2 2 It contains Cs+ and I3– ions.
2 147. Answer (2)
(c) H O 1  2e  2OH
2 2 BeSO4 has hydration energy greater than its lattice
energy.
0
(d) H O1  2OH  2e O  H O 148. Answer (3)
2 2 2 2
Li mainly gives oxide, Na gives peroxide and K
Note : Powers of 'O' are oxidation number of 'O' in
gives superoxide.
the compound.
149. Answer (3)
139. Answer (4)
Mg forms basic carbonate
Ca+2 + 2C8H7SO3–Na+  Ca(C8H7SO3–)2 + 2Na+
1 mol 2 mol 3MgCO3 · Mg  OH2 ·3H2O but no such basic
carbonate is formed by Li.
1 1
The maximum uptake =  mol/g 150. Answer (4)
206  2 412
XeF6 + 3H2O  XeO3 + 6HF
140. Answer (1)
151. Answer (2)
H2O2 can be reduced or oxidised. Hence, it can
In BF3, F forms p- p back bonding with B.
act as reducing as well as oxidising agent.
152. Answer (2)
141. Answer (2)
NH3 is more basic.
There is intermolecular hydrogen bonding in water
153. Answer (1)
H H
F
O O O
H H H H Xe 3 lone pairs
(in water) F

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154. Answer (2) However, it dimerises at low temperature to become
diamagnetic.
155. Answer (3)


2NO 
 N2O2

  
 ClO4  H
HClO4 
Its bond order is 2.5 and it combines with O2 to
 
give nitrogen dioxide.


 ClO3  H
HClO3 
157. Answer (4)


   Because of polarity and weak bond interhalogen
 ClO2  H
HClO2 
compounds are more reactive.

 
158. Answer (4)


 ClO  H
HOCl 
Down the group strength of van der Waal's force of
Resonance produced conjugate base. attraction increases hence Xe have highest boiling
point.

O O O
159. Answer (1)
Cl Cl Cl N2 + O2  2NO
(i) O O

O O

O O
O O O Required temperature for above reaction is around

(ClO4 ) 3000°C which is a quite high temperature. This
O reaction is observed during thunderstorm.

Cl
160. Answer (4)
O O The phosphorous atoms of orthophosphorous acid

O
H3PO3 and pyrophosphorous H4P2O5 have a formal

O O O oxidation state +3.
Cl Cl Cl 161. Answer (4)
(ii) –
O O O

O O O
4Zn + 10HNO3(dil)  4Zn(NO3)2 + N2O + 5H2O
(ClO3–)

O O

Zn + 4HNO3(conc.)  Zn(NO3)2 + 2NO2 + 2H2O
Cl Cl 162. Answer (3)
(iii) –
O O
Xe is oxidised from +4(in XeF4) to +6(in XeF6)
(ClO2–)
Oxygen is reduced from +1 (in O 2F2) to zero
(iv) ClO– is not resonance stabilized. (in O2)
As per resonance stability order of conjugate base 163. Answer (1)
is
Cl2  2NaOH  NaCl  NaOCl  H2 O
Cold & dilute Sodium
ClO4  ClO3  ClO2  ClO 
hypochlorite

Hence acidic strength order is 164. Answer (4)*


BCl3 – electron deficient, incomplete octet
HClO4  HClO3  HClO2  HClO
AlCl3 – electron deficient, incomplete octet
156. Answer (1) Ans-(4) BCl3 and AlCl3
Nitric oxide is paramagnetic in the gaseous state SiCl4 can accept lone pair of electron in d-orbital
as it has one unpaired electron in its outermost of silicon hence it can act as Lewis acid.
shell. The electronic configuration of NO is * Although the most suitable answer is (4).
2 2 1
However, both option (4) & (2) can be considered
2 * 2 * 2
1s 1s 2s 2s 2p 2  2p
z 2p x
2
*
y 2p x
as correct answers.

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e.g., Hydrolysis of SiCl4 173. Answer (3)

Cl Cl 174. Answer (1)


H Number of unpaired electrons of V2+, Cr2+, Mn2+ and
Si + H2O Si O
Cl Cl Cl H Fe2+ are 3, 4, 5 and 4 respectively. Hence the
Cl
Cl Cl given order of paramagnetic behaviour is incorrect.
175. Answer (4)

Cl Cobalt has the highest value of ECo3 /Co2  1.97 V.


Cl Si OH + HCl Other values of standard reduction potential are

Cl EMn3 /Mn2  1.57 V, EFe 3
/Fe2
 0  0.77 V and
Hence option (2), AlCl3 and SiCl4 is also correct.
ECr 3 /Cr 2  0.41V .
165. Answer (4)
176. Answer (4)
NH4 2 Cr2O7 
Δ
 N2 + 4H2O + Cr2O3
O2
Fe 
Heat
Fe3O4
Δ
NH4NO2  N2 + 2H2O
This reaction is corresponding to the combustion of
NH4 2 SO4  2NH3 + H2SO4
Δ Fe.
CO CO
Ba N3 2 
Δ
 Ba  3N2 Fe3O4 
600ºC
FeO 
700ºC
Fe

Among all the given compounds, only (NH4)2SO4 These reactions correspond to the production of Fe
do not form dinitrogen on heating, it produces by reduction of Fe3O4 in blast furnace.
ammonia gas. 177. Answer (2)
166. Answer (2) TiCl3 - Ziegler-Natta polymerisation
V2O5 - Contact process
= 4e–, non-planar = non-aromatic
PdCl2 - Wacker process
167. Answer (3) CuCl2 - Deacon's process
168. Answer (4) 178. Answer (3)
In Hall-Heroult process Al 2 O 3 (molten) is Charge transfer spectra from ligand (L) to metal (M)
electrolyte. is responsible for color of KMnO4.
169. Answer (2) 179. Answer (1)
Sulphide ores are concentrated by froth floatation. CrO2 is strongly attracted towards magnetic field
Galena (PbS) is concentrated by froth floatation. so it is ferromagnetic.
170. Answer (1) 180. Answer (1)
In the highest oxidation states, the transition Identical the number of unpaired electrons higher
metals show acidic character. the magnetic moment
171. Answer (2) Metal ion Unpaired electrons
Ln (III) compounds are generally coloured. [Cr(H2O)6]2+ Cr2+ 4
172. Answer (2)
[Fe(H2O)6]2+ Fe2+ 4
Mn > Cr > Fe > Co
 [Cr(H2O)6]2+ and [Fe(H2O)6]2+ have identical
o
EMn 2
/Mn
 1.18 magnetic moment.
181. Answer (2)
EoCr 2 /Cr  0.91
In (a), ZnO acts as acidic oxide as Na2O is basic
o oxide.
EFe 2
/Fe
 0.44
In (b), ZnO acts as basic oxide as CO2 is acidic
EoCO2 /CO  0.28 oxide.

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182. Answer (3) 190. Answer (2)

en en B
V G

Co en en Co R Y
O
NH3 NH3
NH3 NH3 The energy of red light is less than that of violet
light.
So energy order is
183. Answer (1)
Red < Yellow < Green < Blue
SCN– is an ambidentate ligand.
The complex absorbs lower energy light lower will
184. Answer (3) be its strength. So order of ligand strength is
N 3+
N 3+
L1 < L3 < L2 < L4
N N N N
191. Answer (2)
Co Co
The complex
N N N N [CoCl(NH3)5]+ decomposes under acidic medium,
N N so
Optically active [CoCl(NH3)5]+ + 5H+  Co2+ + 5NH4+ + Cl—.
3 192. Answer (2)
Exist as enantiomeric pair ⎡⎣Co  en3 ⎤⎦
a b a c a b
185. Answer (2)
Pt Pt Pt
2.675 d c d b c d
Moles of complex =  0.01
267.5 as per question a = Cl, b = py, c = NH 3 and
d = NH2OH are assumed.
4  78
Moles of AgCl precipitated =  0.033 193. Answer (1)
143.5
It means 3Cl– are released by one molecule of Cl
complex Cl
en Co
 [Co(NH3)6]Cl3
186. Answer (3)
en
NH3 enCN– CO

Field strength
 Strong field ligand has no plane of symmetry, so it is optically active.
194. Answer (2)
187. Answer (4)
[ Co(NH 3 ) 2 (en) 2 ] 3 + will exhibit geometrical 1.2  1022
isomerism ( [ Ma2(A – A)2 ] ± n type complex ). Millimoles of AgNO3 =  1000 = 20
6  1023
188. Answer (1)
Millimoles of CoCl3·6H2O = 0.1 × 100 = 10
189. Answer (3)
 Each mole of CoCl3·6H2O gives two chloride
[Co(NH3)3Cl3) has two geometrical isomers, namely ions.
fac. and mer. Both of them have a plane of
symmetry. So, they are not expected to show  [Co(H2O)5Cl]Cl2·H2O
optical isomerism. 195. Answer (4)
NH3 NH3 The solution which shows maximum freezing point
Cl NH3 Cl NH3 must have minimum number of solute particles.
Co Co
Cl NH3 Cl Cl (1) [Co(H2O)6]Cl3  [Co(H2O)6]3+ + 3Cl–, i = 4
Cl NH3 (2) [Co(H2O)5Cl]Cl2  H2O
fac. mer.  [Co(H2O)5Cl]2+ + 2Cl–, i = 3

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50 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

(3) [Co(H2O)4Cl2]Cl  2H2O  [Co(H2O)4Cl2]+ + 198. Answer (1)


Cl–, i = 2 (NH4)3[As (Mo3O10)4], BaCrO4 and K3[Co(NO2)6] are
(4) [Co(H2O)3Cl3]  3H2O  [Co(H2O)3Cl3], i = 1 yellow colored compounds but Zn2[Fe(CN)6] is not
So, solution of 1 molal [Co(H2O)3Cl3]  3H2O will yellow colored compound.
have minimum number of particles in aqueous 199. Answer (1)
state. Region "2" is the hottest region of Bunsen flame.
Hence, option (4) is correct.
200. Answer (2)
196. Answer (3)
Na2C2O4  H2SO4 
 Na2SO4  H2C2O4
⎡⎣Cr H2 O 6 ⎤⎦ Cl3 ⇒ x  0  6 – 1 3  0
( X) Conc. oxalic acid

 x  3 H2 C2 O 4 
2 4 Conc. H SO
 CO  CO2 
 
–H2O (effervescence)
⎡⎣Cr  C6H6 2 ⎤⎦ ⇒ x  2  0  0
Na2 C2 O 4  CaCl2  CaC2 O 4   2NaCl
x0 ( X) white ppt.

 2
2MnO4–  5C2O2–
4  16H  2Mn  10CO2  8H2O
K 2 ⎡⎣Cr  CN2  O2  O2  NH3 ⎤⎦
⇒ 1 2  x – 1  2 – 2  2 – 2  1  0 201. Answer (3)

⇒x – 6  0 4– 1 3–
[Fe(CN) 6] + H O + H+ [Fe(CN)6] + H2O
2 2 2
x  6
3– 1
197. Answer (2) [Fe(CN)6] + H O + OH
2 2 2 1
4–
Br [Fe(CN)6] + H2O + O 2
NH3 2
Br
202. Answer (3)
Excess
NH3 NH3 Al3  
NaOH
 Al  OH 3  
NaOH
 NaAlO2
White gelatinous ppt. Sodium meta
NH3 alu minate
(so lub le)
cis-isomer

+Br
2Al  OH3 
Strong heating
 Al2O3  3H2O
Br Br Al2O3 is used in column chromatography.
NH3 Br NH3 Br 203. Answer (1)
+
CH3
NH3 Br NH3 NH3 1 2 3
CH3 – C – CH3
NH3 Br
fac- mer- CH3
(2 isomer)
IUPAC name : 2, 2-dimethylpropane
Br Br
NH3 NH3
204. Answer (2)
NH3 NH3

CCl3 > C6H5 CH2 > (CH3)2 CH > (CH3)3 C

NH3 Br 205. Answer (2)


NH 3 NH3
Br Br CH3 CH3 CH3 H
trans Mer (1 isomer) C C and C C
H H H CH3
So option (2) is correct. cis-2-Butene trans-2-Butene

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 51
206. Answer (1)
1 60 1 20
    (ngeq )NH3
Θ 5 1000 10 1000
R  COO  HC  CΘ  NH2  R

increasing basic strength 6 1
  (ngeq )NH3
500 500
As sp3 C is less electronegative than sp3 N alkyl
5 1
carbanion R  is more basic than NH . However
Θ
(ngeq )NH3  
2 500 100
sp hybridized carbon is more electronegative than
Θ 1
Θ (nmol )N  (nmol )NH3  (ngeq )NH3 
sp3 N. Hence NH2 is more basic than HC  C 100
207. Answer (4) 14
(Mass)N   0.14 g
1.4 NV 100
%N 
W
0.14
Percentage of "N"  100 = 10%
1.4  0.1 (20  15) 1.4

29.5 103 211. Answer (1)
Percentage of Br
700
  23.7
29.5 Weight of AgBr Mol. mass of Br
= Mol. mass of AgBr  Weight of O.C.  100
208. Answer (4)
Benzyl carbocation (III) is more stable than allyl
carbocation (I) as it has more number of resonating 141 80
=  100
structures. n-propyl carbocation (II) is least stable 188 250
as it is stabilised by +I and +H effects of ethyl
group. = 24%

209. Answer (4) 212. Answer (3)


As glycerol decomposes before reaching its boiling
⎛ y⎞ y
CxHy  ⎜ x  ⎟ O2  xCO2  H2O point under 1 atm pressure. So, in order to prevent
⎝ 4⎠ 2 its deomposition, it is distilled under reduced
pressure.
3.08
Number of moles of CO2   0.07; x  0.07 213. Answer (2)
44
However, all molecules given in options are
0.72 stabilised by resonance but compound given in
Number of moles of H2O   0.04; y  0.08
18 option (2) is least resonance stabilised (other three
are aromatic)
x : y = 7 : 8.
Therefore, empirical formula of hydrocarbon is C7H8 O O–
210. Answer (2)
As per question

Normality Volume
N 214. Answer (2)
H2SO4 60mL
5 Kjeldahl method is not applicable for compounds
N containing nitrogen in nitro, and azo groups and
NaOH 20mL
10 nitrogen in ring, as N of these compounds does
not change to ammonium sulphate under these
conditions. Hence only aniline can be used for
(ngeq )H2SO4  (ngeq )NaOH  (ngeq )NH3
estimation of nitrogen by Kjeldahl’s method.

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52 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

215. Answer (2) 222. Answer (1)


H H +
CH2 – CH – CH3
OH CH3 O +
CH3 Cl
CH2–CH–CH
H
CH2–CH–CH CH2=CH – CH3 + Cl More stable intermediate
CH3 +
CH3 CH2 – CH – CH3
Cl
CH3
CH—CH– C –
+ OH
(B) H CH3
CH2 – CH – CH3 CH2 – CH – CH3
H (A)
Cl Cl OH
CH3
(A) 223. Answer (2)
CH = CH–CH
CH3 CH3
Extension of conjugation
(More stable) HBr
CH3 – CH = C – CH2 – CH3
 Major product R2O2
CH3 3-methyl pent-2-ene
(B)
CH2–CH = C
CH3
(Minor) CH3
* *
CH3 – CH – C – CH2 – CH3
216. Answer (4)
Br H
(i) O3 Product (X)
CH3 CH CH CH3 CH3 CHO
(ii) Zn-H2O
44 amu Since product (X) contains two chiral centres and
it is unsymmetrical.
217. Answer (1)
So, its total stereoisomers = 22 = 4.
218. Answer (1)
224. Answer (3)
219. Answer (3)
Na/liq. NH3 CH3 H
Cl CH3 – C  C – CH3 C=C
Ag H CH3
2Cl—C—CH3 CH3C  CCH3 + 6AgCl Trans alkene
Cl So, option (3) is correct.
1, 1, 1-trichloroethane
225. Answer (1)
220. Answer (1) Fact.
For geometrical isomerism doubly bonded carbon 226. Answer (1)
must be bonded to two different groups which is
only satisfied by 1 - Phenyl - 2 - butene. Methylisocynate (CH3NCO) a deadly poisonous gas
leaked from a storage tank of the Union Carbide
H H H CH3 Plant in Bhopal gas tragedy.
C=C C=C 227. Answer (2)
Ph – CH2 CH3 Ph – CH2 H
The maximum limit of nitrate in drinking water is 50
cis trans ppm.

221. Answer (2) Excess nitrate in drinking water can cause blue
baby syndrome.
5-keto-2-methylhexanal is
The prescribed limit for fluoride is 10 ppm.
O O
The prescribed limit for lead is 50 ppb.
H The prescribed limit for iron is 0.2 ppm.
228. Answer (1)
O3 Zn
O O –
+
Permissible limit of F in drinking water is upto 1
H –
H ppm. Excess concentration of F  10 ppm
causes decay of bones.

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 53
229. Answer (3) 234. Answer (3)
F– ions make the teeth enamel harder by On moving down a group basicity decreases but
converting nucleophilicity increases.

[3Ca3 (PO4 )2 .Ca(OH)2 ] to [3Ca3 (PO4 )2 .CaF2 ] 235. Answer (2)


Hydroxyapatite Fluorapatite
236. Answer (3)
230. Answer (2) 237. Answer (3)

CH3CH = CH – CH (OH)Me has CH3 CH3
SbCl5 –
CH3 H H — C — Cl C+ + SbCl6
C C + its enantiomer H C6H5
H CH(OH)Me C6H5
(–)
Me H H Me CH3 CH3
C=C C=C H — C — Cl + Cl — C — H
H C Me Me C H
C6H5 C6H5
H OH HO H (Racemic mix.)
238. Answer (4)
H H
C C + its enantiomer 
CH3 CH(OH)Me CH2Br CH2NO3
alc. AgNO 3
+ AgBr
CH3 CH3
H H H H (A) (Light yellow ppt.)
C=C C=C COOH CO
Me C Me Me C Me
Oxidation

O + H2O
COOH CO
H OH HO H (B)

Note: Compound (A) reacts with alc. AgNO3 to give


231. Answer (2) light yellow ppt. of AgBr and not white ppt. as
Formation of carbocation is rate determining step given in the question.
in SN1 reaction. Hence alkyl halide which gives 239. Answer (2)
more stable carbocation is more reactive towards
SN1 reaction Rate of SN2 reaction depends on steric crowding
of alkyl halide. So order is
Me Me
CH3Cl > (CH3)CH2 – Cl > (CH3)2CH – Cl > (CH3)3CCl
> Me > Me Br
Br Br 240. Answer (4)

decreasing order of SN1 reactivity Swart's reaction


232. Answer (4)
CH3  Cl  AgF 
 CH3F  AgCl
H H 241. Answer (4)
C Et Et C
1 3 CH3
2 MeONa
Me Me CH3 CH2 CH2 C CH3
MeOH
3-methyl-1-pentene mirror image SN1 & E1 path
Cl
Chiral  Chiral
Non superimposable
OMe
233. Answer (1)
Fact. + +

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242. Answer (1) So, II < I < III


Increase stability of carbocation and hence increase
CH2OH
1
reactivity of halides.
H OH
2 245. Answer (4)
H Cl
CH3 Br
H t-BuOK
C6H5 C6H5
At (1), 
C6H5 (E-2) C6H5
(+)
3 1
246. Answer (2)
4 1 2 3 CH3O– is a strong base and strong nucleophile, so
2 4 favourable condition is SN2/E2.
Given alkyl halide is 2° and C's are 4° and 2°, so
It is 'S' configurated.
sufficiently hindered, therefore, E2 dominates over
At (2), SN2.
2 1 Also, polarity of CH3OH (solvent) is not as high as
H2O, so E1 is also dominated by E2.
4 1 3 2

3 4  Br
 CH3O–
It is 'R' configurated.  H
E2

243. Answer (1) (Major product)


(2°)

247. Answer (2)

OH OH
NBS/h COOH
CO2
NaOH

Salicylic acid
248. Answer (3)
More stable
Alcohols which give more stable carbocation is
Br –H more reactive with Lucas reagent
O
NBS H2O/K2CO3 (Anhy. ZnCl2 + conc. HCl)

OH
| 
Anhy. ZnClHCl
CH3  C  CH2  CH3   CH3  C  CH2CH3
244. Answer (4) | |
CH3 CH3
Rate of SN1 reaction  stability of carbocation More reactive More stable tertiary
carbocation

I. CH3 – CH – CH2 – CH3 CH3 – CH – CH2 – CH3 249. Answer (3)


Cl D>C>A>B

II. CH3 – CH2 – CH2 – Cl CH3 – CH2 – CH2 OH OH OH OH

CH2 – Cl CH2 > > >


NO2
NO2 –I  CH3
III.
–R, –I Unsubstituted +R, H

OCH3 OCH3 Order of acidic strength = –R > –I >  > + H > +R

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 55
250. Answer (4) 255. Answer (1)
100°C-110°C
C2H5HSO4 OH OH
140°C CO2, NaOH
COOH
C2H5OH + H2SO4 C2H5OC2H5
Acidification
180°C
CH2 = CH2 (Major)
251. Answer (3) O
OH O–C–CH3
The acidic strength of the given derivatives of
COOH COOH
phenol is decided by the stability of their conjugate (CH3CO)2O
bases. p-nitrophenol is most acidic as –I and –R H2SO4
effects of NO2 group stabilises its conjugate base Acetyl salicylic acid
most effectively. This is followed by p-chlorophenol (Aspirin)
due to –I effect of Cl group, p-cresol due to +I and
+H effects of CH3 group which destabilises its 256. Answer (4)
conjugate base. p-methoxphenol is least acidic due
to +R effect of OCH3 group. O HI I
+
252. Answer (2) Heat I
O OH
Tertiary alcohol gives instant turbidity with Lucas + OH
reagent and the reaction follows SN1 mechanism Hence, option (4) is correct.
due to stability of tertiary carbocation.
257. Answer (3)
253. Answer (1)

H
— Liquid + ethanol  Fruity smell compound
O O O
H O—
— O=C=O  
C
O Carboxylic acid Must be ester

H
OH CH3COOH + C2H5OH  CH3COOC2H5
OH
COOH COO— 258. Answer (3)
+
(CH3CO)2O H
OH
aq. KOH
(B) CH3CHCl2 CH3CH
gem-dihalide OH
OCOCH3
unstable
COOH
–H2O

CH3CHO
(C)
259. Answer (1)
254. Answer (3) In Cannizzaro reaction, the transfer of hydride to
the carbonyl group is the rate determining step.
O O
260. Answer (1)
[Ag(NH3)2]+OH– CH3 – OH/H+
CH3 H
Esterification
O3
CH3 C C CH2 CH3
C=O C=O Zn/H2O
H HO
CH3 O
O (i) CH3MgBr HO CH3
(3 moles)
CH3 C O + CH3 CH2 C H
(ii) H2O acetone
261. Answer (4)
CH3 262. Answer (3)
C – OCH3 HO – C
O CH3 263. Answer (4)

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56 ANSWERS AND SOLUTIONS ARCHIVE - JEE (Main)

269. Answer (3)


CH3CH2COOH + NH3 CH3CH2CO2NH4
O
(A) (B)  –
KOH + Br2
OH3 O O – C – O – CH3
O
CH3CH2NH2 CH3CH2CONH2 + H2O
OH– Cl – C – O – CH3
(C)
264. Answer (4)
Br2
PCC is mild oxidising agent, it will convert
R  CH2  OH R  CHO O
O – C – O – CH3
265. Answer (3)
Ethylene
LiAlH4
CH3COOH CH3CH2OH 'A' Br

PCl5 Hence, option (3) is correct.


270. Answer (4)
CH3CH2Cl 'B'
Alc. KOH NH2 N  NCl F
NaNO2 HBF4
CH2 = CH2 'C'
HCl , 278 K 
266. Answer (4)
Benzene diazonium Fluorobenzene
chloride
CH3 COOH COCl CHO
271. Answer (3)
KMnO4 SOCl2 H2/Pd
BaSO4 + –
(A) (B) (C)
NH2 N2Cl CN
NaNO2 CuCN
267. Answer (3)
HCl 
CH3
+ –
Na O C CH3 272. Answer (2)
O
CH3 R  NH2  CH3COCl  RNHCOCH3  HCl
Br M M 42

CH3 If the increase in molecular mass is 42, the


reactant has one NH2 group.
O O C CH3
Actual increase in molecular mass = 390 –180
CH3
= 210
(Product)

The above product does not have any C = C or 210


Number of NH2 groups  5
C  C bond, so, it will not give Br2-water test. 42
268. Answer (4)
273. Answer (4)
DIBAL — H reduces esters and carboxylic acids
into aldehydes CHCl3 /KOH
R – CH2 – NH2 
C2H5OH
 R– CH – NC
2
O O OH H O
274. Answer (1)
DIBAL-H
Among C6H5NH2, CH3NH2, (CH3)2NH,

COOH CHO (CH3)3N . C6H5NH2 is least basic due to resonance.

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ARCHIVE - JEE (Main) ANSWERS AND SOLUTIONS 57
+ +
NH2 NH2 NH2 278. Answer (3)

NH2 Protonation NH3


(a) 3
1° & sp

Protonation
+ NH NH2
NH2 NH2 (b) 2
sp

+
NH2 NH2 NH2
Protonation

Out of (CH3)3N, CH3NH2, (CH3)2NH . (CH3)2NH is +


most basic due to +I effect and hydrogen bonding (c) NH NH2 NH2
in H2O.
+I effect [Equivalent resonance]
CH3
Protonation
N
(d) NHCH3 NH2–CH3
H 2° & sp3
H3C
+I effect
 Correct order of basicity : b < a < d < c.
O 279. Answer (2)
Hydrogen H H
bonding A typical carbohydrate contains –OH and >C = O.

275. Answer (3) 280. Answer (2)


+ – Biuret test is only given by amides. Carbohydrates
NH2 N 2Cl CN are not amides and hence it does not give biuret
NaNO2/HCl CuCN/KCN
test.
0°C - 5°C 
+ N2
281. Answer (2)

CH3 CH3 CH3 282. Answer (1)

(D) (E) 283. Answer (1)


3 ATP molecules are needed per molecule of CO2.
276. Answer (3) Since one molecule of glucose has 6 C-atoms, the
R – C – NH2 + Br2 + 4NaOH  number of ATP molecules required is 18.
O 284. Answer (1)
RNH2 + Na2CO3 + 2NaBr + 2H2O DNA contains ATGC bases
From the reaction it can easily be said 4 moles of A – Adenine
NaOH and 1 mole of Br2 is used in this reaction.
T – Thymine
277. Answer (1)
G – Guanine

NH2 NH3 C – Cytocine


So quinoline is not present.
H+ NO2
285. Answer (1)
Vitamin C is water soluble vitamin.
NH3 NH3 NH3
286. Answer (2)
NO2
+ + (– SH) Thiol group is present in cysteine.
NO2 HS – CH2 – CH – COOH
(51%) (2%)
NO2
(47%) NH2

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287. Answer (3) 292. Answer (4)


Sugars in which there is free anomeric –OH group C6H5OH + HCHO  bakelite
are reducing sugars
293. Answer (2)
OH 294. Answer (1)
CH2 O CH2 – OH Dacron is polyester formed by condensation
O KOH(aq.) polymerisation of terephthalic acid and ethylene
HO O – C– CH glycol.
3

HOOC COOH + HO—CH2—CH2—OH


OH
OH
CH2 O CH2 – OH —CO CH2—CH2—O—
n
HO Dacron
OH + CH3COOK
Acrylonitrile, Neoprene and Teflon are addition
OH polymers of acrylonitrile, isoprene and tetrafluoro
Free anomeric group ethylene respectively.
288. Answer (1) 295. Answer (2)
Glyptal is used in manufacture of paints and
CHO
lacquires.
HI, 
(CH–OH)4 CH3–CH2–CH2–CH2–CH2–CH3 296. Answer (3)
n-Hexane
CH2–OH Low density polyethene is synthesised by
O2/1000–2000 atm
289. Answer (4) nH 2C = CH 2 [ CH 2 CH 2 ]
trace of peroxide
H (as initiator) catalyst
N
It is poor conductor of electricity, hence option (3)
Histamine is false regarding it.
H NH2 297. Answer (3)
At pH (7.4) major form of histamine is protonated Caprolactam is hydrolysed to produce caproic acid
at primary amine. which undergoes condensation to produce
H Nylon-6.
N
O O
NH H3O +
C
N NH
+
HO (CH2)5 – NH2
3

290. Answer (2) (Caprolactam) (Caproic acid)

Acrylonitrile + 1, 3-butadiene  Buna-N 298. Answer (4)


(Bu = Butadiene, Na  Sodium, a 299. Answer (3)
polymerising agent, N = Nitrile) Phenelzine is not antacid, it is anti-depressant.
291. Answer (3) 300. Answer (1)
Nylon 6, 6 involves amide linkage therefore, it will Sodium lauryl sulphate  Anionic detergent;
also have very strong intermolecular hydrogen cetyltrimethyl ammonium bromide  (Cationic
surfactant)
bonding between N H O C group of
Glycerol oleate  [oil]
two polyamide chains Sodium stearate  [soap]

  
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