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CHEMISTRY
SECTION – I
Straight Objective Type
rHe p He M O2
1. (c) =
rO 2 p O 2 M He
n He / t He p He M O2
=
n O2 / t O2 p O2 M He
7.07  t O 2 32
= = 8=2 2
1  10 4
2  14.14
t O2 = = 4 hr
7.07
2. (b) Let the moles of NaNO3, NaNO2 and O2 at equilibrium be a, b and c respectively and
v1 and v2 will be the volume occupied by ‘a’ moles of NaNO3 and ‘b’ moles of
NaNO2 respectively. They are small and can be ignored with respect to total volume
i.e. (100 ml).
2NaNO3(s) 2NaNO2(s) + O2(g)
Moles at equilib. a b c
1000 a 1000 b 1000 c
Conc. at equilib. = 10 c = Kc
v1 v2 100
Conc. after addn. of 30 g of
1000 c 100 c
NaNO2 (v = 20 cc) same same = = Qc
80 8
Qc > Kc
Conc. after addn. of 30 g of
1000 c
NaNO3 (v = 15 cc) same same = Q c
85
Q c > Kc
In both cases (addition of NaNO2 as well as NaNO3) the reaction will go in backward
direction.
3. (b) Ca (NO 3 )2 (aq ) + Na 2 CO 3 (aq ) ⎯
⎯→ CaCO 3 (s ) + 2 NaNO 3 (aq )
Initial millimoles 6 5 – –
Millimoles after
the reaction 1 0 5 10
CaCO3(s) 2+
Ca + CO 32−
x +1 x
100 100
1

00

Ksp = Ca 2+  CO  2−
3

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5 10−9 =
1
100
 CO32−  
 2−

CO3 = 5  10−7 M
4. (a) The reactions occuring during the electrolysis are
Cathode: Sn2+ + 2e– ⎯→ Sn
Anode: Sn2+ ⎯→ Sn4+ + 2e–
2H+ + 2e– ⎯→ H2
o 0.059 (p H ) 0.059 1
E H+ | H = E H + | H – log + 2 2 = 0 – log
2 2 2 [H ] 2 (10 −7 ) 2
= – 0.059 log (107) = –0.059 × 7 = –0.413 V
9.65  30  60
Moles of e– used at cathode = Moles of e– released at anode = = 0.18
96500
0.18
Moles of Sn2+ oxidised = Moles of Sn2+ reduced = = 0.09
2
Moles of Sn2+ left = 0.5 – 0.18 = 0.32
0.32
Concentration of Sn2+ left in solution = = 0.64 M.
0.5

5. (d) The isomers are [Cu (CN)2 (NCS)2]2–

[Cu (CN) (NC) (NCS)2]2–
[Cu (NC)2 (NCS)2]2–
[Cu (CN)2 (SCN) (NCS)]2–
[Cu (CN) (NC) (SCN) (NCS)]2–
[Cu (NC)2 (SCN) (NCS)]2–
[Cu (CN)2 (SCN)2]2–
[Cu (CN) (NC) (SCN)2]2–
[Cu )(NC)2 (SCN)2]2–
There are a total of 9 linkage isomers.

6. (c) O2– is smaller than O 22 − , thus, with a given metal ion (M+), the lattice energy of M2O
would be greater than that M2O2. Peroxides would be preferably formed with larger
cations because smaller cations will form a stable lattice of M2O. Stability of metal
chlorides, bromides and iodides increases down the group while that for fluorides
decreases. The size of alkaline earth metal ions is smaller than that of alkali metal
ions, so water of crystallization units, of alkaline earth metal salts are higher than
that of alkali metal salts.

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7. (b)
NO3− AsO 33− CO 32− ClO3− SO32− BO33−
N
value 3 4 3 4 4 3
2
No. of lone
pair(s) 0 1 0 1 1 0
Shape Trigonal Trigonal Trigonal Trigonal Trigonal Trigonal
planar pyramidal planar pyramidal pyramidal planar

8. (a)
AlBr3
MeO 1. AlBr3 (3 equiv.)
MeO

C CH2Cl2 
MeO Cl 
O MeO O
AlBr3
–H+
AlBr3
MeO Me–O
H2O 

MeO O Me–O O
AlBr3
One equivalent of AlBr3 will be used to generate acylium ion and rest 2 equivalents
react with MeO group to deactivate the ring (by forming Lewis acid-base complex
having +ve charge on oxygen atom). Thus, acylium ion formed attacks on the other
benzene ring (without MeO groups).

SECTION − II
Reasoning Type
9. (b)
O
1* *
SO32 − ⎯→ S SO32 − ;
+ S8 ⎯ –O−S−O–
8
S*
* *
Ba 2 + + S SO32 − ⎯
⎯→ Ba S SO3
* 1*
Ba S SO3 + 2H3O+ ⎯ ⎯→ SO2 + S8 + 3H 2O + Ba 2 +
8
This reaction sequence indicate that the two sulphur atoms in thiosulphate are not
equivalent and do not exchange with each other.

10. (b, c, d)
O O
H2S2O4: HO – S – S – OH

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O O
H2S2O6: HO – S – S – OH
O O
O O
H2S2O5: HO – S – S – OH
O
O O
H2S2O8: HO – S – O – O –S – OH
O O

11. (a, b, d)
- O
Br Br O Br
O OH
OH – (ii) OH
-
O
O O O
-
(iii) –Br
CO2H

O
The first step of the reaction leads to nucleophilic substitution at acyl carbon while third
step of the reaction involve nucleophilic substitution at alkyl carbon. Overall reaction leads
to ring contraction from 6 to a 5-membered ring.

12. According to Dalton’s law,

p O2 = Ptotal X gas
O2 = 0.20  760 = 152 mm Hg .
According to Henry’s law,
p O2 = k H X liq
O2

152 = 3.04  10 7 X liq

O2

X O 2 = 5  10 −6
n O2 n O2 n O2 n O2
X O2 = = = 
n O 2 + n H 2O n O2 + 1000 / 18 n O2 + 55.56 55.56
 Number of moles of O2 dissolved (n O2 ) = 55.56 × 5 × 10 = 2.77×10 –6 –4

[O2] = 2.77×10–4 M
 (b) and (d)

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SECTION−III
Comprehension Type

13. (c) Double bond equivalents of C11 H12 O = 6

No Tollen’s test : Aldehyde absent, ketone may be present.
OH
O H
O
+
LiAlH4/H CrO3
+ Enantiomer
Py

(A) (B) optically active (A) optically

inactive
COOH COOH
Alkaline NH2 NH2
KMnO4 Base
COOH COOH
(D) (C)

14. (d) C 6 H 12 O 2 (X) double bond equivalent= 1; Give positive Tollen’s test.
 Probable structure is
H OH
Tollen’s reagent

OH O [Ag(NH3)2] +
O
(X) OH
Aq.H2CrO4 (Y) Optically active
Anhydrous
CrO3 HO OH
O O
(Z) Optically inactive
H H Zn-Hg
[Link]
O O
3-Methylpentane
Optically inactive
O
15. (a) HO OH O
BaO

H2O +
O O O

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SECTION−IV
Matrix−Match Type

OH
1. A- Br2
O CH2Cl2 O + HBr
O

Br
H
NH2 H
B- POCl3 Optically active
Dehydrating agent
C N
O
Br
H
C- C–OH racemic mixture
H O
O
D - Ph H Diastereomeric mixture
O
Ans. (A): 2, 3, 4; (B): 3, 4; (C): 1; (D): 2, 3, 5

2. When phenolphthalein is used as indicator :

(A) Equivalent of HCl = Equivalent of NaOH + Equivalent of Na2CO3
2 5.3 2
= + =
40 106 20
2
 Mass of NaCl =  58.5 = 5.85
20
 2
No. of equivalent of HCl = N1 V1 × 10–3 =
20
 2 2  10  1000
VHCl = = = 100 mL
200  0.1  10 −3 200

1
(B) No. of equivalent of HCl = N1 V1 × 10–3 =
40
1 1 1 10  1000
 VHCl =   −3 = = 250 mL
40 0.1 10 40
5.3 1
(C) No. of equivalent of HCl = =
106 20
 1 1 1 10  1000
VHCl =   −3 = = 500 mL
20 0.1 10 20
1.06 1
(D) No. of equivalent of HCl = =
106 100
1
 VHCl =  10  1000 = 100 mL
100

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When methyl orange is used as indicator:

2 5.3 1 1 3
(A) No. of equivalent of HCl = = + = + =
40 53 20 10 20
3
 VHCl =  10  1000 = 1500 mL
20

1 2.1 2 1
(B) No. of equivalent of HCl = + = =
40 84 40 20
1
 VHCl =  10  1000 = 500 mL
20
5.3 2.1 5
(C) No. of equivalent of HCl = + =
106 84 40
 5
VHCl =  10  1000 = 1250 mL
40
1.06 1
(D) No. of equivalent of HCl = = ;
53 50
1
 Mass of NaCl =  58.5 = 1.17 g
50
1
 VHCl =  10  1000 = 200 mL
50
Mass of CaCO3 formed :
Na2 CO3 + CaCl2 → Ca CO3 + 2NaCl
 Moles of Na2 CO3 = Moles of CaCO3
5.3 1
 In (A), moles of CaCO3 formed = =
106 20
100
 WCaCO 3 = =5 g
20
100
In (C), Mole of CaCO3 formed =
20
100
 WCaCO3 = = 5g
20
1.06
In (D), WCaCO3 =  100 = 1g
106
Ans. (A): 3, 5; (B) : 2; (C) : 1, 5 ; (D) : 4

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SECTION−V
Integer Answer Type
CH3NH3 Cl–
+
CH3NH2 + HCl
1. At equivalence point – – 40×0.15 = 6 mmole

CH 3 N H 3 undergo hydrolysis while Cl– remain unhydrolysed.
CH 3 NH 3+ + H 2O CH3NH2 + H3O+
6 6 6
(1 − h ) h h
80 80 80
6 2
h
[CH 3 NH 2 ] [H 3 O + ] 80 6
Ka = +
= − h2
~
[CH 3 NH 3 ] (1 − h ) 80
K a  80
h=
6
6 6 4 6
[H 3 O + ] = h = K a  =  10 −11  = 10 −12
80 80 3 80
[H 3 O + ] = 10 −6 M
 pH = 6.0
2. To prepare a silicone containing ‘n’ Si–O–Si linkages, the total number of units required are
(n+1), of which 2 are chain blocking units, R 3SiOH and (n–1) are chain building units,
R 2Si(OH) 2 . Thus, the number of R 2Si(OH) 2 units needed are 9.

3. R–OH + CH3COCl R–OCOCH3 + HCl

When an alcohol containing one OH group reacts with 1 mole of CH3COCl, the molecular
mass of the product will be 42 units more than that of ROH. If the original compound
contains ‘n’ OH groups, then the molar mass of product will be 42n units more than that of
original compound. In the present case,
166 + 42n = 334
 n=4
Thus, the compound contains 4 – OH groups.

4.  dv = 1.0 pm3
 P   2 dv , where  2  e −2r / a 0
At nucleus, r = 0.
 Pr = 0  e 0 . (1 pm)3 = 1 (pm)3
At a distance r = a 0 ,
Pr = a 0  e −2 .(1.0 pm3 ) = 0.14  1 pm3
 Pr =0 1
= = 7.1 = 7
Pr =a 0 0.14

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