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CHEMISTRY
SECTION – I
Straight Objective Type
1. (d) Tributyl stannane reduces alkyl halide to corresponding alkane by free-radical
mechanism.
•

CIS: Me2C(CN)–N=N–C(CN)Me2 ⎯
⎯→ N2 + Me2C(CN)
• •

Me 2C(CN) + Bu3Sn–H ⎯→ Bu 3S n + Me2CH(CN)

Br . .
CPS: Bu3Sn
+ Bu3Sn–Br

. .
ring Bu3Sn–H + Bu3Sn
closure

Ease of formation of a five membered ring is greater than that of a six membered
ring.

d[A] k 1 [ A]
2. (b) – =
dt 1 + k 2 [ A]
At high concentration of A ([A] >> k2), 1 + k2[A] ~− k2[A]
d[A] k
– = 1 = k.
dt k2
Thus, order of the reaction is zero.
At low concentration of A([A] << k2), 1 + k2[A] = 1
d[A] k [A]
– = 1 = k1[A]
dt 1
The order of the reaction is unity.

N 1.004  10 23 1
3. (a) n= = = .
NA 6.023  10 23 6
PV 11 6
T= = = = 73.08 K ~− 73 K.
nR 1 0.0821
 0.0821
6
3RT 3  8.314  73
 RMS = = = 9.1  10 5 ms −1 .
M 2  10 −3

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4. (c) The second ionization energy of M refers to the reaction, M+(g) ⎯→ M2+(g) + e–
M(g) ⎯→ M2+(g) + 2e– …. H5
M+(g) + e– ⎯→ M(g) …. –H3
M+(g) ⎯→ M2+(g) + e– H IE 2 = H5 – H3

SECTION − II
Multiple Correct Choice Type

5. (a, d) The reaction is an example of ring opening of cyclopropane in presence of acid.


O OH
H+ H+
O  OH
O O O
O O
–H+

O OH
O O

6. (a, b, c)
HA + NaOH ⎯→ NaA + H2O
10 mL 10 mL of 2 × 10–3 M

10  2  10 −3
[HA] = = 2 × 10–3 M
10
HA(aq) + H2O A–(aq) + H3O+(aq)
2 × 10–3(1 – 0.2) 2 × 10–3 × 0.2 2 × 10–3 × 0.2

2  10 −3 (0.2) 2
Ka = = 1 × 10–4
0 .8
[H3O+]HA = 2 × 10–3 × 0.2 = 4 × 10–4
pH = –log(4 × 10–4) = 4 – log 4 = 3.4
After the neutralization of weak acid (HA) with NaOH, salt (NaA) is formed. NaA
gets hydrolysed as
A–(aq) + H2O HA(aq) + OH–(aq)
1 × 10–3 (1 – h) 1 × 10–3 h 1 × 10–3 h

Kw 1  10 −14
Kh = = −4
= 1 × 10–10
Ka 1  10

ch 2 Ka 1  10 −10
Kh = ~− ch2 ; h = =
1− h c 1  10 −3

[OH–] = 1 × 10–3 × 10 × 10–4 = 10 ×10–7 M

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(
pH = –log 10  10 −7 = 6.5 )
pH = 7.5

Cl
H3C
7. (b, d) C=O H–C–Cl
H3C
Cl
The mixture of acetone and chloroform show negative deviation because the
interaction between acetone and CHCl3 is stronger than that between acetone alone.
Pure acetone cannot be obtained from the mixture at azeotropic composition.

8. (a, c) The mechanism of the reaction is as follows:

.. slow fast
H2O: + X X k1 H+ + HO–X–X k2
X– + HOX
Rate = k1[X2] [H2O] = k 1 [X2]
where k 1 is a pseudo first order rate constant with units of sec–1 (time–1). It is a
displacement reaction. H–O–X is not a linear molecule but has a bent shaped
structure.

SECTION − III
Reasoning Type

9. (c) The product of the reaction of aqueous FeSO4 and NO is [Fe(H2O)5NO]SO4, in which
Fe is in +1 oxidation state and NO is also in +1 form. It has sp3d2 hybridisation.
Paramagnetic species should contain unpaired electron(s) but total number of
electrons may be even in the species (for example O2, S2).

3 5
10. (c) For monoatomic gas ; Cv = RT, Cp = RT
2 2
5 7
For diatomic gas; Cv = RT, Cp = RT
2 2
3 5
1  RT + 1  RT
Cv for mix = 2 2
2
5 7
1  RT + 1  RT  Cp 
Cp for mix = 2 2 ;  
 = 1.5
2  v  mix
C


11. (c) CH2(COOH)2 CH3COOH + CO2
P2O5, 
C3O2 + 2H2O

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
1,3-dioic acid ⎯
⎯→ Monocarboxylic acid
− CO 2


1,4 and 1,5-dioic acid ⎯
⎯→ Cyclic anhydride
− H 2O


1,6 and 1,7-dioic acid ⎯
⎯→ Cyclic ketone
−CO 2 , − H 2O

Malonic acid undergoes decarboxylation on heating alone as the reaction proceeds

via 6-membered transition state while heating with P2O5 promotes loss of H2O as
P2O5 is a good dehydrating agent.

12. (a)

SECTION−IV
Comprehension Type
Passage-I

13. (b) s = [Al3+] + [Al(OH) −4 ]

K sp
s= + Kc [OH–]
[OH − ]3
For minimum solubility, differentiate s w.r.t. [OH–] and set it equal to zero.
ds − 3K sp
−
= + Kc = 0
d[OH ] [OH − ]4
3K sp
= Kc
[OH − ]4
1
 3K sp 4
[OH − ] =  

 Kc 
14. (b) Solubility of Fe(OH)3 decreases with increase in concentration of [OH–] or decrease
in concentration of [H+].
Addition of further amount of NH4Cl will increase the concentration of NH +4 and
thus the ionization of NH4OH is suppressed. This lowers the [OH–] concentration and
thus pOH increases or pH decreases.
In NH4I solution, NH +4 ion hydrolyses giving H3O+, thus making the solution acidic
while in HCO2K solution, HCO −2 ion hydrolyses to give OH–, thus solution is basic
in nature.
15. (b) AgCl(s) + 2NH3(aq) Ag ( NH 3 ) +2 (aq) + Cl–(aq)
[(Ag ( NH 3 ) +2 ] [Cl − ]
K1 = Kf × Ksp(AgCl) = 1.6 × 10–10 × 107 = 1.6 × 10–3 =
[ NH 3 ]2
AgCN(s) + 2NH3(aq) Ag ( NH 3 ) +2 (aq) + CN–(aq)

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[(Ag ( NH 3 ) +2 ] [CN − ]
K2 = Kf × Ksp(AgCN)= 2.5 × 10–16 × 107 = 2.5 × 10–9 =
[ NH 3 ]2
[Cl − ] 1.6  10 −3 x2
−
= −9
= 6.4 × 10 5
; K 1 = ; x = [Cl–] = 0.037 M
[CN ] 2.5  10 (1 − 2 x) 2

0.037
[CN–] = = 5.78 × 10–8 M.
6.4  10 5

Passage-II
[] mixture
16. (b) The optical purity of racemized alcohol = × 100
[] pure
−6
= × 100 = 60%.
− 10
Optical purity of alcohol
17. (c) Percentage inversion = × 100
Optical purity of bromide
[] mixture
Now, optical purity of bromide = × 100
[] pure
30
= × 100 = 83%.
36
60
 Percentage inversion = ×100 = 72%.
83

18. (a) Total inversion = Pure inverted product + Half of racemized product
1 
= 72 +   28  = 86%
2 
1
 Percentage of front side attack = ×28 = 14%.
2
SECTION−IV
Matrix−Match Type

CH2
NH2
CO2 NH2

1. (A) − 2, 3, 4, 5 ; Cr CH2 is optically active due to absence of a plane of

H2N CO2
CO2
CH2
CH2
NH2
CO2 CO2

symmetry and centre of symmetry. It’s geometrical isomer is Cr CH2 .

H2N NH2
CO2
CH2

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Cr3+ has d3 configuration, so magnetic moment will be 15 and is octahedral in

shape.
(B) − 1, 2, 3, 4, 5 ; It can show linkage isomerism due to SCN ligand. Co2+ has 3d7
configuration, so s will be 15 . It can show geometrical isomerism and has
Cl
Br Cl

Co
octahedral geometry. Its optically active isomer will be .
Br SCN
SCN

(C) − 5 ; Its an octahedral complex.

(D) − 1, 4 ; Linkage isomerism is shown due to NO2 ligand. It is an square planar complex,
which is always optically inactive. It can show geometrical isomerism (3 isomers).

2. (A) − 1, 4, 5 ; (A) has a chiral centre and can show geometrical isomerism. Stereogenic
units are structural units around which stereoisomers can be generated.
(B) − 2, 3, 5 ; (B) is optically inactive due to presence of plane of symmetry and it has
2 stereogenic units.
(C) − 1, 4 ; (C) is optically active as it has one chiral centre.
(D) − 2, 3, 5 ; (D) is optically inactive due to symmetry (plane of symmetry) and possesses
two stereogenic units.

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