February Attempt Online JEE Main 2021 01

25 FEB SHIFT-II CHEMISTRY

·· F F
3. (c) Statement (c) is false whereas other statements are true. Corrected
1. (c) (a) ·· XeF4 Þ statement is as follows :
Xe
F F Viscosity of hydrophilic sols is higher than that of the dispersion
medium, i.e. H 2O, because there is a high concentration of
dispersed phase in water.
Xe (sp 3d 2-hybridised)
4. (c) Among halogens ( F2, Cl2, Br2 and I2), bond dissociation enthalpy (
Geometry : Octahedral
D dissHº) of I 2, is minimum because of larger size of I-atom there is a
Shape : Square planar
steric repulsion between bonded I-atoms, which makes
It has four equivalent Xe ¾ F bonds in the same plane. I ¾I bond weakest.
F Whereas, smaller size and highest electronegativity of F-atom cause
highest electron density on F-atom of F2 molecule. As a result, F ¾ F
(b) SiF4 Þ bond becomes weaker due to electrostatic repulsion between
Si bonded
F F F-atoms.
F Thus, the order of D dissH° (in kJ mol -1) is
Si ( sp 3-hybridised) Cl ¾ Cl > Br ¾Br > F ¾F > I ¾I
(242.6) (192.3) (158.8) (151.1)
Geometry and shape : Tetrahedral Electrostatic Steric
repulsion repulsion
It has four equivalent Si ¾ F bonds.
(c) ·· SF4 Þ F 5. (c) Zone refining method is very helpful for producing
semiconductor and other metals of high purity,
F
Axial e.g., Si, Ge, B, Ga, In etc.
S bonds
F 6. (c) Water (steam) can produce CO on reacting with CH 4 , C and
Equatorial C3H 8 as,
bonds F 1270 K
CH 4 + H 2O ¾¾® CO + 3H 2
Ni
S (sp 3d -hybridised) 1270 K
C + H 2O ¾¾® CO + H 2
Geometry : Trigonal bipyramidal
1270 K
Shape : see-saw C3H 8 + 3H 2O ¾¾® 3CO + 7H 2
Ni
Axial S ¾ F bonds are longer than equatorial bonds.
But, water on reaction with CO2 produces carbonic acid (H 2CO3),
F
not CO.
CO2 + H 2O ¾® H 2CO3
(d) BF4- Þ B 7. (c) Two crystalline allotropic forms of sulphur (Sa and Sb) can
F F
change reversibly between themselves with slow heating (above 369
F K) or cooling.
B (sp 3-hybridised) > 369 K

Geometry and shape : Tetrahedral

Sa - Sb
(Rhombic) Cooling (Monoclinic)
It has four equivalent B ¾ F bonds.
So, statement I is true.
Hence, among given species only SF4 has unequal bond lengths.
At room temperature or at standard conditions of pressure and
2. (a) Let, solubility of Ca(OH) 2 in pure water = S mol/L temperature, rhombic sulphur is the thermodynamically most stable
crystalline allotrope of sulphur ( D f H º = 0).
Ca(OH) 2 q Ca 2+ + 2OH -
S mol/L 2 ´ S (mol/L) So, statement II is false.
Ksp = [Ca 2+ ] [OH - ]2 = S ´ (2 S) 2 = 4 S 3 (mol/L)
8. (b) The major components of German silver are
The expression of Ksp can also be written as, Cu : 25-30%, Zn : 25-30% and Ni : 40-30%.
Ksp = xx × y y × S x + y
9. (a) Spin only magnetic moment, m = n(n + 2) BM
= 11 × 2 2 × S1 + 2
where, n = number of unpaired electrons and m µ n.
= 4S 3
[Q For Ca(OH) 2 : x = 1, y = 2] (i) [FeF6 ]3- Þ Fe3+ = (3d 5) + 6 ´ F- (weak field ligand).
x and y are the coefficients of cations and anions respectively Thus, pairing of electron does not take place.
1/ 3 1/ 3
æ 5.5 ´ 10 -6 ö 3d 4s 4p 4d
æK ö
S = ç sp ÷ =ç ÷
è 4 ø è 4 ø
= 1.11 ´ 10- 2 mol/L sp3d2 (Fe), n=5
02 Online JEE Main 2021 February Attempt

Å
(ii) [Co(NH 3) 6 ]3+ Þ Co3+ = (3d 6) + 6 ´ NH 3 (strong field ligand). H— C== O
(ii) CH 3CH 2 — CH== CH 2 ¾¾¾®
Thus, pairing of electron takes place. Slow
But -1-ene
3d 4s 4p Å
CH 3CH 2 — CH — CH 2 — CHO
Fast ½ Hs
¯
d2sp3 (Co), n=0
CH 3CH 2CH 2CH 2CHO (major)
(iii) [NiCl4 ]2- Þ Ni2+ = (3d 8) + 4 ´ Cl- (weak field ligand). Thus, Pentanal
pairing of electron takes place.
14. (b) Benzene on reaction with CH 3COCl / AlCl3 gives acetophenone
3d 4s 4p
which on reduction with Zn-Hg/HCl gives ethyl benzene.
Bromination of ethyl benzene give 4-bromo-ethylbenzene which
upon nitration gives 4-bromo-2-nitroethyl benzene.
sp3 (Ni), n=2
2+ 2+ 9 CH3— C==O CH2CH3
(iv) [Cu(NH 3) 4 ] Þ Cu (3d ) + 4 ´ NH 3(strong field ligand).
Thus, pairing of electron takes place. CH 3COCl/AlCl 3 Zn-Hg/HCl
3d 4s 4p (Friedel-Craft (Clemmensen
acylation) reduction)
Benzene Acetophenone Ethyl benzene

sp3 (Cu), n=1 Bromination Br2/AlCl3

So, the decreasing order of m is CH2CH3 CH2CH3

m i > m iii > m iv > m ii 1
( n = 5) ( n = 2) ( n = 1) ( n = 0) 6
2 NO2
HNO3/H2SO4
3 (Nitration)
10. (a) The pH of rain water is normally 5.6. If it pH drop below 5.6, it is 5
4
called acid rain.
Br Br
\ Both statements are correct. 4-bromo-2-nitro 4-bromo-ethyl
ethyl benzene benzene
11. (c) Nitric acid is added to sodium extract before addition of silver (Major)
nitrate for testing halogens. Because it decomposes NaCN and Na 2S
[-I-effect of Br directs NO-2 at its meta-position]
or else they interfere in the test.
So, option (b) is the correct sequence of reagents used.
The reaction are as follows :
15. (c) OH COOH COOH COOH
NaCN + HNO3 ¾® NaNO3 + HCN ­
Na 2S + HNO3 ¾® NaNO3 + H 2S­
Sodium extract Nitric acid

12. (b) The reaction take place as follows : (–R)

NO2(–I) CH3(+I)
NO2 (I) (II) (III) (IV)
+
H
Step I Acidity of phenol (I) is weaker than any carboxylic acid.
Electron withdrawing nature (-R, - I ), of ¾NO2 group at para
NO2 NO2
+ + position increases acidic strength of (II), whereas + I effect of ¾ CH 3
CH3  CH  CH  CH3 + CH3  CH  CH2  CH2 group at para position decreases acidic strength of (IV).
(More stable intermediate) (Less stable intermediate) So, the order of acid character is II > III > IV > I.
2° carbocation 1° carbocation
16. (c) When ethylene glycol is heated with oxalic acid at 210ºC, first
NO2 we get an unstable cyclic-diester (ethylene oxalate) which readily
⊕ decarboxylate to give ethylene as the major product.
CH3 CHCH  CH3 (For major product)
Step II +
O O
CH2O H OH CH2 O
CH3 CHCH2  CH2 (For minor product) C 210ºC C –2CO2 CH2
+
NO2 –2H2O CH2
CH2O H OH C CH2 O C
NO2 O O
Ethylene
NO2 Ethylene Oxalic Ethylene (Major)
glycol acid oxalate
+
17. (d)
(Major product) NH2 NH2 NH2 NH2
HNO3, NO2
13. (a) The major product of the reaction is CH 3CH 2CH 2CH 2CHO. H2SO4
+ + +
Here, electrophilic addition of H — C== O (formylation) take place 288K
NO2
to the alkene through Markownikoff addition. Aniline (B) (C)
NO2
·· Å
[47%] [2%]
Rh (A)
(i) H 2 + ·· C== O ·· ¾¾¾® [H — C== O] H
s m-nitroaniline o-nitroaniline
(Catalyst)
[51%]
Water gas
p-nitroaniline
 February Attempt Online JEE Main 2021 03

During nitration, in strongly acidic medium, aniline gets protonated Note n-factor of NaOH = 1
Å
to form the anilinium ion i.e, ( C6H5 ¾ N H 3) which is meta-directing n-factor of H 2C2O4 = 2 (oxalic acid)
Å N=M´n
as ¾ N H 3 is an electron withdrawing ( - I) group. As a result, we get
Z ´M
meta-nitro aniline (B) as the major product. 22. (9077) Density of copper, d =
a 3 ´ NA
18. (c) Aniline on carbylamine reaction produces a foul smelling gas,
phenyl isocyanide (C6H5NC). Given, Z = 4, for fcc lattice,
M = 63.54 g mol- 1
NH2 NC
∆
+ CHCl3 + 3KOH – 3 KCl = 63.54 ´ 10- 3 kg mol- 1,
Ethanolic – 3 H2O a = 3.596 Å = 3.596 ´ 10- 10m,
Aniline Phenyl
[1º amine] isocyanide NA = 6.022 ´ 1023 mol-1

Carbylamine test is used to detect aliphatic and aromatic primary On putting given values, we get
amines. 4 ´ (63.54 ´ 10-3)
Þ d = kg / m3
19. (c) Maltose is a disaccharide which is made of two a-D-glucose units (3.596 ´ 10-10) 3 ´ (6.022 ´ 1023)
in which C1 (anomeric carbon) of one glucose (I) is linked to C4 of = 9076.26~ - 9077 kg / m3
another glucose unit (II).
23. (180) Energy of EMR = IE of the metal (A)
6 6
hc hc
CH2OH CH2OH = hn = atom-1 = - ´ NA mol-1
5 5 l l
O H O H
H H (6.63 ´ 10-34 ) ´ (3 ´ 108) ´ (6.02 ´ 1023)
H H = J mol-1
4 1 4 1 (663 ´ 10-9)
OH H OH H
OH
O
OH [Q l = 663 nm = 663 ´ 10- 9m]
3 2 3 2 -1
= 180600 J mol = 180.6 kJ mol-1 ~
- 180 kJ mol-1
H OH H OH
(I) C1-C4 (II) Free anomeric 24. (15) The gas performs isothermal irreversible work (W ).
Glycosidic carbon (C1) to
linkage show reducing where, DU = 0 (change in internal energy)
property From, 1st law of thermodynamics,
Þ DU = DQ + W
Maltose
Þ 0 = DQ + W
20. (a) Both statements are true. Dimethyl glyoxime (DMG) is a neutral Þ DQ = - W
bidentate ligand (DMG - ).
Now, W = - p ext (V2 - V1)
Ni2+ ion is identified with DMG in presence of NH 4 OH to give a red
æ nRT nRT ö æ1 1ö
ppt. Its reaction is as follows. = - p ext ç - ÷ = - p ext ´ nRT ç - ÷
è p2 p1 ø è p 2 p1 ø
OH Given, p ext = 4.3 MPa, p1 = 2.1 MPa, p 2 = 1.3 MPa,
CH3—C N n = 5 mol,T = 293 K and R = 8.314 J mol-1 K -1
2.
NH4OH
+ Ni2+ 1 1ö
CH3—C N = - 4.3 ´ 5 ´ 8.314 ´ 293 æç - ÷
è1.3 21
.ø
O– H—O
–
O—H = - 15347.70 J mol-1
(DMG ) CH3—C N N C— CH3 = - 15.347 kJ mol-1 ~
- - 15 kJ mol-1
Ni2+
CH3—C N N C— CH3 Þ DQ = 15 kJ mol-1
O—H O– 25. (3) As AB is a binary electrolyte,
or [Ni(DMG)2] \ AB q A + + B- , n = 2
(Red ppt.)
75
i = 1 + a (n - 1) = 1 + (2 - 1) = 1.75
21. (6) Average burette reading = Volume of NaOH solution (V1) 100
4.5 + 4.5 + 4.4 + 4.4 + 4.4 Given, DTb = 2.5 K
=
5 Kb = 0.52 K kg mol-1
= 4.44 mL
\ DTb = Kb ´ m ´ i
Strength of NaOH solution = S1(M) (say) = S1 (N)
DT b 2.5
Volume of oxalic acid solution (V2) = 10 mL Þ m= =
Kb ´ i 0.52 ´ 175
.
Strength of oxalic acid solution ( S2) = 125
. M
= 125
. ´2N = 2.74~
- 3 mol / kg
So, V1S1 = V2S2 (Q Law of equivalence) 26. (4) Cell-I (HNO3 ¾® NO)
V2S2 10 ´ (1.25 ´ 2)
Þ S1 = = = 5.63 N 3Cu + 2NO-3 + 8H + ¾® 3Cu2 + + 2NO + 4H 2O
V1 4.44
[Cu2+ ]3 ´ ( p NO) 2
~- 6 M= 6 M Q1 =
[NO3- ]2 ´ [H + ]8
04 Online JEE Main 2021 February Attempt

E1º = 096
. - ( - 034
. ) = 13
. V Ea 25
Q log 5 = ´
0.059 2.303 ´ 8.319 300 ´ 325
E1 = 1.3 - log Q1
6 Ea = 52194.78 J mol-
Cell-II (HNO3 ® NO2) = 52.194 kJ mol- 1
Cu + 2NO-3 + 4H +
¾® Cu 2+
+ 2NO2 + 2H 2O - 52 kJ mol- 1
~
[Cu2+ ] ´ ( p NO ) 2 28. (1) Given metals (Li, Na, Rb, Cs) are alkali metals (Group 1). Their
Q2 = 2

[NO-3 ]2 ´ [H + ]4 ionisation energy (IE) decreases down the group.

Q E2º = 0.79 - ( - 0.34)V = 1.13 V Here, Cs has lowest IE, i.e. it has lowest value of threshold energy
(E0) or work function (W ). Hence, it can be used as electrode in
0.059 photoelectric cell.
E2 = 1.13 - log Q 2
2 -
29. (2) Z = 29 [Cu] ¾-¾¾
2e
® Cu 2+ = [Ar] 3d 9
Now, E1 = E2
0.059 0.059 3d 9= ;
1.3 - log Q1 = 1.13 - log Q 2
6 2 Number of unpaired electron, n = 1
0.059 0.059 Q \ Spin only magnetic moment,
. =
017 [log Q1 - 3log Q 2 ] = log 1
6 6 Q2 m = n(n + 2)BM = 1(1 + 2) BM = 3 BM
0.059 [Cu2+ ]3 ´ ( p NO) 2 [NO3- ]6 ´ [H + ]12 = 1.73 BM~
- 2 BM
= log ´
6 [NO3- ]2 ´ [H + ]8 [Cu2+ ]3 ´ ( p NO ) 6 30. (1) Structure of given compounds are as follows
2

0.059 [H + ]4 ´ [NO3- ]4 SO3H

= log [Q p NO = p NO2 ]
6 ( p NO ) 4
2
(i) (Sulphanilic acid) ⇒
0.059 [HNO3 ]4
= log
6 ( p NO ) 4
2
NH2
Now, p NO2 º [HNO3 ] OH
0.059
So, 0.17 = log [HNO3 ]8 O2N NO2
6
0.059 (ii) (Picric acid) ⇒
= ´ 8 log [HNO3 ]
6
log[HNO3 ] = 2.16 NO2
[HNO3 ] = 102.16M = 10x M COOH
\ x = 2 .16 OCOCH3
Þ 2 x = 2 ´ 2 .16 = 4.32 ~
- 4 (iii) (Aspirin) ⇒
27. (52) T1 = (273 + 27) = 300 K, T2 = (273 + 52) = 325 K
Given, temperature coefficient of the reaction, OH–
K
aT = 325 = 5 HO CH—CH2OH
K300
KT 2 Ea æ T - T1 ö (iv) (Ascorbic acid) ⇒ O
log = ´ç 2 ÷
KT1 2 .303R è T1T2 ø HO
K Ea æ 325 - 300 ö
log 325 = ç ÷
K300 2.303 ´ 8.314 è 300 ´ 325 ø Only one compound (iii) contains ¾ COOH group.