March Attempt Online JEE Main 2021 01

16 MARCH SHIFT-I CHEMISTRY

1. (d) 97 Bk(Berkelium) and 93Np (Neptunium) are present in actinide B. Ostwald’s process - HNO3 synthesis
series. Due to actinoid contraction, there is gradual decrease in size 4NH 3( g ) + 5O2( g ) → 4NO( g ) + 6H 2O( g )
of M 3 + ions across the period due to poor shielding of 5f-electrons.
2NO( g ) + O2( g ) → 2NO2( g )
So, Bk 3 + is smaller than that of Np3+ due to actinoid contraction.
So, A is true and R is false. 4NO2( g )+ 2H 2O(l)+ O2( g ) → 4HNO3( aq)

2. (b) Vitamin A and vitamin D are stored in our body relatively for C. Contact process - H 2SO4 synthesis
longer duration. These are water insoluble and soluble in fats and 2SO2( g ) + O2( g ) → 2SO3( g )
oils. Hence, these are called fat soluble vitamins.
Thiamine (vitamin B) and ascorbic acid (vitamin C) are water soluble SO3( g ) + H 2SO4 ( aq) → H 2S2O7 (l)
Oleum
vitamins and must be supplied regularly in diet. These vitamins are
H 2S2O7 (l) + H 2O(l) → 2H 2SO4 ( aq)
not stored in our body.
3. (b) The dehydration of hydrated chlorides, bromides and iodides of D. Hall-Heroult process- Aluminium extraction
Ca, Sr, Ba is possible but hydrated halides of Be and Mg on heating 2Al2O3 + 3C → 4Al + 3CO2
suffer hydrolysis due to their small size or high charge density.
Correct match is, A → (iii), B → (i), C → (iv), D → (ii)
∆
CaCl2 ⋅ 6H 2O → CaCl2 + 6H 2O 6. (b) For aromatic compounds following conditions should be satisfied
Anhydrous
(i) planarity
∆ (ii) complete delocalisation of π-electrons in the ring.
MgCl2 ⋅ 8H 2O → MgO + 7H 2O + 2HCl
(iii) presence of ( 4n + 2) π-electrons in the ring, where n = 0, 1, 2, …
MgCl 2 can be made anhydrous by heating in presence of dry HCl.
. This is called Huckel rule.
MgCl2 ⋅ 6H 2O  ∆( Calcination
 ) → MgCl2 + 8H 2O
Dry HCl(g ) e.g. n = 0, 2 π e −
Hence, on heating CaCl2 ⋅ 6H 2O undergoes dehydration but n = 1, 6 πe −
MgCl2 ⋅ 8H 2O does not.
n = 2,10π e −
Metal oxides are generally basic. In alkaline earth metal BeO is
amphoteric and shows anomalous behaviour while other oxides are
basic. (C)
So, both statement I and statement II are false.
6πe– (Huckel′s rule
4. (b) DIBAlL is added to produce aldehyde from ester by keeping the planar followed, i.e.
temperature low while at higher temperature it can perform different aromatic)
conversions.
Complete reaction is as follows: (B) (C) (A) CH 2
OH
(Planar) 6πe–
4πe– No complete
–78°C CHO (Huckel's rule delocalisation
O (Not
aromatic) of π-electrons in
followed, i.e.
O i) DIBAL-H,
aromatic) the ring
Toluene
(P)
(Not aromatic)
ii) H3O + OH

25°C
7. (c) Aniline reacts with NaNO2, HCl at 273-278 K to give benzene
CH2OH + −
diazonium salt (C6H5 N 2 Cl = X) which on hydrolysis (H 2O / ∆) gives
phenol.
Diisobutyl aluminium hydride (DIBAL-H) is parallel to LAH (Lithium Complete reaction is as follows
aluminium hydride) as a reducing agent but it is more selective.
+ –
It forms different product at different temperature. NH2 N2Cl OH
Role of DIBAL-H is shown below
NaNO2, HCl H2O/D (A)
Reagent DIBAL-H DIBAL-H DIBAL-H 273-278 K
(− 78 °C) (25° C) (–78°C)
Aniline Benzene Phenol
diazonium
Reactant Ester Ester Cyanide chloride
(X)
Product Aldehyde Alcohol Aldehyde
+ –
N2Cl
Note : DIBAL-H does not reduce double bond.
5. (c) A. Haber’s process - NH 3 synthesis So, X = and A = H 2O/∆
N 2 ( g )+ 3H 2( g ) → 2NH 3( g )
02 Online JEE Main 2021 March Attempt

° 4 + +3 = 1.74 (data given)

8. (d) ECe 13. (b) Oxidising smog (photochemical smog) gets increased during the
/ Ce
4+ 3+
day time and in the presence of O3.
Ce can be reduced to Ce and can oxidise water.
It occurs in warm, dry and sunny climate. When fossil fuels are
Ce4+ + e − → Ce3+
burnt, hydrocarbons (unburnt fuels) and nitric oxide (NO) are
4+ 0
Ce is having noble gas configuration [Xe]4 f but it is strong produced. Ozone reacts rapidly with the NO to generate NO2.
oxidant and gets converted to Ce3+ . NO( g ) + O3( g ) → NO2( g ) + O2( g )
Statement I is correct but statement II is incorrect. Ozone is a toxic gas and both NO2 and O3 are strong oxidising
agents and can react with the unburnt hydrocarbons in the polluted
9. (b) Antihistamines interfere with the natural action of histamines by air to produce chemicals such as formaldehyde, acrolein and
competing with histamine for binding sites of receptor. peroxyacetyl nitrate (PAN).
Hence, they act as antacid and antiallergic.
e.g. Seldane, dimetapp, cimetidine. 14. (b) Enol form of acetone [CH 3COCH 3 ] exists in
Histamine stimulates the secretion of pepsin and hydrochloric acid < 0.1% quantity as monocarbonyl are more stable in keto form due
in the stomach. It is also responsible for nasal congestion associated to high bond energy.
with common cold and allergic response to pollen. O OH
 Tautomerisation 
10. (d) Lindlar catalyst (H 2/Pd, CaCO3) is poisoned palladium catalyst. It CH 3  C  CH 3 → CH 3  C == CH 2
is known as also partially deactivated palladised charcoal. It is Keto Enol
composed of powdered calcium carbonate coated with palladium The enol form of acetyl acetone [CH 3COCH 2OCCH 3 ] exists in
and poisoned with quinoline. approximately 15% quantity as it is stabilised by intramolecular
It is used for reduction of alkyne to alkene and acid chloride to hydrogen bonding, which is not possible in enol form of acetone.
aldehyde. CH
Stereochemistry involved is syn-addition. CH3—C C—OC2H5
CH3—C—CH2—C—O—C2H5
H 3C CH 3 O O
H2/Pd δ−
H 3C — C C— 2CH 3 CaCO C 2C H
3 δ+
H H
(More stable
11. (c) Alcohols undergo dehydration (removal of water molecule) in the enol form due
to H-bonding)
presence of protic acids (conc. H 2SO4 ,H 3PO4 ) at high temperature
to give Saytzeff alkene (more alkylated) as major product. So, both A and R are true and R is the correct explanation of A.
CH3 15. (c) Methyl ketone gives haloform reaction to form carboxylic acid
H3C OH
H salt which on heating with NH 3 forms amide. Amide is reduced to
20% H3PO4/D amine by LiAlH 4 .
+
E1 reaction
– +
1-methyl Major Saytzeff CH2—C—CH3 CH2—C—ONa
cyclohexanol alkene (A)
More alkylated (i) NaOH/H+ (ii) NH3
Br2 D
Bulky bases like tert-butoxide, due to steric hindrance, a bulky base
1-phenyl
abstracts a less hindered proton, that leads to formation of the less propan-2-one
substituted product as, the major one, called the Hofmann product.
C—NH2 CH2—NH2
Cl (iii) LiAlH4/H2O
(CH3)3CO– K+
+ Benzamide Benzylamine
D
1-chloro- Major Hofmann (a) Benzamide undergoes Hofmann bromamide degradation when
1-methyl cyclo alkene treated with bromine and aqueous sodium hydroxide, to
hexane produces benzylamine.
12. (b) H 2O2 can act as both oxidising and reducing agent in basic
medium as in hydrogen peroxide oxygen is present in CH2—C—NH2 CH2—NH2
intermediate-1 oxidation state. So, it can get oxidised to O2 and
reduced to water. Br2/NaOH

H 2O2 → H 2O (reduction) Benzamide Benzylamine

−1 −2
Oxidising (b) Benzene nitrile undergoes alkaline hydrolysis to form
agent
acidamide which further give Hofmann bromamide
H 2O2 → O2 (oxidation) degradation.
−1 0
Reducing
agent
CN C—NH2
In the hydrogen economy, the energy is transmitted in the form of NH2
(i) KOH, H2O
dihydrogen and not as electric power. (ii) Br2/NaOH
So, both statement I and statement II are true. Cyanobenzene
Aniline
 March Attempt Online JEE Main 2021 03

(d) Acid chloride undergoes nucleophilic substitution with NH 3 to 18. (d) Hybridisation of ‘O’ in H 2O is sp 3 as it is having two lone pair
form acid amide. Acid amide undergoes Hoffmann bromamide and two sigma bond. Bond angle of sp 3 hybridised compound
degradation.
should be 109.5°.
But in case of water, it is only 104.5° due to repulsion between the
C—Cl C—NH2 lone pairs. Lone pair-lone pair repulsion is higher than bond
pair-bond pair repulsion.
(i) NH3,NaOH NH2 (VSEPR Theory)
(ii) Br2/NaOH
Benzoyl O
chloride
Aniline 104.5º
lp-lp > bp-bp
H H Repulsion Repulsion
16. (b) The process that involves the removal of sulphur from the ores is
called roasting. So, both A and R are true and R is the correct explanation of A.
In roasting, the ore is heated in a regular supply of air in a furnace at 19. (d) In chromatography technique, the purification of compound is
a temperature below the melting point of the metal. independent of physical state of the pure compound (stationary
Some of the reactions involving sulphide ores are phase). Chromatography is based on the principle of adsorbtion.
2ZnS + 3O2 → 2ZnO + 2SO2 Different substances are differently adsorbed.
2PbS + 3O2 → 2PbO + 2SO2 The technique of chromatography uses the difference in the rates at
2Cu2S + 3O2 → 2Cu2O + 2SO2 which the components of a mixture move through a porous medium
(stationary phase) under the influence of some solvent or gas
17. (a) Following are the structure and oxidation state of given acids. (moving phase).
(A) O 20. (d) BiH 3 is the strongest reducing agent and have strongest reducing
power. The reducing character of the group 15 element hydrides
P increases down the group. Ammonia is only a mild reducing agent
H OH while BiH 3 is the strongest reducing agent amongst all the hydrides.
H This is due to the decrease in bond energy down the group.
H3PO2 Property NH 3 PH 3 AsH 3 SbH 3 BiH 3
Hypophosphorus acid
−1
∆ diss.H kJ/mol 389 322 297 255
H 3PO2 ⇒ 3 + x − 4 = 0
x= +1 NH 3
(B) PH 3
O
AsH 3 (Increase in reducing power)
P
SbH 3
HO OH BiH 3
OH
H3PO4 So, correct answer is Bi (bismuth).
Orthophosphoric acid

H 3PO4 ⇒ + 3 + x − 8 = 0
21. (20) A( g ) c B( g )
Given, T = 495 K, ∆ r G° = − 9.478 kJ/mol
x=+ 5 We know,
(C) ∆G° = − 2.303 RT log K
O O [B ]
Q K=
P—P [A]
HO OH
HO OH where, K = equilibrium constant
H4P2O6 − ∆G °
Hypophosphoric acid Now, log K =
2.303RT
9.478 × 1000
H 4P2O6 ⇒ + 4 + 2 x −12 = 0 log K =
2.303 × 8.314 × 495
⇒ x=+ 4
(D) ∴ logK = 1
O
⇒ K = 10
[B ] nB
P ⇒ = = 10
[ A ] nA
H OH Now, A( g )c B( g )
OH
t =0 22 0
H3PO3
Orthophosphorus acid t =t 22 − x x
[B ] x
K= = = 10
H 3PO3 = + 3 + x − 6 = 0 [ A ] 22 − x
⇒ x=+3 So, x = 20
So, the correct match is A–v, B–i, C–ii, D–iii. Milimoles of B = 20
04 Online JEE Main 2021 March Attempt

22. (3) CxH y +  x +  O2 → x CO2 + H 2O 25. (2) [Co(NH 3) 4 Cl2 ]Cl + 2en → [Co(en) 2 Cl2 ] + 4NH 3
y y
 4 2
NH 3 is the neutral monodentate ligand. Ethylene diamine is a
Any hydrocarbon, on combustion gives CO2 and H 2O. This is neutral didentate ligand.
Liebig’s method for estimation of ‘C’ and ‘H’ percentage. •• ••
H 2 N  CH 2  CH 2  N H 2( en)
Mass of water formed = 210 g
18 g of H 2O contains = 2 g of hydrogen So, two ethylene diamine are equivalent to four ‘NH 3’ ligand.
2 70  M × 1000
210 g of H 2O contains =  × 210 =  g of hydrogen. 26. (9) Molality ( m) =
 18 3 {(1000d ) − M × Msolute}
Given, mass of organic compound = 750 g where, M = molarity
Percentage of hydrogen d = density of solution
Mass of hydrogen Msolute = molar mass of solute
= × 100
Mass of organic compound Putting the values,
M × 1000
6.50 =
70 (1000 × 189
. ) − (M × 56)
= × 100
3 × 750 12285
On solving, M =
= 311
. % 1364
Nearest integer = 3 M = 9 molar
23. (16) Balancing by half-reaction method 27. (9) Given wavelength, if incident light ( λ) = 248 nm = 2480 Å
2MnO−4 + bC2O42− + cH + → xMn +2 + y CO2 + zH 2O Threshold energy = 3.0 eV
+7 +3 +2 +4
We know, for electron de-Broglie wavelength is given by
Step 1 Separate two half-reactions h
λ=
Oxidation half (O.H.) C2O42− → CO2 mv
h
Reduction half (R.H.) MnO−4 → Mn2 + λ=
2 m(KE)
Step 2 Balance all the atoms except oxygen and ‘H’.
KE = q × V (where, q = charge of particle)
O.H. C2O42– → 2CO2
V = voltage applied
R.H. MnO−4 → Mn2+ h
λ=
Step 3 Balance ‘O’ by adding H 2O and ‘H’ by adding H + . 2 m(qV )
O.H. C2O42– → 2CO2 . × 10−31 kg
Putting mass of electron, me = 91
R.H. 8H + + MnO4− → Mn2+ + 4H 2O . × 10−19 C
Charge of electron, q = 16

Step 4 Balance charge by adding electron 150

λ= Å …(i)
V
−
O.H C2O42– → 2CO2 + 2 e
We know, Eapplied = φ + KEmax …(ii)
R.H. 5e − + 8H + + MnO−4 → Mn2+ + 4H 2O
where, φ = threshold energy
Step 5 Balance electron by multiplying O.H. by ‘5’ and R.H. by ‘2’. φ = 3 eV
O.H. 5C2O42− → 10 CO2 + 10e − 12400 12400
Eapplied = = = 5 eV
R.H.10e − + 16H + + 2MnO4− → 2Mn2+ + 8H 2O λÅ 2480
Step 6 Add both half-reaction Putting value in Eq. (ii),
16H+ + 5C2O2– −
4 + 2MnO4 → 10CO2 + 2Mn
2+
+ 8H 2O 5 = 3 + KEmax
So, c = 16 ⇒ KEmax = 2 eV
Voltage = 2
24. (106) AB2 → A 2 + + 2B −
150
λe = = 8.6 Å [Eq. (i)]
Elevation in boiling point, ∆Tb = iKb m 2
where, i = van’t Hoff factor Nearest integer = 9
Kb = molal elevation constant
28. (50) Let the solubility of A 2X be ‘S’.
m = molality
i = 1 + (n − 1)α A 2X( s) c 2 A + ( aq) + X 2–( aq); Ksp1 = 4 × 10−12
2S S
(n = 3, α = degree of dissociation) + 2
Ksp1 = [ A ] [ X 2– ]
i = 1 + (3 − 1) ⋅1
= 1.2 4 × 10−12 = (2 S) 2( S)
Putting the values, 4 × 10−12 = 4 S 3
∆Tb =1.2 × 0.5 × 10 ⇒ S =10−3 M
∆Tb = 6
Let the solubility of MY be ‘S1’.
Tb = 100°C + 6 °C
MY ( s) c M + ( aq) + Y − ( aq), Ksp 2 = 4 × 10−12
Tb = 106 °C S1 S1
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Ksp 2 = [M + ][Y − ] Putting the value,

2 3 × 27 = 2 × a fcc
Ksp 2 = ( S1)
⇒ a fcc = 33 Å
4 × 10−12 = ( S1) 2
⇒ S1 = 2 × 10 −6
M 30. (10) Given, T1 = 200 K, T2 = 300 K
[ A 2Y ] S 10 −4 Ea = Activation energy = 11488
. kJ/mol
= = = 50
[MY ] S1 2 × 10−6 Rate constant (k2) at 300 K = 10−3 s −1
To find = rate constant (k1) at 200 K
29. (33) In bcc structure, spheres touch along body diagonal for bcc
structure, 4r = 3a We know,
k E 1 1
where, r = radius of sphere log 2 =  − 
k1 2.303R  T1 T2 
a = edge length
3 × abcc 10−3 11488
. × 103  1 1 
r= … (i) log =  − 
4 k1 2.303 × 8.314  200 300 
For fcc structure, 4r = 2 a as spheres touch along face diagonals. 10−3
log =1
2 a fcc k1
So, r = … (ii)
4 10−3
log = log10
So, from Eq. (i) and (ii), k1
3 × abcc 2 × a fcc ⇒ k1 =10−4
=
4 4 = 10 × 10−5 s −1
Given, abcc = 27 Å