(B)
5
4.0 10
(C)
4
5.0 10
(D)
6
4.0 10
Sol. (A)
According to Henrys law,
2
N
p = K
H N
2
(
2
N
p is partial pressure of N
2
in gaseous phase
,
N
2
is the molefraction of N
2
in solution phase)
Given, total pressure = 5 atm
Mole fraction of N
2
= 0.8
Partial pressure of N
2
= 0.8 x 5 = 4 atm
5
0.8 5 1 10
2
N
=
2
2
5
4 10
10
N
N
n
n
=
+
2
10
N
n + 10
2
4
4 10
N
n
=
2. The correct acidity order of the following is
OH OH
Cl
COOH
COOH
CH
3
(I) (II) (III) (IV)
(A) (III) > (IV) > (II) > (I) (B) (IV) > (III) > (I) > (II)
(C) (III) > (II) > (I) > (IV) (D) (II) > (III) > (IV) > (I)
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Sol. (A)
Acids are stronger than phenols.i.e III and IV are stronger than I and II.
Out of III and IV, III is stronger, due to +I and Hyperconjugation of CH
3
group
Out of I and II , II is stronger, due to I effect of - Cl group.
OH OH
Cl
COOH
COOH
CH
3
(I) (II) (III) (IV)
pKa=9.98 pKa=9.38
pKa=4.17 pKa=4.37
Decreasing order of acidic strength : III > IV > II > I
3. The reaction of P
4
with X leads selectively to P
4
O
6
. The X is
(A) Dry O
2
(B) A mixture of O
2
and N
2
(C) Moist O
2
(D) O
2
in the presence of aqueous NaOH
Sol. (B)
2
N
4 2 4 6
P +3O P O (exclusively)
N
2
prevents further oxidation of P
4
O
6
to P
4
O
10
.
4. Among cellulose, poly(vinyl chloride), nylon and natural rubber, the polymer in which the
intermolecular force of attraction is weakest is
(A) Nylon (B) Poly(vinyl chloride)
(C) Cellulose (D) Natural Rubber
Sol. (D)
Natural rubber has weak vander Waals forces , which are weakest forces of attraction.
Cellulose and nylon are fibres. So, their intermolecular forces are strongest.
Polyvinyl chloride is a thermoplastic polymer. So, intermolecular forces are intermediate to
elastomers and fibres
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5. Given that the abundances of isotopes
54
Fe,
56
Fe and
57
Fe are 5%, 90% and 5% respectively, the
atomic mass of Fe is
(A) 55.85 (B) 55.95
(C) 55.75 (D) 56.05
Sol. (B)
The average isotopic mass or atomic mass
i i
i
x
=
x
m
(where m
i
is the mass of i
th
isotope and x
i
is the abundance of i
th
isotope)
54 5 56 90 57 5
100
+ +
=
= 55.95
6. The IUPAC name of the following compound is
CN
OH
Br
(A) 4-Bromo-3-cyanophenol (B) 2-Bromo-5-hydroxybenzonitrile
(C) 2-Cyano-4-hydroxybromobenzene (D) 6-Bromo-3-hdyroxybenzonitrile
Sol. (B)
-CN is given highest priority.
Least sum rule is to be followed. Do not go for OH.
Therefore, IUPAC name of the compound is 2-Bromo-5-hydroxybenzonitrile
(should be 2-Bromo-5-hydroxybenzenecarbonitrile, as per latest IUPAC recommendation)
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7. Among the electrolytes Na
2
SO
4
, CaCl
2
, Al
2
(SO
4
)
3
and NH
4
Cl, the most effective coagulating agent
for Sb
2
S
3
sol is
(A) Na
2
SO
4
(B) CaCl
2
(C) Al
2
(SO
4
)
3
(D) NH
4
Cl
Sol. (C)
Sb
2
S
3
is a negative sol. So, a positive ion can cause coagulation.
Acc to Hardy Schulze rule, the greater the valence of the flocculating ion added, the greater is its
power to cause precipitation.
Therefore, Al
2
(SO
4
)
3
is the most effective coagulating agent for Sb
2
S
3
sol.
Order of effectiveness of cations given is :
3+ ++ + +
4
Al >Ca >Na >NH
8. The term that corrects for the attractive forces present in a real gas in the van der Waals equation
is
(A) nb (B)
2
2
an
V
(C)
2
2
an
V
(D) nb
Sol. (B)
In Vanderwaals equation, ( )
2
2
an
P+ V-nb =nRT
V
| |
|
\
, the pressure correction term
2
2
a n
V
| |
|
\
is a measure
of force of attraction among the molecules.
SECTION-II
Multiple Correct Choice Type
This section contains 4 multiple choice questions. Each question has 4 choices (A), (B), (C) and (D) for its
answer, out which ONE OR MORE is/are correct.
9. The compound(s) formed upon combustion of sodium metal in excess air is(are)
(A) Na
2
O
2
(B) Na
2
O
(C) NaO
2
(D) NaOH
Sol. (A) or (A , B) ( By IITs)
On combustion in excess of air, sodium forms monoxide Na
2
O and peroxide Na
2
O
2
4 Na +O
2
2Na
2
O (oxide)
2Na +O
2
Na
2
O
2
(peroxide)
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10. The correct statement(s) about the compound H
3
C(HO)HC CH = CH CH (OH) CH
3
(X)
is(are)
(A) The total number of stereoisomers possible for X is 6
(B) The total number of diastereomers possible for X is 3
(C) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible for
X is 4
(D) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for
X is 2
Sol. (A, D)
Given molecule has 2 asymmetric centres and a double bond .
So, the molecule will have 6 stereo isomers.
R cis R , S cis S, R cis S and R trans R, S trans S, R trans S.
If the stereochemistry about the double bond in X is cis or trans , it gives a pair of enantiomers.
11. The compound(s) that exhibit(s) geometrical isomerism is(are)
(A) ( )
2
Pt en Cl (
(B) ( )
2
2
Pt en Cl (
(C) ( )
2 2
2
Pt en Cl Cl (
(D) ( )
3 2
2
Pt Cl NH (
Sol. (C, D)
Octahedral complexes of the type M(AA)
2
X
2
, where AA is a symmetric bidentate ligand exhibit
geometrical isomerism.
Square planar complexes of the type MA
2
X
2
exhibit geometrical isomerism.
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12. The correct statement(s) regarding defects in solids is(are)
(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion
(B) Frenkel defect is a dislocation defect
(C) Trapping of an electron in the lattice leads to the formation of F-center
(D) Schottky defects have no effect on the physical properties of solids
Sol. (B, C) or (C) (By IITs)
Frenkel defect is shown by ionic substance in which there is a large difference in the size of ions.
Example, ZnS, AgCl, AgBr and AgI due to small size of Zn2+ and Ag+ ions.
Frenkel defect is also called dislocation defect. Because in this defect, the smaller ion (usually cation) is
dislocated from its normal site to an interstitial site It creates a vacancy defect at its original site and an
interstitial defect at its new location, a combination of vacancy and interstitial defects
In Metal excess defect due to anionic vacancies, anionic sites are occupied by unpaired electrons.
These sites are called F-centres (German word Farbenzenter for colour centre). They impart
colour to the crystals.
Schottky defect decreases the density of the substance due to paired cation and anion vacancies
(Schottky pair)
SECTION-III
Comprehension Type
This section contains 2 groups of questions. Each group has 3 multiple choice question based on a paragraph.
Each question has 4 choices (A), (B), (C) and (D) for its answer, out of which ONLY ONE is correct.
Paragraph for Question Nos. 13 to 15
A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr followed by
dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoes
intramolecular aldol reaction to give predominantly S.
13. The structure of the carbonyl compound P is
(A) (B)
(C) (D)
Sol. (B)
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14. The structure of the product Q and R, respectively are
(A)
(B)
(C)
(D)
Sol. (A)
15. The structure of the product S is
(A) (B)
(C) (D)
Sol. (B)
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Solutions for question nos. 13 to 15
Paragraph for Question Nos. 16 to 18
p-Amino-N, N-dimethylaniline is added to a strongly acidic solution of X. The resulting solution is treated with
a few drops of aqueous solution of Y to yield blue coloration due to the formation of methylene blue. Treatment
of the aqueous solution of Y with the reagent potassium hexacyanoferrate (II) leads to the formation of an
intense blue precipitate. The precipitate dissolves on excess addition of the reagent. Similarly, treatment of the
solution of Y with the solution of potassium hexacyanoferrate (III) leads to a brown colouration due to the
formation of Z.
16. The compound X is
(A) NaNO
3
(B) NaCl
(C) Na
2
SO
4
(D) Na
2
S
Sol. (D)
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17. The compound Y is
(A) MgCl
2
(B) FeCl
2
(C) FeCl
3
(D) ZnCl
2
Sol. (C)
18. The compound Z is
(A) ( )
2
6
Mg Fe CN (
(B) ( )
6
Fe Fe CN (
(C) ( )
4
6
3
Fe Fe CN (
(D) ( )
2 3
6
2
K Zn Fe CN (
Sol. (B)
Solutions for the question nos. 16 to 18
+ +
2 2
Na S + 2 H H S + 2 Na
( ) X
Methylene blue
( ) ( )
3 4 4
6 6
3
4 FeCl + 3 K Fe CN Fe Fe CN + 2 KCl
(
(
(
Blue ppt
( ) ( )
3 3
6 6
FeCl + K Fe CN Fe Fe CN + 3KCl
(
(
(
Brown coloration (Z)
( )
2
X - Na S
( )
3
Y - FeCl
( ) ( )
6
Z - Fe Fe CN (
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SECTION-IV
Matrix Match Type
This section contains 2 questions. Each question contains statements given in two columns, which have to be
matched. The statements in Column I are labelled A, B, C and D, while the statements in Column II are
labelled p, q, r, s and t. Any given statement in Column I can have correct matching with ONE OR MORE
statement(s) in Column II. The appropriate bubbles corresponding to the answers to these questions have to be
darkened as illustrated in the following example: If the correct matches are A p, s and t; B q and r; C p and
q; and D s and t; then the correct darkening of bubbles will look like the following:
19. Match each of the compounds in Column I with its characteristic reaction(s) in Column II.
Column I Column-II
(A)
3 2 2
CH CH CH CN (p) Reduction with PdC/H
2
(B)
3 2 3
CH CH OCOCH (q) Reduction with SnCl
2
/HCl
(C)
3 2
CH -CH=CH-CH OH (r) Development of foul smell on treatment with
Chloroform and alcoholic KOH
(D)
3 2 2 2 2
CH CH CH CH NH (s) Reduction with diisobutylaluminium hydride
(DIBAL-H)
(t) Alkaline hydrolysis
Sol. (A p, q, s, t) (B s, t) (C p) (D r)
A p, q, s, t :
pd C
2
H
3 2 2
CH CH CH CN
3 2 2 2 2
CH CH CH CH NH
3 2 2
CH CH CH CN
2
SnCl
HCl
3 2 2 4
CH CH CH CHO + NH Cl
3 2 2
CH CH CH CN
3 2 2 2 2
CH CH CH CH NH
DIBAL-H
3 2 2
CH CH CH CN
2
/ OH H O
3 2 2 3
CH CH CH COOH + NH
B s, t :
3 2 3
CH CH OCOCH
3 2
2 CH CH OH
DIBAL-H
2
/ OH H O
3 2 3
CH CH OCOCH
3 3 2
CH COOH + CH CH OH
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C p :
pd C
2
H
3 2
CH -CH=CH-CH OH
3 2 2 2
CH CH CH CH OH
D r : ( Carbyl amine reaction)
3 2 2 2 2
CH CH CH CH NH
3
CHCl
alc KOH
3 2 2 2
CH CH CH CH NC
20. Match each of the diatomic molecules in Column I with its property/properties in Column II.
Column-I Column-II
(A) B
2
(p) Paramagnetic
(B) N
2
(q) Undergoes oxidation
(C)
2
O
= .
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It has unpaired electrons. So, paramagnetic.
Undergoes mixing of s and p orbitals.
Undergoes reduction.
B s, t :
( ) 2 2 2 2 2
2
1
2 2 2
1 2 2 2 2
14
z
x y s
p
s s s p p
N e
= =
Bond order =
10 4
3
2
= .
Diamagnetic since it has paired electrons.
Undergoes mixing of s and p orbitals.
Doesnot undergo oxidation or reduction since it is stable as such.
C p, q :
( ) 2 2 2 2 2 2 1
2
1
2 2 2
1 2 2 2 2 2 2
17
z
x y x y s
p
s s s p p p p
O e
= = =
Bond order =
10 7
1.5
2
= .
It has unpaired electrons. So, paramagnetic.
Undergoes oxidation.
D p, q, s :
( ) 2 2 2 2 2 1 1
2
1
2 2 2
1 2 2 2 2 2 2
16
z
x y x y s
p
s s s p p p p
O e
= = =
Bond order =
10 6
2
2
= .
It has unpaired electrons. So, paramagnetic
Undergoes oxidation.
.