IIT-JEE 2005-M-1

FIITJEE Solutions to IITJEE2005 Mains Paper

Chemistry
Time: 2 hours
Note:

Question number 1 to 8 carries 2 marks each, 9 to 16 carries 4 marks each and 17 to 18 carries 6
marks each.

Q.1.

Monomer A of a polymer on ozonolysis yields two moles of HCHO and one mole of CH3COCHO.
a) Deduce the structure of A.
b) Write the structure of all cis form of polymer of compound A.

Solution1.

(a)

CH3
CH2 ozonolysis

H2C

(b)

H3C

H3C

H
CH2

H3C
all cis form of polymer of A

H3C

CH2
H

Fill in the blanks

a)

235

b)

82

137

U92 +0 n1

A 52 + 97 B40 + .......................

Se34 2 1e + ....................

Solution 2. (a)
(b)
Q.3.

CH2

CH2

Q.2.

235

U92 + 0n1 137A52 + 97B40 + 2 0n1

Se34 2 -1e0 + 82Kr36

82

a) Calculate the amount of Calcium oxide required when it reacts with 852 gm of P4O10.
b) Write the structure of P4O10.

Solution 3. a) 6CaO + P4O10 2Ca3(PO4)2

852
Moles of P4O10 =
=3
284
Moles of CaO = 3 6 = 18
Wt. of CaO = 18 56 = 1008 gm.
O
(b)
P
O

O
O
O

O
P

O
P
O

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IIT-JEE 2005-M-2

Q.4.

An element crystallizes in fcc lattice having edge length 400 pm. Calculate the maximum diameter of
atom which can be placed in interstitial site without distorting the structure.

Solution4. In FCC, interstitial sites will be octahedral voids & tetrahedral voids.
For octahedral voids
For tetrahedral voids
r1
r1
= 0.414
= 0.225
r2
r2
Where r1 = radius of atom in interstitial sites
r2 = radius of atom arranged in FCC.
i.e. 4r2 = 2 a ,
For maximum diameter of atom in interstitial site, octahedral voids will be considered.
400
= 117.1 pm
Diameter = 2r1 = 2(0.414 r2) = 2 0.414
2 2
Q.5.

20% surface sites have adsorbed N2. On heating N2 gas evolved from sites and were collected at
0.001 atm and 298 K in a container of volume is 2.46 cm3. Density of surface sites is 6.0231014 / cm2
and surface area is 1000 cm2, find out the no. of surface sites occupied per molecule of N2.

Solution 5. PN2 = 0.001 atm , T = 298 K, V = 2.46 cm2

By ideal gas, PV = nRT
PV 0.001 2.46 10 3
nN2 =
=
= 1.0 107
RT
0.0821 298
Now molecules of N2 = 6.023 1023 1 10-7 = 6.023 1016
Now total surface sites available = 6.023 1014 1000 = 6.023 1017
20
16
Surface site used to adsorb N2 =
6.023 1017 = 12.04 10
100
Sites occupied per molecule of N2 =

Q.6.

12.04 1016
6.02 1016

=2

Predict whether the following molecules are iso structural or not. Justify your answer.
(i) NMe3 (ii) N(SiMe3)3

Solution 6. N (Me )3 & N ( SiMe3 )3 are not isostructural. N(Me)3 is trigonal pyramidal while N ( SiMe3 )3 is
trigonal planar due to back bonding.
Si(Me) 3

N
Me

N
Me

(Me) 3Si

Me

Si(Me) 3

Q.7.

OH
+

1. O

H /
NaOH
3

Y
2. Zn/CH COOH
3

Identify X and Y.

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IIT-JEE 2005-M-3
H

Solution 7.
OH

CH2

O
H

H /

ring expansion

H
O

O
O
O3
H

Zn/CH3 COOH

NaOH

CH3

Q.8.

(X)

Which of the following disaccharide will not reduce Tollens reagent?

CH2OH
b) HOH2C
a)
CH2OH
HO
HO
OH
O
O H H
O H H
H
OH
H HO
H HO

O
H

(Q)

OH

OH

OH

H
H

OH

H
OH

CH2OH

OH

(P)
Solution 8. In structure (P)
both the rings are present in acetyl form therefore it will not hydrolyse in
solution that why Fehling solution cannot react with this.
In structure (Q) one ring present in the form of hemiacetal. This will hydrolyse in solution and it
can reduce Fehling solution.
Q.9.

Write balanced chemical equation for developing a black and white photographic film. Also give
reason why the solution of sodium thiosulphate on acidification turns milky white and give balance
equation of this reaction.

Solution 9. a) Reactions used in developing the photographic film

2AgBr + C6 H4 ( OH)2
Hydroquinone
( developer )

AgBr
se nsitive,
un exp osed
emulsion

b)

Q.10.

2Ag
black silver
particles

+ 2HBr + C6 H4 O2

+ 2Na2 S2 O3 Na3 Ag ( S2 O3 )2 + NaBr

Hypo solution

Na2 S2 O3 + 2H+ 2Na+ + H2 SO3 +

quinone

colloidal sulphur

SCN (excess)
F (excess)
Fe3 +
blood red(A)
colourless (B)

Identify A and B.
a) Write IUPAC name of A and B.
b) Find out spin only magnetic moment of B.
Solution 10.

aqueous
Fe ( SCN)(H2 O )
Fe3 + + SCN
5

( excess )

2+

( A )( blood red)

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IIT-JEE 2005-M-4

Fe ( SCN)(H2 O )
5

( A )( blood red)

2+

+ 6F [FeF6 ]

( excess )

(B )( colourless )

+ SCN + 5H 2 O

a) Pentaaquathiocyanato iron (III) ion

hexafluro ferrate (III)
b)
Q.11.

Magnetic moment = n ( n + 2 ) =

35 = 5.92 B.M., where n = number of unpaired electrons

2X( g) 3Y( g) + 2Z( g)

100
Time (in Min) 0
Partial pressure of X
800
400
(in mm of Hg)
Assuming ideal gas condition. Calculate
a) Order of reaction
b) Rate constant.
c) Time taken for 75% completion of reaction.
d) Total pressure when Px = 700 mm.
Solution 11.

200
200

2X(g) 3Y(g) + 2Z(g)

a) By the given data, we can observed that t1/2 of the X is constant i.e. 100 min. therefore
order of reaction is one.
0.693
b) Rate constant K =
t1/ 2
0.693
= 6.93 10 3 min1
100
c) Time taken for 75% completion of reaction = 2 t1/2
=

d)
2X 3Y + 2Z
Initial pressure
800
0
0
At any time
800 x
3/2 x x
Given 800 x = 700 mm
x = 100 mm
Total pressure = 700 + 150 + 100 = 950 mm
Q.12.

a) Calculate velocity of electron in first Bohr orbit of hydrogen atom (Given r = a0).
b) Find de-Broglie wavelength of the electron in first Bohr orbit.
c) Find the orbital angular momentum of 2p orbital in terms of h/2 units.

Solution 12.

a)

o
nh
r = ao = 0.529 A
2
nh
v=
= 2.18 106 m / sec (n = 1)
2mr

mvr =

o
h
6.63 10 34
=
= 0.33 10 9 m = 3.3 A

31
6
mv 9.1 10 2.18 10
c) For 2 p value of A = 1
h
Orbital angular momentum = A(A + 1)
2
h
= 2
2

b)

Q.13.

NaNO ,HCl

2
C5 H13 N
Y (Tertiary alcohol + other products)
N2
(X)
(Optically active)
Find X and Y. Is Y optically active? Write the intermediate steps.

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IIT-JEE 2005-M-5
H

Solution13.
X is

H3C

C 2H5

NH2

CH2

H3C

CH3

H3C

CH

or

CH

NH2

(X)

H
H 3C

NH2

NaNO2 +HCl

H 3C

H 3C

N2

H3C

H3C

CH3

C
-

CH

CH

CH

H3C

CH3

H shift

CH3

H 3C

Give reasons:
H3 C
a) i)

H HO
2

CH2

CH

C
H3C

(X)

Q.14.

OH

H3 C

CH3

CH3
(Y) (optically inacticv

Br
CH3

C2H5 OH (aq)

acidic solution

CH3

ii)

C2H5 OH (aq)

neutral

Br
CH3

b)

i)

NaOH (aq)

F- (liberated)

O 2N
CH3
F

ii)

NaOH (aq)

F- is not liberated

H3C
CH2NO2

c)

i)

NO2
Conc. HNO3

Conc. H2 SO4

NO2

ii)

NO2

NO2

Conc. HNO3

Conc. H2 SO4

NO2

d)

Pd / C

3 mole of H

is formed but not

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IIT-JEE 2005-M-6
CH3

Solution14.(a) (i)
H 5C 6

CH3
C2 H5 OH ( aq )
Br
H 5C 6

C
CH3

OC2H5

HBr (acid)

CH3
CH3

(ii)

CH
CH3
( )

No reaction
NaOH aq

Br
F

(b) (i)

OH
NaOH ( aq )

O 2N

is liberated

O 2N
CH 3

CH 3

This is a bimolecular reaction. Rate of this reaction is being enhanced by presence

of electron withdrawing groups at ortho and para positions.
F
(ii)
is not liberated.
( )

F
NaOH aq

CH2NO2

Bimolecular mechanism is not possible is this case.

(c) (i) Due to presence of lone pair on nitrogen atom NO group is electron donating and ortho, para
directing.
(ii) NO2 group is electron withdrawing and meta directing.
(d) Due to reduction of central ring, three four membered antiaromatic rings become stable while on
reduction of terminal ring only one antiaromatic ring can be stabilized.
Q.15..

CH3

Brown fumes and

conc.HNO3
NaBr+MnO2
A

C ( intermediate ) D (Explosive product )

B
pungent smell

Find A, B, C and D. Also write equations A to B and A to C.

Solution15.

(A)
(B)
(C)

H2SO4
Br2
NO
2
CH3

(D)
O 2N

NO2

NO2

Reactions involved are:

2H2 SO 4 + 2NaBr + MnO2
(A)

Br2

(B )(Brown fumes )

+ Na2 SO 4 + MnSO4 + 2 H2 O

H2 SO 4 + HNO3 HSO 4 + NO
2 + H2O
(A)

(C)

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IIT-JEE 2005-M-7
CH3

CH3
O 2N

NO2

3 NO 2

3H

NO2
(D)

Q.16.

Moist air
(B)

white fumes having

pungent smell

(Explosive)
Zn

MCl4
(M = transitionelement
colourless)

(A)
(purple color)

Identify the metal M and hence MCl4. Explain the difference in colours of MCl4 and A.
Solution 16.
M = Ti
3+

A = Ti (H2 O )6
B = TiO2
Ti(+IV) ion contains no d-electrons, while d d transition of single electron of Ti(+III) will cause
colour change.
Q.17.

obs =

i i

Where i is the dipole moment of stable conformer and xi is the mole fraction of that conformer.
a) Write stable conformer for Z CH2 CH2 Z in Newmans projection.
If solution = 1.0 D and mole fraction of anti form = 0.82, find Gouche.
CHDY
b) Write most stable meso conformer of

CHDY
If (i) Y = CH3 about C2 C3 rotation and (ii) Y = OH about C1 C2 rotation.
Solution17.a)

Z
H

H
Z
(Anti)
(Gauche)
Mole fraction of anti form = 0.82
Mole fraction of Gauche form = 0.18
ob. = 1
1 = (anti) 0.82 + (Gauce) 0.18

(anti) = 0
1 = (Gauche) 0.18
Gauche =

1
= 5.55 D
0.18

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IIT-JEE 2005-M-8

CH3

b)
i)

ii)

O
D

OH

CH3
Q.18.

a) Calculate Gr0 of the following reaction

Ag(+aq) + Cl(aq.) AgCl( s )

Given
G0f ( AgCl )

109 KJ / mole

( )
( Ag )

- 129 kJ/mole

G0f Cl
G0f

77 kJ/mole

Represent the above reaction in form of a cell.

Calculate E of the cell. Find log10Ksp of AgCl.
b) 6.539 102 g of metallic Zn (amu = 65.39) was added to 100 ml of saturated solution of AgCl.
Zn2+

. Given that
Calculate log10
2
+
Ag

Ag+ + e Ag

E0 = 0.80 V

Zn2+ + 2e Zn

E0 = 0.76 V

Also find how many moles of Ag will be formed?

Solution18.Cell reactions are
1
Ag + Cl2
AgCl
2
Ag
Ag+ + e-

.(i)

(ii)

1
Cl- (iii)
Cl2 + e
2

Ag+ + Cl-
AgCl

(i ii iii)

hence cell representation is Ag | Ag+ | AgCl | Cl- | Cl2 ,Pt

Ag+ (aq) + Cl (aq) AgCl(s);

i)

ii)

G G
o
P

o
R

Go = 109 ( 129 + 77)

= -109+129 77
= 20 77 = -57 = -1 F Eo
-57 = -1 96500 Eo
57000
Eo =
= 0.59 Volts
96500
-57 = -2.303 RT log K0
57 1000
log K0 =
2.303 8.314 298
log K0 = 9.98 10
K0 = 1010

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IIT-JEE 2005-M-9

Ksp = 1/K0
Ksp = 10-10
log Ksp = -10

iii)

ZZZ
X
10 AgCl(s) YZZ
Z Ag (aq) + Cl (aq)

10-10 = S2
S = 10-5 m / L
b) When

65.39 10 2
= 10 3 moles of Zn has been added,
65.39

2Ag+ + 2e 2Ag;

E0 = 0.80V

Zn Zn2+ + 2e;
E0 = 0.77V

2+

2Ag(+aq) + Zn( s ) Zn( aq) + 2Ag( S );

E0 = 1.57V

10-6 mole 10-3 moles

log10 K ( eq) = 52.8
Therefore, this reaction will move in forward direction completely. Hence moles of Ag formed will
be 10-6
At equilibrium, (Ecell = 0)
Zn2+
+0.0591

0
ECell =
log10
2
2
+
Ag

+
2
Zn
1.56 2

= log
= 52.8

2
0.0591
+
2
Ag

Note: FIITJEE solutions to IITJEE, 2005 Mains Papers created using memory retention of select
FIITJEE students appeared in this test and hence may not exactly be the same as the
original paper. However, every effort has been made to reproduce the original paper in the
interest of the aspiring students.

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