IIT-JEE 2005-M-1

FIITJEE Solutions to IITJEE–2005 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 O O O

CH2 ozonolysis 2
H2C H H H3C H
A
(b) H3C H H3C H

CH2 CH2

CH2 CH2

H3C H
“all cis” form of polymer of A

Q.2. Fill in the blanks

235 137
a) U92 0 n1 o A 52  97 B40  .......................
b) 82
Se34 o 2 1eR  ....................

235
Solution 2. (a) U92 + 0n1 o 137A52 + 97B40 + 2 0n1
82
(b) Se34 o 2 -1e0 + 82Kr36

Q.3. 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 o 2Ca3(PO4)2
852
Moles of P4O10 = 3
284
Moles of CaO = 3 × 6 = 18
Wt. of CaO = 18 × 56 = 1008 gm.
(b) O

P
O
O
O
O
O P P O

O O
P

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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
Diameter = 2r1 = 2(0.414 r2) 2 u 0.414 u = 117.1 pm
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 6.023×1014 / 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 u 2.46 u 10 3
nN2 1.0 u 107
RT 0.0821 u 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 u 6.023 u 1017 = 12.04 × 10
100
12.04 u 1016
? Sites occupied per molecule of N2 2
6.02 u 1016

Q.6. 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
N
Me Me
(Me) 3Si Si(Me) 3
Me

Q.7. O
OH

+
H /ǻ 1. O NaOH
 o X  3
2. Zn/CH COOH
o Y o
3

Identify X and Y.

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Solution 7. H
OH CH2
O

H

o HÅ /ǻ

o ring expansion
 o

H
O
O

O
NaOH O3
m  H m
Zn/CH3 COOH


CH3
(X)

Q.8. Which of the following disaccharide will not reduce Tollen’s reagent?
a) CH2OH CH2OH b) HOH2C CH2OH
HO HO
O H H O OH O H H O OH
H HO H OH H HO OH H
O O
H H
H H
OH H OH H OH H H OH
(Q)
(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 o 2Ag  2HBr  C6 H4 O2
Hydroquinone
 developer 
 black silver
particles  quinone

AgBr  2Na2 S2 O3 o Na3 ª¬ Ag  S2 O3 2 º¼  NaBr

§ se nsitive, · Hypo solution
¨ un exp osed ¸
¨ emulsion ¸
© ¹

b) Na2 S2 O3  2H o 2Na  H2 SO3  Sp

colloidal sulphur

 
SCN (excess) F (excess)
Q.10. Fe3   o blood red(A)  o colourless (B)
Identify A and B.
a) Write IUPAC name of A and B.
b) Find out spin only magnetic moment of B.
aqueous 2
Solution 10. Fe3   SCN o ªFe  SCNH2 O  º
¬ 5¼
 excess 
 A  blood red

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 IIT-JEE 2005-M-4

2 3
ªFe  SCNH2 O  º
¬ 5¼
 6F o >FeF6 @  SCN  5H 2 O
 excess  B  colourless 
 A  blood red

a) Pentaaquathiocyanato iron (III) ion

hexafluro ferrate (III)
b) Magnetic moment n n  2 = 35 = 5.92 B.M., where n = number of unpaired electrons

Q.11. 2X g o 3Y g  2Z g
Time (in Min) 0 100 200
Partial pressure of X
800 400 200
(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. 2X(g) o 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 u 10 3 min1
100
c) Time taken for 75% completion of reaction = 2 t1/2
d) 2X o 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/2S units.
nh o
Solution 12. a) mvr r ao 0.529 A
2S
nh
v 2.18 u 106 m / sec (n 1)
2Smr
h 6.63 u 10 34 o
b) O 0.33 u 10 9 m 3.3 A
mv 9.1 u 10 31 u 2.18 u 106
c) For 2 p value of A 1
h
Orbital angular momentum A(A  1)
2S
h
2
2S
NaNO ,HCl
Q.13. C5 H13 N  2
N2
o Y (Tertiary alcohol + other products)
(X)
(Optically active)
Find X and Y. Is Y optically active? Write the intermediate steps.

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 IIT-JEE 2005-M-5

Solution13. H
C 2H5
H3C C NH2
X is
or CH
CH H3C CH2
H3C CH3
NH2
(X)
H H H
H 3C H H3 C OH
C
H 3C C NH2 H 3C C N2 - H 3C C H HO
NaNO2 +HCl
 o H shift
o 
2
o CH2 C CH
CH
CH CH C
H3C CH3
H3C CH3 H3C CH3 H3C CH3 CH3
(Y) (optically inacticv
(X)

Q.14. Give reasons:

a) i) H3 C
Br

C2H5 OH (aq)
CH3  o acidic solution

ii) CH3
C2H5 OH (aq)
Br  o neutral
CH3
b) i) F
NaOH (aq)
 o F- (liberated)
O 2N
CH3
ii) F
NaOH (aq)
 o F- is not liberated
H3C

CH2NO2
c) i) O O O
N N N
NO2
Conc. HNO3

Conc. H2 SO4
o

NO2
ii) NO2 NO2

Conc. HNO3

Conc. H2 SO4
o
NO2
d)

Pd / C is formed but not


3 mole of H
o
2

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Solution14.(a) (i) CH3 CH3

C2 H5 OH  aq 
H 5C 6 C Br  o H 5C 6 C OC2H5 HBr (acid)

CH3 CH3
(ii) CH3

CH
CH3
NaOH aq
 
 o No reaction
Br
(b) (i) F
OH
NaOH  aq 
o F is liberated
O 2N
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)
 
 oF
is not liberated.
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 · NaBr+MnO2 conc.HNO3

¨ ¸ B m  A  o C  intermediate  o D Explosive product 
© pungent smell ¹
Find A, B, C and D. Also write equations A to B and A to C.

Solution15. (A) H2SO4

(B) Br2
(C) NO† 2
(D) CH3

O 2N NO2

NO2
Reactions involved are:
2H2 SO 4  2NaBr  MnO2 o Br2  Na2 SO4  MnSO4  2 H2 O
A B Brown fumes 
H2 SO 4  HNO3 o 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) (Explosive)

Q.16. Moist air

(B) m MCl4 Zn
 o (A)
white fumes having (M = transitionelement (purple color)
pungent smell colourless)

Identify the metal M and hence MCl4. Explain the difference in colours of MCl4 and A.
Solution 16. M = Ti
3
A ªTi H2 O  º
¬ 6¼
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. Pobs = ¦P x i i

Where Pi 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 Newman’s projection.
If Psolution = 1.0 D and mole fraction of anti form = 0.82, find PGouche.
b) Write most stable meso conformer of CHDY

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

Solution17.a) Z Z

H H H Z

H H H H

Z H
(Anti) (Gauche)
Mole fraction of anti form = 0.82
Mole fraction of Gauche form = 0.18
Pob. 1
1 P(anti) u 0.82  P(Gauce) u 0.18
P(anti) 0
? 1 P(Gauche) u 0.18
1
PGauche 5.55 D
0.18

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b) CH3 ii) H
O
i)
D H D OH

H D
D H
CH3
H

Q.18. a) Calculate 'Gr0 of the following reaction

Agaq  Claq. o AgCl s 
Given
'G0f  AgCl  109 KJ / mole

 
'G0f Cl - 129 kJ/mole

'G0f  Ag 
 77 kJ/mole

Represent the above reaction in form of a cell.

Calculate Eq of the cell. Find log10Ksp of AgCl.
b) 6.539 u 102 g of metallic Zn (amu = 65.39) was added to 100 ml of saturated solution of AgCl.
ª Zn2 º
¬ ¼
Calculate log10 2
. Given that

ª Ag º
¬ ¼
Ag  e  o Ag E0 0.80 V

Zn2  2e o Zn E0 0.76 V

Also find how many moles of Ag will be formed?

Solution18.Cell reactions are

1
Ag + Cl2  o AgCl ….(i)
2
o Ag+ + e-
Ag  …(ii)
1
o Cl- …(iii)
Cl2 + e 
2

Ag+ + Cl- 
o AgCl …(i – ii – iii)
hence cell representation is Ag | Ag+ | AgCl | Cl- | Cl2 ,Pt
Ag (aq)  Cl (aq) o AgCl(s); ¦ 'G  ¦ 'G
o
P
o
R

i) 'Go 109  ( 129  77)

= -109+129 – 77
= 20 – 77 = -57 = -1 × F × Eo
-57 = -1 × 96500 × Eo
57000
Ÿ Eo 0.59 Volts
96500
ii) -57 = -2.303 RT log K0
57 u 1000
log K0
2.303 u 8.314 u 298
log K0 = 9.98 | 10
K0 = 1010
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? Ksp = 1/K0
? Ksp = 10-10
? log Ksp = -10

ZZZ
X  
Z Ag (aq)  Cl (aq)
10 AgCl(s) YZZ
iii)
S S
10-10 = S2
? S = 10-5 m / L

65.39 u 10 2
b) When 10 – 3 moles of Zn has been added,
65.39
2Ag  2e o 2Ag; E0 0.80V
2 0
Zn o Zn  2e; E 0.77V

2
2Agaq  Zn s  o Zn aq  2Ag S ; E0 1.57V
-6 -3
10 mole 10 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)
ª Zn2 º
0.0591 ¬ ¼
E0Cell log10 2
2 
ª Ag º
¬ ¼
ª Zn2 º
1.56 u 2 ¬ ¼
? log 2
52.8
0.0591 ª Ag2 º
¬ ¼

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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