FIITJEE Solutions to IITJEE2004 Mains Paper

Chemistry
Time: 2 hours
Note:

Question number 1 to 10 carries 2 marks each and 11 to 20 carries 4 marks each.

1.

For the given reaction

A + B Products
Following data were given
Initial conc. (m/L).
[A]
0.1
0.2
0.1
a) Write the rate equation.
b) Calculate the rate constant.

Initial conc. (m/L)

[B]
0.1
0.1
0.2

Initial rate [mL-1s-1 ]

0.05
0.1
0.05

Sol.

a)

Let the order w.r.t A & B are x any y respectively

r = K[A]x [B]y
0.05 = K[0.1]x [0.1]y
0.1 = K[0.2]x [0.1]y
or 2 = [2]x
x =1
0.05 = K[0.1]x [0.1]y
0.05 = K[0.1]x [0.2]y
1 = [2]y
y=0
b) rate equation = r = K[A] [B]0
0.1 = K[0.2]
K = 0.5 Sec-1

2.

100 ml of a liquid contained in an isolated container at a pressure of 1 bar. The pressure is steeply increased
to 100 bar. The volume of the liquid is decreased by 1 ml at this constant pressure. Find the H & U.

Sol.

H =0, qp = U-W
W = PdV
= 1001 atmmL
= 10-2 KJ = U

3.

Draw the shape of XeF4 and OSF4according to VSEPR theory. Show the lone pair of electrons on the
central atom

Sol.
F
Xe
F

(square planar)
(sp3d2)

S
F

(Trigonal bipyramidal)
(sp3d)

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IIT-JEE 2004-M-2

4.

The structure of D-Glucose is as follows

CHO
a)
Draw the structure of L Glucose.
b)
Give the reaction of L Glucose with Tollens reagent.
H

OH

HO

OH

OH

HO

Sol.

CHO
H

OH

HO

Ag( NH3 )2

OH

HO

(L glu cos e)

HO

5.

Sol.

HO

HO

OH
H
OH
H

HO

a) Draw New mann`s projection for the less stable staggered form of butane.
b) Relatively less stability of the staggered form is due to
i) Torsional strain.
ii) Vander Waals strain.
iii) Combination of the above two.
CH3
a)
CH3

H
.

b) Less stability is due to Vander Waals strain

6.
Sol.

Arrange the following oxides in the increasing order of Bronsted basicity.

Cl2 O7 , BaO, SO3 , CO 2 , B2 O3
Cl2 O7 < SO3 < CO 2 < B2 O3 < BaO

7.

AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes soluble. On
addition of BF3 ,AlF3 is precipitated. Write the balanced chemical equations.

Sol.

3KF + AlF3 K3AlF6

K3AlF6 + 3BF3 AlF3 + 3KBF4

8.

The crystal AB (rock salt structure) has molecular weight 6.023 y amu. where y is an arbitrary number in
amu.. If the minimum distance between cation & anion is y1/ 3 nm and the observed density is 20 Kg / m3 .
Find the
a) density in Kg / m3 and
b) type of defect

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IIT-JEE 2004-M-3

Sol.

Density =

a)

4 6.023 y
[Since a = 2y1/3]
6.023 1023 8 y 1027

= 5 103 g / m 3
= 5Kg / m 3
Since the (density) calculated < density observed, it means the defect is metal excess defect.

b)
9.

Which of the following is more acidic and why?

+

NH3

NH3

F
+

Sol.

is more acidic due to inductive effect of fluorine

NH3

10.

7-bromo-1,3,5-cycloheptatriene exists as ionic species in aqueous solution while 5-bromo-1,3

cyclopentadiene doesnt ionise even in presence of Ag + (aq), Explain.

Sol.

Br

Ag aq.

Aromatic Ion
(highly stable)

Ag

Antiaromatic Ion
(highly unstable)

Br

11.

a)

The schrodinger wave equation for hydrogen atoms is

3/ 2

1
r r / a
2s =
2 e
1/ 2
a0
4(2) a 0
Where a0 is Bohrs radius. Let the radial node in 2s be at r0. Then find r in terms of a0.
b) A base ball having mass 100 g moves with velocity 100 m/sec. Find out the value of wave length of
base ball.
7
c) 92 X 234
Y. Find out atomic number, mass number of Y and identify it.
6
1

Sol.

a)

22s = probability of finding electrons at any place

2= 0 at node

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IIT-JEE 2004-M-4

1 1 1
=0=

4 2 a 0

r
r / a
2 e 0
a0

r
r
2a0 = r
2 = 0 2 =
a0
a0

h
6.626 1034
=
mv 100 103 100
= 6.62610-35 m = 6.62610-25 A
Yis 84Po206

b) =
c)
12.

Sol.

On the basis of ground state electronic configuration arrange the following molecules in increasing O-O
bond length order.
KO2, O2, O2[AsF6].
2

1
2p y 2p y
O 2 = 1s 2 , 1s 2 , 2s 2 , 2s 2 , 2p 2x

1
2p z 2p z

bond order =

10 6
=2
2

*
2
2P 2 2Py
O 2 = 1s2 , * 1s2 , 2s2 , * 2s2 , 2P 2 2Pzy2 * 2P 1 in [KO 2 ]
x

bond order =

10 7 3
=
2
2

2P 2
= 1s2 , * 1s2 , 2s2 , * 2s2 , 2Px2 2Pzy2 * 2p y1

in [O2 (AsF6 )]
O +2

10 5 5
=
2
2
Bond length order is O+2 < O2 < O2

bond order

13.

Sol.

a)

In the following equilibrium

N2O4(g)
2NO2(g)
when 5 moles of each are taken, the temperature is kept at 298 K the total pressure was found to be 20
bar. Given that
G 0f (N 2 O 4 ) = 100KJ

G 0f (NO 2 ) = 50KJ
i) Find G of the reaction
ii) The direction of the reaction in which the equilibrium shifts
b) A graph is plotted for a real gas which follows Vander Waals equation with PVm taken on Y axis &
P on X axis. Find the intercept of the line where Vm is molar volume
a) i) N2O4(g)
2NO2(g)
2
PNO
100
2
Reaction quotient =
=
= 10 atm
10
PN O
2

G reaction = 2G f ( NO 2 ) G f ( N 2 O 4 )
0 = 100 100
G = G + RT lnk
G = RT ln Q
= 2.303 .082 298 log 9.9

= 56.0304 Lit atm. = Positive

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IIT-JEE 2004-M-5

ii) Therefore reaction will shift towards backward direction.

b)

a
P + 2 (v m b) = RT
vm

aP 2 PV

P +

b = RT
2

PV
(
)

[PV)2 P+aP2][(PV) b)] = P(PV)2RT

P[(PV)2 + aP] (PV-bP)=P(PV)2RT
Put P = 0
(PV)3 = (PV)2 RT
Intercept = RT
1.22 g C6H5 COOH is added into two solvent and data of Tb and Kb are given as:Tb= 0.17
i) In 100 g CH3COCH3
Kb = 1.7 Kg Kelvin /mol
ii) In 100 g benzene,
Tb = 0.13 and Kb = 2.6 Kg Kelvin/mol
Find out the molecular weight of C6H5COOH in both the cases and interpret the result.
b) 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point. Given Ka(HA)=510-6 and
<< 1

14.

a)

Sol.

a)

In first case
i) Tb = Kbm

1.22
M = 122
M 100 10 3
ii) In second case
Tb = Kbm
1.22
0.13 = 2.6
M 100 103
M = 244
Benzoic acid dimerises in benzene
0.1
b) Since at end point molarity of salt = =
M
2
pH of salt of weak acid and strong base

0.17 = 1.7

pH =

( pK w + pK a + logc )
2
NO2

15.

NO2

1
[14 + 5.3010 + [-1.3010] pH = 9.
2

in not more than four steps. Also mention the temp and reaction
condition.

Convert
to
OH

Sol.

NO2

NO2

Conc.H 2 SO 4

NO2

NaNO2 / HCl

NH 4 HS

0 C 5 C

NO2

NO2

NO2

NH2

H2 O

OH

NCl

16.

Cl

C2 H5 ONa / C 2 H 5 OH
H3 O
SOCl2
KCN

(A)

(B)
(C)
(D)

DMF
C6 H5 CHO /
CH3 NH 2

Identify A to D.

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IIT-JEE 2004-M-6

CN

Sol.

NC

Ph

A=

B=

NH
CH3

COOH

Ph

Ph

C=

17.

D=

A1 & A2 are two ores of metal M. A1 on calcination gives black precipitate, CO2 & water.
n
atio
l ci n
Ca

Black solid + CO2 + H2O

dil HCl

A1

I 2 + ppt

KI

roasting
A 2
Metal + gas

K 2 Cr2 O7 + H2SO4
green colour

Sol.

A1 = Cu(OH) 2 CuCO3
A 2 = Cu 2S
Calcination
Cu(OH) 2 CuCO 3
2CuO + CO 2 + H 2 O

(A1)

(Black Solid)

Cu(OH) 2 CuCO 3 CuCl 2 + CO 2 + 3H 2 O

dilHCl

2CuCl2 + 4KI Cu 2 l2 + I 2 + 4KCl

2Cu 2S + 3O 2 2Cu 2 O + 2SO 2
( A2 )

18.

Sol.

Cu 2S + 2Cu 2 O 6Cu + SO 2
NiCl2 in the presence of dimethyl glyoxime (DMG) gives a complex which precipitates in the presence of
NH 4 OH , giving a bright red colour.
a) Draw its structure & show H-bonding
b) Give oxidation state of Ni & its hybridisation.
c) Predict wether it is paramagnetic or diamagnetic.
H3C

N
C

HO

N
C

CH3

Ni

C
H3C

C
CH3

OH O

Oxidation state of nickel is +2 and hybridization is dsp2

s = n(n + 2) B.M
n=0
s = 0

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19.

Find the equilibrium constant for the reaction

Cu+2 + In+2
Cu+ + In+3
Given that
E Cu +2 / Cu + = 0.15V
E In +2 / In + = 0.4V
E In +3 / In + = 0.42 V

Sol.

Cu+2 +e- Cu+

In+2 + e- In+ +
In+ In+3 + 2 eCu+2 + In+2
- nFE = - 0.59F
E0cell F = 0.59F

G10 = - 0.15 F
G20 = +0.4 F
G30 = - 0.84 F
Cu+ + In+3

G0 = - 0.59 F

E0Cell = 0.59
0.0591
log K c
n
0.0591
log Kc
0.59 =
1
Kc = 1010

Ecell = E -

20.

An organic compound P having the molecular formula C5H10O treated with dil H2SO4 gives two
compounds, Q & R both gives positive iodoform test. The reaction of C5H10O with dil H2SO4 gives
reaction 1015 times faster then ethylene. Identify organic compound of Q & R. Give the reason for the extra
stability of P.

CH3

Sol.
C5 H10 O is

H2C

CH3

CH3

CH3

CH3

H2C

CH3

H+

C
H3C

CH3

H 2O

H3C

+ C2 H 5OH

Highly stable carbocation

P is stabilized by resonance

Note: FIITJEE solutions to IITJEE, 2004 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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