Aieee 2007 Paper

MAHESH JANMANCHI AIEEE 2007
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Maximum Marks: 120

Question paper format and Marking scheme:

1. This question paper has 40 questions.

2. Candidates will be awarded three marks each for indicating correct response for each question.

3. 1/3 rd of the total marks allotted to the question 1 mark will be deducted for indicating incorrect
response.

4. No deduction from the total score will be made if no response is indicated for an item in the
answer sheet.



81. The energies of activation for forward and reverse reactions for
2 2
A +B 2AB are 180 kJ mol
1

and 200 kJ mol
1
respectively. The presence of catalyst lowers the activation energy of both
(forward and reverse) reactions by 100 kJ mol
1
. The enthalpy change of the reaction
( )
2 2
A +B 2AB in the presence of catalyst will be (in kJ mol
1
)
(1) 300 (2) 120
(3) 280 (4) 20

Sol. (4)

So,
a a
H E E
reaction (forward) (backward)
=
= 80-100 = -20kj mole
-1

82. The cell, ( ) ( )
( )
2+ 2+ 0
Zn|Zn 1M ||Cu 1M Cu E =1.10V
cell
, was allowed to be completely discharged at
298 K. The relative concentration of
2+
Zn and
2+
Cu
2+
Zn
2+
Cu
( (
( (

(
(
(
(

is
(1) Antilog (24.08) (2) 37.3
(3)
37.3
10 (4)
4
9.65 10

Sol. (3)

2+ 2+
Zn + Cu Zn + Cu

0
cell cell
2+
Zn
0.0591
E = E log
2+ 2
Cu
(
(

(
(

For complete discharge, E =0
cell

So,
2
0.591
0
E = log
2 2
Zn
cell
Cu
+ (
(

+ (
(



2
0.591
1.1= log
2 2
Zn
Cu
+ (
(

+ (
(

2
37.3
10
2
Zn
Cu
+ (
(

=
+ (
(

83. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA in which
50% of the acid is ionized is
(1) 4.5 (2) 2.5
(3) 9.5 (4) 7.0

Sol. (3)
For an acidic buffer buffer solution

[ ]
[ ]
log
Salt
pH pK
a
Acid
= +

[ ]
[ ]
4.5 log
Salt
Acid
= +
As HA is 50% ionized so [salt] = [acid]

pH = 4.5
pH + pOH = 14
pOH = 14 4.5 = 9.5

84. Consider the reaction,
2A +B Products
When concentration of B alone was doubled, the half-life did not change. When the concentration
of A alone was doubled, the rate increased by two times. The unit of rate constant for this reaction
is
(1)
1 1
L mol s

(2) no unit
(3)
1 1
mol L s

(4)
1
s

Sol. (1)
When conc. of B is doubled, the half life did not change, hence reaction is of first order w.r.t. B.
1/ 2 1
1
n
t
a
, where n is order of the reaction

When concentration of A is doubled, reaction rate is doubled, hence reaction is of first order w.r.t. A.
Hence over all order of reaction is 1 + 1 = 2
So, unit of rate constant mol
-1
lit s
-1
.
Note : For nth order reaction , units of rate constant is
n-1 1- n 1
L mol s



85. Identify the incorrect statement among the following
(1) d-Block elements show irregular and erratic chemical properties among themselves
(2) La and Lu have partially filled d orbitals and no other partially filled orbitals
(3) The chemistry of various lanthanoids is very similar
(4) 4f and 5f orbitals are equally shielded

Sol. (4)
4f and 5f belongs to different energy levels,. 4f orbital is nearer to thenucleus than 5f orbital.
hence the shielding effect on them is not the same.
Shielding of 4f is more than 5f.

86. Which one of the following has a square planar geometry?
(1)
2
4
CoCl

(

(2)
2
4
FeCl

(

(3)
2
4
NiCl

(

(4)
2
4
PtCl

(

Sol. (4)

2 2 2 6 2 6 7 0
1 2 2 3 3 3 4
27
Co s s p s p d s
+

As Cl
is weak field ligand, no forcible pairing

Hence it is sp
3
hybridized and tetrahedral in geometry.

2 2 2 6 2 6 6 0
1 2 2 3 3 3 4 Fe s s p s p d s
+

As Cl

Hence it is sp
3
.
2 2 2 6 2 6 8 0
1 2 2 3 3 3 4 Ni s s p s p d s
+

As Cl

Hence it is sp
3

All the complexes of Pt
2+
are square planar including those with weak field ligand such as halide ions



87. Which of the following molecules is expected to rotate the plane of plane polarized light?
(1) (2)

(3) (4)

Sol. (1)
The plane of polarized light is rotated by optically active compound, i.e. it should be chiral.
(1) has -chiral C-atom. So, it is optically active.

In (2), (3) and (4) plane of symmetry is present.

88. The secondary structure of a protein refers to
(1) -helical backbone (2) hydrophobic interactions
(3) sequence of -amino acids (4) fixed configuration of the polypeptide
backbone

Sol. (1)
Primary structure: Represents the sequence of amino acid
Secondary structure: Indicates the shape in which a polypeptide chain exists.
Secondary structure of proteins involves helical back bone and pleated sheet structures.
Tertiary structure: Represents folding and bondings of a polypeptide chain
Quarternary structure:A protein may be composed of more than 1 poly peptide chains called sub
units.Spatial arrangement of these sub units w.r.t each other is quarternary structure.



89. Which of the following reactions will yield 2, 2-dibromopropane?
(1) C CH + 2 HBr
3
CH (2) CH CH CHBr + HBr
3
=
(3) CH CH + 2 HBr (4) CH CH=CH + HBr
3 2

Sol. (1)

90. In the reaction,
( ) ( ) CH CH NH + CHCl + 3 KOH A + B + 3 H O
3 2 2 3 2
, the compounds (A) and (B) are respectively
(1) C H CN
2 5
and 3KCl (2) CH CH CONH
3 2 2
and 3KCl
(3) C H NC
2 5
and K CO
2 3
(4) C H NC
2 5
and 3KCl

Sol. (4)
It is Carbylamine reaction.
CH CH NH + CHCl + 3 KOH C H NC+ 3KCl + 3 H O
3 2 2 3 2 5 2

91. The reaction of toluene with Cl
2
in presence of FeCl
3
gives predominantly
(1) benzoyl chloride (2) benzyl chloride
(3) o-and p-chlorotoluene (4) m-chlorotoluene

Sol. (3)



CH
3
group is o- and p- directing

92. Presence of a nitro group in a benzene ring
(1) activates the ring towards electrophilic substitution
(2) renders the ring basic
(3) deactivates the ring towards nucleophilic substitution
(4) deactivates the ring towards electrophilic substitution

Sol. (4)

- NO
2
group shows M effect, so withdraws the electron density from o- and p- positions of the ring
and hence deactivates the ring towards electrophilic aromatic substitution.

93. In which of the following ionization processes, the bond order has increased and the magnetic
behaviour has changed?
(1)
+
C C
2 2
(2)
+
NO NO
(3)
2
O
+
O
2
(4)
+
N N
2
2

Sol. (2)
NO :
2 * 2 2 * 2 2 2 2 * 1 * 0
1 1 2 2 2 2 2 2 2 s s s s p p p p p
z x y x y
= = (Paramagnetic)
Bond order =
10 5
2.5
2
= .
NO
+
:
2 * 2 2 * 2 2 2 2
1 1 2 2 2 2 2 s s s s p p p
z x y
= (Diamagentic)
Bond order =
10 4
3
2
= .



94. The actinoids exhibits more number of oxidation states in general than the lanthanoids. This is
because
(1) the 5f orbitals are more buried than the 4f orbitals
(2) there is a similarity between 4f and 5f orbitals in their angular part of the wave function
(3) the actinoids are more reactive than the lanthanoids
(4) the 5f orbitals extend further from the nucleus than the 4f orbitals

Sol. (4)
The actinoids exhibit more number of oxidation states in general than the lanthanoids. This is because
the 5f orbitals extend farther from the nucleus than the 4f orbitals.

95. Equal masses of methane and oxygen are mixed in an empty container at 25C. The fraction of the
total pressure exerted by oxygen is
(1)
2
3
(2)
1 273
3 298

(3)
1
3
(4)
1
2

Sol. (3)
Partial pressure of oxygen = Mole fraction x P
total

=
32
+
32 16
w
w w
x P
=
32
32 3
w
x
w

=
1
3
P

96. A 5.25 % solution of a substance is isotonic with a 1.5% solution of urea (molar mass = 60 g mol
1
)
in the same solvent. If the densities of both the solutions are assumed to be equal to 1.0 g cm
3
,
molar mass of the substance will be
(1) 90.0
1
g mol
(2) 115.0
1
g mol

(3) 105.0
1
g mol
(4) 210.0
1
g mol

Sol. (4)
Solutions with the same osmotic pressure or molar concentrations are isotonic

1 1 2 2
=C RT=C RT=
So, C
1
= C
2

As density of the solutions are same

5.25 1.5
M 60
=
5.25 60
M 210
1.5
= =


97. Assuming that water vapour is an ideal gas, the internal energy change (U) when 1 mol of water
is vapourised at 1 bar pressure and 100
0
C, (Given: Molar enthalpy of vapourization of water at 1
bar and 373 K = 41 kJ mol
1
and R = 8.3 J mol
1
K
1
) will be
(1) 4.100
1
kJ mol
(2) 3.7904
1
kJ mol

(3) 37.904
1
kJ mol
(4) 41.00
1
kJ mol

Sol. (3)
( ) ( )
vaporisation
H O l H O g
2 2

g
n 1 0 1 = =

g
H U + n RT =

g
U H - n RT =

3
41 1 8.3 10 373 U x

=
= 37.9
1
kJ mol

98. In a sautrated solution of the sparingly soluble strong electrolyte AgIO
3
(Molecular mass = 283)
the equilibrium which sets in is
( ) ( ) ( )
+
AgIO Ag +IO
3 s aq aq

If the solubility product constant K
sp
of AgIO
3
at a given temperature is 1.010
8
, what is the
mass of AgIO
3
contained in 100 ml of its saturated solution?
(1)
2
28.3 10 g
(2)
3
2.83 10 g

(3)
7
1.0 10 g
(4)
4
1.0 10 g

Sol. (2)

( ) ( ) ( )
+
AgIO Ag +IO
3 s aq aq

Let the solubility of AgIO
3
be s

+
sp 3
K = Ag IO
( (

8 2
1.0 10 s
=

4
s 10
= mol/litre

4
10 283 / lit g
=

4
10 283
g / ml
1000
=

4
10 283
100
1000
= g/ 100 ml

3
2.83 10 g / 100 ml



99. A radioactive element gets spilled over the floor of a room. Its half-life period is 30 days. If the
initial activity is ten times the permissible value, after how many days will it be safe to enter the
room?
(1) 1000 days (2) 300 days
(3) 10 days (4) 100 days

Sol. (4)
Activity
dN
N
dt
| |
|
\

n
0
1
N=N
2
| |
|
\

n
0
N 1
N 2
| |
=
|
\

n
1 1
10 2
10 2
n
| |
= =
|
\

log 10 = nlog 2

1
3.32
0.301
n = =

112
t n t =
3.32 30 99.6 = = days

100. Which one of the following conformation of cyclohexane is chiral?
(1) Twist boat (2) Rigid
(3) Chair (4) Boat

Sol. (1)
Twisted boat is chiral as it does not have plane of symmetry.

101. Which of the following is the correct order of decreasing SN
2
reactivity?
(1) RCH
2
X > R
3
CX > R
2
CHX (2) RCH
2
X > R
2
CHX > R
3
CX
(3) R
3
CX > R
2
CHX > RCH
2
X (4) R
2
CHX > R
3
CX > RCH
2
X
(X = a halogen)

Sol. (2)
Greater the steric hindrance at the carbon bearing the halogen, lesser is the SN
2
reactivity.



102. In the following sequence of reactions,

P+I H O
Mg HCHO
2 2
CH CH OH A B C D
3 2

ether

The compound D is
(1) butanal (2) n-butyl alcohol
(3) n-propyl alcohol (4) propanal

Sol. (3)

103. Which of the following sets of quantum numbers represents the highest energy of an atom?
(1) n = 3,l = 1,m=1,s= +1/2 (2) n = 3, l = 2,m = 1,s = +1/2
(3) n = 4, l = 0,m = 0,s = +1/2 (4) n = 3, l = 0,m = 0,s = +1/2

Sol. (2)
It has the maximum value of n + l

104. Which of the following hydrogen bonds is the strongest?
(1) O H.N (2) F H.F
(3) O H.O (4) O H.F

Sol. (2)
The hydrogen bond in HF is strongest, because fluorine is the most electronegative element.

105. In the reaction,
( ) ( ) ( ) ( ) ( )
3+ -
2Al + 6 HCl 2 Al + 6 Cl +3 H
aq aq 2 g s s
,
(1) 6 L HCl
(aq)
is consumed for every 3L H
2(g)
produced
(2) 33.6 L H
2(g)
is produced regardless of temperature and pressure for every mole Al that reacts
(3) 67.2 L H
2(g)
at STP is produced for every mole Al that reacts
(4) 11.2 H
2(g)
at STP is produced for every mole HCl
(aq)
consumed

Sol. (4)

( ) ( ) ( ) ( ) ( )
3+ -
2Al + 6 HCl 2 Al + 6 Cl +3 H
aq aq 2 g s s

For each mole of HCl reacted, 0.5 mole of H
2
gas is formed at STP.
1 mole of an ideal gas occupies 22.4 lit at STP.
Volume of H
2
gas formed at STP per mole of HCl reacted is 22.4 0.5 litre = 11.2 lit



106. Regular use of which of the following fertilizer increases the acidity of soil?
(1) Potassium nitrate (2) Urea
(3) Superphosphate of lime (4) Ammonium sulphates

Sol. (4)
(NH
4
)
2
SO
4
is a salt of strong acid and weak base, on hydrolysis it produces H
+
ion.
This will increase the acidity of soil.
( )
+ 2-
NH SO 2 NH + SO
4 4 4 4
2

+
NH H O NH OH + H
4 2 4
+
+

107. Identify the correct statement regarding a spontaneous process
(1) For a spontaneous process in an isolated system, the change in entropy is positive
(2) Endothermic processes are never spontaneous
(3) Exothermic processes are always spontaneous
(4) Lowering of energy in the reaction process is the only criterion for spontaneity

Sol. (1)
For a spontaneous process in an isolated system, the change in entropy is positive.

108. Which of the following nuclear reactions will generate an isotope?
(1) neutron particle emission (2) positron emission
(3) -particle emission (4) -particle emission

Sol. (1)

1
0
A-1
A
Z
Z
X X
n
( Having difference in no of neutrons Isotopes)

A
A
Z - 1
Z
X Y

A - 4
A
Z - 2
Z
X Y

( Isodiaphers)

A
A
Z + 1
Z
X Y
( Isobars)

109. The equivalent conductances of two strong electrolytes at infinite dilution in H
2
O (where ions
move freely through a solution) at 25C are given below:
0 2
3
CH COONa = 91.0Scm /equiv
0 2
HCl = 426.2Scm /equiv
What additional information/quantity one needs to calculate
0
of an aqueous solution of acetic
acid?
(1)
0
of NaCl
(2)
0
of CH
3
COOK
(3) The limiting equivalent conductance of
( )
+ 0
H
H
+

(4)
0
of chloroacetic acid ( )
2
C/CH COOH



Sol. (1)
From Kohlrauschs law

3 3
0 0 0 0
CH COOH CH COONa HCl NaCl
= +

110. Which one of the following is the strongest base in aqueous solution?
(1) Trimethylamine (2) Aniline
(3) Dimethylamine (4) Methylamine

Sol. (3)
In aqueous solution basicity order of 1
o
, 2
o
and 3
o
amine with methyl groups is 2
o
>1
o
>3
o
.
In case of aniline lone pair of nitrogen is involved in resonance, so it is weaker base than aliphatic
amines.

111. The compound formed as a result of oxidation of ethyl benzene by KMnO
4
is
(1) benzophenone (2) acetophenone
(3) benzoic acid (4) benzyl alcohol

Sol. (3)
Any aliphatic carbon with hydrogen attached to it, in combination with benzene ring, will be oxidized to
benzoic acid by KMnO
4
/H
+
.

112. The IUPAC name of is

(1) 1, 1-diethyl-2,2-dimethylpentane (2) 4, 4-dimethyl-5, 5-diethylpentane
(3) 5, 5-diethyl-4, 4-diemthylpentane (4) 3-ethyl-4, 4-dimethylheptane

Sol. (4)

The correct answer 3-Ethyl-4, 4-dimethylheptane



113. Which of the following species exhibits the diamagnetic behaviour?
(1)
2
2
O

(2)
2
O
+

(3)
2
O (4) NO

Sol. (1)

2
2
O

:
2 * 2 2 * 2 2 2 2 * 2 * 2
1 1 , 2 2 , 2 , 2 2 , 2 2 s s s s p p p p p
z x y x y
= = ( Diamagnetic)
2
O
+
:
2 * 2 2 * 2 2 2 2 * 1 * 0
1 1 , 2 2 , 2 , 2 2 , 2 2 s s s s p p p p p
z x y x y
= = ( Paramagnetic)
2
O :
2 * 2 2 * 2 2 2 2 * 1 * 1
1 1 , 2 2 , 2 , 2 2 , 2 2 s s s s p p p p p
z x y x y
= = ( Paramagnetic)
NO :
2 * 2 2 * 2 2 2 2 * 1 * 0
1 1 , 2 2 , 2 , 2 2 , 2 2 s s s s p p p p p
z x y x y
= = ( Paramagnetic)

114. The stability of dihalides of Si, Ge, Sn and Pb increases steadily in the sequence
(1)
2 2 2 2
GeX SiX SnX PbX << << << (2)
2 2 2 2
SiX GeX PbX SnX << << <<
(3)
2 2 2 2
SiX GeX SnX PbX << << << (4)
2 2 2 2
PbX SnX GeX SiX << << <<

Sol. (3)
Due to inert pair effect ( reluctance of valence s
2
e
-
s to participate in bonding ) the stability of higher
oxidation decreases and that of lower oxidation state increases down the group.
So,the stability of +2 oxidation state increases down the group.

115. Identify the incorrect statement among the following
(1) Ozone reacts with SO
2
to give SO
3

(2) Silicon reacts with NaOH(aq) in the presence of air to give Na
2
SiO
3
and H
2
O
(3) Cl
2
reacts with excess of NH
3
to give N
2
and HCl
(4) Br
2
reacts with hot and strong NaOH solution to give NaBr, NaBrO
4
and H
2
O

Sol. (4)
Br
2
reacts with hot and conc or strong NaOH to give NaBr, NaBrO
3
and H
2
O.

2 3 2
3 6 5 3 Br NaOH NaBr NaBrO H O + + +

116. The charge/size ratio of a cation determines its polarizing power. Which one of the following
sequences represents the increasing order of the polarizinig power of the cationic species, K
+
,
Ca
2+
, Mg
2+
, Be
2+
?
(1)
2 2 2
, , , Mg Be K Ca
+ + + +
(2)
2 2 2
, , , Be K Ca Mg
+ + + +

(3)
2 2 2
, , , K Ca Mg Be
+ + + +
(4)
2 2 2
, , , Ca Mg Be K
+ + + +

Sol. (3)
Higher the charge/size ratio, more is the polarizing power.

2 2 2
, , , K Ca Mg Be
+ + + +



117. The density (in g mL
1
) of a 3.60 M sulphuric acid solution that is 29% H
2
SO
4
(Molar mass =
98 g mol
1
) by mass will be
(1) 1.64 (2) 1.88
(3) 1.22 (4) 1.45

Sol. (3)

( ) %strength of solution density or specific gravity of solution 10
M=
grammolecular weight of solute

( ) 29 density or specific gravity of solution 10
3.6=
98

Density = 1.215 = 1.22 g/ ml

118. The first and second dissociation constants of an acid H
2
A are 1.0 10
5
and 5.0 10
10

respectively. The overall dissociation constant of the acid will be
(1)
5
5.0 10
(2)
15
5.0 10
(3)
15
5.0 10
(4)
5
0.2 10

Sol. (3)

+
H A HA +H
2

+
HA H
K =
1
H A
2
(
(
(
(

(

(

(1)

2
HA H +A
+

2
H A
K =
2
HA
+ (
(
(
(

(

(

..(2)
For the reaction

2
H A 2H +A
2
+

[ ]
2
+ 2-
1 2
2
H A
K = = K K
H A
( (

5 10
1 10 5 10

=

5
5 10
=

119. A mixture of ethyl alcohol and propyl alcohol has a vapour pressure of 290 mm at 300 K. The
vapour pressure of propyl alcohol is 200 mm. If the mole fraction of ethyl alcohol is 0.6, its vapour
pressure (in mm) at the same temperature will be
(1) 350 (2) 300
(3) 700 (4) 360

Sol. (1)


According to Raoults law

0 0
total A A B B
P P P = +
0
290 200 0.4 0.6
B
P = +
0
290 80
350
0.6
B
P

= = mm Hg

120. In conversion of lime-stone to lime,
( ) ( ) ( )
3 2
CaCO s CaO s CO g +
the values of H and S are +179.1 kJ mol
1
and 160.2 J/K respectively at 298 K and 1 bar.
Assuming that H do not change with temperature, temperature above which conversion of
limestone to lime will be spontaneous is
(1) 1008 K (2) 1200
(3) 845 K (4) 1118 K

Sol. (4)
G H T S =
At equilibrium , 0 G =
H T S =

179.1 1000
160.2
T

=
= 1118 K
So, at temperature above this, the reaction will be spontaneous.

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MAHESH JANMANCHI AIEEE 2007

visit us at www.chemistrycrest.com Page 1

, where n is order of the reaction

is weak field ligand, no forcible pairing

is weak field ligand, no forcible pairing

is weak field ligand, no forcible pairing

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