Aieee 2009 Paper

MAHESH JANMANCHI AIEEE 2009
visit us at http://www.chemistrycrest.com/ Page 1



Maximum Marks: 144

Question paper format and Marking scheme:

1. This question paper has 30 questions.

2. Question No. 31 to 39 and 46 to 60 consist FOUR (4) marks each and Question No. 40 to 45
consist EIGHT (8) marks each for each correct response.

3. (one fourth) of total marks allotted to each question 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.



31. Knowing that the Chemistry of lanthanoids (Ln) is dominated by its +3 oxidation state, which of
the following statements in incorrect ?
(1) Because of the large size of the Ln (III) ions the bonding in its compounds is predominantly
ionic in character.
(2) The ionic sizes of Ln (III) decrease in general with increasing atomic number.
(3) Ln (III) compounds are generally colourless.
(4) Ln (III) hydroxides are mainly basic in character.

Sol. (3)

Ln
+3
compounds are mostly coloured in solid state aswellas in aqueous solutions.Colour appears due to
presence of unpaired f electrons which undergo f - f transitions.

32. A liquid was mixed with ethanol and a drop of concentrated H
2
SO
4
was added. A compound
with a fruity smell was formed. The liquid was :
(1) CH
3
OH (2) HCHO
(3) CH
3
COCH
3
(4) CH
3
COOH

Sol. (4)

As the compound formed has fruity smell, it must be an ester.

Esterification reaction :

( ) ( ) ( ) ( )
2 4
H SO
CH COOH + C H OH CH COOC H + H O
3 2 5 3 2 2 5 l l l l

33. Arrange the carbanions,
( ) ( )
CH C , CCl , CH CH , C H CH
3 3 3 6 5 2
3 2
,
in order of their decresing stability:
(1)
( ) ( )
C H CH > CCl > CH C > CH CH
6 5 2 3 3 3
3 2
(2)
( ) ( )
CH CH > CCl > C H CH > CH C
3 3 6 5 2 3
2 3

(3)
( ) ( )
CCl > C H CH > CH CH CH C
3 6 5 2 3 3
2 3
> (4)
( ) ( )
CH C CH CH C H CH CCl
3 3 6 5 2 3
3 2
> > >

Sol. (3)

Generally + I effecting groups decrease the stability of carbanion, while I effecting groups
increase their stability.
Benzyl carbanion is stabilized due to resonance.
2
0
carbanion is more stable than 3
o
and Cl is I effecting group.



34. The alkene that exhibits geometrical isomerism is :
(1) propene (2) 2-methyl propene
(3) 2-butene (4) 2- methyl -2- butane

Sol. (3)

35. In which of the following arrangements, the sequence is not strictly according to the property
written against it?
(1) CO
2
< SiO
2
< SnO
2
< PbO
2
: increasing oxidizing power
(2) HF < HCl < HBr < HI : increasing acid strength
(3) NH
3
< PH
3
< AsH
3
< SbH
3
: increasing basic strength
(4) B < C < O < N : increasing first ionization enthalpy.

Sol. (3)
Correct basic strength is NH
3
> PH
3
> AsH
3
> SbH
3
. This order is due to the fact that, on going down
the group availability of lone pair of electrons at the central atom decreases as the size of the atom
increases.

36. The major product obtained on interaction of phenol with sodium hydroxide and carbon dioxide
is :
(1) benzoic acid (2) salicylaldehyde
(3) salicylic acid (4) phthalic acid

Sol. (3)

The KolbeSchmidt reaction/Kolbe process is a carboxylation chemical reaction that proceeds by
heating sodium phenolate (the sodium salt of phenol) with carbon dioxide under pressure, then treating
the product with sulfuric acid. The final product is an aromatic hydroxy acid,which is also known
as salicylic acid

OH
ONa OH
OH
COOH
NaOH
CO
2
0
6atm,140 C
COONa
+
3
H O
Salicyclic Acid



37. Which of the following statements is incorrect regarding physissorptions?
(1) It occurs because of vanderwaals forces.
(2) More easily liquefiable gases are adsorbed readily.
(3) Under high pressure it results into multi molecular layer on adsorbent surface.
(4) Enthalpy of adsorption H
adsorption
| |
|
\
is low and positive.

Sol. (4)

Enthalpy of adsorption regarding physisorption is negative since it is an exothermic reaction.
For adsorption H, S and G all are -ve

38. Which of the following on heating with aqueous KOH, produces acetaldehyde ?
(1) CH
3
COCl (2) CH
3
CH
2
Cl
(3) CH
2
ClCH
2
Cl (4) CH
3
CHCl
2

Sol. (4)

Ethylidine chloride, a geminal halide on heating with aq KOH gives acetaldehyde

aq.KOH
CH CHCl CH CH
3 2 3
2
H O
CH CHO
3
OH
OH

39. In an atom, an electron is moving with a speed of 600 m/s with an accuracy of 0.005%. Certainity
with which the position of the electron can be located is (h = 6.6 10
34
kg m
2
s
1
, mass of electron,
-31
e =9.110 kg)
m

(1)
4
1.5210 m
(2)
3
5.1010 m

(3)
3
1.9210 m
(4)
3
3.8410 m

Sol. (3)

Heisenbergs uncertainity principle,

h
x. mv =
4

h
x =
4mv

0.005
v = 600 0.03
100
=

34
31
3
6.625 10
x =
4 3.14 9.1 10 0.03
1.92 10 m

=



40. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer.
The reaction is
( ) ( ) ( ) ( )
3 2 2 2
3
CH OH + O g CO g +2H O
2
l l
At 298K standard Gibbs energies of formation for ( ) ( )
3 2
CH OH , H O l l and ( )
2
CO g are
-166.2, -237.2 and -394.4 kJ mol
-1
respectively. If standard enthalpy of combustion of methanol
is -726kJ mol
1
, efficiency of the fuel cell will be
(1) 80% (2) 87%
(3) 90% (4) 97%

Sol. (4)
( ) ( ) ( ) ( )
-1
3 2 2 2
3
CH OH + O g CO g + 2 H O ; H 726kJ mol
2
l l =
Also ( )
0 -1
f 3
G CH OH 166.2kJ mol l =
( )
0 -1
f 2
G H O 237.2kJ mol l =
( )
0 -1
f 2
G CO 394.4kJ mol l =

0
f
G = G Q (products)
0
f
- G (reactants)
( ) [ 394.4 2 237.2 ] ( 166.2) = +

1
702.6kJ mol
=
% efficiency of fuel cell =
G
100
H

=
702.6
100
726

= 97%

41. Two liquids X and Y form an ideal solution. At 300K, vapour pressure of the solution containing 1
mol of X and 3 mol of Y is 550 mm Hg. At the same temperature, if 1 mol of Y is further added to
this solution, vapour pressure of the solution increases by 10 mm Hg. Vapour pressure (in mmHg)
of X and Y in their pure states will be respectively :
(1) 200 and 300 (2) 300 and 400
(3) 400 and 600 (4) 500 and 600

Sol. (3)

0 0
T X X Y Y
P = P X + P X

X
X = mol fraction of X

Y
X = mol fraction of Y

0 0
X Y
1 3
550 = P + P
1+3 1+3
| | | |
| |
\ \

0 0
X Y
P 3P
= +
4 4



( ) ( )
0 0
X Y
550 4 = P + 3P ............. 1
Further 1 mol of Y is added and total pressure increases by 10 mm Hg.
0 0
X Y
1 4
560= P + P
1+4 1+4
| | | |
| |
\ \

( ) ( )
0 0
X Y
560 5 = P + 4 P ............. 2
Solving (1) and (2)
We get,
0
X
P = 400mmHg
0
Y
P = 600mmHg

42. The half life period of a first order chemical reaction is 6.93 minutes. The time required for the
completion of 99% of the chemical reaction will be (log 2=0.301) :
(1) 230.3 minutes (2) 23.03 minutes
(3) 46.06 minutes (4) 460.6 minutes

Sol. (3)
For a first order reaction,

0.693 0.693
1
min
6.93
1/ 2
t

= = Q

Also
[ ]
[ ]
0
2.303
log
A
t
A
=

[ ]
0
A = initial concentration (amount)
[ ] A = final concentration (amount)

2.303 6.93 100
t log
0.6932 1
=
= 46.06 minutes

(Or)
Using simplified formula,
1 1
2 2
log( / )
log( / )
t a a x
t a a x

50
99
log(100 / 100 50)
log(100 / 100 99)
t
t

99
6.93 log 2
log100 t
=

t
99
= 46.06 minutes


43. Given
0 0
E = - 0.036V, E = - 0.439V
3+ 2+
Fe /Fe Fe /Fe
. The value of standard electrode potential
for the change,
( )
3 2
+ e Fe
( )
aq
Fe
aq
+ +
will be:
(1) -0.072 V (2) 0.385 V
(3) 0.770 V (4) -0.270

Sol. (3)

3 0
3 ; 0.036 Fe e Fe E V
+
+ = Q
( )
0 0
1 1
3 0.036 G nFE F = =
=+0.108 F
Similarly,
2 0
2 ; 0.439 Fe e Fe E V
+
+ =

0 0
2 2
G nFE =
( ) 2 0.439 F =
= +0.878 F

0
E for
( )
( )
3 2
aq
Fe e Fe aq
+ +
+ :

0 0
G nFE =

0 0 0
1 2
G G G = Q

0
0.108 0.878 G F F = Q

0
0.108 0.878 FE F F = + Q

0
0.878 0.108 E = Q
= 0.77 V

44. On the basis of the following thermochemical data :

( )
( )
0
0
aq
G H
+
=
( ) ( )
2
; 57.32 H O l H OH aq H kJ
+
+ =
( ) ( ) ( )
2 2 2
1
; 286.2
2
H g O g H O l H kJ + =
The value of enthalpy of formation of OH
-
ion at 25
0
C is:
(1) -22.88 kJ (2) -228.88 kJ
(3) +228.88 kJ (4) -343.52 kJ

Sol. (2)

Adding the two equations given,

( ) ( ) ( ) 2 2
1
; 57.32 ( 286.2)
2
g g aq
H O H OH H kJ
+
+ + = + (Here
0
f
H of
( )
0
aq
H
+
= )

0
f
H of OH
-
= - 228.88 kJ



45. Copper crystallizes in fcc with a unit cell length of 361 pm. What is the radius of copper atom?
(1) 108 pm (2) 127 pm
(3) 157 pm (4) 181 pm

Sol. (2)

For FCC lattice,
2 4 a r = (Particles touch each other along the face- diagonal)

2 2 361
4 4
a
r

= =
= 127 pm

46. Which of the following has an optical isomer?
(1) ( )
+
3
3
Co NH Cl (

(2) ( ) ( )
2+
3
2
Co en NH (

(3) ( ) ( )
3+
2
4
Co en H O (

(4) ( ) ( )
3+
3
2 2
Co en NH (

Sol. (4)

It is an octahedral complex of the type ( )
2
2
AA M X (

Where AA is bidentate ligand.

47. Solid Ba (NO
3
)
2
is gradually dissolved in a 1.0 10
4
M Na
2
CO
3
solution. At what concentration of
Ba
2+
will a precipitate begin to form ?(K
sp
for BaCO
3
= 5.1 10
-9
).
(1)
5
4.1 10 M
(2)
5
5.1 10 M

(3)
8
8.1 10 M
(4)
7
8.1 10 M

Sol. (2)



( )
3 3 3 3
2
2 Ba NO CaCO BaCO NaNO + +

[ ]
2 4
3 2 3
10 CO Na CO M

( = =

( )
2 2
3
9 2 4
5.1 10 10
2 5
5.1 10
K Ba CO
sp
Ba
Ba
+ ( (
=
( (

+ (
=
(

+ (
=
(

At this concentration , precipitation just starts.

48. Which one of the following reactions of Xenon compounds is not feasible?
(1) XeO +6 HF XeF +2 H O
3 6 2

(2)
2 3 2
3 XeF +6 H 2Xe+XeO 12 1.5
4
O HF O + +
(3)
2 2
2 XeF + 2 H 2Xe + 4HF + O
2
O
(4) ( )
7
XeF + RbF Rb XeF
6

Sol. (1)

This reaction is not feasible, as XeF
6
formed will further produce XeO
3
by hydrolysis.

6 2 3
XeF + 3 H XeO + 6HF O

49. Using MO theory predict which of the following species has the shortest bond length?
(1)
2
2
O
+
(2)
2
O
+

(3)
2
O
(4)
2
2
O

Sol. (1)
Bond length
1
bond order

Bond order =
no.of bondinge- no.of antibondinge
2

E.C of O
2
molecule is

( ) 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

= = =

( ) 2 2 2 2 2 0 0
2
1
2
2 2 2
1 2 2 2 2 2 2
14
z
x y x y s
p
s s s p p p p
O e
+
= = =

Bond order =
10 4
3
2
= .



( ) 2 2 2 2 2 1 0
2
1
2 2 2
1 2 2 2 2 2 2
15
z
x y x y s
p
s s s p p p p
O e
+
= = =

Bond order =
10 5
2.5
2
= .

( ) 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
= .

( ) 2 2 2 2 2 2 2
2
1
2
2 2 2
1 2 2 2 2 2 2
18
z
x y x y s
p
s s s p p p p
O e

= = =

Bond order =
10 8
1
2
= .
So, O
2
2+
has shortest bondlength.

50. In context with the transition elements, which of the following statements is incorrect?
(1) In addition to the normal oxidation states, the zero oxidation state is also shown by these
elements in complexes.
(2) In the highest oxidation states, the transition metal show basic character and form cationic
complexes.
(3) In the highest oxidation states of the first five transition elements (Sc to Mn), all the 4s and 3d
electrons are used for bonding.
(4) Once the d
5
configuration is exceeded, the tendency to involve all the 3d electrons in bonding
decreases.

Sol. (2)

In higher oxidation states transition elements, they no longer have tendency to give away electrons.So,
they show acidic nature and form anionic complexes.

51. Calculate the wavelength (in nanometer) associated with a proton moving at
3 1
1.0 10 ms

(Mass of proton =
27
1.67 10 kg
and h =
34
6.63 10 Js
):
(1) 0.032 nm (2) 0.40 nm
(3) 2.5 nm (4) 14.0 nm

Sol. (2)

De Broglies equation,

34
27 3
6.63 10
1.67 10 10
0.40 nm
h
mv
= =

=



52. A binary liquid solution is prepared by mixing n-heptane and ethanol. Which one of the following
statements is correct regarding the behaviour of the solution ?
(1) The solution formed is an ideal solution
(2) The solution is non-ideal, showing +ve deviation from Raoults law.
(3) The solution is non-ideal, showing ve deviation from Raoults law.
(4) n-heptane shows +ve deviation while ethanol shows ve deviation from Raoults law.

Sol. (2)
The solution is non-ideal, showing +ve deviation from Raoults law.The interactions between n
heptane and ethanol are weaker than that in pure components. Originally, ethanol molecules are held
together by strong H bonds. These forces become weaker on mixing n-Heptane.

53. The number of stereoisomers possible for a compound of the molecular formula
CH
3
CH = CHCH OH Me is :
(1) 3 (2) 2
(3) 4 (4) 6

Sol. (3)

Given compound has a C=C bond and one chiral carbon
About the double bond, two geometrical isomers are possible and the compound is having one chiral
carbon. So each geometrical isomer will have d and l isomers
Therefore total stereoisomers = 4.

54. The IUPAC name of neopentane is
(1) 2-methylbutane (2) 2, 2-dimethylpropane
(3) 2-methylpropane (4) 2,2-dimethylbutane

Sol. (2)
H C C CH
3 3

CH
3
CH
3
Neopentane is

IUPAC name is 2, 2-Dimethylpropane

55. The set representing the correct order of ionic radius is
(1)
2 2
Li Be Na Mg
+ + + +
> > > (2)
2 2
Na Li Mg Be
+ + + +
> > >
(3)
2 2
Li Na Mg Be
+ + + +
> > > (4)
2 2
Mg Be Li Na
+ + + +
> >

Sol. (2)
In a period, from left to right, ionic radii decrease due to increase in effective nuclear charge as the
additional electrons are added to the same principal energy level.
In a group, from top to bottom, ionic radii increase because the additional electrons are added to same
new principal energy level.
Li
+
and Mg
2+
are diagonally related.


56. The two functional groups present in a typical carbohydrate are:
(1) OH and COOH (2) CHO and COOH
(3) > C = O and OH (4) OH and CHO

Sol. (3)

Carbohydrates are polyhydroxy carbonyl compounds.So, the two functional groups present in
carbohydrates are aldehyde and ketone

57. The bond dissociation energy of B F in BF
3
is 646 kJ mol
1
whereas that of C-F in CF
4
is 515 kJ
mol
1
. The correct reason for higher B-F bond dissociation energy as compared to that of C- F is:

(1) smaller size of B-atom as compared to that of C- atom
(2) stronger bond between B and F in BF
3
as compared to that between C and F in CF
4

(3) significant p - p interaction between B and F in BF
3
whereas there is no possibility of such
interaction between C and F in CF
4
.
(4) lower degree of p - p interaction between B and F in BF
3
than that between C and F in CF
4
.

Sol. (3)

In BF
3
, B is sp2 hybridised and has vacant 2p orbital which overlaps laterally with a filled 2p
orbital of F forming strong p p bond
In CF
4
, C doesnot have vacant p orbitals to undergo p p bonding.
So, bond energy of B F bond is greater than that of C - F bond.

58. In Cannizzaro reaction given below

( )
( )
..
2
2 2
OH
PhCHO PhCH OH PhCO
+
the slowest step is:
(1) the attack of
( )
OH
at the carboxyl group

(2) the transfer of hydride to the carbonyl group
(3) the abstraction of proton from the carboxylic group
(4) the deprotonation of Ph CH
2
OH

Sol. (2)
Hydride transfer is the slowest step.



Mechenism of Cannizaro reaction :

Step 1: Addition of hydroxide ion to carbonyl group (Fast)
OH

C
6
H
5
C
H
O
C
6
H
5
C
H
O
OH
Hydroxy alkoxide ion

Step 2: Transfer of hydride ion to another aldehyde molecule. This is RATE DETERMINING STEP

Step 3: Transfer of proton from acid to phenoxide (Rearrangement)

59. Which of the following pairs represents linkage isomers?
(1) ( ) [ ]
3 4
4
Cu NH PtCl (

and ( ) [ ]
3 4
4
NH CuCl Pt (

(2) ( ) ( )
3
2 2
PPh NCS Pd (

and ( ) ( )
3
2 2
PPh SCN Pd (

(3) ( )
3 3 4
5
CO NH NO SO (

and ( )
3 4 3
5
CO NH SO NO (

(4) ( )
2 3 2
4
PtCl NH Br (

and ( )
2 3 2
4
PtBr NH Cl (

Sol. (2)

Linkage isomerism is exhibited by complexes containing ambidentate ligand
NCS
-
is ambidentate ligand and it can be linked through N (or) S

( ) ( )
3
2 2
PPh NCS Pd (

(linked through N) and
( ) ( )
3
2 2
PPh SCN Pd (

(linked through S)


60. Buna-N synthetic rubber is a copolymer of:
(1)
Cl
|
H C=CH C CH
2 2
and H C=CH CH-CH
2 2

(2) H C=CH CH CH
2 2
and H C -CH=CH
5 6 2

(3) H C=CH-CN
2
and H C=CH CH=CH
2 2

(4) H C=CH CN
2
and H C=CH C =CH
2 2
|
CH
3

Sol. (3)

Buna-N in a copolymer of
Buta- 1,3-diene and acrylonitrile

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at the carboxyl group

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