BOOKLET CODE

Invigiiator'sSignature
ENTRANCE EXAMINATION -2010
M.Sc. Chemistry

TIME: 2 HOURS MAXIMUM MARKS: 100
HALL TICKET NUMBER:
BOOKLET CODE:
D
INSTRUCTIONS
t
L Write your HALL TICKET NUMBER and the BOOKLET CODE in the space provided above and also in the OMR ANSWER SHEET given to you.
2.
Make sure that pages numbered from 1 -21 are present (excluding pages assigned for rough work).

3.
There are 100 questions in this paper. All questions carry equal marks.

4.
There is negative marking. Each wrong answer carries -0.33 mark.

5.
Answers are to be marked on the OMR answer sheet following the instructions provided there upon.

6.
Hand over both the question paper booklet and OMR answer sheet at the end of the examination.

7.
In case of a tie, the marks obtained in the first 25 questions (PART will be used to determine the order of merit.




8. No additional sheets will be provided. Rough work can be done in the space provided at the end of the booklet.

9.
Calculators are allowed.

10.
Useful constants are provided on top of PART A in the question paper.


1
S-l f
Useful Constants:
Rydberg constant =lO97l7 Faraday constant =96500 Cmor1; Planckconstant 6.625 x lO-34
Js; Speed oflight =2.998 x lO8 Boltzmann constant 1.380 x lO-23 Gas constant 8.314 I
JK-Imor;Mass ofelectron=9.lO9x lO-31kg;Mass ofproton 1.672 x lO-27 kg; Charge of electron 1.6x lO-19C;1D =3.336 X 10-30 Cm; 1 bar lOS RTIF =0.059 V.

PART-A
1. The dipole moment ofBrF is 1.29 and its bond length is 178 pm. What is the percent ionic character ofthe Br-F bond?
3.9 33 8.5 15
2.
The major product obtained in the following transformation is
H20 2• NaOH


&CHO
CH2CI2, rt



&C0H &OH
I

h2
C02H


qCHO

0

OH
3. What is the charge required to make V(CO)6 an 18-electron species?

4. If 10gJO Y then 10gJO x
logy x z logz x=y
logz y logx y

2

S-II

5. The following reaction is an example of
CH3 CH2Br


6 6
fu, • Hfu

nucleophilic substitution electrophilic substitution


free radical substitution nucleophilic addition


6. Vhich among the foliowing is the strongest acid?

Sulfuric acid


Hydrobromic acid



A solution ofantimony pentafluoride in fluorosulfuric acid


Fluorosulfuric acid



7. The critical solution temperature of water-phenol mixture at constant pressure is

invariant bi-variant


uni-variant tri-variant



8. Which ofthe following functions changes its magnitude most rapidly at x

9. A capillary tube with an internal diameter of0.2 mm is dipped into water. The surface tension ofwater is 73.6 dynes/cm. The height to which water rises in the capillary is
10em 100em 15em 20cm
10. Ifthewavenumber oftheO-HstretchvibrationintheIRspectrum ofCH0His3300
3
the wave number ofthe Q-D stretch vibration ofCH30D is
3300 em-I 2391 em-I 2900 em-I 1439 em-I
3


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Booklet code C
11. The decreasing order ofC-e single bond length in the following compounds is

H H
H 3
2

4>1

4

12. An aqueous solution containing NRtCI, and MnCh is treated with NRtOH solution. The observation is that

both Fe3 and Mn2 will precipitate as hydroxides.


only Fe3 will precipitate as hydroxide.


only Mn2 will precipitate as hydroxide.


NRtCI will crystallize out from the solution.


13. The curve that passes through the intersection point ofthe two lines x 1 and is
Y x2 y2 x

14. A certain mass of gas occupies 5.50 liters at 300 K and 650 Torr. What will be its volume (liters) ifit is cooled t0283 K and its pressure is increased to 980 Torr?
3.44 2.44 1.54
6.47

15. The locus ofpoints equidistant from and in the plane is
4 Y 4 X 3.
16. Among the following, which one is a crystallographic point defect?

Edge dislocation Screw dislocation


Schottky defect Stacking fault


4





17. An alkaloid contains N and O. Quantitative analysis ofthis compound showed the weight ofC, HandN tobe,respectively, 70.8, 6.2, and4.1. Theempiricalformula ofthe alkaloid is

18. The number ofelements expected in the g-block ofthe periodic table is 14 18 22 26
19. Which equation represents the following figure?


y 4x2
3Y 3x2

20. Choose the correct statement regarding the relative stabilities of the enolates I and II.
6:o


I is less stable than II


II is less stable than I


I and II have same stability


No comparison of stability can be made



21. Which ofthe following compounds undergoes hydroiodination to give roughly equal quantities oftwo products?
I-butene 2-butene 2-methyl-2-butene 2-pentene
5

5-11

22.
The curve y x 2 X -30 has a minimum at

23.
Which ofthe following is not suitable as an antacid?



Sodium bicarbonate


Calcium carbonate


Sodium sulfate


Magnesium hydroxide


24. You are given ten one-rupee coins and asked to make a close packing on the desktop. The highest coordination number that can be achieved in two dimensions is

25. Among Rb02, AI02-, Sr02 and unpaired electron is present in
N02+ Rb02 sr02
6


oS-I I

PART-B


26. Which one among the given arrangements ofone molecule of HCI and one molecule of HBr will have the lowest energy?
H-CI


.I

I
II





.I
II
H-ct
0111 I000

27. The determinant ofthe matrix
IS
10 00 1000
1 3

28. Crystalsofanelementpossessabody-centeredcubic(bcc)latticestructure. Ifthecrystal undergoes a crystallographic transition to a face-centered cubic lattice. the unit cell length will change by a factor of
...J3/...J2 1/...J2 (C)...J3 ...J2/...J3
29. An amino acid containing sulfur is
proline cystine serine alanine
7


S-l





Booklet code C
30. The product obtained in the following transformation is




0-0


cr

31. Applicationofthecondition ofexactnessofthedifferential, dE TdS leads to

av as avaT
s v T v


T
apas ap aT
s p

32. Foramolecule MX3withzerodipolemoment andMbelonging tothesecondperiod,the orbitals on M involved in a-bonding are of the type
pure p sp hybrid Sp3 hybrid Sp2 hybrid
33. Onemoleofaperfectmonatomic gasat5.0mbarpressureandoccupyingavolume of1.66 m3undergoes isobaric expansion to avolume of16.6m3.The workdone by the gas and the temperature change (degree) during expansion are, respectively,

3.8, +1000 7.5, 900


-1000 900


8




Booklet code C
34. The major product obtained in the following transformation is
o
KOH

CH30H
o

0

0 0


0 0

35. The equation r where r is the distance ofthe point from the origin and is the angle ofrotation from the x axis represents a

wave monotonically decreasing function


circle spiral


36. Which ofthe following is responsible for global warming?
UV radiation Visible radiation a-Radiation Infrared radiation
37. In normal silicates, each silicon atom is surrounded by

five oxygen atoms in a trigonal bipyramidal geometry


four oxygen atoms in a square planar geometry


four oxygen atoms in tetrahedral geometry


six oxygen atoms in octahedral geometry


38. Consider the following equilibrium:
HA +H20 H30+
Given the following acids and their equilibrium constants at 25 which is the
strongest acid?


HF, Kc 3.5 x 10-4 HN02, Kc =4.5 x 10-4


HOBr, Kc =2.0 x 10-9 Kc 1.7 x 10-1


9


39. Given the relation 2fZ(x) the value off(x) for which is
0 1/2 1 3/2
40. In the aluminothermit process, the function ofaluminium is to act as
a flux a solder a reducing agent an oxidizing agent
41.
Which one among the following set ofarrangements is not feasible?

42.
The metal present in Gilman reagent is


n 1 ml ms
5 3 0
4 2
3 2
3 0 0

Au

43. Decomposition ofdinitrogen pentoxide is described by the chemical equation 2 N20 S N02 +02 The rate ofappearance ofN02is equal to 0.560 mol/min at a particular moment, what is the rateofappearanceofO2at that moment?

1.12 mol/min 0.280 mol/min


0.140 mol/min 2.24 mol/min



44. upon bombardment with a neutron gives 14C +X. In another reaction, upon bombardment with an a-particle gives 170 +Y. X and Y are

positron and neutron, respectively


proton and neutron, respectively


p-particle and proton, respectively


both protons


10


S-If

45. The Newman projection and stereochemical structures A and B are given below. The similarity between the two structures is that both


B


are enantiomers have the same chirality R


have the same chirality S are diastereomers


46. Potassium crystallizes in a body centered cubic lattice with a 5.20 A. The distance in A between the nearest neighbors, the number ofnearest neighbors and the number of K atoms in the unit cell are, respectively,

3.69, 8 and 2


4.50, 8 and 2


4.50, 6 and 4


3.69, 8 and 9



47. The integrating factor ofthe equation (2x2 +y2 +xydy is
x log x


48. In acid medium, one mole ofKMn04 will be equivalent to

2.0 moles of sulfite ion


2.5 moles ofsulfite ion


5.0 moles of sulfite ion


0.4 moles of sulfite ion


11


-ll

49. Which of the following olefins will give the racemic alcohol after hydroboration reaction using B2H6 in THF followed by oxidation with H20 21NaOH?


o o

o

o o
50. One mole ofan ideal gas expands isothermally from 1.0 liter to 10.0 liter at 300 K. The work done by the gas is
5757 J 5102 J 2501 J 1250 J
51. If =sin(ax2 then of is
Ox


cos ax 2 2ax cos ax2



2ax cos(ax2 cos(ax2


52. Choose the pair in which an effective acid base titration is not feasible.

weak acid, strong base


weak acid, weak base


strong acid, strong base


strong acid, weak base



53. The major product obtained in the following transformation is
CH3
H3C+CI
H3C

Vv
PJCI3



12



S-IJ
54. If a and Pare the roots ofthe equation, 3x2 2x I then J.... is equal to
a fJ

2/3 I i..,j8
55. Consider the three processes: sublimation of a solid, cooling a sample ofCots) from 60°C to 25 and combustion ofcharcoal to form CO2(g) and H20(g). The signs of LlH and LlS for the three processes and are

8H>0 and 8H<0 and 8H<0 and 88>0


8H>0 and 8H<0 and 8H<0 and £8<0


8H<0 and £H<O and £H>O and £8>0


8H<0 and 8H>0 and £H<O and £8>0


56. The net charge on the amino acid residue of aspartic acid at physiological pH is


57. The number of lone pair of electrons around xenon in XeF4 and XeO) are, respectively,
1,2 and 1
and 1
Iand2
(D)1,2and2


58. A reaction follows the general rate law, Rate Ifthe concentration ofB is increased by a factor of the rate of reaction will

increase by a factor of4 increase by a factor of2


decrease by a factor of 12 decrease by a factor of


13



59. The strongest nucleophile among the following is




0

N
N
6NMe2


I

NN

60. The sum ofthe infinite series J 2x 4x3 is(IXI< 1

lnx
I-x


61. If y lxi, dy is
dx

for x 0and -1forx<0 00 for-oo<x<oo for x 0 and +1forx
62. A supercritical fluid is a substance

that is in the liquid crystal state


with zero viscosity



existing at a temperature and pressure above its Tc and Pc


at its triple point



63. Among [Ni(CN)4f-and [NiCI4f-,

Ni(CO)4 and [NiC14]2-are planar while [Ni(CN)4f-is tetrahedral


[Ni(CN)4f-and [NiCI4f-are planar while Ni(CO)4 is tetrahedral


Ni(CO)4 and planar while [NiCI4]2-is tetrahedral


[Ni(CN)4f-is planar while Ni(CO)4 and [NiCI4f-are tetrahedral


14




64. The preferred conformation ofthe compound given below is
Me OMe




Et OMe

OMe
Me


OMe

Et

65. According to the following half reaction, the molarity corresponding to a OAN solution of Na2Cr207 is Cr20l-+ 6 14 2 7 H20
OAM O.IM 0.067M 204M
66. The complex number i)2 in polar form corresponds to
r e=7tl4 r
7tl2 e=1tI2
67. Consider a relatively weak acid with pKa 3.90. A base is added to this acid in order to
obtain a buffer with pH 4.12. Which ofthe following is closest to correct acid: base ratio in the buffer?
3.12 0.623 3.1 x 103 0.603
68. The line segments corresponding to 2x 8 and x +3y constitute the diametersofacircleofarea616 sq. units. Theequation ofthecircleis

196 196


=616 =616


15



69. A condensation (step-growth) polymer among the following is

Polystyrene


Polyvinyl chloride


Poly(ethylene terephthalate)


Polypropylene



70. Which one ofthe following salts will be attracted most strongly by a magnet?
MnS04 CoS04 ZnS04 CUS04
71. The proton NMR spectrum of3-pentanone shows

one triplet and one quartet


one singlet and one doublet


one quartet and one doublet


one singlet



72. The formal oxidation number ofcarbon in formaldehyde is


73. 72 g ofozone gas contained in a closed vessel at 1.0 atm pressure and 700 K temperature decomposes completely to oxygen gas. The pressure in the vessel changes to
0.67 atm 1.0 atm 1.5 atm 2.0 atm
74. Three vectors, and C are defined as: A =21 -4k B 2k and C 31-3}-k.Their vector triple product is given by
311 -Sk 31t
301-32}-Sk 311

75. Which one ofthe following ions does not interfere with the brown ring test for the nitrate ion?

r

16


76. Which one ofthe following is not aromatic?
HH




(AlO o
77. The carbonyl stretching band ofketones is usually observed around
1200 cm-i 1700 2200 cm-i 3600
78. The solubility product ofAgBr at 2SoC is [EOAgBr(S)IBr-=0.071 V and EOAg+/Ag =0.799 V at
25 DC]


4.58 x 10.13 6.28 x 10-7


9.12 x 10-2 4.58x 10-15



79. The mole percentages ofN2, O2, and Ar in dry air are, respectively, 78, 21 and 1. The average molecular weight ofair is
29.0 92.0

59.0 18.0
80. The characteristic violet color of biuret test is used to identify urea in a qualitative analysis. The structure ofbiuret is




2NJlJlNH2 JlJlJl
HN H2NNN NH2H

HH H 0'YNyO



HNI(NH J:Jr
H2N N NH2
H


81. The soldering material used by electricians is an alloy of
Cuand Pb Zn and Cu Sn and Pb Fe andZn
17 82. The order ofdecreasing rate ofsolvolysis with aqueous ethanol (fastest slowest) for the


following bromides is
Br CH3








Br BrH3C CH
3

(III)

I III I II> III II III II> III
83. A three digit number divisible by 3 is to be formed using the and without repetition. The total number of ways this can be done is
6 10 12 15
84. The correct order for increasing thermal stabilities among K2C03, MgC03, BeC03and CaC03 is

K2C03 MgC03< CaC03< BeC03


BeC03 MgC03< CaC03< K2C03


BeC03 MgC03< K2C03 CaC03


MgC03 CaC03 BeC03< K2C03


85. Ifa general point in the Cartesian coordinate system is represented by and if a line is drawn from to then what is the angle between this line and the z axis?
0° 45° 90° 180°
86. The most probable outer electronic configuration for several lanthanides is given below. La: 6s25d1, Ce: 6s24f5d1, Pr: 6s24f" Eu: 6s24f7, Gd: 6s24f7Sd1, Dy: 6s24flO, Er 6s24f2, Tm 6s24f3 Yb: 6s24f4, Lu: 6s24fl45d1 The elements that can have as a stable oxidation state are
Gd and Dy Pr and Er La and Lu Eu and Yb
87. A fused five-and six-membered carbocyclic ring is an integral part of
quinidine cholesterol a-pinene chlorophyll
18



88. Brominehasaheat ofvaporizationof30.91 kJmorlanditsboilingpointis59°C.Whatis the entropy ofvaporization of bromine?

-301 JmorlK-1 10.7 JmorlK-1


-93.1 JmorlK-1 93.1 JmorlK-1


89. Choose the statement that is incorrect.

Many SN2 reactions are slowest in protic (hydroxylic) solvents.


SN2 reactions are the slowest in polar aprotic (nonhydroxylic) solvents


SN1 reactions are subject to large solvent effects.


SN1 reactions are favored by polar protic (hydroxylic) solvents.


90. A workshop contains 10 white, 5 black and 6 red cars to be repaired. If4 cars are taken out at random, the probability that they consist oftwo white, one black and one red car is
0.0251 0.0521 0.0125 0.0512
91. If22gofN20Sreactswith 10gofwatertoproduce22g ofnitricacid,thepercentageyield ofnitric acid is
32 69 87 100
92. If the vertices ofa quadrilateral are A B C and D then ABCD is

a square a parallelogram


a rectarigle a trapezoid


93. Ifsum ofa series is defined as, Sn 1 2 4 8 16 2n, the value ofS20 is:
221 220 201 220 202
19




94. The product obtained in the following transfonnation is
dO,CH,
N
oJ.yPh
o













95. The boiling point of0.1 M glucose solution under 1 atm pressure is 100.02 0c. The boiling point of0.25 M· K2S04 solution under 1 atm pressure would be
100.5°C 100.6°C 101.4 °c 100.15°C
96. Two van der Waals gases and have the same values of but different values of The correct statement among the following is

Both are equally compressible


Gas with lower value is more compressible


Gas with higher value is more compressible


Neither A nor B is compressible.


97. Liquids A and B fonn an ideal solution at all mixing ratios. At 50°C, a solution containing 1mole ofA and2moles ofBhasatotalvaporpressure of110mmHg. When 1mole ofA is added to this solution, the total vapor pressure changed to 105 mm Hg. If 1 mole ofB is now added to this solution containing 2 moles ofA and 2 moles ofB, the total vapor pressure (in mm Hg) will be
106 108 110 112
20


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· Booklet code C
98. Which change in the system will drive the equilibrium to the left in the reaction below? N20s N02 N0
3
an increase in the amount ofN025 a decrease in the amount ofN03(C) an increase in pressure an increase in volume.

99. For the reaction 2HI H2 the values ofrate constants are 1.2 x 10-3 and 3.0 x 10.5
3 11

dm mor sec· at 700 K and 629 respectively. The activation energy ofthe reaction is
l

40.0 kcalmor 54.0 kcalmorl 45.5 kcalmorl 54.5 kcalmor'
100. The valence electronic configuration oftwo atoms with atomic numbers Zl and Z2 are
2
3s 3p3 and 4s24p5, respectively. The difference Z2 -Zl is

8
10
18
20
21