SUBJECT CODE BCKUL&T CODE

2012 \@) CHEMICAL SCIENCES TEST BOOKLET

Time :3.40 Hours

Maxintum Marks: 200

LNSTRUCTIONS
1.

2.

3.
-

4.

You have opted for English as medium of Question Paper. T h ~ Test s Booklet contauis one hundred and fort) five (20 PartLA't5O Pan 'B' t 7 5 Part 'C') Multiple Choice Questions (MCQs). You are required to answer a maximum 6f 15, 35 and 25 quest~clls from part ' P . ' 'B' and 'C' respectively. If more than requued nwnbet of quesbons are ansurered, only first 15,35 and 25'questions in Parts 'A' 'B' and 'C' respectively, will be taken up fol evaluation. Answer sheet has been provided separate!^. Before you start filling up your particulars. please ensure that the booklet contalns requist~enumber of pages and that these are not torn or mutdated If it is sc. you may request the Invigilator to change the booklet Likewise, check the answer sheet also. Sheets for rough work have been appended to the test booklet. -Wr~te your Roll No., Name, Your address and Serlal N d e r of this Test Bocklet an the Answer sheet in the space provided on the slde 1 of Answer sheet. Also put y~ signatures inthe space ~dentliied. Number, Y!u must &ken the approoriate circles with a pencil related to aaswer sheet. If isthe Subtect Code, Bookkt Gade and Centre G o 4 an t h e sole r e s ~ o n s i ~ of fi the candidate to metieuluusly_faH~w the inSfBtstLonyiven the Answer Sheet, failisg which. the computer shsfi nai be able to deClPher lthe
.+
--

GL-.$*;~> %* f
A

-.

5.
6.

7.
8.
9.

10.

.Ea2Kqu&tion5r-~arl 'A' and 'B' carries 2 marks and Part 'C' questiofib carry 4 marks each ~ ~ q c c t i v e lThere y . will be negativemrkmg @ 25% for each wrong answkf. Below each question in Part 'A', 'B' and 'C' four aitemarives or responses aTe glvel). Only one of these alternatives 1s the '.correctv option to the question. You have to find, for each question, the correct or the best answer. Cand~datesfound copyme or resortme to anv unfair means are l~able to be disaualified from this and future exarnmations. Candidate should not ~ v r ~ anything te anywhere except on answer sheet or sheets for rough work. After the test IS over. you MUST hand over the Test Booklet and answer sheet (OMR) to the mnvlgilator. Use of calculator 1s not pern~ltted.

l<oll No.. ......................

1 have verified all the information filled in by the. csndidatr. . .

..............................
Signature of the Invigilator

3 1 1 V ; ) & ? ? m ) ~ ~ #1 ym 'B' + 75 ym 'C' F) )

~ ~ ~ $ ~ ? 7 ym'AqF)+50 ? ~ ( i&x m=i (MCQ)& w d I amd ym 'A' TY i+ sllamTm15 a k y m ' B ' d 3 5 n m ) m y m ' C ' $ 8 2 5 n m ) & m H d I xf? f%d&i8~ns?)&mftpwrn&mwdw~ 3')A 15 ' , m f B ' 3)35 aw w~'C'825Jiin)$lm$lt) I i3a?wm3)RVTWl#l m * ~ * * m T ? m ~ ~ ~

~ m ~ t a ~ f t i r m r $ $ m 3 ~ i , 3 1 f 3 ? # d a w m ? i + m t - & ; I f f1 i ?s R ~ 6 i = i t ~

sr~+~*~&mr*m&dl*m+mw&m)m
d'1j3jy~~d3rfimm&3i?iy3lftftrAd3T'7.Tc1# I

m m & p 1 d&w3emwm*311;r=irqm3m;l~m$Tm gftirmrmrrmrmml&~*ff8/ md&mmm*#**rn~gftiJmr***&* 3 J ' i i r i e i J ~ @ m ) ~ ~ 1 ~ w tw ; m d h 4 7 & ~ 8 1 8 a ~ m g ? m I ) : R p w W m r @ d * w d * ; r m 3 ; ) ~ ~ 14Q3rrll:m#*3)~;TA:m3mm*deMm

~?mgftirmr&mrfte,&3liibSftd I
~'A'iwrym'B'd~~hm=i&2 wd~i'~ C, ' d ~ i & m 4 a + m r ~1mk5 #

9.11 x 1 0 3 ' K g 6.63 x 10-"J sec

1.6 x

1.38 1 0-2' J/K 3.0 x 1 On mlSec

10-19c

1.097 x 10' m-' 6.033 x 1 0" mole-'

USEFUL FUNDAMENTAL CONSTANTS

Mass of electron Planck's constant Charge of electron Boltzrnann constant Velocity of Light 1.6 x 1 0 - I ~ J
9.11
x x

10-"Kg
lo-''' J sec

6.63

I .6 x lo-" C

I .67 x I o-27 kg
6.67 r lo-' Nm'kg-? Rydberg constant Avogadro number 8.854 x lo-'' Fm-'
47t x 1 0-7Hm-'

Molar Gas constants

LIST OF THE ATOMIC WEIGHTS OF THE ELEMENTS

Element Actinium Aluminium Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Boron Bromine Cadmium Calcium Californium Carbon Cerium Cesium Chlorine Chromium Cobalt Copper Curium Dysprosium Einsteinium Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese Mendelevium Svmbol Ac Al Am Sb Ar As At Ba Bk Be Bi B Br Cd Ca Cf C Ce Cs CI Cr Co Cu Cm DY Es Er Eu Fm F Fr Gd Ga Ge Au Hf He Ho H In I Ir Fe Kr La Lr Pb Li Lu Mg Mn Md Atomic Number 89 13 95 51 18 33 85 56 97 4 83 5 35 48 20 98 6 58 55 17 24 27 29 96 66 99 68 63 100 9 87 64 31 32 79 72 2 67 1 49 53 77 26 36 57 103 82 3 71 12 25 101 Atomic Weight (227) 26.98 (243) 121.75 39.948 74.92 (210) 137.34 (249) 9.012 208.98 10.81 79.909 112.40 40.08 (251) l2.Ol1 140.12 132.91 35.453
52.00 63.54 (247) 162.50 (254) 167.26 151'96 (253) 19'00 (223) 157'25 69.72 72.59 196.97 178.49 4.003 164.93 1,0080 114.82 126.90 192.2 55.85 83.B0 138.91 (257) 207.19 6.939 174.97 24,312 54.94 (256)

Element Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium ~olonium potassium Praseodymium Promethium protactinium Radium Radon Rhenium Rhodium Rubidium Ruthenium samarium Scandium selenium silicon silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium
Tin Titanium

Symbol Hg Mo Nd Ne NP Ni Nb N No 0s 0 Pd P Pt Pu Po K Pr Pm Pa

Atomic Number 80 42 60 10 93 28 41 7 102 76 8 46 15 78 94 84 19 59

61 91 88 86 75 45 37 44 62 21 34 .14 47 1I 38 16 73 43 52 65 81 90 69 50 22 74 92 23 54 70 39 30 40

Atomic Weight 200.59 95.94 144.24 20.183 (237) 58.71 92.91 14.007 (253) 190.2 15.9994 106.4 30.974 195.09
(242) (210) 39.102 140.91 (147) (231 (226) (222) 186.23 102.91 85.47 101.1 150.35 44.96 78.96 28.09 107.870 22.9898 87.62 32.064 180.95 (99) 127.60 158.92 204.37 232.04 168.93 118.69 47.90 183.85 238.03 50,94 131.30 173.04 88.91 65.37 91.22

Ra
Rn Re Rh Rb Ru Sm Sc Se Si . Ag Na Sr S Ta Tc Te Tb TI Th Tm Sn Ti W U V Xe Yb
Y Zn Zr

Tungsten Uranium Vanadium Ytterbium Yttrium Zinc Zirconium

'Rased on mass of CI2 at 12.000... . The ratio of these weights of those on !he order chemical scale (in which oxygen of natural isotopic composition was assigned a mass of 16.0000 ...) is 1.000055. (Values in parentheses represent the most stable known isotopes.)

? 8~ l r l a r u~ -&: i L & T 1z.T - i *

Which of the following numbers is the largest?

234 ,243 ,324 3 4 ' ,42i ,432

2.

h . r ) ' m A B C D E F G H mm*a &3crfm814f)4FA,C m F $Emh-mehm& The cube ABCDEFGH in the figure has each edge equal to a. The area of the triangle with vertices at A, C and F is

3.

ww

UGCCSIR

$ 3 T e n ) & h f h d & f f ~ $

&U

UI

I-I?-Aw

d?

What is the number of distinct arrangements of the letters of the word UGCCSIR so that U and I cannot come together?

Suppose the sum of the seven positive numbers is 21. What is the minium possible value of the average of the sqaures of these numbers?

f39z)r7+ml7788?

Which of the following is true?

6.

XYm$Rwr5 ~

&

y--mT)'6 ~ ~ i m m ~ 5 d 8 1 & h j : ~ 8 : A circle of radius 5 units in the XY plane has its centre in the first quadrant, touches the x-axis and has a chord of length 6 units on the y-axis. The coordinates of its centre are

7.

6 4? T.T-Ldrnds3m)nTlLft m ~ a p j ? v t i $ - ? ~ m m r n 8 i % m m ) o 7 $ ~ ~ &

z m m h B m m 8 i m & = p m m m m m Grm?i%m8: ~
A wire of length 6m is used to make a tetrahedron of each edge lm, using only one strand of wire for each edge. The minimum number of times the wire has to be cut is

8.

M 8i7?10g2x ~ j ~ m~j ~xm i ? ?

If the sum of the next two terms of the series below is x, what is the value of logzx ?

2, -4, 8, -16, 32, -64, 128,.........

A conical vessel with semi-vertical angle 30' and height 10.5 cm has a thin lid. A sphere kept inside it touches the lid. The radius of the sphere in cm is

10.

~ ~ M F + ? * T % % M W ~ ipi7-3n%%wm*ammm81m ~ ? $

~ * 8 1 m 3 m F c ) m 8 1 W m ~ & 8 1 * & M a m ; f * &

~ z m i T ~ 8 1 & F m * ~ m # 8 ? Amar, Akbar and Anthony are three friends, one of whom is a doctor, another is an engineer and the third is a professor. Amar is not an engineer. Akbar is the shortest. The tallest person is a doctor. The engineer's height is the geometric mean of the heights of the other two. Then which of the following is true? 1. 2. 3. 4. Amar is a doctor and he is the tallest Akbar is a professor and he is the tallest Anthony is an engineer and he is shortest Anthony is a doctor and he is the tallest

11.

m 1 0 0 m 1 0 0 h 4 1 0 0 *!lKH78&7
TW +IT?

r n d 7 *

If 100 cats catch 100 mice in 100 minutes, then how long will it take for 7 cats to catch 7 mice?

12.

f39&i%mlmm8?
What does this digram demonstrate?

13.

913Bw&~Nm~&sff819T3&Nwm~81~mwm~
E?*f3rm7;Ji.)g

w*M&&m&=mM&&mh?

Suppose there are socks of N different colors in a box. If you take out one sock at a time, what is the maximum number of socks that you have to take out before a matching pair is found? Assume that N is an even number.

1. N

2. N + 1

3. N-I

4. N/2

At what time after 4 0' clock, the hour and the minute hands will lie opposite to each other?

15.

f-ts&~*-i~~+~~jj.)fj2m'p8? Which of the following curves just touches the x axis?

$ * ~ M V W ~ ?
If AB is paralled to CD and AO=20D, then the area of triangle OAB is bigger than the area of triangle OCD by a factor of

R ~ & w ~ m J : w ~ r n w J r w f u 3 w ~ m k 7 m r 8 1 m J ~m%wM&$*&mfoftv~d48~81&&&8:
A semi-circular arch of radius R has a vertical pole put on the ground together with one of its legs. An ant on the top of the arch finds the angular height of the tip of the pole to be 45". The height of the pole is

Suppose we make N identical smaller spheres from a big sphere. The total surface area of the smaller spheres is X times the total surface area of the big sphere, where Xis

19.

wpm241 301 331 391 511 ................ $7 aW? v%r m %? What is the next number in the sequence 24, 30, 33, 39, 5 I,------?

20.

w m z ) m w m ~ e m i r ) = l * d m; & r**M%/F
mW&~&31)mf*@Wd)sftW%1wmm&&;Td)*

&*8
Four lines are drawn on a plane with no two parallel and no three concurrent. Lines are drawn joining the points of intersection of the previous four lines. The number of new lines obtained this way is

21.

For an odd nucleon in 'g' nuclear orbital and parallel to I, spin and parity are:
1. 912 and (+)

2. 712 and (+)

3 . 912 and (-)

4 . 712 and (-)

22. I?gT-*s;mPbd*s:W, 1. PbC12 2. PbS04

3. Pb(Et)4

4. Pb(BF4)2

22. For the deposition of Pb by electroplating, the best suited compound among the following is

(A)

(B)

*mYiJ-i

J m l ? T ift

(C)

(D)

m ift 3mQF m m @7 rn

23. Appropriate reasons for the deviation form the Beer's law among the following are
(A) Monochromaticity of light (B) Association of analyte
1. A , B a n d D 2. B, C andD
(C) Very high concentration of analyte (D) Dissociation of analyte

3. A, C and D

4. A, B and C

24.

Which one of the following shows the highest solubility in hot concentrated aqueous NaOH ?

25. In the vibrational spectrum of COz, the number of fundamental vibrational modes common in both infrared and Raman are
1. three

2. two

3. one

4. zero

and the deep blue color of [CoC14]" are due to 26. The light pink color of [co(H~o)~]*"
1. MLCT transition in the first and d-d transition in the second 2. LMCT transitions in both 3. d-d transitions in both 4. d-d transition in the first and MLCT transition in the second

In [ M O ~ ( S ~ cluster ) ~ I ~ -the number of bridging s : 1. 2andB 2. 2 a n d 6

and coordination number of Mo respectively, are

3.

land8

4.

1 and6

H NMR spectrum of HD would show

1. a singlet 3 , a triplet with intensity ratio 1:2:1

2. a doublet 4. a triplet with intensity ratio 1:1:1

[Ru(PPh3)2(acac)2](acac =$i#%%?i-$i#Wk) VW%T iwm&d $7 ???iw 8:

1. 2 2. 3
3. 4

4. 5

The number of possible isomers of [R~(PPh;)~(acac)~] (acac = acetylacetonate) is:

1. 2

2. 3

3. 4

4. 5

~rn(II)W9~&+t:-\mftz Cr rur - o m & ~ m 8

1. 10

2. 6

3. 8

4. 4

The total number of Cu - 0 bonds present in the crystalline copper(I1) acetate monohydrate is
1. 10

2. 6

3. 8

4. 4

1. Li, Cl

2. K , F

3. Na, Cl

4. Li, F

The electronegativity difference is the hlghest for the pair 1. Li, CI

2. K,F

3 . Na, Cl

4. Li, F

Which ones among CO;~-,SO;, XeO; and N03- have planar structure?
1. CO;~-,so3and X ~ O ; 3. CO;'-, Xe0; and NO3-

2. SO;, Xe0; and NO34. CO;'-, SO3and NO3-

33. The substitution of q5- Cp group with nitric oxide is the easiest for

1. Cr, Re+

2. Mo, V

3. V, Re+

4. Cr, V

34. The molecule /OCH3 (C)5M=C\Ph

obeys 18 e rule. The two 'M' satisfying the condition are 1. Cr, ~ e '
2. Mo, V

3 . V. Rei

4. Cr, V

1. Fe, Mo, Cu, Zn

2. Fe, Cu, Co, Ru

3. Cu, Mn, Zn, Ag

4. Fe, Ru, Zn, Mg

35. The correct set of the biologically essential elements is,

1. Fe, Mo, Cu, Zn

2. Fe, Cu, Co, Ru

3. Cu, Mn, Zn, Ag

4. Fe, Ru, Zn, Mg

36.

[~u(eth~lenediamine)~]*+ i4Mk & c m f3?;z;T EPR dqp?8 cviV d ad?hv?@ i + m 8 : [Cu m;rrfjfm *(I) 312 m r N mr 1 ]

36. The number of lines exhibited by a lugh resolution EPR spectrum of the species,
[~u(eth~lenediamine)~+is [Nuclear spin (I) of Cu = 312 and that of N = 1 ]

& T) (II), ?l(II) 277 m (11) 8 m F ? g7l$$Ft akRh=l 4T rn ~ 3 i JiT +m 3 i + m ~ m 3 m 8 1 ~ ~ ~ P :

37. Degradation of penicillin G

gives penicillamine that can utilize nitrogen, oxygen or sulfur atoms as donors to bind with lead@), mercury(I1) or copper(I1). The structure of penicillamine is

38. The molecule that has an S6 symmetry element is

39. The electric dipole allowed transition in a rl' atomic system is

When a hydrogen atom is placed in an electric field along the y-axis, the orbital that mixes most with the ground state 1s orbital is

1. 4 10 J K-' mol-' 3. 41 J K-' mol"

For water, AH,, approximately

41 kJ mol-' . The molar entropy of vaporization at 1 atm pressure is

If A and B are non-commuting hermitian operators. all eigenvalues of the operator given by the commutator [A, B] are

1. complex

2. real

3. imaginary

4. zero

The value of the commutator [x ,p:] is given by

The correlation coefficient between two arbitrary variables x and y is zero, if

45.

A Carnot engme takes up 90 J of heat from the source kept at 300 K. The correct statement among the following is
1. 2. 3. 4.

it transfers 60 J of heat to the sink at 200 K it transfers 50 J of heat to the sink at 200 K it transfers 60 J of heat to the sink at 250 K it transfers 50 J of heat to the sink at 250 K

46.

El m E 2 d & $ M d ~ ~ ~ i . r g ~ u / ~ 8 # & d ~ ~ n 1 / (312) exp [-(El -E2)lk~T] 8 6'm rn81w k ~ ~ W W g2lg1 T 8

46.

The relative population in two states with energies E l and Ez satisfying Boltzman distribution is The relative degeneracy g2/gl is given by nllnz= (312) exp [-(El-E2)kBT].

47.

The Daniel1 cell is

1. P ( s ) (s) n 2 + ( a q ) u 2( a )

( 1t

I(

2. ptI (s)Jzn(s)lzn2+ (aq)l1-4gi (aq)/Ag(s)Ipt~~ (s)

3. Pt, ( s ) l ~ e ( s ) l ~(aq)llcu2' e~+ (~~)~CU(S (s) ) I R ~ 4. ~ Pt, (S)~H? (g)H2s04 (a9))1~ (~~) +/ C Y ( S(s) )IP~II

48.

If the concept of half-life is generalized to quarter-life of a first order chemical reaction, it will be equal to

49. Kohlrausch's law is applicable to a dilute solution of

1. potassium chloride in hexane 3. hydrochloric acid in water
2. acetic acid in water 4. benzoic acid in benzene

1. I 50.

2 . NO;

3. Nai

4. Ag'

A &lute silver nitrate solution is added to a slight excess of sodium iodide solution. A sol of AgI is formed whose surface adsorbs 1. I 2.

NO;

3. Na'

4. Ag'

51.

The absorption spectrum of O2 shows a vibrational structure that becomes continuum at 56875 ern-'. At the continuum, it dissociates into one ground state atom (O$ and one excited state atom (0,). The energy difference between 0, and 0, is 15125 cm-I. The dissociation energy (in cm") of ground state of O2 is

52. The angle between the two planes represented by the Miller indices (1 10) and (1 11) in a simple cubic lattice is

The correct representation of the variation of molar conductivity (y-axis) with surfactant concentration (x-axis) is [CMC = critical micelle concentration]

Ag20 MeOH hv

54.

The major product formed in the following reaction is

p h J + N 2

*
MeOH hv

55.

If the pK, value for p-methoxybenzoic acid is 4.46 and that of benzoic acid is 4.19, the o , , for methoxy group is

cadinene

56. The biosynthetic precursor of cadinene is

cadinene

1. shilumic acid

2. mevalonic acid

3. arachidonic acid

4. prephenic acid

57.

The correct order of acidity of the compounds A-C is

..qPh
pipe"dine*

COOEt

COOEt

1. E~-I?WRR
58.

2. El--

3. syn f3&mr;r

4. Elcb-Rzmm

The mechanism involved in the following conversion is

HN

qPh
COOEI

p~per~dine-

& o < o

8
+

z COOEt p h

COz

1. E2-elimination

2. El-elimination

3. syn elimination

4. El cb-elimination

Me02S

("1
N H

DMSO
K2C03

M e 0 2 S - @ d

59. The correct statement(s) A-D are given for the following reaction. The correct one(s) is (are)

Me02S

("1
N H

DMSO
K2C03

M e 0 2 Se N n w 0

(A) aromatic @so substitution reaction (B) aromatic electrophilic substitution 1. A and B only

(C) aromatic nucleophilic substitution (D) aromatic free radical substitution

2. A and C only

3. C and D only

4. C only

60. The following photochemical transformation proceeds through

'Ph

1. Norrish type I reaction 3. Barton reaction

2. Norrish type II reaction 4. Paterno-Buchi reaction

1. Phe-Ala-Gly

2. Phe-Gly-Ala

3. Ala-Gly-Phe

4. Gly-Ala-Phe

61. A tripeptide gives the following products on Edman degradation.

The tripeptide is

1. Phe-Ala-Gly

2. Phe-Gly-Ala

3. Ala-Gly-Phe

4. Gly-Ala-Phe

62.

293 K m &%a ~33 7T;I)F 'H NMR d z p ~ Ti: F & ? & I F dffjtm (C3H7NO),?&a7 & 6 7.8 (1 I % F 8' H, s), 2.8 (3 H, s) m 2.6 ( 3 H, s) T & 8'1 w #

2.

H 62. In the 'H NMR spectrum recorded at 293 K, an organic compound (C3H7NO), exhibited signals at
6 7.8 (1 H, s), 2.8 (3 H, s) and 2.6 (3 H, s). The compound is

me-^

OMe

3.

0 NH ~ M ~ , ~ " AMe&Me ~

63.

In the IR spectrum ofp-nitrophenyl acetate, the carbonyl absorption band appears at 1. 1670 crn-'

2. 1700 cm-'

3. 1730 cm-'

4. 1760cm-"

64.

The absolute configuration at the two chiral centres of (-)-camphor is

65. The major product formed in the following reaction is

CHO

66.

The first person to separate a racemic mixture into individual enantiomers is 1. J. H. van't Hoff

3. L. Pasteur

3. H. E. Fischer

4. F. Wohler

(A) QF-81 Zf' am'i% M 6 9.28 sn qwf&iFH 81 (B) 'H NMR (C) %l%i&TZf' m? mi?/

67. Consider the following statements for [18]-annulene

(A) it is aromatic

(B) the inner protons resonate at 6 9.28 in its 'H NMR spectrum (C) there are six protons in the shlelded zone.
The correct statements are
1. A , B , C 2. AandBonly
3 . B and C only

4. A and C only

, and between Br', Br2is 68. In the compound gven below, the relation between H ~HBj

1. H*, HBare enantiotropic; and Br', ~ r are ' diastereotopic 2. HA,HBare diastereotopic; and Br', B? are enantiotropic 3. HA,HBare diastereotopic; and ~ r ' Br2 , are homotopic 4. H ~H~ , are enantiotropic; and Br', ~r~ are homotopic

BOc,~/\ro~~
OTBDMS
1. HCl, EtOH, m $ d

Boc~~/\ro~
OTBDMS
2. Bu4NF 4. CF3COOH, EtOH, rt

3. K2C03, MeOH
69.

The most appropriate reagent to effect the following chemoselective conversion is

Bocx~/\ro~c OTBDMS
1. HC1, EtOH, reflux

Boc,~/y\~~
OTBDMS
2. Bu4NF 4. CF,COOH, EtOH, rt

3. K2C03,MeOH

70

Among the following, an example of a "Green Synthesis" is

1. synthesis of malachite green 2. Friedel-Craft's acylation of anisole with Ac20/anhydrous AlC13 3. Jones' oxidation of benzyl alcohol to benzoic acid 4. Diels-Alder reaction of furan and maleic acid in water.

71. The recoil energy of a Mossbauer nuclide of mass 139 amu is 2.5 Mev. The energy emitted by the
nucleus in keV is

72. am

f~c-[Mo(CO)~(m3rft?)~] mi'

+& C - 0 m dS +$ /?qr

d 8.

m: PF3 (A); PC13 (B); P(Cl)Ph2 (C); PMe3 @)

v(CO), cm": 2090 (i); 2040 (ii); 1977 (iii); 1945 (iv)

1 2. 3. 4.

( A (B-ii) (C-iii) ( A - (B-i) (C-iv) (A - v ) (B - i ) (C - ii) (C-i) (A-)(B-v)

(D-iv) (D-iii) (D - i) (D-ii)

72. Complexes of general formula, fac-[M~(CO)~(phosphine);] have the C-0 stretching bands as given
below. Phosphines: PF3 (A); PC13 (B); P(Cl)Ph2 (C); PMe3 (D) v(CO), cm-': 2090 (i); 2040 (ii); 1977 (iii); 1945 (iv) The correct combination of the phosphine and the streching frequency is, 1 2. 3. 4 ( ( ( ( A A A A (B-ii) (B-i) (B-i) (B-v) (C-iii) (C-iv) (C-i) (C-i) (D-iv) (D-iii) (D-i) (D-ii)

73. On subjecting 9.5 ml solution of pb2' of X M to polorographic measurements, Id was found to be 1 PA.
When 0.5 ml of 0.04 M ~ b " was added before the measurement, the Id w a s found to be 1.25 PA. The molarity X is

@I
A CH3COOH, faftff;r 4
(i)
LWZ WW

B CH3COOH, &So4 J? C HClO4, H2S04 r): D SbF5, HF r):

(ii)
(iii) (iv)
JFW HRT

rn

1. (A-i) (B-ii) (C-iii) ( W i v ) 3. (A-iii) (B-iv) (C-ii) (D-i)

2. ( A - (B-i)

4. (A-iv) (B-ii)

(C-iii) (ITiv) (C-iii) ( S i )

74.

Match each item from the list I (compound in solvent) with that from the list I1 (its behaviour) and select the correct combination using the codes given below List I CH3COOH in pyridme CH3COOH in HrSO,j HC104 in H2S04 SbFSin J 3 F List Il (i) strong acid (ii) weak acid (iii) strong base (iv) weak base

A B C D

75.

Structure of a carborane with formula, CZB4H8 is formally derived from

2. Nideborane 4. Conjuncto-borane

76. Boric acid is a weak acid in aqueous solution. But its acidity increases significantly in the presence
of ethylene glycol, because
1. ethylene glycol releases additional H ' 2. B(OH)4- is consumed in fonning a compound with ethylene glycol 3. ethylene glycol neutralizes H 'released by boric acid 4. Boric acid dissociates better in the mixed-solvent

77. Be2C3,M
1. 2

CaFz & ??WIT FL) i%?~&b 8 4 "C" & ~TWTiq-FJ;JV 8

2. 4

3. 6

4. 8

77. Coordination number of "C" in Be2C3whose structure is correlated with that of CaF2,is
1. 2 2. 4

3. 6

4. 8

78.

f39

~2

1. A ? C
78. For the molecule below,

2. B J C

3. A J D

4. B J D

consider the following statements about its room temperature spectral data.
A. 'H NMR has singlets at 5.48 and 3.18 ppm B. 'H NMR has multiplet at 5.48 and singlet at 3.18 ppm C. IR has CO stretchng bands at 1950 and 1860 cm-' D. IR has only one CO s t r e t c h g band at 1900 an-'

The correct pair of statements is,

1. A a n d C

2. B andC

3. A a n d D

4. B a n d D

In the cluster [CO~(CH)(CO)~] obeying 18e rule, the number of metal-metal bonds and the bridging ligands respectively, are

1. 3 a n d l CH

2. Oand3CO 3.

3 and 1 CO

4. 6 and 1 CH

1. Gd (III), Lu (I@ 3. Sm (Ill), Gd ( I D )

2. Eu(III), Lu (III) 4. Sm (III), Eu (III)

Consider the ions Eu(III), Gd(III), Sm(II1) and Lu(II1). The observed and calculated magnetic moment values are closest for the pair
2. Eu(III), Lu (ID) 4. Sm (111), Eu (111)

Silicates with continuous 3D frame work are

The correct spinel structure of C0304 is

83. In the solid state, the CUCI~'ion has two types of bonds. These are
1. three long and two short 3. one long and four short 2. two long and three short 4. four long and one short

1. Ala, Leu, His 3. Leu, Glu, Cys

84.

2. Glu, His, Cys 4. Ala, His, Glu

In metalloenzymes, the metal centers are covalently llnked through the side chains of the amino acid residues. The correct set of amino acids which are involved in the primary coordination spheres of metalloenzymes is
1. Ala, Leu, His 3. Leu, Glu, Cys 2. Glu, His, Cys 4. Ala, His, Glu

-1
A.

?i+T

1 1

[(R)-BINAPIRU~' [Rh(C0)2121Pd(PPh3)4

(i) (ii) (iii)

mm%i e
WPT% +*;i

B.
C.

WFV?FJT

85. Consider the catalyst in column I and reaction in column I1

Column I
A.
[(R)-BINAP]RU'-

Column I1 (i) Hydroformylation

B.
C.

[Rh(CO),12]Pd(PPh3)4

(ii) Asymmetric hydrogenation (iii) Asymmetric hydrogen transfer

D.

(iv) Heck coupling

The best match of a catalyst of Column I with the reaction under Column I1 is

86. A solution of 2.0 g of brass was analysed for Cu electrogravimetrically using Pt-gauze as
electrode. The weight of Pt-gauze changed from 14.5 g to 16.0 g. The percentage weight of Cu in brass is

87. The platinum complex of NH3 and C1- ligands is an anti-tumour agent. The correct isomeric
formula of the complex and its precursor are:

1. c i ~ - P t ( N H ~ ) ~ and cl~ P~c&'-

2. tran~-Pt(NH~)~Cl~ and F'tch2-

3. c i ~ - P t ( N H ~ ) ~ and cl~ P~(NH~)~~+

4. trans-Pt(NH3)2C12 and P~(NH~).,~'-

88. Fe(N03)3-9H20& & $ mNaC1, H3PO4,KSCN m N a F J : & bh F? L) d%?k

m V W ~ ? ? C ) & m ~ ~ ? t m ~ 8

88. Successive addition of NaC1, H3P04,KSCN and NaF to a solution of Fe(N03)3.9H20gives yellow,
colorless, red and again colorless solutions due to the respective formation of:

89. Which one of the following will NOT undergo oxidative addition by methyl iodide?

90. In hydrofomylation reaction using [Rh(PPh3)3(CO)(H)] as the catalyst, addition of excess PPh3
would 1. increase the rate of reaction 3. not influence the rate of reaction
2. decrease the rate of reaction 4. stop the reaction

91. Find out the number of lines in the 3 1 N~M R signal for

1. (i) > (ii) > (iii) > (iv) 3. (ii) > (iii) > (iv) > (i)

2. (i) > (iv) > (iii) > (ii) 4. (iii) > (i) > (iv) > (ii)

(ii) 92. The rate of exchange of OH2present in the coordination sphere by "OH2 of, (i) [cu(oH~)~]~'; [M~(oH~)~]"; (iii) P ~ ( O H ~ ) ~(iv) ]~+ W ; ~ ( O H ~ )follows ~ ] ~ ~ an , order
1. (i) > (ii) > (iii) > (iv) 3. (ii) > (iii) > (iv) > (i) 2. (1) > (iv) > (iii) > (ii) 4. (iii) > (i) > (iv) > (ii)

#&m-*8:
1. A m B 2. B M C

3. C M D

4. A M D

93. Based on the behaviour of the metalloenzymes, consider the following statements.
A. B. C. D.

In the enzymes, the zinc activates O2 to form peroxide species. In the enzymes, the zinc activates H 2 0 and provides a zinc bound hydroxide. In the oxidases, the iron activates O2 to break the bonding between the two oxygens. Zinc ion acts as a nucleophile and attacks at the peptide carbonyl.

The set of correct statements is,

1. A a n d B

2. B a n d C

3. C a n d D

4. A a n d D

94.

~.e~'-~oIphynns fail to exhibit reversible oxygen transport and cannot differentiate CO fi-om 02. However, the hemoglobin is fiee from both these pit falls. Among the following, ns p-oxodimer formation and the same is prevented in case of the A. ~ e ' + - ~ o r p h ~ r iundergo hemoglobin. B. Fe-CO bond strength is much low in case of hemoglobin when compared to the Fe2+porphy-rins.

C. While Fe-CO is linear, Fe-O2 is bent and is recognized by hemoglobin. D. The interlinked four monomeric units in the hemoglobin are responsible to overcome the pitfalls. The correct set of statements is, 1. A a n d B
2. A a n d C

3. C a n d D

4. B and D

(A)

SnC12 + C O ~ ( C O ) ~

(OC)4CoSnCo(C0)4

95. Reactions A and B are, termed as respectively

C1

(B) Me2SnC12 + 2NaRe(CO)5- ( O C ) 5 R e S n R e ( C O ) 5 Me

1. Insertion, Metathesis 3. Oxidative addition, Metathesis

2NaCl

2. Metathesis, Insertion 4. Oxidative addition, Insertion

96. A metal crystallizes in fcc structure with a unit cell side of 500 pm. If the density of the crystal is
1.33 glcc, the molar mass of the metal is close to

97. The activation energy for the bimolecular reaction A + BC -+AB + C is Eo in the gas phase. If the
reaction is camed out in a confined volume of h3,the activation energy is expected to 1. remain unchanged 3. decrease with decreasing h
2. increase with decreasing h 4. oscillate with decreasing h

98. In a many-electron atom, the total orbital angular momentum (L) and spin (S) are good quantum numbers instead of the individual electron orbital (I,, 12) and spin (s,, s2) angular momenta in the
presence of

1. inter-electron repulsion 3. hyperfine coupling

2. spin-orbit interaction 4. external magnetic field

99. The packing fraction of a simple cubic lattice is close to

34
100. The number of IR active vibrational modes of pyridine is

101. One of the excited states of Ti has the electronic configuration [ h ] 4 s 23d14~7'.The number of
microstates with zero total spin (S) for thls configuration is

102. For the reaction A? + 2A in a closed container, the relation between the degree of dissociation (a) and the equilibrium constant K, at a fixed temperature is given by

103 The fugacity of a gas depends on pressure and the compressibility factor

Z(=p T/ IRT)through the relation [ V is the molar volume]

For most gases at temperature T and up to moderate pressure, this equation shows that
1. f < p , i f T + O 2 . f < p , i f T +ca

104. The internal pressure (aU/dV), of a real gas is related to the compressibility factor Z = p V I R Tby
[ V is the molar volume]
1. (aulav), = RT(az/dv)T
2. ( 8 ~ 8 = ~ RTI( ) ~

VZ)

105. Suppose, the ground stationary state of a harmonic oscillator with force constant k is given by
~ /= o exp [-Ax2]

Then, A should depend on k as

1. Axk-'I2 2. A a k

3. A a k ' "

4 . AcckIt3

106. Combining two real wave functions

B = p l + i h , C = #1
1. 2. 3. 4.
- '

and h , the following functions are constructed: A zh, D = i(#l+ h ) . The correct statement will then be

= qh

+ h,

A and B represent the same state A and C represent the same state A and D represent the same state B and D represent the same state

107. Crystal A difficts fiom (1 11) and (200) planes but not fiom (I 10) plane, while the crystal B
diffracts fi-om (1 10) and (200) planes but not fiom the (1 11) plane. From the above, we may conclude that
1. A has fcc lattice while B has bcc lattice 2. A has bcc lattice while B has fcc lattice
3. A and B both have fcc lattice

4. A and B both have bcc lattice

108. The decomposition of NH3 on Mo surface follows Langrnuir-Hinshelwood mechanism. The

decomposition was carried out at low pressures. The initial pressure of NH3 was 10.' tom. The pressure of NH3 was reduced to lo4 ton in 10 minutes. The rate constant of decomposition of NH3 is 1. 9 . 9 l~~ ~ t o r r m i n - ' 3. 9.9 x 1 oJ torr min"

q am ~qy?&%~ p (P.D.I.) 8 :

37
109. A polymer sample has the following composition.

The polydispersity index (P.D.I.) of the polymer is

110. The equilibrium constant for .an electrochemical reaction 2 ~ e+ ~ snZ' ' +2 ~ e "+ Sn4'
is [EO (Fe3' /Fe2') = 0.75V,E0(Sn4' /Sn2') =O. 15V, (2.303RT / F ) = 0.06VI

111. A bacterial colony grows most commonly by cell division. The change in the population due to cell division in an actively growing colony is dN = /Z,N d l . The population of bacterial colony at
time t is [No= N(t = 0)]

112. The Arrhenius parameters for the thermal decomposition of NOC1, 2 NOCl(g) +2 N 0 (g) +C12(g), areA= 1013M-'s-', E,= 105 kJmol-' and ~ ~ = 2k~mol-I. . 5 The enthalpy (inkJ
mol-I) of the activated complex will be

113. The rotational partition function of Hz is

3. exp [ - ~ r ] l r

4.

KY

114. The potential in Debye-Hiickel theory is proportional to

3. exp [ - ~ r ] l r

4.

KY

115. The vibrational frequency and anharrnonicity constant of an alkali halide are 300 cm-' and 0.0025, respectively. The positions (in crn-') of its fundamental mode and first overtone are respectively

116. The adsorption of a gas is described by the Langmuir isotherm with the equilibrium constant K = 0.9 kPa-' at 25OC. The pressure (in kPa) at which the fractional surface coverage is 0.95, is

1 117. The energy of a harmonic oscillator in its ground state is -Am . According to the virial theorem, 2
the average kinetic (7) and potential ( V ) energies of the above are

118. The energy of a hydrogen atom in a state is

the state will be

(R,

- hcR, 25

= Rydberg constant). The degeneracy of

119. The trial wave function of a system is expanded as cy, =c,q, + c2p2 . The matrix elements of the
Hamiltonianare ( 9 1 1 ~ l p l ) = ~ ; I ~ / p ~ ) = 2 . 0 = ( 9 ~ and (V21~/V2),,)=3.0. The approximate ground-state energy of the system fiom the linear variational principle is

1 ~ 1 ~ )

120. One molecular orbital of a polar molecule AB has the form c , y A + cB%, where % and % are normalized atomic orbitals centred on A and B, respectively. The electron in this orbital is found on atom B with a probability of 90%. Neglecting the overlap between ly, and cy, , a possible set
of c, and CB is

1. 6 171 (C-4), 162 (COOH), 133 (C-3 & 5), 122 (C-1) and 2. 6 171 (COOH), 162 (C-4), 133 (C-2 & 6 ) , 122 (C-1) and 3. 6 171 (C-4), 162(COOH), 133 ( C - 2 & 6 ) , 122(C-1)and 4. 6 171 (COOH), 162 (C-4), 133 (C-3 & 5), 122 (C-1) and

116 (C-2 & 6)

1 16 (C-3 & 5) 116(C-3 & 5 ) 1 16 (C-2 & 6)

121. 4-Hydroxybenzoic acid exhibited signals at 6 171,162,133,122 and 116 ppm in its broadband
decoupled I3c W spectrum. The correct assignment of the signals is

1. 2. 3. 4.

6 171 (C-4), 162(COOH), 133(C-3&5), 122(C-1)and 6 171 (COOH), 162 (C-4), 133 (C-2 & 6), 122 (C-1) and 6 171 (C-4), 162 (COOH), 133 (C-2 & 6), 122 (C-1) and 6 171 (COOH), 162 (C-4), 133 (C-3 & 5), 122 (C-1) and

116(C-2&6) 116 (C-3 & 5) 116 (C-3 & 5) 116 (C-2 & 6)

IR:3400, 1680 c m ' ;

1

HNMR:67.8(1H,d,J=8Hz),7.0(1H,d,J=8Hz),6.5(1H,s),5.8(1H,s,D20
3.9 ( 3 H, s), 2.3 (3 H, s).

I % ' $ ,

2.

o -e

0 OMe

HO.

3.

M OMe

e OMe

122. An organic compound (C9H1003) exhibited the following spectral data: IR: 3400,1680 cm-';
I

HNMR:67.8(1H,d,J=8Hz),7.0(1H,d,J=8Hz),6.5(1H,s),5.8(1H,s,DzO

exchangeable), 3.9 (3 H, s), 2.3 (3 H, s). The compound is

OM^

OMe

123. The [a],, of a 90% opticallly pure 2-arylpropanoic acid solution is +135". On treatment with a base at RT for one hour, [ a ] changed ~ to +120. The optical purity is reduced to 40% after 3 hours. If so, the optical purity of the solution after 1 hour, and its [aID after 3 hours, respectively, would be
1. 80%; and 60"
3 . 80%; and 90"

2. 70%;and 40"

4. 70%; and 60"

124. In the following pericyclic reaction, the structure of the allene formed and its configuration are

(optically pure)

2.

Me,, Ph

iC

hv / CON

A I DIS

A I CON

125. In the following sequence of pericyclic reactions X and Y are

hv I DIS

"CCOOH
hv 1 CON

.
"-COOH

A I DIS

4.

Q Q H h

AI CON

126. The major product formed in the following reaction is

127. The following conversion involves

1. 2. 3. 4.

a 1,3-dipolar species as reactive intermediate, and a cycloaddition. a carbenium ion as reactive intermediate, and a cycloaddition. a 1,3-dipolar species as reactive intermediate, and an aza Wittig reaction. a carbanion as reactive intermediate, and an aza Cope rearrangement.

128. The following transformation involves

CHO
+

HO M e M~HN&

-, +

1. an iminium ion, [3,3]-sigmatropic shift and Mannich reaction. 2. a nitrenium ion, [3,3]-sigmatropic shift and Michael reaction.

3. an iminium ion, [I ,3]-sigmatropic shift and Mannich reaction. 4. a nitrenium ion, [1,3]-sigmatropic shift and Michael reaction.

COOH
X

boucooHOH
A

@LOOH
C

HO

129. With respect to the following biogenetic conversion of chorismic acid (A) to 4hydroxyphenylpyruvic acid (C), the correct statement is
COOH

boncooH OH A

-X
B Y

fj+:oo.
C

H0

1. X is Claisen rearrangement; Y is oxidative decarboxylation. 2. X is Fries rearrangement; Y is oxidative decarboxylation. 3. X is Fries rearrangement; Y is dehydration. 4. X is Claisen rearrangement; Y is dehydration.

i. P - M ii. iwHh iii. 9"m;f.T iv. p?@=r

a . M , - W b. ea%+$q &ffh

&

d. amfh g ~ d k !lZ%%

1. i-c; ii-d; iii-b; iv-a

3. i-c; ii-b; iii-d; iv-a

2. i-b; ii-a; iii-c; iv-d

4. i-a; ii-d; iii-b; iv-c

130. Match thk following

i. P-arnyrin ii. squalene iii. morphine iv. ephedrine a. alkaloid; secondary alcohol b. alkaloid, phenol c. triterpene, secondary alcohol d. acyclic triterpene, polyene

1. i-c; ii-d; iii-b; iv-a

3. i-c; ii-b; iii-d; iv-a

2. i-b; ii-a; iii-c; iv-d

4. i-a; ii-d; iii-b; iv-c

131. In the following reaction, the structure of B, and the mode of addition are

Re-Si facial

Si-Si facial

132. In the following reaction A and B are

i. a--d3$@f%ii. y%%~ 3$ mz%& iii. m ?? f+%B %---A

1. i-d; ii-a; iii-c; 3. i-b; ii-a; iii-c;

a. 6 7 b. NADH
C.

- m

d. f;i/?&icm<&
2. i-a; ii-b; iii-d; 4. i-d; ii-b; iii-c;

133. Match the following biochemical transformations with the coenzymes involved
i. a-ketoglutarate to glutamic acid ii. uridine to thymidine iii. pyruvic acid to acetyl coenzyme A a. tetrahydrofolate b. NADH c. thiamine pyrophosphate d. pyridoxamine
2. i-a; ii-b; iii-d; 4. i-d; ii-b; iii-c;

1. i-d; ii-a; iii-c; 3. i-b; ii-a; iii-c;

CHO

HO

COOH

CH20H

HO

OH

OH COOH

OH COOH

134. The structure of the major product B formed in the following reaction sequence is
CHO

COOH

COOH

H2, Pd, 250C

(e,e conformer)

1. 0.9 kcal/mol

2. 1.8 kcal/mol

3. 2.7 kcal/mol

4. 3.6 kcallmol

135. Given the energy of each gauche butane interaction is 0.9 kcaYmol, AG value of the following
reaction is

HZ,Pd, 2 5 0 ' ~

(e,e conformer)

COOEt

Hz, 10% PdIC

Me0

MeOH

Me0

0 4. NaH, ~;$-COOQ

Bi

Me0

&
COoEt COOEt HZ, 10% PdlC MeOH

136. In the following reaction, the reagent A and the major product B are

Me0

Me0

&

Y
4. NaH. ~ T - C O O E ~ B i
COOEt Me0

137. The major product formed in the following reaction sequence is

1. 80 g, CI',

2. 40g, CI',

3. 60 g, CHI^

4. 30 g,

CHI^

138. 12.0 g of acetophenone on reaction with 76.2 g of iodine in the presence of aq. NaOH gave solid A in 75% yield. Approximate amount of A obtained in the reaction and its structure are

139. Consider the following reaction mechanism.

The steps A, B and C, respectively, are

1. 2. 3. 4.

oxidative addition; transmetallation; reductive elimination. oxidative addition; carbopalladation; P-hydride elimination. carbopalladation; transmetallation; reductive elimination. metal halogen exchange; transmetallation; metal extrusion.

1. CHCI3, NaOH 2. H202, NaOH

4.

0 HOOC

140. The major product formed in the following reaction sequence is

1. CHCI3, NaOH 2. H202, NaOH

4.

-0 HOOC

141. The major product B formed in the following reaction sequence is

1.

M e'

2.

&

OMe

Me

142. The major product B formed in the following reaction sequence is

2.

&
Me

OMe

NNHPh

CH20H
A

143. The osazone A could be obtained from

NNHPh

CH20H
A

1. glucose and mannose. 3. gulose and fructose.

2. mannose and galactose. 4. galactose and fructose

1. Li, liq. NH 3, t~~~~ 2. H 3 0 + 3. K O H , MeOH

144. The major product formed in the following reaction is

1. Li, liq. NH3, 'BUOH

2. H30' 3. K O H , MeOH

cL
1. "BuLi,

o ~ e

HN-SiMe,

O C 0 O E t

2. H30+ 3. HZ, Raney Ni

NH2

COOEt
2.

,,\COOEt

145. In the following enantioselective reaction, the major product formed is

3. Hi, Raney Ni

SCIENCES
Roll Number

ANSWERSHEET BooldetCode Mdhml abjectcode Cen$sCods - -

m-w /
t -

4
F2

ANSWER COLUMNS

7XK 1 ANSWER

0 0 0 0
e O 0 0 0 0 0 0 e 0 e 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O O Q 0 0 0 0 . 0 0 0 0 0 . 0 0 0 . 0 0 . 0 0 0 . 0 0 0 0 0 0 0 0 0 ,O 0 0 0 0 0 . 0 0 0 0 0 . 0 0

0 0 0 0

3 Z1ANSWER

o o o e
e e 0 a . 0 e 0 0 0 0 0 0 0 0

0 0 . 0

o e o o o e o o
e 0 a 0 0 0 0 0 0 0 . 0 0 0 0 0 0 . . 0 0 0 0 .

.
0

o e o o
. 0 0 0 0 0 0 0 . . 0 0 0 . 0 0 0 . . 0 0 0 0

8
0 0 0

0 0 . 0 0 0 0 0 0 . 0 0 0 0 0 0 0 . 0 0 0 0 0 0 0 0 . 0 0 0 0 0 .

e o o o e 0 0 0--o o e o
0 0 0 0 a 0 0 0 e 0 0 0 . 0 0 0

e o o o
0 . 0 0 0 . 0 0

. o o o
0 0 0 0 a 0 0 0 . 0 0 0

o e o o
. o o o
0 0 0 0 0 0 0 . e 0 0 0 0 . 0 0 0 0 0 . 0 . 0 0 0 0 0 .

e o o o
0 0 m 0 0 0 0 . 0 . o 0 . 0 . . 0 0 0 o 0 0 0 0

e o o o o e o o e o o o
0 0 . 0 0 0 0 a 0 0 0 . 0 0 a 0 0 a 0 0
0 0

o e o o
a 0 0 0 O O C O 0 0 . 0

0 0

e o o o o e o o
9 0 0 0