i?h+n:..1..?;-.1.?;.: 0 ............... 4 577 ym .......................... OMR m w-5 ?%T:.!.A.m.O ......

9.11 x 10-~11cg

6.63 x I@" J sec

1.6 x 10-'9c

1.38 x 10-= J/K

3.0 x lVm/Sec C

'eV

amu

G

RY

N A

E O

P o

6.023 x l O" mole-'

USEFUL FUNDAMENTAL CONSTANTS

- Mass of electron 9.1 1 x 10-J'Kg

~lanck's constant , 6 .63~10-~Jsec

Charge of electron 1.6 x 10-l9 C

Boltzmann constant

Velocity of Light

1.6 x 1 0 - ' 9 ~ I,v amu

Rydberg constant 1 .097~ 107m-I

6.023 x 100 mole-' Avogadro number

8.854 x 10-'2Fm4 3

47t x 1 0 - 7 ~ '

Molar Gas constants

LIST OF THE ATOMIC WEIGHTS OF THE ELEMENTS

Element Symbol Atomic Atomic Element Svmbol Atomic Atomic Number Weight . Number Weight

Actinium Ac - 89 (227) Mercury Hg 80 200.59 Alum~nium A l 13 26.98 Molybdenum M o 42 95.94 Americium A m 95 (243) Neodymium Nd 60 144.24 Antimony Sb 51 121.75 Neon Ne 10 20.183 Argon A r 18 39.948 Neptunium NP 93 Arsenic

(237) A s 33 74.92 Nickel Ni 28 58.71

Astatine At 85 (210) Niobium Nb 41 92.91 Barium Ba 56 137.34 Nitrogen N 7 14.007 Berkelium Bk 97 (249) Nobelium No 102 (253) Beryllium Be 4 9.012 Osmium 0 s 76 190.2 Bismuth Bi 83 208.98 Oxygen 0 8 15.9994 Boron B 5 10.81 Palladium Pd 46 106.4 Bromine B r 35 79.909 Phosphorus P 15 30.974 Cadmium Cd 48 112.40 , Platinum Pt 78 195.09 Calcium C a 20 40.08 Plutonium PU 94 Californium C f 98 (251) ~ o l o n i u m

(242) Po 84

Carbon C 6 12e011 potassium (210)

K 19 39.102 Cerium C e 58 140.12 Praseodymium p r 59 140.91 Cesium C s 55 132.91 Promethium

Pm 61 Chlorine CI 17 35.453 protactinium

(147) Pa 91

Chromium C r 24 (231) 52'00 Radium

Cobalt Ra 88

Co 27 (226)

58.93 Radon Rn 86 Copper Cu 29 (222)

Curium 63'54 Rhenium Re 75 186.23

C m 96 (247) Rhodium Rh 45 102.91 Dysprosium DY 66 162'50 Rubidium Rb 37 85.47 Einstein~um Es 99 Erbium

(254) Ruthenium 68

Ru - 4 4 101.1 Er 167.26 Samarium-

63 Sm

Europium 62 150.35

Eu Fermium F m 100

151.96 Scandium Sc 21 44.96

Fluorine F 9 (253) selenium S e 34 78.96

Fra-ncium Fr 87 19'00 silicon Si 14 28.09

Gadolinium Gd 64 (223) silver Ag 47 107.870

Gall~um Ga 31 69.72 Na .- 157.25 Sodium 11 22.9898

Germanium G e 32 72.59 Strontium S r 38 87.62

Gold A u 79 196.97 Sulfur S 7 6 32.064

Hafnium H f 72 178.49 Tantalum - Ta 73 180.95

Helium He 2 4.003 Technetium Tc 43 (99)

tjolmium Ho 67 164.93 Tellurium Te 52 127.60

Hydrogen H 1 1,0080 Terbium Tb 65 158.92

Indium I n 49 114.82 Thallium TI 81 204.37 Iodine I . 53 126.90 Thorium Th 90 232.04 Iridium Ir 77 ' 192.2 Thulium Tm 69 168.93 Iron Fa 26 55.85 Tin S n 50 118.69 Krypton Kr 36 83.80 Titanium Ti 22 47.90 Lanthanum La 57 138.91 Tungsten W 74 183.85 Lawrencium L r 103 (257) Uranium U - 92 238.03 Lead Pb 82 207.19 Vanadium V 23 9 , 9 4 Lithium L i 3 6.939 Xe 54 131.30 Lutetium L u 71 174.97 Ytterbium Yb 70 173.04 Magnesium M 9 12 24.312 Yttrium Y 39 88.91 Manganese M n 25 54.94 Zinc Z n 30 65.37 Mendelev~um M d 101 (256) Zirconium Zr 40 91.22

'Based on mass of Cqz at 12.000 ... . The ratio of these weights of those on the order chemicalqcale (in which Oxygen of natural isotopic composition was assigned a mass of 16.0000 ...) is 1.000050. (Values in parentheses represent the most stable known isotopes.)

f f 2.

'4; / PART 'A'

1. The following diagram shows 2 perpendiculply inter-grown prismatic crystals (twins) of identical shape and size. What is the 3.

volume of . the object shown (units are - ' arbitrary)?

Suppose in a box there are 20 red, 30 black, 40 blue and 50 white balk. What is the minimum number of balls to be dr~wn, witl~out replacement, so that you are certain about getting 4 red, 5 black,. 5 blus and ,7 white balls?

In the growing years of a child, the height increases as the square root of the age while the weight increases in direct proportion to tlze age. The ratio of the weight to the square of the height in this phase of growth

1. is constant. 2. reduces with age. 3. increases with age. 4. is constant only if the weight and height at

birth are both zero.

~ A $ ~ ~ ~ 3 k W $ 4 0 ,

80,70,50,60,90,301 B * -7 a 40, 80, 35, 70, 85, 45, 50, 75, 60 3hi d l

m*f% - (0) = (3mm 3iF - 3 k )

m W k (RD) =- * I 31, 1.w Am R D = T Bm RD

2 . w Am RD> w Bm RD

3 . Am RD< w Bm RD

4 . w q r A m D c w B m D

4. Students in group A obtained the following marks: 40, 80, 70, 50, 60, 90, 30. Students in group B obtained 40, 80, 35, 70, 85, 45, 50, 75,60 marks. Defme

dispersion @) = (maximum marks - minimum marks), and

dtspenton relative dispersion (RD) = .

Then, 1. RDofgroupA=RDofgroupB. 2. RD of group A > RD of group B. 3. RD of group A < RD of group B. 4. D of group A < D of group B.

5. In 450 g of pure coffee powder 50 g of chicory is added. A person buys 100 g of this mixture and adds 5 g of chicory to that. What would be the rounded-off percentage of chicory in this final mixture? 1. 10 2. 5 3. 14 4. 15 *

6. The time gap between the two instants; one before and one after 12.00 noon, when the angle between the hour hand and the minute hand is 66', is 1. 12min 2. 16 min 3. 18min 4. 24 min

7. Wl-4 t% x A y = ( X - Y ) ~ x o y = ( X + Y ) ~ x * y = ( x x y ) - l X - y = x x y

7. Suppose

x A y = (x-y)' x o y = (x+ y)Z x * y = (xxy l - I x . y = x x y

+, - and x haveitheir usual meanings. What is the value of ' 6

li

((197 o 31s) -i(197 A 315)) . (197 * 31517 1 1. llfl 2. 512 1 3. 2 4 4 . 4 .j

. . . .- %:I

8. ~ A X B = ~ ~ , B X C = ~ ; ~ , C X D = ~ ~ i

*Ax D i

l .m*~.ml j

8. I f A x B = 2 4 , B x C = 3 a 1 C x D = 4 8 then A x D 1. cannot be found. 1 2. is a perfect square. P 3. is a perfect cube. 4. is odd.

9. If all horses are donkeys, some donkeys are monkeys, and some monkeys are men, then which statement mGst be true? 1. All donkeys are men. 2. Some donkeys may be men. 3. Some horses are men. 4. All horses are also monkeys.

7 i2 10. A rectangular area of sides 9 and 6 units is to

be covered by square tiles of sides 1, 2, and 5 units. The minimum number of tiles needed for this is 1. ' 3 2. 11 3. 12 4. 15

ll. Suppose n is a positive integer. Then (n2 + n)(2n + 1)

1. may not be divisible by 2. 2. is always divisible by 2 but may not be

divisible by 3. 3. is always divisible by 3 but may not be

divisible by 6 . 4. is always divisible by 6.

12. There is a train of Length 500 m, in which a man is standing at the rear end. At the instant the rear end crosses a stationary observer on a platform, the man starts walking from the rear to the front and the front to the rear of the train at a constant speed of 3 kmhr. The speed of the train is 80 km/hr. The distance of the man from the observer at the end of 30 minutes is 1. 41.5 km. 2. 40.5 krn. 3. 40.0 km. 4. 41.Okm.

Three identical flat equilateral-triangular plates of side 5 cm each are placed together such that they form a trapezium. The length of the longer of the two parallel sides of this trapezium - is

14. An archer climbs to the top of a 10 m high building and aims at a bird atop a tree 17 m away. The line of sight from the archer to the bird makes an angle of 45' to the horizontal. What is the height of the tree? 1. 17m 2. 27m 3. 37m 4. 47m

J'i$ A B = A C = ~ . * 4hT m, Wi 3TiW

APOQ 3kT d h 3iX 8, * r n r n * * p . o r 8 1 r n ( r r m a ; r r * q m ~ * m ~ m ~ ~ r r A ~ o . 2 i ~ ~ ~ m 8 1

15. Consider ;right-angled triangle ABC where AB = AC = 3. A rectangle APOQ is drawn

- inside it, as shown, such that the height of the rectangle is twice its width. The rectangle is moved horizontally by a'distance 0.2 as shown schematically in the diagram (not to scale).

C n

Area of AABC What is the value of the ratio

Area of AOST ?

1 . 625 2. 400 3 . 225 4. 125

16. 80 gsrn paper is cut into sheets of 200 mm x 300 mm size and assembled in packets of 500 sheets. What will be the weight of a packet? (gsm = dm2) 1. 1.2kg 2. 2.4 kg 3. 3.6 kg 4. 4.8 kg

17. Find the missing letter A B C D F I L 0 K P U Z P W D ?

18. A merchant buys equal numbers of shirts and trousers and pays Rs. 38000. If the cost of 3 shirts is Rs. 800 and that of a trouser is Rs. 1000, then how many shirts were bought?

19. 3M W {1711 1 7 ~ ~ - * * , 17~~). , 21. The correct order of basicity for the following f h l ? l ~ ~ T b & ~ ~ 3 k 3 anions is

m 0 1. 60 2. 75 0 3. 100 4. 150

19. Consider the set of numbers {1711 172, ,.-, 17~~~). HOW many of these numbers 1. 60 end with the digit 3? 2. 75

&N02 / & NO2 0 NO2 3. 100 4. 150 I I I 111

1. 16 2. 96 3. 50 4. 80 -

20. Find the missing number in the triangle.

PART 'B'

22. The major product formed in the reaction of 2,s-hexanedione with P p 5 is

23. The absolute configuration of the two stereogenk (chiral) centres in the following malcc-"le-i-s - - ---

I

24. The correct statement about the following molecule is

A e c u l e is chiral and possesses a chiral plane -

2. Molecule is chimi and possesses a chjral / - -

axis-. . 3. Molecule is achiral as it possesses a plane

of symmetry 4. Moiecule is achiral as it possesses a centre -

of symmetry -

A. cis- KT4 fW $ trans--

* * I

B. tram- tl~~444 3fEW f?%T 8 cis--

* * I c . t r a m - m 37 m rn m 8 I

D. cis-- ZW srPdaiS;;r m 8 I

25. Consider the following statementsabout - cis- and tr&dccalins- A. c5-isomer is more stable than trdns-isomer B: tr--isomer is mire stable than ckisomgr C. trans-isomerundergoes ring-flip - D. cis-isomer undergoes ring-flip ,

The orrect statements among theabove are d a n d D 2. AandC

3. AandD 4. .BandC

26. I3is@I!$%X ~ M I ~ ~ & T T J ~ ) Y

~ ( I I ) * m,

In bis(dimethylglyoximato)nickel(IQ, the number of Ni-N , N& and intramolecul~

respectively, are 2. 2,2 and 2

3. 2 ,2and0 4. 4,O and 1

27. f%7 FhPh, (A) Ni(I1);

!+T$m- ' GRx, (B) AI(II1);

If an enzyme @s N2 in plants by evolving H2, the ? u ~ b e r of electrons and protons

i$edSith that, respectively, ? ? f and 6 3. 6 and 8

2 . 3 d 8 4. 8and6

29. The particles postulated to always accompany the positron emission among (A) neutrina,-'(B) anti-neutrino, (C) electron,

8 z r P P , % 8 30.

1. A,B?lW C 2. A?TUTB

3. A?iW C 47 B?TUT C - 27. hLong the following species, (A) NKII)

as dihe@lglyo@nate, (8) Al(IIQ. & ox';iate, (C) Ag(1) as chloride, those thaj 31. precipita'te with the urea hydrolysis . method are 1. A,BandC 2. AandB 3. AandC 4. BandC

are 1. A,BandC 2. AandB 3. A and C 4. BandC

Toxicity of cadmium and mercury in the body is being re?&i'Sed% proteins, mainly using theamino acid residue, 1. Glycine 2. Leucine 3. Lysine 4. Cysteine

31. NiBr2 reacts with (EtXphhP a at ., -78 - OC in CS2 tii--@ie ki compound; 'A', which upon standing at room temperature turn green to give compound, 'B', of the same formula. The meamred magnetic moments of ' A ' ' '5 are 0.0 and 3.2 BM, re~~ectively.~The- - geometrii of ' ~ ' z d -e, c~

1. -Square $war and Tetrahedral -

2. ~ d e d r a l and Square planar 3. Square planar and Octahedral 4. Tetrahedral and Octahedral

U.+&&netic, paramagnetic and d i a m a p t i c 2. paramagnetic,diamagnetic ma ~armlagnetic 3. diank-gnetic, paramagnetic and diamagnetic 4. p&magnetic, diamagnetic and diamagnetic

- - -

35. -m*f i -e* dvmrnif

. 1. Na2Cr04 ?iW F%03

2. Na2Cr207 ?iW %%03

3. Crz(C03), FIT Fe(OH)3

I .SC12 1,- .2. SClz am I,' 35. Chromite ore on h i o n with sodium

3.SC12 iV4T ClF; 4. 1,'SX ClF; carbonate gives 1. Na2CrC?4 ~ i i d Fe203

32. The correct non-cinear and iso-structural pair is 2. Na2Cr207 and Fez03 ,;/%I2 and b* I. SClz and'I3- 4 - 3. Cr2(C03)3 and Fe(OH)3

-\ 3. .?(&and CjFf : " 4. J; and .!!IF; 4. Na2Cr04 and Fe~(C03)3 t3 5' . I .,A f s 7 y ., I ! i!.

'33. -mpFT 36. 221 - 298 K FWT ?7 * [(r15-c5H5)

33. Ozone present in upper atmosphere protects a+--__ .--- -

people on the earth 1. due to its diamagnetic nature, 2. due to its blue colour 3. due to absorption of radiation of

wavelength at 255 nm ' 4. by destroying chlorofluoro carbons .

36. The ligand(s) that is (are) fluxional in [(l15-c5H5) -+'

( q 1 , ; ~ s ~ 5 ) ~ e ( ~ ~ ) 2 ] in the temperature range I 221 - 298 K, is'iare)

1. q 5 - ~ 5 ~ 3 G4--Trc5~5

3. q 5 - ~ 5 ~ 5 and CO 4. ' q ' - ~ 5 ~ 5 and CO . /-\-.

1

2. NH33W 1,10-- 34. 9R L Vii ?zmf w* mz if, -m 3. H20 m 1,lO- lwiah%a, mfbf [AgL412', [AgLa]" ?iW [ A ~ L ~ I ~ ' 9T?J: i?

-- 4. HzO ? P I T NH3

-1 !JkFGlQ 2. qy-&~, m 33qg6al6cl 37. [COL~]~' is red in colour whereas [coL'~]'~ is

3. -, 32YcslCh?~ FT green. L and L' respectively corresponds to, 1. NH3 and H20

4 . ~ , m y a 7 4 h 3 W - 2. NH3 and 1,lO-phenanthroline 3. H20 and 1,lO-phenanthroline

34. If L is a neugal monodentate ligand, the species, f4ii 4. H20 and NH3

[ A ~ L ~ ] ~ ' , [ A ~ L ~ ] ~ ' and [ A ~ L ~ ] ~ ' .respectively, are + , 4 ' ;

V : +--b \ H - \

1 p( . -. , i

4, < \ I cd 1

' 4 4 . I d ,./

n ,(Y Ca .., f,- -- --' ' 1 !.r

b 'r

' 38. [N~~(co)~]'-* 18 $- f h W Ni * $ic - V

aic 3 m m f V J T ~ ~ ~ - ~ ~ * ic *i!! I ic 1. Ni(-II), 1 2 N i , 2 =

3. Ni(-I), 1 3-ll3XT 4. N i i , 3 3TiTZT L e

li 38. The oxidation state af-Ni and the number of r metal - metal bonds in ~ i $ ~ ~ 1 2 - that are

f. consistent with the 18 electron rule are J 2. Ni(lV), 2 bonds

$-I), 1 bond 4. N i o , 3 bonds I(

5) 1 t ...

39. Structures pf SbPh5 and P P ~ ~ respectively are 1. trigonal bipyramidal, squarqpyramidal

. - 3 8 2. square pyramidal, trigonal gipyramidal 6 3. trigonal bipyramidal, trigonal bipyrarnidal i l ! 4. square pyramidal, square pyramidal

The typical electronic configurations of the transition metal centrid , . far oxidy&vzaddit,ion ar< 1. do and d8 2. d6 and d8 3. d8 and dl0 4. d and dl0

B- -- /* - --',& 41. Gelatin added during the polarographic measure

ment carried out using dropping mercury electrode 1. reduces streaming motion of Hg drop 2. decreases viscosity of the solution 3. eliminates migrating current 4. prevents oxidation of Hg

I COOH ( P K ~ = 3-91

2. H 3 N x COO 0

COO 0

H2NvCO0

0 COO

,,&,l;;c*. '

b: j The pK, values of i e followir~g sali of , :~ I-. .. . . L. .,.. aspartic acid are indicated below. , The

predomi-nant - species that wauld exist at pH = -- -- 5 is *- I--* , I .

1 @ \ !. (pK, = 9.9) H3N COOH (pK, = 2.0) .

Y

0 d

HINxco: I

\ fi/t ' L-

COO

H - " ;,,l cc

COO 0

H j N r C O r '3 - ' :- ' ' .

COO . ;./ :

a .

44. The pair o f solvents in which PC15 does NOT . - ionize, is 1 . CH3CN, CH3N02 2. CHFN, CC4 3. GH6, CC4 4. CH3CN, C,jH6

48. trans-lm-3-1' * DMF A 9. c h m s ; r ~ W T l m f % ? p q 5 % # t f h x M ~ & ~ A m W 1. C, 2. (3" m g r s s m 8 3. & \A. D3d r

50. The symmetry point group of propyne is 1. C3 2. C 3 v

3. Q 4. DM 2. 1.

51. ~~r i * * *~+ - * f3 t !

"b., ['I' vs TlWT W *, [A]o Z~(K) [Al,TIKQ t = O m t * & 5;

3. I 4. '1 1. vmmIi=mmam4*** -

48. The major product formed in the reaction of 3wfthiT5 I tram- 1 -bromo-3-methylcyclobutane with 2. ~ , - z T i T * 3 V l R $ t ? i d l d sodium i6dde in DMG is mtrJrir; I

me^ "'Q 51. For a first .order reaction A+ prod@, the

plot of in (p) v , time, where [Ale and [A], A10

/ I 4. '1 5

refer to concentrations at time t = 0 and t is

traight line _with a mi,t.iy~Lgie. 49. si if it^^ * passlng through origin '

2. a straight line with a negative slope

l . m m ; R r ~ ~ * * passing through origin

3. an exponential curve asymptotic to the. mmif 1 time-axis

2 . i ? m T ~ ; R r 3 ? T f % ~ k * 4. a curve asymptotic to the in (-) [At axis mm3 I 7- . . 1.410 -

2. *m 49.. When Si is doped with a Group 1_V element,

1 . donor levels are created close to the 3 . ~ ~ ~ ,

valence band - a o n o r levels are created close to the

conduction band radical chain polymerizatioe, the quantity. 3. acceptor levels are created close to the iven by 'the rate, -6f monomer depletion,

valence band by the .rate of propagating radidal 4. acceptor levels are created close to the formation', is called

conduction band \.

., ..* 5

L\ i *:. 6" ( .,, . c-t-. :: ... .

, - 1 ; /.*-..'-

f 0 \. L' 3Y'. &,,. *.- ,.. f i.

pi -- - @ j !, , ! .. ,.> C<, .i *,.: -. ,!.., -- - t I. " 'C-*.. % ! ', p

\. '.. . (?

Minet ic chain length 2. propagation efficiency 3. propagation rate constant 4. polymerization time

53. Number of rotati0~1 syrnrnethy axes for triclinic crystal system is 1. 4 2. 3 3. 1 4. 0

54. Generally, hydrophobic colloids me flocculated efficiently by ions of opposite type and high charge number. This is consistent with the 1. pepization principle 2. Krafft theory 3. Hardy-Schulze rule 4. Langrnuir adsorption mechanism

tine the following first order consecutive @/yan reactions. The rate cons@t (in s-' units) for each step is given above the amow mark.

5 5 . f a = s @ m m m a ?mwm - w m m i =K%

I ( r 1 a & + m i

105 lo8 (A) P - Q 3 p

' /

Steady-state approximation can be applied to . , 1.Aonly ' -3i c o d y 3. B and k only 4. A and D only

m m w r n g 105 108

56. The figure below represents the path followed by a gas daeriog expansion from A -+ B. The work done is (L am.)

(A) P+ Q -4 R * lo5 10'

(B) P + Q + a 10' 107

(C) P-+ Q + R , lo2 10"

@) P - + Q + R Y L

I II iii

i: 1 : ij;di 11 7.2; ~ f i : i)2 2. I : 9.2; 11 : 7.2; III : 5.4 3. I : 9.2; I1 : 5.4; IU : 7.2

*-. 4. I : 7'2; II i 9:E 1tf : 3;4 57. An aqueous solution o f an optically pure

compound of concentration 100 mg in f mt T ~ c && iiiiich of the 'H Nn4R chemical

of water and measured in a?@Z&-'iltk 6''- shifts (6) of the following species/compounds is

5 cm length was found to be -3". The specific rotation is 1. -30' 3. -6" 4. +6" I fl'& ii!

1. I : 5.4; I1 : 7.2; 111 : 9.2

58. VT Fhb $;r SliaFeTT (UPIT P ) W +. I : 9.2; I1 : 7.;; Ifl : 5.4

3; ! ! 9.2; fi : 3.4; IU : 7.2 33TFWfif. I ~ , p ' i ~ ~ p M f t ; m 4. I : 7.2; I1 : 9.2; IU : 5.4

1. Ta=Tp,pa#~p, k = C p 61. 2. Ta#Tp,~a=Pj3, P ~ = C L P 3. Ta=TptPa=pp,c~a=~lp 8 4. Tct = Tp, pa = pp, pa # CLP . - - ,AEt i . h3e*a+ t

58. Two phases (a and P) of a species are in ii. ~36' equilibrium. The correct relations observed among the variables, T, p and p are

1. 1. T a = T P , p a # p p , k = c l p 2. T c t # T p t p a = p P t b = * - + f%c-Cl~t%

3. ' I ' ,=Tp,pa=pptk=clp 4- Ta=Tp,pa= pP, k # ~ p

30 2.

59. The number of configurations in the most probable state, according to Boltzmann formul~ is

-

. - r ; !. &. t.' ' -

/*n ,. : . , . . . . . ~ ' < g .. , -.. . '-!

6 7 major products f o n d in the foll&q) " reaction are

X " - i. Ph&Na+

1 Y

ii. H30+ ---- .-

c.Y*~&?~~x**

4. B r n C

63. Consider the statkrnents about d?e following k structures X and Y.

CN

I A. X and Y are pso-yqce structyres .

B. X and Y are tautomers C. Y is more basic than X D. X is more basic than Y

- v , --- - I The correct itatement(s) among the above '

62. Z % T f - & Z T m % R V I % d ? ? & i f i is(are) 1. AandC 2. C

hdif&63Tf%@m?hw-%% 3. Band D 4. BandC

4. (2542)-2,4- &T7l3i$-$7 Y

62. In a.,Diels-Alder reaction, the most reactive - p$ IHeat pH -

$ene amongst the following is I

I ; 1.y + ii. (E~OW 1. (44-1,4-hexadiene Pk 2. (42)-1,4-hexadiene '

3. (2E, 40-2,4-hexadiene . - 1 ; [1,3]--

4 4 2 ) - 2 , 4 - h e x a d i e n e 2. [3,3] f3-R 3 . [l,sjEm$m Rw

. . 63. - $ ~ T & x W ~ Y % ~ W '4. [2,3] f&W@%F f%E !, 'i m m w f a m - m

. clic reaction involved in one of the

r ;L; : 4 : , i

2<,"J> q ?/' " P' I \

. . , . .I .I i . .

.. .5-**> " ' .. y:' -:. .,

I

i 2.

1. 3 2. 4 4. 6

1. [1,3] sigmatropic shift 2. [3,3] sigmatropic shift

2. 3P 4. 'D

65. Q?hd%T C ~ S I T * ~ ' ~ ~ F F

t i o o c " y y O H

65. Atowastatin (structure given below) is a

I . cholesterol loyering drug , 2. blood sugar lowering drug

3. anti-plasmodial d i g 4. anti-HNdrug

:,- 62ii The maximum bond -----: order obtained ... .. from the .,-A molecular orbitals -of a transition metal dimer;

. ! , .- ..- .

'formed as linear combinations of d-orbital-;- 5

alone, 'is

68. If the ionization energy of H atom is x, the . ioniition energy of ~ i ~ ' is. . .

1. 2x /3x , 3. 9x 4. 27x

69. If temperature is do-ubled .qd the mass .. of,the gaseous molecule ishalved, the rms speedof :,,..*7";c" the molecule will change by a factor of 1. 1 2. ' 2

3.wldlemwm-h°-sl 1. ~ w q j ~ r t i q a - ~ a m ~ ~ m it&Jm w-8 I

2. A W I ~ - ~ - ~ ~ ~ B W @ T w-8 I

3. c W I ! ~ X T ~ Q T - ~ ? ~ W D W @ T p,. Reductjoo of ~ 3 ] ~ i s o n i e o t i ~ i d e ) ] 3 +

w-Bl " " d \ with [ @ r ( ~ 2 0 ) 6 ] ~ ~ occurs by inner sphere 6,' ($ . . rgechaniim lutd raterate%I?th; ie&=n is---

4. c W I @ & T - m a ~ r D W M &6&3Ard& -----a=-.-

-Sjl dGsi?ion-=O,f&e_ successor ,+---&--A -

faga-8 I complex It is due to the 1. he r t ruthmiurn bridged to inert chromium

70. In the graph below, the m m t optiorl, according to Kohhusch law&

1. A is a weak electroJyte and B is a strong . .-- - electrolfle

2. A is a strong electrolyte and B is a weak electrolyte

3. C is a strongelectrolyte and D is a weak electrol3e

4. C is a weak electrQlyte and D is a strong electrolyte

?

PART 'C'

centre ~ J Q C ~

-~rt ruthenium bridged to labile -4

chromium centre 3. l a b G t h e n i u m bridged to inertx

chromium centre 4. labile ruthenium bridged to l a w e

c h r o 2 m centre , .

w m m : [F@~o)~]~+ / [ F ~ ( H ~ o ) ~ ] ~ + 4.0 W' S ~ C - '

[ ~ e ( ~ h e n ) ~ ] ~ + / [ ~ e ( ~ h e n ) ~ ] ~ + 3.0 x 1 o7 M-' sec-' (phen = 1,lO-phenanthroline) -

1. 'phen' W n-?Il'@ f?lT3 b 3hr $d'TFi

2. 'phen* W n-ZFiT f h F 5 $

! 71. [~u(~~~)~(isonicotinarnide)]~+ w [~r(H20)6]~+ 3. 'phen' W 3WTW 8 3 iKh =Sl7hW

! * - m & f m w m * ~ * ~ ~ & $ m - m m m w qal-m$ I

3 l m f a T * h m ~ s F r n $ 1 3 s r ; r ; r 4. 'phen' - 8 3WRF '7f?Z% F@3

8 % ~ 72. Consider the second order rate constants for

2 . 3 @ X v m t W ~ ~ ~ * the following outer-sphere electron transfer reactions:

5

LO kJ ~ e ( H ~ 0 ) ~ ] ~ + 1 p e ( ~ ~ o b ] ~ + 4.0 M-' sz-' ,--@

pt(1l)iT @3 ma - zf;r q [ ~ e ( ~ h e n ) ~ ] ~ + / [ ~ e ( ~ h e ~ ) ~ ' I ~ + .0 x 10' M-I

# $ A @ ,I dq4 '

--..,A /- P

(phen = l,l0-phenanthidline) 1. Nl 2. N3 The enhanced rate constant for the second 3. N7 4. N9

reaction is due to th'e fact that 1. The :phen' is a x-acceptor ligand that

diows mixing of electron donor and acceptor orbitals that enhances the rate sf electron transfer.

2. The 'phen' is a xdonor Iigand that enhances the rate of e l m n transfer.

3. The 'phen' forms charge -fer complex with iron and facilitates' the electron' transfer. - -,

4. The 'phen' fonns, kinetically labile complex with iron and' facilitates the ' electron transfer. J

74. In low chloride ion concentration, the anticancer drug cis-platin hydrolyses to give a diaquo complex and this binds to DNA via adjacent guanine

(guanine)

The coordinating atom of guanine to Pt(LI) is 1. Nl 2. N3-1--- 3. N7 4. N9

75. CF3 ' 9 ~ NMR .- 8 I . wT-ma&tt;npih-@

am ffP;, 2 . v 5 f % l Z m a m ~ * * r n

'Fmi

I 73. The compound . [Re~We~pPhkC41 .@)-- .- .

3 .w~f~srrnPiT~m'*rn havini~-configuration of $&%* ?, can be v5T ..y"'" .,--" ' . -. ,.

oxkilzed to and M'' ' The forha1 metal - - ' metal h n d order in 3% y' and I&+, 4 . ~ T - 3 m l T = ! 3 ~ f ElVZpKTm I I - r l y , are v5T

.0,3.5 and 4.0 2 , -3:,5;-4;0.-md3;0. .$ t.,

3.;--4;0,3.5 and 3.0 4: . 3.0,4.0 and 3.5 spec-hm of ClF3 shows triplet-for aT;shaped structure -- '.

'74. ,F5iRl$3 Him $3 alziZ3 d J e l aSR , . 2. slnglet for a trigonal planar structure

mm-*;sm-m*- 4 3. ~inglet for a trigonal pya~$d.a!.struw -- - .; --4+ -.-.*:a< - ..., , . +- . .. ,.

4. doubfj anifsiiiglet for a T-shaped ~ T ~ T F T M ~ ~ ~ ~ W V ~ ~ stiuctpre - &:*t--8

76. !%T am (- 98 O C ) W '%'w d r I I SF4f%$ihT%??!hr$ I

$ $ . I l

'1. C3" 2. C4" 3. Td 4. CZY

H . .

I ' 7 .

(guanine) ii f- 1 ' (i I: .Z' n I 2'

lA ;;.-, 1.3. 5. - '

.I ! s Q

%, ; " .

i: I '2

<

pr :I

/ '

I! . ..

ii I! ><.-.-:<.-.

: e-.

76. The low tempergwe (- 98 OC) 1 9 ~ ts. ? i @ m h d m t m v k ~ ~ ~ , a ~ r H ~ S O ~ spectrum of'sF4 -;-" shows - doublet of -trip ets. It is cojii*t ytth th iG-Gaup symrnw-

a ~ m ~ ~ 1- c!v k 4 0 6 T f r t T &?(so4)3 3- Jd- 2. As(No,)5 &?(S04)3

3- w6m H&O4

77. &~~RTJT (A), (B) am Mfdr- 4. H&04714 h 4 0 6

(€1 * $T ~ i c b * 79. Reactions of elemental As with hot and conc ~ m $ i - c 3 m w m & ~ ~ ~ , HN03 and H2SO4, respectively, give

2. As(NC&)~ and A s ~ ( S O ~ ) ~ 3. h 4 O 6 and H3As04 4. H W 4 and As406

77. Amongst organolithium (A), Grignarc! (B) 80. pes(co),5c] % I

organoalurnini& (C) compounds, those react w - i ~ Sic4 tr, give wplpound containing Si - C b.ond are z l = h T & ~ ~ $ ~ l : .

2. B a n d C 1. 74 i3W nido 2. 60 FFlT closo $) ; A, B andC,

3. 84 aSr arachno 4. 62 ?RTT nido 8

80. The total valence electron..cou.nt-..&d.,_the -xdmi *, ~ ~ 1 7 , 8 0 0 (vl) TW q m ~ structure type adopted -by ' he- complex 25,700 (vt) cm'~--qgih i$ I w .. . P T C ] respectively, are

1.. 4 and nido . 2. 60 and closo 3. 84andmachno 4 . - 62 and nido

81. [ q S - ~ 5 ~ S ) ~ h ( ~ t & ) Z ] %-20 OC W d 'H

NMR . . -'$IT f i 3li%lW6 AA'XX' itZ;;f @KCIT 8 I iWT

. d-70 oc mi W ~ F P T - ~ T W mm; f ; zmw~**m

- = r l a g l 3 f T ; f i T w $

exSlibits two absorption .bands, one at 1 7,800 1. f-n?r-- a 3 n a ~ t ~ % & vf%b (vl) and the second at 25,700 (v2) cm-'. The correct assignment of these bands, respectively, is 1. v! = 3 ~ 1 g ( ~ ) 3 3 ~ 2 & ~ ) -

vz = 3 ~ ~ g ( ~ ) + 3 ~ ~ g ( ~ ) 2. VI = 3 ~ ~ g ( ~ ) 3 3 ~ ~ & ~ )

v2 = 3 ~ I & ~ ) + 3 ~ 2 g ( ~ ) 3. vl = 3 ~ 2 i 3 3 ~ l g ( ~ )

v2 = 3 ~ 2 g 3 3 ~ 2 g ( ~ ) 4. V, = 3 ~ 2 g + 3 ~ 2 g ( ~ )

5

v2 = 3 ~ 2 g 3 3 ~ l g ( ~ ) 7-

. rq rs" *!

?. "5

S

81. 'H NMR spectrum of [q5-~S~s)Rh(~2&),1 at -20 "C shows a typical AAXX' pattern in - - the olefinic region. 0n increasing-the

.. . -- --

Pro

temperature to -70 "C, the separate lines collapse into a single line which is due to 1. free rotation of the ethylene ligand about

the metal-olefin bond 2. intramolecillar exchange between the

ethylene ligands 3. intermolecular exchange between the

ethylene ligands 4. change in hapticity of:the cyclopentadienyl

.. - - ligand - $2. mfazm-adm.-

w=*-g ,wi? (A) U 3 ~ (B) 2 3 5 ~ (C) 2 3 9 ~ ~ (D) 23%h 1. A,BiT$T D 2. A,CimT D

3. B,CiTW D 4. A, B m T C

( ~ ) $ a k a t j ~ ~ h a ~ m m - d

eqqmit1 1. A,BimT C 2. B,C=D

3. C,DiPJl A 4. D , A m B

84. The correct statements for hollow cathode lamp (HCL) from the following are (A) HCL is suitable for atomic absorption

spectroscopy (k4S) (B) lines emitted from HCL are very narrow (C) the hardening of lamp makes it unsuitable

for AAS @) transition elements used in the lamps

have short 1 i fe 1. A,BandC 2. B,CandD 3. C,DandA 4. D, A and B

82. The nuclides among the foIlowing, capable of $5. N ~ ( H ~ o ) ~ ~ ~ + [cu(IHzo)~]'+ * under oing fission by thermal neutrons, are (A) Ju (B) 235u (c) 2 3 q ~ ~ (D) 232n 1. A, B and D 2. A,CandD 1 . 5 t F h ~ & R ? z f T ~ ~ ~ Ni-0 3. B, C and D 4. A,BandC am c u - ~ m & , m $ m $ I

2. ~i--O@%i?h) FfW ~u-0- 83. 8lRFfF5 &&WT (TGA) A mfi3 & -?qa=ii$i$ i m p r : ~i-0(3RRrr) iTW

sffit;-4-* ~u-o(mfm-)ift *'wit I

1.-mW$ 3. W f ? ~ i 4 m @ m m $

2.mm-P * c u - o ( ~ m 43 * Cu- 3 . m a m - 8 S ~ ~ * $ I 4.mmmg 4 . t B R C t O m i f t m m i t

The use of dynamic inen atmosphere in thermogravimetric analysis QTGA) 1. decreases decomposition temperature 2. decreasks weight loss 3. reduces rate of decomposition 4. increases weight loss

(A) HCE WRFJdh 3ERibPT

3FlwmTmhg1 3 3

Identi@ the correct statement about ~(Hzo)~]~' and [ c u ( H ~ o ) ~ ] ~ ~ i

T a l l V i a and Cu-0 bond lengths - . qf -individual species &xqual

2. N@u?orial) and Cu-Q(equ.atorial) lengths are shorter than Ni-O(axial)

a d Cu-O(axial) ones respectively 3. all N i 4 bond leqghs are q y a l .whe~as

A h ( ' & a ~ ~ ~ n d s -a shorter than @-axial) bonds

$.%I1 F& bond lengths are equd whereas Edieqaaatorial) bonds m shorter than

86. Reaction of nitrosyl tetrafluoroborate to V&ka's complex gives complex A with L M-N-O =124". The complex A and its N-O stretching frequency are, respectively 1. [hCI(CO)(NO)(PPh3b]BF4, 1620 cm-I 2. [IIC~(CO)(NO)~(PP~~)I(BF~)~, 1730 cm-I 3. [hCl(CO)(NO)2(PPh3)](BF4)2, 1 520 cm-' 4. [IrCI(CO)(NO)(PPh3)21, 1 820 cm-'

87. -The correct order of decreasing electro- negativity of the following atoms is, 1. As>Al>Ca>S 2. S>As>AI>Ca 3. Al>Ca>S>As - 4. S>Ca>As>AI

88. M ~ ~ N ~ H ~ C H ~ C H ~ P P ~ ~ iTW KSCN % 1:2

m91n~ K2[PdC14] Wi d?i??IT

F @ i T A & f l i f ; I ~ A ~ ~ G l ? l l

~ 8 ~ ~ ~ ~ @ ~ t r a n s ~ , $ ~

famfaZmm**- (A) P, N (B) N, S (C) P, S (D) N, N 1. A m B 2. A m D

3. BPTT C 4. CPJT D -

88. A 1 :2 mixture of Me2NCH2CH2CH2PPh2 and KSCN with K2[PdCI4] gives a square planar complex A. ldentify the correct pairs of donor atoms trans to each other in complex A from the following combinations.

P, N (B) N, S (C) P, S (Dl N, N

(B) m m - * ~ * -mt

(C) af3Vm-f ' Q r n s f ; l r l f t r l l o r

89.' For a low energy nuclear reaction, 24 Mg(d, a)"~a, the correct statements from the following are (A) kinetic energy of d particle is not hlly

available for exciting " M ~ (B) total number of protons and neutrons is

conseried (C) Q value of nuclear reaction is much

higher in magnitude relative to heat of chemical reaction

(D) threshold energy is I Q value 1. A , B a n d C 2. A,BandD 3. B , C a n d D 4. A,CandD

99. At pH 7, the zindIl) ion in carbonic anhydmw reacts with C02 to give

91. Molybdoenzymes can both oxidize as well as reduce the substrates, because I. Mow0 is more stable than M o w ) 2. Mo(lV) can transfer oxygen atom to the

substrate and Mo(VJ.) can abstract oxygen atom from the substrate

3. conversion of M q I ) to Mo(IV) is not favoured

4. M o o can transfer oxygen atom to the substrate and Mo(1V) can abstract oxygen atom from the substrate

a. A comparison of the valence electron 'configuration of the elements, Sm and Eu suggests that

1. Sm is a better one electron reductant than Eu

2. Sm is a better one electron oxidant than Eu 3. facile oxidation state is +2 for both the

elements 4. both of these display similar redox

behaviour

93. The cooperative binding of Oz in hemoglobin is due to - -

1. a decrease in size of iron followed by changes iq the protein conformation

2. an increase in size of iron f~llowed by chimges in the protein confoxmatior!

3. a decrease in s@ of iron that is NOT accompanied by the protein conformational changes

4. an increase in size of iron that is NOT accompanied'6y the protein conformational changes

94. Amongst the following which is not isolobal pairs

1. M~(CO)S, CH3 2. Fe(C0)4, 0 3. Co(CO),, R2Si 4. Mn(C0)5, RS

L q+ 2.gp ti" ti H

95. The correct order of the size of S, s2-, s2+ and s4+ species is, 1. s>s2+>s4+>s2- 2. s2+ > s4+ > s2- > S 3. sZ- > s > sz+> s4+ 4. s4+ > sZ- > s > s2+

d m J p

\

KB~I.&H Al BN

&

benzene reflux

1. i. Ph3P+CH20MeCI-, BuLi; ii. ~ ~ 0 ' ; iii.

Jones' 36%d% 2. i. H2N-NHTs; ii. BuLi (2 equiv.); iii. DMF 3. i. H2N-NHTs; ii. BuLi (2 equiv.); iii. C 0 2 4. i. CICHZCO2Et, LDA; ii. BF3-OEtz; iii.

DMSO, (COC1)2, Et3N, -78 OC to rt

97. The correct combination of reagents to effect -

the following conversion is

\-'

____t

H 1. i. P~~P'cH~oM~cI-, BuLi; ii. ~ ~ 0 ' ; iii. Jones'

, . ...- reagent

2. i. H2N-NHTs; ii. BuLi (2 equiv.); iii. DMF m z N - N H T s ; ii. BuLi (2 equiv.); iii. C02 ----

96. The major product formed in the following 4. i. ClCH2C02Et, LDA; ii. BF3.0Et2; iii. reaction is DMSO, (COC1)2, Et3N, -78 OC to rt

E3u4N%r' *

anhyd. CF3COOH CH2CI2

2+ Br

F 8 7 ~ h e major product formed in the following w reaction is

99. Consider the following reaction.

The appropriate intermediate involved in this reaction is

100. ~t a-e it IWGT & f l?R " c ~ h p t t (6)

*f*mZt: ,

100. The correct 13c NMR chemical (6) shifi values of carbons labeled a-e in the following ester are

B. ATP 43 q C. NADPH * a SiqS ~ . m m * a q m**-iF

1. 1. A ,BaSr D 2. A m B

A: dOABie 6 : dN H 3. B r n ,C 4. A,C?Rll D

2. 102. The biosynthesis of isopentenyl

A : s%". B: & pyrophosphate fiom acetyl CoA involves:

H A. Four molecules of acetyl CoA

/ / B. Three molecules of ATP 3.

0 0 C. Two molecules of NADPH

A : 6 . a,n D. Two molecules of lipoic acid /

Me0 H

The c o m t options among these are: A 1. A,BandD 2. AandB ..

3. BandC 4. A, C and D

103. -RMd%5 -. .e 0 m ~ ~ , * w A * g

' 3 ?) .

The-prod.u.ctsA .md.B.~n..the~following .-

reaction sequence are ..

hv . .

A - B . .

1. A t&.---* C D

0 1 . A?fW C H Y B ~ c

2. 3. A m D .%=.--'

103. Amongst the following, the major products formed in the following photochemical

3. reaction are

d n i $ m u r ~ ~ - ~ $ : 1. AandC 2. B and C ' .'

4. AandB

A : A B: 105. Anthranilic acid, on treatment with iso-amatrife

H2N MeO - furnishes a produet which displays a strong peak at

76 ( d e ) in its mass spectrum. The structure of the product is

The products A and B in the following sequence are -

1 0 7 . - f % f T J r ~ * - = ~ *

f rn m -c9h ?dl (n=0, t?rrrr2)*

1. ~ ; R * i f f 5 t l f % m m d h m f T ~ p , , = 0.633, pi = 0.233 ?lW ~2 ' 0.086 8 h 4Shw n 2 3 A @ ~ ~ F w * * . % . mBm8 I

2. 1. 0.032 2. 0.048 3. 0.952 4. 1.000

107; Usmg Boltimarirl d i b u t i o n , the probability of 3. ~ o&ill&or &g the first three levels (n =

0, 1 &ti 2) b f a d to be po = 0.633, p, = 0.233 and p2 = 0.0$6. The probability of findiig aii oscillator in enegy levels n-2 3 is

H Zn 1; 0,032 2. 0.048 4. 3. 0.952 4. 1.000 . .

106. The, organoborane. X, when reacted with 108. f b d % & i 3 ~ f W m r s m r A ~ - m 1 q ~ Et2Zn falowed bE-iodotoluene in the ., atrr ~g pyi -(J 5 ~0 pr%i5ni-of catalyti a m o x of ' pd(P~h,), i. P~NCO fumikhes a .. tris;b&tuted , , a- The Et3N Hz, Raney Ni intermediate and .&S$iZGUC<6f the reaction, A - B

.. ii. MeOH. H f l respectively,'are ACOH

L A:

2. A :

X . 3. A:

1. . 4 A:

/

and H Zn

108. The major products A and B in the following reaction sequence are

i. PhNCO Et3N Hz, Raney Ni

\NO2 - A - B ii. M e O H . H f l

A c O H

. - ? - ,. : ;: ., ;:.-.> . . >.,, ',.' .- :;*, <..*:. .: + rfi :, ,<..z~,~~:z~. '- ,,

110. An organic compound gives followinp: *n%-z-... .. -$-="--. -- . *.- . . : . . . .-.-? $++&$=&:?. . .

spectraldata. *-. -,- . - ---.--:< ::.<

R 2210, 1724 cm-'; 'HNMR: 6 1.4 (t, J= . .,... ., .".. a A,.: 7.1Hz,3H),4.4(qY J=7.1Hz,2H),7.7(d,J

= 7.0 Hz, 2H), 8.2 (4 J= 7.0 Hz, 2*, 13c NMR:S 16,62, 118, 119,125,126,127,168.

Ia=Tfa%&f ~ 3 m W F F The compound is

M = m K A * X

1. i. Na, my, MqSiC1, mci; ii. H30t

2 i: Na, m, am; ii. H202, NaOH

3. i. NaOEt, EtOH; ii. Na, X$'8k7, ?WT ' ;

4. i. TiC13, Zn-Cq Me3SiC1, m, ii. H30* C -

109. The correct combination of reagents requ-ued to effect the following conversion is ..

- 1. i.Na, xylene, Me3SiC1, heat; ii. H~O' 2. i. Na, xylene, heat; ii. H202, NaOH 3. i. NaOEt, EtOH; ii. Na, xylene, heat 4. i. Tic&, Zn-Cu, MqSiCl, heat; ii. H3O*

110. m - mlT laMfMa3 * - &hP - IR: 2210, 1724 cm-'; 'H NMR: 6 1.4 (t, J = 7.1 HZ,~H), 4.4(q, J = 7.1 Hz, 2H), c 7 (d, J = 7.0 Hz, 2H), 8.2 (d, J = 7.0 Hq 2H); "C NMR: 6 16, 62, 11.8, 119, 125, 126, 127, 168. *

w-rtKam;P

11 1. The major product formed in the following reaction is

1. A = odo2; B = K+ -00~-N=N-COOX+, AcOH

2. A = 02, m M, h ~ ; B = K+-OOC-N=N- COOX+,ACOH '

3. A= 02, m m, hv; B =Hz, Pd/C 4. A = O ~ , ~ M , & B=H2,Pd/C

112.The correct combination of reagents for effecting the foflowing- sequence of reactions is

1. A = 03/02; B = K+ -00~-N=N-COOX+, AcOH

2. A = 02, Rose Bengal, hv; B = K+-OOC- N=N-cOOX', AcOH

3. A = 0 2 , Rose Bengal,&v; B. = Hz, PdC U1, Rose Bengal, A; B = H2, PdC

113. The correct combination of reagents required to df& the following conversion is

4. s-BuLi -78 'C followed by ICH2C&I L / r - -

114. Consider a particle confined in a cubic box The degeneracy of the level, that has an energytwice.that of the lowest level, is 1. 3 2. 1

I1 - ii. BrCH2CH2Br 0

115. Only two products are obtained in the following reaction sequence. The structures of the products from the list I-IV are

a

- i. NaNHp

C

ii. BrC&CH#r Mac&'-: QCDP* o \ / ~ o o ~ e

3. H 4. OH

(&-p 4 @ 117. ~ ~ I @ # Z ~ T ~ ~ ~ ~ X K A ~ B ~

I \

u a rt

,L,,J.---A oq. NaCN. Mn4

dbxme - 6

-i. IandII 2. II andN refha Wr0)1. MefiH

3. I and III 4. n1 and IV 1.

116. ~ 3 l # f h T f f ~ ~ A $ I A: )-Jy B: a\ c0 MeOOC- COOMe - A 2.

-> > % Heat < A : e: u'(

OOMe 117. The products A and B in the following .. reaction sequence are

3. H 4. OH so2 aq. NaCN. M n 4

-- A dioxane

- B IPrOH. Mc2NH

reflux

116. The major product A formed in the following reaction is 1. #

I co MeOOC-COOMe A : 6 : + A 2.

Heat - A : 0 : 0J-f COOMe

COOMe

3. 0

2.

The spatial part of the wayefU~ctionof-the atom in its ground state is ls(1) 142). The spitrpai€Gould be 1. a(l)a(2) 2. P(lIP(2) 3. [a(l)P(2) + P(l)a(2)1

NO, 0 2 NO2 % f i % % FGJ=4

f 3 r o r ; 4 ~ r ~ ~ w ~ ~ ~ ,

The number of phases, eornponents and -

degrees of freedom, wnen ~r is added to an eqGZbrium mixture of NO, O2 and NO2 in gas phase are, respectively, 1. 1,3,5 2. 1,4,5 3. 1 ,3 ,4 4. 1,4,4 -

pyridine T - OH

120. The major product formed in the following reaction is 5 TsCI

pyridine

121. A particle in a one dimensional harmonic oscillator in x-direction is perturbed by a -

a potential hx (I is a number). The fi~st-order correctioxo the energy of the ground state 1. is&o 2. is negaiive 3. is positive 4. may be negative or positive but NOT

zero

Ph HO*OM~ B. ?LO A= HO. 3. OH H OH

122. The pioducts A and B in the followkg sequence of reactions are

1. HX= HF andA= Br

2. HX= HCl and A = Br & 3. HX=HBrandA= Br & 4. HX = HBr and A = Br

H OH HoLCHo MeOH I H* . . - . refbx, 24 h

- A OH i ) ~ H+ The mass spectrum of the product A, formed

in the following reaction, exhibits M, M+2, ' M+4 in the ratio of about 1 :2: 1. The

OH Ph reagent HX;and the pr0duct.A . are . -. ' -

A = H&+OM. 6= $-OMe

.. ' .$- --% '.

- 7 .''.Hx ) 1. OH . I OH c

c , ... . . . . A

Br Hoq- . -

A= HO B=

3 'O' LC

1. HX = HF and A = Br A = HO

'3. H OH

A = HHOO&~d B= 2. HX = HCI and A = Br 4. OH 8'

125. A ..particle in a onedimensional box (potential zero between 0 to a and infinite outside) has the ground state energy

above - L i l t o n i i n -- with +(x) = x(x - a ) -

yields aa energy . . . El . . . Using a linear c o m b i o n &-two even func t lon~x(x~a1

- + '

and xZ(x - a)', we obtain. yriatibnk m i n i to the ground state energy as E2. Which <f-tfie-following relations holds for Eo, El and E2 ? 1. Eo< E l < E 2 2. Eo < E2 < a El 3. El < Eo c E2 4. E2 < Eo < El

124. Match the following natural products in column A with their structural features in column B

3 Column A Column B I - (I) Cblchicine (a) Tetrahydromepine

(II) Strychnine (b) Phenanthrene (III) Quinine (c) Tropolone (IV) Ephedrine (d) Phenylethylamine

(e) Quinoline - (f) Benzofuran

126. The dissociation constant of a weak acid HX at a given temperature is 2.5 x lo-'. The pH of 0.01 M NaX at this temperature is 1. 7.3 2. 7.7 3. 8.3 . 4. 8.7

- Identifjl the correct match from the following

125. QTf&fhTWRl (Om a * W f & I ' T

? p $ s t h w - B A m t 127. The ground state energy of hydrogen atom is

-13.598 eV. The expectation values of kinetic energy, (I) and potential energy, (V), in units of eV, are 1. (l)=13.598, (V)=-27.196 2. (2')~- 27.196,(V) = 13.598 3. (I)=-6.799,(V)= -6.799 4. (l)= 6.799, ( V ) = - 20.397

128. If y = 0.8 PA + 0.4 p~ is a normalized molecular orbital of a diatomic molecule

. . . , , . .. . ~ - - - . -

A 4 constructed from PA and % which ax - . ., _^ I).i_.._,..___ 0--ii - . .,,. . < .:**, .-.. .; ,. .

also normallzed, .- the over1.y +.2. between- . . .A.v...L. PA and is '. . ~,.

1. 0.11 2. ' 0.31 3. 0.51 4. 0.71.

129. At a given temperature consider Fe203(s) + 3CO(g) + 2Fe(s) + 3C02(g); K1 = 0.05 2C02(g) + 2CO(g) + Ol(g); K2 = 2x 1 0-l2 The equilibrium constant for the reaction

mol-') increased the tempemlure by 4 K. If 'the heat capacity of the calorimeter along with that of the rgaterial is 2.4 kJ K-', the molar internal energy of combmion, in kJ, is 1. 1000 2. -1000 3. 20 4. -20

131. The translational, rotational and vibrational padtion functions for a molecule are

f-lation N 10'' m-'7 fmtation N 10, fv~~ration N

1, (ksTh) E 1 O? at room temperature,

Using the approximate data given above, the frequency factor (A) for a reaction of the type: atom + diatomic molecult? -t

nonlinear ' transition state 4 product, accordinp to the conventional transition state theory is 1. 2 x lo3 2. 6 x lo7 3. 2 x 1012 4. 6 x l0l3

1. 1000 2. -1000 . 132. The interplanar spacing of GO) planes in a 3. 20 4. -20 cubic unit cell with lattice

130. In a bomb calorimeter, the combustion of 0.5 g of compound A (molar mass = 50 g

39 -

. . 133. A P,B, ft * $1- Vf * e fluorescence llfetlme of a molecule in a

7 8 h q h m * r n m - solution is 5@ s. The sum of all the nonradiative rate-constants (Zk,,,) for the

A ' a m m r f i t g ~ ~ m ~ .-

decay of excited st$e is 1 . 2 ~ 108 s -'. n e d t ~ ~ w & % X l xP ITy i f ; fluorescence $uantumsd%fthe - .- - molecule

m g, m r is 1. 0.1 1. 4,4 2. 4,8 2. 0.2

3. 8,4 4. 4,2 3. 0.4 w . 6

133. A compound A,B, has a cubic structure with 137. W - W % 3K&f A atoms ~ c c ~ ~ ~ ~ ~ a l l t h e corners of the cube as well as all the face cen i i sZI 'o%. The3

r m r r $ m % s t h * r n ~ -I .

I atoms occupy four tetrahedral voids. The 4 , 2 5 m 81 8 I p H - a l R m a f * ~ I v a l d s - o ~ ~ e l y , are .= ~ f ; s r f F e @ * w 1 g 4 , 4 * - 2. 4,8, -

3. 8,4 4J4,2 - 8 1. 4,253W 81. 2. 2,5 -r(PTT 9.

134. CD3 (D* -1 a % ESR -* 3. ili, 115 FisTT 119 4. i , I m 1

-*-it; 137. Solutions of three elecl~olytes have the same 1. 1 2. 3

I 3. 4 v 7 ioniestrengtli m d - d i R & e ~ ~ ~ c C C O n i

I as 27?25 ifid xi.- \ 134. The number of lines in the ESR spectrum of magnitude bf Debye-HUckc-l _ _ _ screening . __ lengths 2, f

CD3 is (the spin of D is 1) of the three solut6ns are

1. 1 2. 3 1. 4,25and81. 2. 2,5 and 9.

3. 4 4. 7 3. 112, 115 and 119 4. 1 , l a n d l $0 =r

135. COz C=O 3TlTXT ZWT$ 120 pm 8 I C02 1 . @ 3lT%ZT fhl3 * t; *-% --r;---&- fA-&c;I;IY &-% $ r\

I. ~ - ~ ~ ~ ~ 9 6 ~ . m 3 ( C m 0 Fh$?T 8 ?iiX?T: 1.9x10-~~ k g ~ e m $

- 2 . 5 ~ 10"~ kg) 2. cis- --* m tram---* ~ 1. 1 . 8 x 1 0 ~ ~ k ~ m ~ , 2. 3.6x10-~~kgm~ 3. 5 . 4 ~ lo4' kg m2 4. 7 . 2 ~ 1 0 ~ ' k g m ~

* m a $ 3. cis- --&! 7 w ~ ?11s+cli'=m3$- r\

135. The C=O bond length is 120 pm in C02. The &fiav?T&T$ moment of inertia of C 0 2 would be close ta (makes of C and 0 are 1 . 9 ~ 1 0-27 kg and

4. f i m * * r n h v - 2.5X kg, respectively) mT%Fr @$,8 1. 1 . 8 ~ 1 0 ~ ' kgm2 3. 5 . 4 ~ 1 0 ~ ' kg m2

2' 3.6x lo4' kg m2 138. Simple H i i c e molgcular orbital theory 4. 7 . 2 ~ 1 0 ~ ' k g r n ~ 1. considers electron-electron repulsion

136.f%FbT * V 5 3iqS ?T m S f I 5 W F f explicitly

2. distinguishes cis-butadiene and trans- 5 ~ 1 0 - ~ s $ I 3 d f % 3 ~ % t ; * f ? R butadiene

mfr 363f%m CT mEib3 % a h (EL) Tr 3. distinguishes cis-butadiene and

m 1.2x108 s -' it; 1 q ai m nf;TAf4T cyclobutadiene

4. has different coulomb integrals for non- mlXm*'f equivalent carbons 1. 0.1 2. 0.2

t

--

40 .< -27 .\$A '.: 1

. ' i~w.#' . t ul. In thii tiii&eaver-~urk of (&i~jaliite]-' -7(--T&& c o n & ~ o n ) -1 for &,

enzyme-.. catalyzed reaction followiiig - . MichaeliiMenten mechanism, the ...- i-: .

139. FiW ?RE 30 bar W W &El RTF

intercept is-' s. If the initial ---.a enzymnzyme mcenEratiun is 1 x104 M, the turnover - number is 1. 2 . 5 ~ 1 0 ~

. . 2. 1.ox1o4 3. 2 . 5 ~ 1 0 ~ 4. 2 . 0 ~ 1 0 ~

139. For the nondissociative Langmuir type adsorption of a gas on a solid s;;face- at_ a particular temperature, t h e h t i o n of surface coveme- is-35 at - 30 bar. ~ h i p T u isotherm constant (in bar-' units) at this temperature is p

1. 0.05 2. 0.20 I,

3. 2.0 4. 5.0

142. The E 6i1 E direct product in Dj point group contains the irrkduGble representations

140. For a set of 10 observed data points, the mean is 8 and the variance is 0.04. The 'standard deviation' and the 'coefficient of variation' of the data set are, respectively, 1. 0.005,O.l % 2. 0.02, 0.2 % 3. 0.20,2.5 % 4. 0.32, 1.0 %

3 4 4 ~ ' aFmTr -' 47 a.x --& 3d73 W y- 3 k Ek 5000 M-' s '8 I

143. The result of the product Cz (x)Cz (y) is

I 144. Given; ! I r ~ =

I A. F $ O Q (s), + 2e- + Fe(s) + 2 0 H (aq); E0 = - 0.877 V

B. A13+(aq) + 3e-+.Al(s); EO = -1 -66 V C. AgBr(aq) + e- +Ads) + Br- (aq);

EO = 0.07 1 V

The overall r e e m for the cells in the directi6.a. of.. w"faii-eo"S. cG.ge-wOU-i* be

--. ....- -- . . - . . . . . - 1. Cell with A&B : Fe reduced

cehvith'A&c ' : Fereduced 2. cell wi& A&B . : Fe reduced

Cell with A&C : Fe oxidized 3. Cell with A&B : Fe oxidized

Cell with A&C : Ee oxidized 4. Cell with A&B : -Fe oxidized

Cell with A&C :. Fe reduced

1 S18 CSMH 4-1 CH-4 i-7 3

145. The reagent A used and the major product B formed in the following reaction sequence are