10 years gate solved papers CHEMISTRY(Upto 2014)

2007 CY: Chemistry

Duration: Three Hours Maximum Marks: ISO

Read the following instructions carefully.

I. This question paper contains 85 objective type questions. Q.I to Q.20 carry one mark

each and Q.2 I to Q.85 carry two marks each.

2. Attempt all the questions.

3. Questions must be answered on Objective Response Sheet (ORS) by darkening the

appropriate bubble (marked A, B, C, D) using HB pencil against the question number on

the left hand side of the ORS. Each question has only one correct answer. In case you

wish to change an answer, erase the old answer completely.

4. Wrong answers will carry NEGATIVE marks. In Q.l to Q.ZO, 0.25 mark will be

deducted for each wrong answer. In Q.21 to Q.76, Q.78, Q.80, Q.82 and in Q.84, 0.5

mark will be deducted for each wrong answer. However, there is no negative marking in

Q.77, Q.79, Q.81, Q.83 and in Q.85. More than one answer bubbled against a question

will be taken as an incorrect response. Unattempted questions will not carry any marks.

5. Write your registration number, your name and name of the examination centre at the

specified locations on the right half of the ORS.

6. Using HB pencil, darken the appropriate bubble under each digit of your registration

number and the letters corresponding to your paper code.

7. Calculator is allowed in the examination halJ.

8. Charts, graph sheets or tables are NOT allowed in the examination hall.

9. Rough work can be done on the question paper itself. Additionally blank pages are given at the end of the question paper for rough work.

10. This question paper contains 24 printed pages including pages for rough work. Please

check all pages and report, if there is any discrepancy.

51121 FoodlO6-CY-1A CY J/24

Some Useful Data I. Physical Constants

2.

(a) Universal gas constant, R = 8.3145 J K-I mol-I = 0.082 L atm K-I mol-'

(b) Planck constant, h = 6.626 X 10-34 J s

(c) Avogadro number, N = 6.022 X 1023 mol-I

(d) Faraday constant, F = 96500 C mOrl

(e) Electron charge, e = 1.602 x 10-1• C

(I) Speed oflight, c = 2.998 X 108 m 5-1

(g) Boltzmann constant, kb = 1.381 x 10-23 J K-I

Atomic Numbers

8=5 Si = 14

V=23 Cr= 24

Co=27 Ni=28

Eu=63 Dy=66

Lu = 71 Re = 75

CY 2/24

Ti=22

Mn=25

Xe=54

Yb =70

Pt= 78

51121 FoodlO6-CY-1B

Q. 1 - Q. 20 carry ooe mark each.

Q. l The rate of sui phonation of benzene can be significantly enhanced by the use of

(A) a mixture of HNO) and H2S04 (B) conc. H2S04 (C) a solution of SO) in H2S04 (D) S03

Q.2 The reaction

0:0.... 1 + """-"""- 2 Na + 2 C2HsOH

is an example of a

(A) Birch reduction (B) elemmenson reduction (e) Wolff-Kishner reduction (D) hydride reduction

Uq. "H, • 0 ' 'C,H,oN.

Q.3 The major product (X) of the monobromination reaction is

H3C

(A)

~~-O (C)

Br

H,c

NBS ---=-=---;.~ (X)

(B)

H3C

(D) Br

Br

CH3

Q.4 Benzene can not be iodinated with 12 directly. However, in presence of oxidants such as HNO), iodination is possible. The electrophile formed in this case is

(B) (C) (D)

[ r 1 [ .0 .0 ]+ 1········0Hz [

.0 -0 ]+ I········OHz

ey 3124

Q.5 Classify the following species as electrophiles (E) and nucleophiles (N) in routine organic synthesis

SO, Ci+ CH1NH2 H10+ BHl CN-

(A) E = SOl, CI+, BHl (B) E = CI+, H,O+ (C) E = CI+, H,O+, BH, (D) E = SO" CI+, H,O+, BH,

N = CH,NH2, H,O+, CN-N = SO" CH1NH2, BH1, CNN = SOl, CH1NH2, H10+, CW N = CH1NH2, CW

Q.6 The major product obtained upon treatment of compound X with H2S04 at 80°C is

HO (X)

(A) (B)

>0 (C) (D)

~

Q.7 BaTi[Si}09J is a class of

(A) ortho silicate (B) cyclic silicate (C) chain silicate (D) sheet silicate

Q.8 The ground state term for V'+ ion is

(C) lp

Q.9 In photosynthesis, the predominant metal present in the reaction centre of photosystem II is

(Al Zn (B) Cu (C) Mn (D) Fe

Q.IO The octahedral complex I complex ion which shows both facial and meridianal isomers is

(A) Triglycinatocobalt(III) (C) Dichlorodiglycinatocobalt(III)

(B) Tris( ethylenediam ine )cobalt(lII) (D) Trioxalatocobaltate(lII)

Q.II Zn in carbonic anhydrase is coordinated by three histidine and one water molecule. The reaction of C02 with this enzyme is an example of

(A) electrophilic addition (C) nucleophilic addition

(B) electron transfer (D) electrophilic substitution

CY 4124

Q.12 The difference in the measured and calculated magnetic moment (based on spin-orbit coupling) is observed for

(A) Pm3+

Q.13 For a redox reaction, Cd2+ + 2e- ~ Cd, the (Ep)anodic observed in cyclic

voltametry at hanging mercury drop electrode is -650 mY vs. SCE. The expected value for (Ep)cathod" is

(A) -708 mY (B) -679 mY (C) -650 mY (0) -621 mY

Q.14 The dimension of Planck constant is (M, Land T denote mass, length and time respectively)

Q.15 For a homonuclear diatomic molecule, the bonding molecular orbital is

(A) cru oflowest energy (B) cru of second lowest energy (C) 1Ig of lowest energy (0) 1Iu oflowest energy

Q.16 The selection rules for the appearance of P branch in the rotational-vibrational absorption spectra of a diatomic molecule within rigid rotor- harmonic oscillator model are

(A) Ilv = ± I and 6J = ± 1 (C) ~v = +1 and ~J =-1

(B) ~v = +1 and 6J = +1 (0) Ilv = - 1 and ~J = - I

Q. I 7 The S2 operation on a molecule with the axis of rotation as the z axis, moves a nucleus at (x, y, z) to

(A) (-x, -y, z) (B) (x, -y, -z) (C) (-x, y, -z) (0) (-x, -y, -z)

Q.18 The expression which represents the chemical potential of the ith species (fli) in a mixture (i '" j) is

(A) (aE / an; }s, V,n)

(B) (aH / ani }s, v, nj

(C) (aA / ani }s , v, nl

(0) (aG / ani }s. v, nJ

CY 5124

Q.19 Which of the following statements is NOT correct for a catalyst?

(A) It increases the rate of a reaction (B) It is not consumed in the course of a reaction (C) It provides an alternate pathway for the reaction (0) It increases the activation energy of the reaction

Q.20 The value of the rate constant for the gas phase reaction 2N~ + F2 --. 2N02F is 38 dm) mol-I S-I at 300K. The order of the reaction is

(A) 0 (B) I (C) 2 (0) 3

Q. 21 to Q. 75 carry two marks each.

Q.21 Boric acid in aqueous solution in presence of glycerol behaves as a strong acid due to the formation of

(A) an anionic metal-chelate (B) borate anion (C) glycerate ion (0) a charge transfer complex

Q.22 Match the compounds in List I with the corresponding structure / property given in List II

(A) a- iii (B) a- iv (C) a- iii (0) a- iv

List I (a) (Ph)P»)RhCI (b) LiC6 (c) PtF6 (d) Ni)S.

b-i c-ii b-ii c- iii b-ii c-i b - iii c-ii

d- iv d- i d- iv d- i

List II (i) Spinel (ii) Intercalation (iii) Oxidising agent (iv) Catalyst for alkene hydrogenation

Q.23 W(CO)6 reacts with MeLi to give an intermediate which upon treatment with CH2N2 gives a compound X. X is represented as

(A) WMe6 (C) (CO),W=C(Me)OMe

(B) (CO),W-Me (0) (CO), W "CMe

Q.24 Considering the quadrupolar nature of M-M bond in [Re2Claf-, the M-M bond order in [Re2Ci.(PMe2Ph).r and [Re,CI.(PMe2Ph).] respectively are

(A) 3.0 and 3.0 (B) 3.0 and 3.5 (C) 3.5 and 3.5 (0) 3.5 and 3.0

CY 6/24

Q.25 A student recorded a polarogram of 2.0 mM Cd2+ solution and forgot to add KCI solution. What type of error do you expect 1n his results?

(A) Only migration current will be observed (B) Only diffusion current will be observed (C) Both migration current as well as diffusion current will be observed (D) Both catalytio current as well as diffusion current will be observed

Q.26 The separation of trivalent lanthanide ions, Lu3+, Vb3+, Oy3+, Eu3+ can be effectively done by a cation exchange resin using ammonium a-hydroxy isobutyrate as the eluent. The order in which the ions will be separated is

(A) (8) (C) (D)

Lu3+ Yb3+ Oy3+ Eu3+ , , , E 3+ 0 3+ Yb3+ L 3+ U , y, ) u o 3+ Yb3+ Eu3+ Lu3+ y, , , Yb3+ Oy3+ Lu3+ Eu3+ , , ,

Q.27 Arrange the following metal complexes in order of their increasing hydration energy

(A) P < S < Q < R (B) P < Q < R <S (C) Q < P < R < S (0) S < R < Q < P

Q.28 In the complex, [Nh('1'-Cph(COhJ. the IR stretching frequency appears at 1857 cm-' (strong) and 1897 em" (weak). The valence electron count and the nature of the M-CO bond respectively are

(A) 16 e-, bridging (B) 17e-, bridging (C) 18 e-, terminal (D) 18 e-, bridging

Q.29 The correct classification of[B,H,]2-, BsH9 and B,H 11 respectively is

(A) c1oso. arachno, nido (C) c1oso, nido, arachno

(B) arachno, c1oso, nido (D) nido, arachno, c1oso

Q.30 The compounds X and Y in the following reaction are

EtOH. (X)

(A) X = (Et)2P(S)SH ; Y = (Et)2P(S)CI (8) X = (EtO)2P(S)SH ; Y = (EtO)2P(S)CI (C) X = (EtO)2PSH ; Y = (EIO)2PCI (D) X = (Et)3PO ; Y = (Et)3PCI

CY 7/24

Q.31 Consider the reactions

I. [Cr(H,O)6]2+ + [CoCI(NH,),]'+ --> [Co(NH,),(H,O)]'+ + [CrCl(H,O),]'+ 2. [Fe(CN)6]'- + [Mo(CNls]'---> [Fe(CN)6]'- + [Mo(CNls]4-

Which one of the following is the correct statement?

(i) Both involve an inner sphere mechanism (ii) Both invol ve an outer sphere mechanism (iii) Reaction I follows inner sphere and reaction 2 follows outer sphere mechanism (iv) Reaction I follows outer sphere and reaction 2 follows inner sphere mechanism

(A) i (B) ii (C) iv (D) iii

Q.32 The pair of compounds having the same hybridization for the central atom is

(A) XeF4 and [SiF6]'(C) Ni(CO). and XeO,F,

(B) [NiCI4]'- and [PtCI4]'-(D) [CO(NH')6]'+ and [CO(H,O)6]'+

Q.33 In the reaction shown below, X and Y respectively are

(A) [Mn(CO)4f-. [CH,C(O)Mn(CO)'r (B) [Mn(CO),r, CH,C(O)Mn(CO), (C) [Mn(CO),r, CIMn(CO), (D) [Mn(CO)4]'-, [CIMn(CO),r

Q.34 The Lewis acid character ofBF" BCI, and BBr, follows the order

(A) BF, < BBr, < BC" (C) BF, < BCI, < BBr,

(B) BC" < BBr, < BF, (D) BBr, < BCI, < BF,

Q.3S The compound which shows Lf-M charge transfer is

(A) Ni(CO), (C) HgO

Q.36 The reaction of [PtCI4]'- with NH, gives rise to

(A) [PtCI4(NH,h]'(C) [PtCI,(NH,),]

Q.37 Zeise's salt is represented as

(A) H,PtCI6 (C) [ZnCI,f-

(B) Irans-[PtCI2(NH,h] (D) cis-[PtCI,(NH)h]

(B) [PtCI,]'-(D) [PtCb(,, ' -C,H4)r

Q.38 The catalyst used in the conversion of ethylene to acetaldehyde using Wacker process is

(A) HCo(CO). (C) V,O,

(B) [PdCI,l'-(D) TiCI, in the presence of AI(C,H,»)

CY 8124

0.39 The temperature of 54 g of water is raised from 15°C to 75°C at constant pressure. The change in the enthalpy of the system (given that CPo m of water = 75 JK-' mol-') is

(A) 4.5 kJ (8) 13.5 kJ (C) 9.0 kJ (0) 18.0 kJ

0.40 The specific volume of liquid water is 1.0001 mL g-' and that of ice is 1.0907 mL g-' at O°C. If the heat of fusion of ice at this temperature is 333.88 J g-', the rate of change of melting point of ice with pressure in deg atm-' will be

(A) - 0.0075 (8) 0.0075 (C) 0.075 (0) - 0.075

0.41 Given that Eo(FeJ+, Fe)= -0.04 V and Eo(Fe2

+, Fe) = -0.44 V, the value of Eo(F e3

., F e2+) is

(A) 0.76 V (8) - 0.40 V (C) - 0.76 V (D) 0.40 V

0.42 For the reaction P + 0 + R -4 S, experimental data for the measured initial rates is given below

Expt. Initial conc. P Initial cone. 0 Initial conc. R Initial rate (M) (M) (M) (M s-')

I 0.2 0.5 0.4 8.0 x 10-5

2 0.4 0.5 0.4 3.2x 10-4 3 0.4 2.0 0.4 1.28 x 10-3

4 0.1 0.25 1.6 4.0 x 10-5

The order of the reaction with respect to P, 0 and R respectively is

(A) 2,2, I (8) 2, 1,2 (C) 2, I, I (D) I, 1,2

0.43 Sucrose is converted to a mixture of glucose and fructose in a pseudo first order process under alkaline conditions. The reaction has a half life of28.4 min. The time required for the reduction of a 8.0 mM sample of sucrose to 1.0 mM is

(A) 56.8 min. (8) 170.4 min. (C) 85.2 min. (0) 227.2 min.

CY 9124

S/121 FoodlO6-CY- 2A

Q.44 The reaction

proceeds via the following steps

(A) 2kb [NO] [0,] (C) 2kb [NO]' [0, ]

(B) (2k,kb[N0]' [O,]) I (k.+ kb[O,]) (D) k.[NOf[O, ]

Q.45 40 millimoles ofNaOH are added to 100 mL ofa 1.2 M HA andY M NaA buffer resulting in a solution of pH 5.30. Assuming that the volume of the buffer remains unchanged , the pH of the buffer (KHA = 1.00 x 10-') is

(A) 5.30 (B) 5.00 (C) 0.30 (D) 10.30

Q.46 The entropy of mixing of 10 moles of helium and 10 moles o(oxygen at constant temperature and pressure, assuming both to be ideal gases, is

(A) 115 .3 JK- 1 (B) 5.8 JK- 1 (C) 382.9 JK- 1 (D) 230.6 JK-1

Q.47 The ionisation potential of hydrogen atom is 13.6 eV. The first ionisation potential of a sodium atom, assuming that the energy of its outer electron can be represented by a H-atom like model with an effective nuclear charge of 1.84, is

(A) 46.0 eV (B) I J.S eV (C) 5.1 eV (D) 2.9 eV

Q.48 The quantum state of a particle moving in a circular path in a plane is given by

'f'.,(¢) = (I 1 &)e,ml ,m = O,t 1, ±2, ....

When a perturbation H1= P cos ¢ is applied (P is a constant), what will be the first order correction to the energy of Ihe m" state

(A) a (B) P/(2rr) (C) P/(4rr)

CY 10/24

$/121 Food/06-CY-2B

Q.49 The correct statement(s) among the following islare (i) The vibrational energy levels of a real diatomic molecule are equally spaced. (ii) At 500K, the reaction A ~ B is spontaneous when !>.H ~ 18.83 kJ mor' and

!>.S ~ 41.84 J K-' mol-'. (iii) The process of fluorescence involves transition from a singlet electronic state to

a,~other s inglet electronic state by absorption of light. (iv) When a constant P is added to each of the possible energies of a system, its

entropy remains unchanged.

(A) only i (B) only ii (C) both i and iii (D) both ii and iv

Q.50 Assuming H2 and HD molecules having equal bond lengths, the ratio of the rotational partition functions of these molecules, at temperatures above lOOK is

(A) 3/8 (B) 3/4 (C) 1/2 (D) 2/3

Q.51 N non interacting molecules are distributed among three non degenerate energy levels eo~ 0, &, ~ 1.38 X 10-2

' J and &2~2.76 x 10- 2' J at lOOK. If the average total energy

of the system at this temperature is 1.38 x 10-18 J, the number o f molecules in the system is

(A) 1000 (B) 1503 (C) 2354 (D) 2987

Q.52 The J ~ 0 ~I rotational transition for ' H79 Br occurs at 500.72 GHz. Assuming the molecule to be a rigid rotor, the J ~ 3 ~ 4 transition occurs at

(A) 50.1 cm-' (8) 66.8 cm-' (C) 16.7 cm-' (D) 83.5 cm-'

Q.53 The rate constants of two reactions at temperature Tare k,(T) and k2(T) and the corresponding activation energies are E, and E2 with E2> E,. When temperature is raised from T, to T2, which one of the following relations is correct?

(A) k,(T,) ~ beT,) k,(T,) beT,)

(C) k,(T,) > beT,) k,(T,) - k,(T,)

(8) k,(T,) > beT,) k,(T,) k,(T,)

(D) k,(T,) < k,(T,) k,(T,) beT,)

Q.54 The number of degrees of freedom for a system consisting ofNaCI(s), Na+(aq) and Cqaq) at equilibrium is

(A) 2 (8) 3 (C) 4 (D) 5

CY 11/24

Q.55 Match the structures in List I with their correct names given in List II

List I (a)

dO"' 0

(b)

C) ~

(c)

CA"", (d)

HO

(e)

(A) a-vii b-ii c-vi (C) a-vii b-ii c-vi

d-iii e-iv d-iii e-v

List II

(i) 2-methyl furan

(ii) Imidazole

(iii) 5-hydroxybenzothiazole

(iv) 2-amino piperidine

(v) 2-amino morpholine

(vi) 2-amino azine (vii) 3-methyl furan (viii) 4-hydroxybenzothiazole

(8) a-vii (D) a-I

b-ii b-ii

c-vi c-vi

d-viii e-Iv d-iii e-iv

Q.56 The result of the reduction of either (R) or (S) 2-methyJcycJohexanone, in separate reactions, using LiAIH. is that the reduction of

(A) the R enantiomer is stereoselective (8) the R enantiomer is stereospecific (C) the S enantiomer is stereospecific (D) both the Rand S enantiomers is stereoselective

CY 12/24

Q.57 The increasing order of basicity among the following is

NIGH,), NIGH,),

(X)

(A) Y<X<Z

Q.58 In the reaction

NIGH,), NIGH,),

H,GO ~ ~

OGH,

#' #'

(V)

(8) Y<Z<X

H,C

C2H'"II,}-sr

C,Hl

(C) X<Z<Y

OH- (aq) •

NIGH,), NIGH,),

~

#'

OGH, (Z)

OGH,

(D) X<Y<Z

if the concentration of both the reactants is doubled, then the rate of the reaction will

(A) remain unchanged (8) quadruple (C) reduce to one fourth (D) double

Q.59 Match the structures in List I with the coupling constant ['H J (Hz)] given in List II

(a)

(b)

(c)

(A) a-i (C) a-iii

b-ii b-ii

List I

c-iii C-I

(8) a-ii (D) a-iii

CY 13/24

List II

(i) - I Hz

(ii) - 10 Hz

(iii) - 15 Hz

b-iii b-i

C-I

c-ii

Q.60 Phenol on react ion with formaldehyde and dimethyl amine mainly gives

(A) (3) OH OH

CH,N(CH3), ~

#

CH,N(CH3"

(C) (D) CHO CHO

~ CH,N(CH3), ~

# #

CH,N(CH3"

Q.61 The mono protonation of adenine (X) in acidic solution CD

0·JYs '" l)-NCD \Y \

H

mainly occurs at

(A) position I (C) position 3

(3) position 2 (D) either position 4 or 5

Q.62 In the following reaction

)IN' __ ---'-hc:..v __ .... (X)

benzophenone H H

(X) and (V) respectively are

(Al i:CH, and cis 1,2 dimethylcyclopropane (3) ':CH, and cis 1,2 dimethylcyclopropane

) ----< .... (V)

(C) i: CH, and a mixture of cis / trans 1,2 dimethylcyclopropane (D) 3:CH, and a mixture of cis / trans 1,2 dimethylcyclopropane

CY 14124

Q.63 The major products obtained upon treating a mixture of

()I-I() .. «!-I"() CH,

with a strongly acidic solution of H2S04 is

(A) H,C

NH,

CH,

(8)

NH,

CH,

(C) H,C H,C NH,

H,N NH,

(D) H,C

H,N f and CH,

H,N

Q.64 Match the observed principal absorbtions in the visible spectrum shown in List I with the bond that shows this absorbtion in List II

List I (a) CI ~ cr(b) n~CI' (c) n, rr(d) rr, rr-

(A) a-i (C) a-ii

b-ii b-i

c-iii c-iv

d-iv d-iii

List II

(il C - C (ii ) C-O (iii) C = 0 (iv) C = C

(8) a-i b-iii (D) a-iv b-ii

CY 15/24

c-ii d-iv c-iii d-i

Q.65 Among the isomers ofe lOH'4 shown,

p Q R s the isomer that can be identified uniquely by mass spectrometry alone is

(A) P (8) Q (C) R (D) S

Q.66 The direction of rotation of the following thermal electrocyclic ring closures

Q.67

o 0> o

respectively is

(A) disrotatory, disrotatory, disrotatory (8) con rotatory, conrotatory, conrotatory (e) disrotatory, disrotatory, con rotatory (D) disrotatory, conrotatory, disrotatory

The molecule(s) that exist as meso structure(s)

~ (Ll

is / are

(A) only M (8) both K and L (C) only L

ey 16/24

(1\1)

(D) only K

Q.68 The stereochemical descriptors for the atoms labeled H, and Hb in the structures H. ~Hb

~ .. ~, ....

HO (X)

respectively are

(A) X-homotopic, Y-enantiotopic and Z-diasterotopic (B) X-enantiotopic, V-homotopic and Z-diasterotopic (C) X-diasterotopic, V-homotopic and Z-enantiotopic (D) X-homotopic, Y -diasterotopic and Z-enantiotopic

HX~Hb " " .. ' CI

(Z)

Q.69 Treatment of the pentapeptide Gly-Arg-Phe-Ala-Ala, in separate experiments, with the enzymes Trypsin, Chymotrypsin and Carboxypeptidase A respectively, gives

Q.70

(A) Gly-Arg + Phe-Ala-Ala ; Gly-Arg-Phe + Ala-Ala; Gly-Arg-Phe-Ala + Ala (B) Gly-Arg-Phe + Ala-Ala; Gly-Arg-Phe + Ala-Ala; Gly-Arg-Phe-Ala + Ala (C) Gly-Arg + Phe-Ala-Ala; GIY-Arg-Phe-Ala + Ala; Gly-Arg-Phe + Ala-Ala (D) Gly-Arg + Phe-Ala-Ala; Gly-Arg-Phe + Ala-Ala; Gly + Arg-Phe-Ala + Ala

Hordenine (X), an alkaloid, undergoes Hoffman degradation to give compound (Y).

HO-Q-,CH2CH2N(CH2h __ (X)

(Y) on treatment with alkaline permanganate gives (Z). Y and Z respectively are

(A) (B) OH OH OCH 3 OCH3

~ ~ ~ ~

~ and ~ ~

and ~

~ eOOH eaOH ---:P (C) (D)

OCH3 OCH3 OCH3 OCH3

~ ~

and ~

and ~

CH 2 COOH ~ eOOH

CY 17/24

Common Data Questions

Common Data for Questions 71,72,73:

Trans I, 2 difluoroethylene molecule has a 2-fold rotational axis, a symmetry plane perpendicular to the rotational axis and an inversion centre.

Q.71 The number of distinct symmetry operations that can be performed on the molecule is

(A) 2 (B) 4 (C) 6 (D) 8

Q.72 The number of irreducible representations of the point group of the molecule is

(A) I (B) 2 (C) 3 (D) 4

Q.73 When two H atoms of the above molecule are also replaced by F atoms, the point group of the resultant molecule will be

(A) C i

Common Data for Questions 74, 75:

Reactivity of aryl amines towards electrophilic aromatic substitution is much higher than that of aliphatic amines. Hence differential reactivity of the amino group is desirable in many reactions.

Q.74 The compound which on reacting with aniline will NOT form an acetanilide is

(A) (B)

(C) (D)

Q.7S Aniline can be distinguished from methylamine by its reaction with

(A) p-toluene sulphonyl chloride 1 KOH (B) (i) NaN02 1 HCI, o-soc eii) alkaline p naphthol (C) Sn 1 HCI (D) acetyl chloride

CY 18/24

Linked Answer Questions: Q.76 to Q.85 carry two marks each.

Linked Answer Questions 76 & 77: Q.76 In the reaction

0 3

W. H20 (X) + Acetone + 2 Formaldehyde

Compound X is

(A) (B) 0

c; H CHO

0

0

(C) (D) 0

H

CHO

H

Q.77 Oxidation of X with chromic acid chiefly gives

(A) (8)

(C) (D)

COOH

CY 19124

(COOH

YCOOH

o

COOH

COOH

Linked Answer Questions 78 & 79:


Compound X is

(A) Adenine (C) 2,6 - diaminopurine

(8) Xanthine (D) Adenosine

Q.79 Compound X on treatment with conc. HCI gives

(A) Uric acid (8) Adenine (C) Hypoxanthine (D) Guanine


Q.80 The reaction of ammonium chloride with 8Cl l at 140°C followed by treatment with NaBH., gives the product X. The formula of X is

Q.81 Which of the following statement(s) is/are true for X? (i) X is not isoelectronic with benzene. (ii) X undergoes addition reaction with HCI.

(D) [BH-NHln

(iii) Electrophilic substitution reaction on X is much faster than that of benzene. (iv) X undergoes polymerization at 90°C.

(A) i and ii (8) only ii (C) ii and iii (0) i and iv


Q.82 Consider a particle of mass m moving in a one-dimensional box under the potential V=O for 0 ;!; x ;!; a and V = <Xl outside the box. When the particle is in its lowest energy state the average momentum «Px» of the particle is

(A) <Px>= 0 h

(8) <Px>=-a

h (C) <Px>=-

2a

h (D) <Px>=-

2,ra

Q.83 The uncertainty in the momentum (t.px) of the particle in its lowest energy state is

(A) t.px=O (8) h

t.px =a

h (C) t.px =-

2a

CY 20/24

h (D) t.px=-

21/"a


Q.84 In the mixture obtained by mixing 25.0 mL 1.2 x 10-3 M MnCh and 35.0 mL of 6.0 x 10-4 M KCI solution, the concentrations (M) of Mn2+, K+ and cr ions respectively are

(A) 6.0 x 10-4, 3.0 X 10-4, 1.5 X 10-3

(C) 5.0 X 10-4,3.5 X 10-4, 1.35 X 10-3 (B) 6.0 x 10-4, 3.0 X 10-4,9.0 X 10-4 (D) 5.0 x 10-4,3.5 X 10-4,8.5 X 10-4

Q.85 The activity (M) of Mn2+ions in the above solution is

(A) LOx 10-4 (B) 2.0 x 10-4 (C) 3.0 X 10-4 (D) 4.0 x 10-4

END OF THE QUESTION PAPER

CY 21124

2008 MAIN PAPER-CY

CY : CHEMISTRY

Duration: Three Hours Maximum Marks: 150

Read the following instructions carefully

Cy

I. This question paper contains 24 printed pages including pages for rough work. Please check all pages and report discrepancy, ifany.

2. Write your registration number, your name and name of the examination centre at the specified locations on the right half of the ORS.

3. Using HB pencil, darken the appropriate bubble under each digit of your registration number and tbe letters corresponding to your paper code.

4. All the questions in this question paper are of objective type.

5. Questions must be answered on Objective Response Shcet (ORS) by darkening the appropriate bubble (marked A, B, C, D) using HB pencil against the question number on the left hand side of the ORS. Each question has only onc correct answer. In case you wish to change an answer, erase the old answer completely. More than one answer bubbled against a question will be treated as a wrong answer.

6. Questions I through 20 are I-mark questions and questions 21 through 85 are 2-mark questions.

7. Questions 71 through 73 is one set of common data questions, questions 74 and 75 is another pair of common data questions. The question pairs (76, 77), (78. 79), (80, 81), (82, 83) and (84, 85) are questions with lillked answers. The answer to the second question of the above pairs will depend on Ole answer to the first question of the pair. I [Ole first question in the li,lked pair is wrongly answered or is un-attempted, then the answer to the second question in the pair will not be evaluated.

8. Un-attempted questions will carry zero marks.

9. NEGATIVE MARKING: For Q. I to Q.20, 0.25 mark will be deducted for each wrong answer. For Q.21 to Q.75, 0.5 mark will be deducted for each wrong answer. For the pairs of questions with lirlked answers, there will be negative marks on ly for wrong answer to tbe first question, i.e. for Q.76, Q.78, Q.80, Q.82 and Q.84, 0.5 mark will be deducted for each wrong answer. There is no negative marking for Q. 77, Q.79, Q.81, Q.83 and Q.85.

to. Calculator without data connectivity is allowed in the examination hall.

II. Charts, graph sbeets and tables are NOT allowed in the examination hall.

12. Rough work can be done on the question paper itself. Additional blank pages are given at the end of the question paper for rough work.

1124

2008

cy

MAIN PAPER - CY

Some Useful Data

1. Physical Constants:

Universal gas constant, R = 8.314 J K-' mor' = 0.082 L atm K"' mor'

Planck constant, h = 6.626 x 10-34 J s

Avogadro number, NA = 6.023 x 1023 mor'

Faraday constant, F 96485 C mor'

Electron charge, e = 1.602 x 10-'9 C

Speed of light, c = 2.998 X 108 m sol

Boltzmann constant, ke = 1.381 x 10-23 J K-'

Electron mass, llle = 9.1 09 X 10-3' kg

2. Atomic Numbers:

B= 5; F=9; Al = 13; Si = 14; P = 15; S = 16; Cl = 17; Ti = 22; V= 23; Cr= 24; Mn =25;

Fe = 26; Co = 27; Ni = 28; ClI = 29; Ru = 44; Rh = 45; Re = 75; Os = 76.

2/24

2008 MAIN PAPER - CY

Q. 1 - Q. 20 Carry one mark each

Q.I The total number of isomers ofCo(enj,CI, (en ~ ethylenediamine) is

(A) 4 (B) 3 (C) 6 (D) 5

Q.2 Metal-metal quadruple bonds are well-known for the metal

(A)Ni (B) Co (C) Fe (0) Re

Q.3 The reaction of AI,C, with water leads to the formation of

(A) methane (B) propyne (C) propene (0) propane

Q.4 The correct statement about Coo is

(A) Coo is soluble in benzene

(B) Coo does not react with tert-butyllithium

(C) C60 is made up of 10 five-membered and 15 six-membered rings

(0) Two adjacent five-membered rings share a common edge

Q.5 The lattice parameters for a monoclinic crystal are

(B) a ~ b * c ; a * 13 * y

(C) a * b * c ; a * 13 * y

Q.6 n,e magnetic moment of [Ru(H,O),]'+ corresponds to the presence of

(A) four unpaired electrons (B) three unpaired electrons

(C) two unpaired electrons (D) zero unpaired electrons

Q.7 The compound that is NOT aromatic is

(A) (B) o o $ e

(C) (D) e o a e

•

cy 3/24

2008 MAIN PAPER CY

Q.8 The order of stabili ty for the following cyclic olefms is

II III IV

CAl I < II < III < IV (Bl II < III < IV < 1

(C) 1I < III < I < IV (D) IV < 11 < I < 111

Q.9 The most acidic species is

(A) (B)

W ,N,

M ,N,

H H H H

(C) (D)

W NMe2

0 N I H N

I H

Q.IO The major product of the fol lowing reaction is

~ il Naniq. NH:JiTHF, -40°C

• iil H30+

(Al (B) ~ ~

(C) (D) ~ ~

Q. I I In the carbylamine reaction, R-X is converted to R- Y via the intermediate Z. R-X, R-Y and Z, respectively, are

(Al R-N H" R-NC, carbene (B) R-NH, , R-NC, nitrene

(C) R-NC, R-NH, , carbene (D) R-OH, R-NC, nitrene

cv 4/24

2008 MAIN PAPER CV

Q.12 The compound that is NOT oxidized by KMnO. is

(A) (B)

Mese Me

I'" "" N

Me~MeMe Me H

I'" /.

N

(C) (D)

Mese OH

I'" "" N

Me(SMeMe

I'" /.

N

Q.13 Cyanogen bromide (CNBr) specifically hydrolyses the peptide bond fonned by the C-side of

(A) methionine (B) glycine (C) proline (D) serine

Q.14 The lIammett reaction constant p is based on

(A) the rates of alkaline hydrolysis of substituted ethyl benzoates

(B) the dissociation constants of substituted acetic acids

(C) the dissociation constants of substituted benzoic acids

(D) the dissociation constants of substituted phenols

Q.15 The lifetime of a molecule in an excited electronic state is 10.10 s. The uncenainty in the energy (eV) approximately is

(A) 2 x 10" (B) 3 x 10.6 (C) 0 (D) 10.14

Q.16 For a one component system, the maximum number of phases that can coexist at equilibrium is

(A)3 (B) 2 (C) I (0)4

Q.17 At T = 300 K, the thermal energy (ke T) in cm" is approximately

(A) 20000 (B) 8000 (C) 5000 (D) 200

cv 5!24

2008 MAIN PAPER CY

Q.18 For the reaction 2 X] = 3 X" the rate of formalion of X, is

(A) 3 ( - d[X]] / dt) (8) 1/2 ( -d[X]] / dt) (C) 1f3 ( -d[X]] / dt) (D) 3/2 ( -d[X]] / dt)

Q.19 The highest occupied molecular orbital of HF is

(A) bonding (8) antibonding (C) iomc (D) nonbonding

Q.20 The residual entropy oftbe asymmetric molecule N,O in its crystalline state is 5.8 J K" mol" at absolute zero. The number of orientations that can be adopted by N,O in its crystalline state is

(A) 4 (8) 3 (C) 2 (D) I

Q. 21 to Q.75 Carry two marks each

Q.21 The spectroscopic ground state symbol and tile total number of electronic transitions of [Ti(H,O).]" are

(A) '1'" and 2

(C) ]T,& and 3

(8) ] A,. and 3

(0) ] A,. and 2

Q.22 The structures of the complexes [Cu(N HJ),](CIO,), and [Cu(NI-I])4](CIO,) in solution respectively are

(A) square planar and tetrahedral (8) octahedral and square pyramidal

(C) octahedral and trigonal bipyramidal (D) tetrahedral and square planar

Q.23 In biological systems, the metal ions involved in electron transport are

(A) Na' and K+ (8) Zn'+ and Mg" (C) Ca" and Mg'+ (D) Cll" and Fe"

Q.24 In a homogeneous catalytic reaction. I.OM of a substrate and I.O].IM of a catalyst yields 1.0 mM of a product in 10 seconds. The tumover frequency (TOF) of the reaclion (s') is

(A) 10" (8) 10' (C) 10" (D) 10]

C'y 6:'24

2008 MAIN PAPER CY

Q.25 The expected magnetic moments of the first-row transition metal complexes and those of the lanthanide metal complexes are usually calculated using

(A) fl •• equation (s. o. = spin only) for both lanthanide and transition metal complexes

(B) !! • • equation for lanthanide metal complexes and fl, equation for transition metal complexes

(C) !! '.0 equation for transition metal complexes and fl, equation for lanthanide metal complexes

(D)!! L.S equation for transition metal complexes and fl, o equation for lanthanide metal complexes

Q.26 The Bronsted acidity of boron hydrides follows the order

Q. 27 Nael is crystallised by slow evaporation of its aqueous solution at room temperature. The correct statement is

(A) The crystals will be non-stoichiometric

(B) The crystals should have Frenkel defects

(C) The percentage of defects in the crystals will depend on the concentration of the solution and its rate of evaporation

(D) The nature of defects will depend upon the concentration of the solution and its rate of evaporation

Q.28 eaTiO, has a perovskite crystal structure. The coordination number of titanium in eaTiO, is

(A) 9 (B) 6 (C) 3 (D) 12

Q.29 If eLF, were to be stereochemically rigid, its I9F NMR spectrum (I for I9F = v,) would be (assume that el is not NMR active)

(A) a doublet and a triplet (B) a singlet

(C) a doublet and a singlet (D) two singlets

Q.30 The point group of NSF, is

(A) Dld (B) e'h (D) e"

,v


Q.31 When NiO is heated with a small amount ofLi,O in air at 1200 °c, a non-stoichiometric compound Li,Ni(l _,p is fonned. This compound is

(A) an n-type semiconductor containing only Ni [.

(B) an n-type semiconductor containing Ni [. and Ni'·

(C) a p-type semiconductor containing NiH and Ni'·

(D) a p-type semiconductor containing only Ni'·

Q.32 White phosphorus, P" belongs to the

(A) closo system (B) /lido system

(C) arachllo system (D) hypha system

Q.33 Among the compounds Fe,O" NiFe,O, and Mn,O,

(A) NiFe,O, and Mn,O, are nonnal spinels

(B) Fe,O, and Mn,O, are nom,.1 spinels

(C) Fe,O, and Mn,O, are inverse spinels

(D) Fe,O, and NiFe,O, are inverse spinels

Q.34 The number of M-M bonds in Ir,(CO) " are

(A) four (B) six (C) eight

Q.35 Schrock carbenes are

(D) zero

(A) triplets and nucleophilic (B) triplets and electrophilic

(C) singlets and nucleophilic (D) singlets and electrophilic

Q.36 The INCORRECT statement aboullinear dimethylpolysiloxane, [(CH,),SiO]", is

CA) it is extremely hydrophilic

(B) it is prepared by a KOH catalysed ring-opening reaction of[Me,SiO],

(C) it has a very low glass transition temperature

(D) it can be reinforced to give silicon elastomers

Cy 8124


Q.37 Match the entries a-d with their corresponding structures p-s.

a bridged system p

b atropisomeric system q 8 c spiro system

r

MeO Me

< < p Me OMe

d fused system s 0 (A) a-s; b-r; c-q; d-p (8) a-p; b-s; c-q; d-r

(C) a-q; b-p; c-s; d-r (D) a-s; b-r; c-p; d-q

Q.38 The reaction between X and Y to give Z proceeds via

Ph Q: «R OJ: {; + • "" . ~ :

-'Ph PhH 0 0

X Y Z

(A) 4n-conrolatory opening of X followed by endo Diels-Alder cycloaddirion

(8) 4n-disrolalory operung of X followed by endo Diels-Alder cycioaddilion

(C) 4n-conrotatory opening of X followed by exo Diels-Alder cycioaddition

(D) 4n-disrotatory opening of X followed by exo Diels-Alder cycioaddilion

Cy 9/24

:!O08 MAIN PAPER CY

Q.39 The major products P, and P" respectively, in Ole following reaclion sequence are

9 e Me~Me l>.

P1 H2! Ni

Me-C= N- O + • • P 2 H2O

(A) N- O HN- O

Me~·" Me and Me~·" Me Me Me

(B) N- O 0 OH

Me~· " Me and MeY ·" Me

Me Me

(e) N- O 0 OH

MeY Me and MeY Me

Me Me

(D) H

NH2 0H N OH

Me~·" Me and Me~· " Me Me Me

Q.40 The products Y and Z are formed, respectively, from X via

c/ I 0 y

-------- -ceo H

-----.... Cf 0

X I _ H Z

0

(A) hv, conrotatory opening and l>., disrotalory opening

(B) hv, disrotatory opening and l>., conrotatory opening

(C) l>., conrotatory opening and hv, disrotatory opening

(D) l>., disrotatory opening and hv, conrolatory opening

Cy 10124

2008 MA IN PAPFR CY

Q.41 o-Bromophenol is readily prepared from phenol using the following condilions

(A) i) (CH,CO),O; ii) Br,; iii) HCI-H,O, I!.

(B) i) H,S04, 100 DC ii) Br, iii) H,O', 100 DC

(C) N-Bromosuccinimide, dlbenzoyl peroxide, CCl., I!.

(D) Br,lFeBr,

Q.42 The major producl of the fo llowi ng reaction is

Ti(O-'Pr}4, L-( + }-dielhyl la rtarale

•

(A) (B)

O:::COH iPr

O~OH 'Pr

(C) (D)

O~OH 'Pr

~OH 'Pr

Q.43 The phOiochemical reaction of2-methylpropane with F, gives 2-!luoro-2-melhylpropane and 1-!luoro-2-methylpropane in 14:86 ralio. The correspondi ng ratio of the bromo products in the above reaclion using Br, is mosl likely to be

(A) 14: 86 (B) 50 : 50 (C) I: 9 (D) 99: I

Q.44 The major product P of lhe following \eactions is

0 0 i}X

(!)

EtO~Me , H, tJ.

OH OH P •

ii) MeMgBr (excess)

iii) H30 (!)

(A) (B) o OH

EtOW~e Me OH 0

M~Me (C) (D)

o 0 Me!O\Me Me~Me Me I: Me

cy 11,'24

2008 MAIN PAPER CY

Q.45 The reagent X in the following reaction is

n ° n

~ X A ° 0 HO Ph3P, PhC02H, Ph O~ •

""- THF

(A) (B) H02CN=NC02H Et02CHC=CH-C02Et

(C) (D) Et02CN=NC02Et

o-N=C=N-Q

Q.46 The major product of the following reactions is

•

(A) (B)

HO~oJl HO~OH (C) (D)

~oJl OH

~OH Q.47 The major product of the following reaction is

0 C02CH3

H2, Pt02 (cat.) .. AcOH, room temperature

(A) (B)

0 C02CH3 0 CH20H

(C) (D)

0 C02CH3 0 C02CH3

CY 12124

2008 MAIN PAPER - cv

Q.48 [n the following compound, the hydroxy group that is most readily methylated with CH,N, is

(A) P (8) q

q P

H~_ H)=(H T'o~o

HO s

(C) r (D)s

Q.49 The most appropriate sequence of reactions for carrying out the following transformation is

0 • C NH

(A) i) O,JH,O,; ii ) excess SOCI,/pyridine; iii) excess NH,; iv) LiAllt,

(8) i) O,/Me,S; ii) excess SOCl,Ipyridine; iii) LiAll1,; iv) excess NH,

(C) i) O,IH,O,; ii) excess SOCI,/pyridine; iii) LiAlH,,; iv) excess NH,

(D) i) O,IMe,S; ii) excess SOCI,/pyridine; iii) excess NH,; iv) LiAIH.

Q.50 The number of optically active stereoisomers possible for 1,3-cyclohexanediol in its chair conformation IS

(A) 4 (8) 3 (C) 2 (D) I

Q.5 ! The major product of the following reactions is

c5 •

(A) (8) Me Me

6 0H 6," OH

(e) (D) Me Me c:r 0 °

Cy 13124

2008 MAIN PAPER CY

Q.52 In the following reaction,

CHO

Ht OH

CH20H

D-Glyceraldehyde

HCN -------,l.~ X + y

(2 diastereomers)

The absolute configurations ofrhe chiral centres in X and Yare

(A) 2S, 3R and 2R, 3R (B) 2R, 3R and 2R,3S

(C) 2S, 3S and 2R, 3R (D) 2S, 3R and 2S, 3R

Q.53 The IR stretching frequencies (cn'-') Cor the compound X are as follows: 3300-3500 (s, br); 3000 (m); 2225 (s); 1680 (5).

o

~H NC~OH

X

The COtTect assignment of the absorption bands is

(A) V(OH) = 3300-3500; V(CH) = 3000; "(CN) = 2225; v(CO) = 1680

(B) V(OH) = 3000; V(CH) = 3300-3500; V(CN) = 2225; v(CO) = 1680

(e) V(OH) = 3300-3500; V(CH) = 3000; V(CN) = 1680; "(CO) = 2225

(D) V(OH) = 3000; V(CH) = 3300-3500; V(CN) = 1680; v(CO) = 2225

Q.54 The To point group has 24 elements and5 classes. Given that it has two 3-dimensional irreducible representations, the number of one dimensional irreducible representations is

(A) I (B) 6 (C) 2 (D) 3

Q.55 The total number of ways in which two nonidentical spin Y:, particles can be oriented relative to a constant magnetic field is

(A) I (B) 2 (C) 3 (0)4

Cy 14124

2008 MAIN PAPER CY

Q.56 Approximalely one hydrogen atom per cubic meter is present in interstellar space. Assuming that ule H-atom has a diameter of 10-'0 m, the mean free path (m) approx.imately is

(A) 10'0 (8) 10" (C) 10" (D) 10"

Q.57 The wave function of a diatomic molecule has the form", = 0.89 <p ,.,,',,' + 0.45 <p , •• ". The chance that both electrons of the bond will be found on the same atom in I 00 inspections of the molecule approximately is

(A) 79 (8)20 (C) 45 (D) 60

Q.58 For the reaction given below, the relaxation time is 10.0 s. Given that 10% of A remains at equilibrium, the value of k, (5') is

A

(A)9x 10' (8) 10-'

.. k -I

.. (C) 10'

8

(D) 9 x 10·'

Q.59 The minimum number of eleclrons needed to fonn a chemical bond between two atoms is

(A) I (8) 2 (C) 3 (D) 4

Q.60 The ground state electronic energy (Hartree) of a helium atom, neglecting the inter-electron repulsion, is

(A) - 1.0 (8) - 0.5 (C) - 2.0 (D) - 4.0

Q.61 A particle is confined to a one-dimensional box of length I mm. lfthe length is changed by 10·'111, the % change in the ground state energy is

(A) 2 x 10" (8) 2 x 10·' (C) 2 X 10.2 (0)0

Q.62 A certain molecule can be treated as having o,uy a doubly degenerate state lying at 360 cm·' above the nondegenerate ground state. The approx.imate temperature (K) at which 15% of the molecules will be in the upper state is

(A) 500 (8) 150 (C) 200 (D) 300

Q.63 A box of volume V contains one mole of an ideal gas. The probability that all N particles will be found occupying one half of the volume leaving the other half empty is

(A) 112 (8) 21N (C) (1/2)N (D) (1/2) 6N

Cy

2008 MAIS PAPER CY

Q.64 According to the Oebye-Hiickel limiting law, the mean activity cocfticient of 5 x 10" mol kg" aqueous solution of CaCI, at 25·C is (the Oebye-Hiickel constant' A' can be taken to be 0.509)

(A) 0.63 (B) 0.72 (C) 0.80 (D) 0.91

Q.65 The operation of the commutator [x, dldx] on a function f(x) is equal to

(A) 0 (B) f(x) (C) -f(x) (D) x dfldx

Q.66 If a gas obeys the equation of state P (V - nb) = nRT, the ratio (Cp _ Cv)! (Cp _ Cv)""" is

(A) > I (B) < I (C) I (0)(1 - b)

Q.67 Physisorbed panicles undergo desorption at 27 · C with an activation energy of 16.628 kJ mor'. Assuming first-order process and a frequency factor ono" Hz, the average residence time (in seconds) of the panicles on the surface is

(A) 8 x 10'" (B) 8 x 10' " (C) 2 x 10" (D) I x 10'"

Q .68 The rotational constants for CO in the ground and the first excited vibrational states are 1.9 and 1.6 cm-I

, respectively. The % change in the internuclear distance due to vibrational excitation is

(A) 9 (B) 30 (C) 16 (0)0

Q.69 The mechanism of enzyme (E) catalysed reaction of a substrate (S) to yield product (P) is

E+P -drS) = k tk2[S)-k_ tk_2[P) [E)o

dt kl [S)+k..2[P)+k_ l+k2

If a sma)) amount ofS is convened to P, the maximum rate for the reaction will be observed for

(A) (k., + k,) » k, [S] 0 (B) (k., + k,) « k, [S] 0

(C) (k.2 + k,) = (k_, + k,) (D) k., « k,

Q.70 The lowest energy state of the (Is)' (2s)' (3s)' configuration of Be is

(A) 'So (B) '02 (C) ]S, (D) ]p,

cv

2008 MAIN PAPER CV


Common Data for Questions 71, 72 and 73:

An electron accelerated through a pOlential difference of q> volts impinges on a nickel surface, whose (100) planes have a spacing d = 351.8 x 10·" m (351.8 pm).

Q.71 The de-Broglie wavelength of the electron is A I pm = (al q»' I The value of , a' in volts is

(A) 1.5 x 10·" (B) 1.5 x 10' (C) 6.63 x 10·' (D) 2.5 x 101•

Q.72 The condition for observing diffraction from the nickel surface is

(A) A» 2d (B) A =:: 2d (C) A=::ad (D) A?: ad

Q.73 The minimum value of q> (V) for the electron to diffract from the (100) planes is

(A) 3000 (B) 300 (C) 30 (0)3

Common Data for Questions 74 and 75:

An iron complex [FeL.t (L = neutral monodentate ligand) catalyses the oxidation of (CH,),S by per benzoic acid.

Q.74 The formation of the organic product in the above reaction can be monitored by

(A) gas chromatography (B) cyclic voltammetry

(C) electron spin resonance (D) fluorescence spectroscopy

Q.75 The oxidation state of the metal ion in the catalyst can be detected by

(A) atomic absorption spectroscopy (8) Mossbauer spectroscopy

(C) HPLC (D) gas chromatography

CV 17(14

.2008 MAIN PAPER CY

Linked Answer Questions: Q.76 to Q.85 carry two marks each

Linked Answer Questions 76 and 77:

In the reaction,

• X+Y

Q.76 Compound X is CAl (B)

(C) (D)

Q.77 RJl(PPh,hCI reacts very fast with a gaseous mixture ofH, and C,H, to immediately give Z. The structure of Z is

(Al (B)

(C) (D) PPh3 I

Ph3P-Rh-PPh3 _I

18."14

Z008 MAIN PAPER - CY


The reaction of PCi) with methanol in tile presence of triethylamine affords compound X. EI mass spectrum of X shows a parent ion peak at .nlz = 124. Microanalysis of X shows that it contains C, H, 0 and P. The 'H NMR spectrum of X shows a doublet at4.0 ppm. The separation between tile two lines of the doublet is approximately 15 Hz (I for 'H and li p = Vo).

Q.78 Compound X is

(A) (CHJO)JP

(C) (CHJO),P(O)(OH)

Q.79 Upon heating, compound X is converted to Y, which has the same molecular formula as that ofX. The 'H NMR spectrum ofY shows two doublets centered at3.0 ppm (separation of two lines -20 Hz) and 4.0 ppm (separation of two lines - 15 Hz) respectively.

Compound Y is

(A) (CHJO),P(O)(OH)

(C) (CH,O),(CH,)P(O)

Linked Answer Questions 80 and 8]:

For butyrophenone (PhCOCH,CH,CHJ),

(B) (CH,O)JP

(0) (CH,O),(CHJ)P(OH)

Q.80 the most probable fragmentation observed in the electron impact ionization (EI) mass spectrometry is

(A) (B) 0 1·+ 01' -

PhA + H2C= CH2 PhA + H2C= CH2

(C) (0) 0 0

Ph~ + oCH3 PhA H + H2C~CH3

Q.81 photoirradiation leads to the following set of products.

(A) (B) o

H~ (C) (0)

H2C=CH2

Cy 19/24



In the following reaction,

hv ----. [I] -----. P

Q.82 the reactive intermediate I and the product Pare

(A) (B)

carbene and ~ radical and ~ H

(C) (D) carbene and ~ radical and ~

Q.83 the product P shows 'm' and ' n' number of signals in 'H and "e NMR spectra, respectively. The values of Om' and 'n' are

(A) m = 3 and n = 2 (B) m = 2 and n = 3

(C) m = 2 and n = 2 (D) m = 4 and n = 3


The infrared spectmm of a diatomic molecule exhibits transitions at 2144, 4262 and, 6354 cm·' corresponding to excitations from the ground slate to the first, second and, third vibration Slates respectively.

Q.84 The fundamental transition (cm·') of the diatomic molecule is at

(A) 2 157 (B) 2170 (C) 2183 (D) 2196

Q.85 The anharmonicity constant (cm·') of the diatomic molecule is

(A) 0.018 (B) 0.012 (C) 0.006 (D) 0.003


CY 20'24

2009 cv

CY : CHEMISTRY



cv

I. This question paper contains 16 printed pages including pages for rough work. Please check all pages and report discrepancy, if any.

2. Write your registration number, your name and name of the examination centre at the specified locations on the right half of (he Optical Response Sheet (ORS).

3. Using HE pencil, darken the appropriate bubble under each digit of your registration number and the letters corresponding to your paper code.

4. All questions in this paper are of objective type.

5. Questions must be answered on Optical Response Sheet (ORS) by darkening the appropriate bubble (marked A, B, C, D) using HE pencil against the question number on the left hand side of the ORS. Each question has only one correct answer. In case you wish to change an answer, erase the old answer completely. More than one answer bubbled against a question will be treated as an incorrect response.

6. There are a total of 60 questions carrying 100 marks. Questions I through 20 are I-mark questions, questions 21 through 60 are 2-mark questions.

7. Questions 51 through 56 (3 pairs) are common data questions and question pairs (57, 58) and (59, 60) are linked answer questions. The answer to the second question of the above 2 pairs depends on the answer to the first question of the pair. If the flrst question in the linked pair is wrongly answered or is un-attempted, then the answer to the second question in the pair will not be evaluated.

8. Un-attempted questions will carry zero marks.

9. Wrong answers will carry NEGATIVE marks. For Q.I to Q.20, % mark will be deducted for each wrong answer. For Q. 21 to Q. 56, % mark will be deducted for each wrong answer. The question pairs (Q.57, Q.58), and (Q.59, Q.60) are questions with 'linked answers. There will be negative marks only for wrong answer to the ftrst question of the linked answer question pair i.e. for Q.57 and Q.59, % mark will be deducted for each wrong answer. There is no negative marking for Q.58 and Q.60.

10. Calculator (without data connectivity) is allowed in the examination hall.

II. Charts, graph sheets or tables are NOT allowed in the examination hall.

12. Rough work can be done on the question paper itself. Additionally, blank pages are given at the end of the question paper for rough work.

1116

2009

Cy

Some Useful Data

Universal gas constant, R = 8.3145 J K-' mor l = 0.082 L atm K-' mol-I

Boltzmann constant, k8 = 1.381 X 10-23 J ~I

Avogadro number, N = 6.022 X 1023 mol-I

Electron charge, e = 1.602 x 10-19 C

Faraday constant, F = 96500 C mor l

Planck constant, h = 6.626 X 10-34 J s

Speed of light, c = 2.998 X 10' m S-I

Cy

U16

2009

Q. 1 - Q. 20 carry one mark each.

Q,j The lip NMR spectrum ofP,S, consists of

(A) a singlet

(C) a doublet and a quartet

(B) a doublet and a triplet

(D) two doublets

Q,2 The geometry around the central atom in CIF: is

(A) square planar (B) square pyramidal (C) octahedral (D) trigonal bipyramidal

Q,3 The correct statement about the Cu-N bond distances in [Cu(NH3).l" is

(A) all the bond distances are equal

(B) the axial bonds are longer than the equatorial ones

(C) the equatorial bonds are longer than the axial ones

(D) all the bond distances are unequal

Q.4 The reaction of phosgene with an excess of NH3 produces

(A) HN=C=O (B) H,N-C(CI)=O (C) (H,Nj,C=O

Q,j The number of metal - metal bonds in [(C,H,)Fe(CO)h is

(A) zero (B) one (C) two (D) three

Cy

Q,6 The coordination number of the Ba" ions in barium fluoride is g, The coordination number of the fluoride ion is

(A) g (B) 4 (C) 1

Q,7 In the transformation of oxyhaemoglobin to deoxyhaemoglobin

(A) Fe" in the low spin state changes to Fe" in the high spin state

(B) Fe" in the low spin state changes to Fe3• in the low spin state

(C) Fe2• in the high spin state changes to Fe2

• in the low spin state

CD) Fe2• in the high spin state changes to Fe" in the high spin state

Q,g For the compound

MOH o

the stereochemical notations are

(A) 22, 4R (B) 22, 4S (C) 2E,4R

Cy

(D) 2

(D) 2E,4S

3/16

2009

Q.9 The compound co is

CA) aromatic and has high dipole moment (B) aromatic and has no dipole moment

(C) non-aromatic and has high dipole moment (D) anti-aromatic and has no dipole moment

Q. JO In the reaction o

MeD +qo excess anhydrous AICI3

o the major product X is

(A) ~ Me~

o

(C) ~ MeN lCOOH

Q.II In the reaction

rr'Y°i* V ~ (* = I3C labelled carbon)

/!.

the major products X and Y are

..

(A) ~OH ~OH I and I .0 "'" -:? .0

* *

(C) ~OH ~OH I and I .0 "'" -:? .0

* *


.. [X]

(B)

CD)

[X] +[Y]

(B)

CD)

o Ph~CHO

Ph3P=CHCOOEt ---=------.... [X]

CY

the major product X is

(A)

(e)

H'(COOEt

Ph~CHO

o H Ph~COOEt

I'i

CB)

CD)

o Me

Me o

6¢ o

~OH ~OH I and I .0 "'" -:? .0

* *

~OH ~OH I and I .0 "'" -:? .0

* *

EtOOCyH

Ph~CHO

o H H

Ph~COOEt

Cy

4/16

2009 CY

Q.13 The most suitable reagent combination to bring out the following transfonnation

o hl-OH

• ~""O)lPh is

(A) PhCOCI and pyridine

(C) PhBr, CO and Pd(PPh3)4

Q.14 In the two steps reaction sequence

F

¢rN02 Me H 0 I: + H2N~r:\)lOH o Ph

N02

the major product Y is

(A)

Me --f"\- )-eOOH

02N \=( NH

N02

(C)

(B) DCC and PhCOOH

(D) EtOOC-N=N-COOEt, PPh3 and PhCOOH

mild base H30· -"-".:.:c:c:....,.~ [ X 1 • [ y 1

Hooe

(B) --f"\- )""Ph

02N \=( NH

N02

(D)

Q.15 Among the following, the system that would require the least amount of thermal energy to bring its temperature to 80 ·C is

(A) 200 g of water at 40 ·C

(C) 150 g of water at 50·C

(B) 100 g of water at 20 ·C

(D) 300 g of water at 30 ·C

Q.16 Among the following, the reaction that is accompanied by a decrease in the entropy is

(A) N2 (g) + 3Hz (g) -+ 2NH3 (g)

(8) C~'206 (s) + 60, (g) -+ 6CO, (g) + 6H,O(l)

(C) PCls (s) -+ PCI3 (I) + CI, (g)

(D) 2H,O (I) -+ 2H, (g) + 0, (g)

Q.17 The number of degrees of freedom of a system consisting of solid sucrose in equilibrium with an aqueous solution of sucrose is

(A) 0 (8) 1

Q.18 The lowest allowed energy is equal to zero for

(A) the hydrogen atom

(C) a hannonic oscillator

CY

(C) 2 (D) 3

(B) a rigid rotor

(D) a particle in a 3-dimensional box

5116

2009 CY

Q.19 According to the Debye-Hilckellimiting law, if tbe concentration of a dilute aqueous solution of KCI is

increased 4-fold, the value of In y ±' (y± is the molal mean ionic activity coefficient) will

(A) decrease by a factor of 2

(C) decrease by a factor of 4

(B) increase by a factor of 2

(D) increase by a factor of 4

Q.20 For the parallel first order reaction shown below

the value of kl is I X 10-4 S-I. If the reaction starts from X, the ratio of the concentrations of Y and Z at

any given time during the course of the reaction is found to be [y] = ~

The value of k2 is

(A) 1 x 10-4 S-I

(C) 4 X 10-4 S- I

[z] 4

(B) 2.5 X 10-5 S-I

(D) 4 x 104 S-I

Q, 21 to Q. 60 carry two marks each.

Q.21 The correct order of Veo for the compounds [Mo(CO),(NMe3)31, [Mo(CO)3(P(OPh)3hJ. [Mo(CO)3(PMe3hl, [Mo(COl3(PCh)31 in the IR spectrum is

(A) [Mo(CO),(NMe3)31 > [Mo(COh(P(OPh)3)31 > [Mo(CO),(PMe3)31 > [Mo(COl3(PCl,)31

(B) [Mo(CO)3(PCh)31 > [Mo(CO),(NMe3)31 > [Mo(CO)3(P(OPh)3)31 > [Mo(CO)3(PMe3)31

(C) [Mo(CO)3(PCI3hl > [Mo(CO)3(P(OPhh)31 > [Mo(CO),(PMe3hl > [Mo(CO)3(NMe3)31

(D) [Mo(CO)3(PMe3)31 > [Mo(COh(NMe3)31 > [Mo(CO)3(PCI3)3] > [Mo(CO),(P(OPh)3)31

Q.22 2.5 g of an iron compound upon suitable treatment yielded 0.391 g of iron(III) oxide. The percentage of iron in the compound is

(A) 10.94 (B) 12.15


Mel [ X 1

n-BuLi • • [Y 1

the compounds X and Y, respectively, are

(A) [Ph3P(Me)I]; Ph3P=CH-CH,--CHr-CH3

(C) [PhJP(Meh]; PhJP=CH2

Q.24 The IH NMR spectrum of lID consists of a

(A) singlet (B) 1:1 doublet

CY

(C) 11.31

(atomic weight of Fe: 55.847, 0: 15.994)

(D)9.11

(B) [ph3P(Me)][1]; Ph3P=CH2

(D) [ph3P(Me)] [I]; Ph3P(J

(C) 1:1: 1 triplet (D) 1 :2: I uiplet

6116

2009 CY

Q.25 The X-ray powder pattern of NaCl shows an intense cone at e = 15.87° using X-rays of wavelength 1.54 x 10-8 cm. The spacing between the planes (in A) of NaCl crystal is

(A) 1.41 (B) 2.82 (C) 4.23

Q.26 Among the following, the isoelectronic and isostructural pair is

(A) CO2 and S02

(C) N02• and Te02

(B) S03 and Se03

(D) SiO.4- and PO.3-

(D) 5.63

Q.27 Two samples have been given to you: [NiCh(PPh3hl and [PdCh(PPh3hl. A physical method that can be used to identify these compounds unambiguously is

(A)HPLC

(C) 13C NMR spectroscopy

(B) magnetic susceptibility

(D) Mossbauer spectroscopy

Q.28 In the reaction HSO.- (aq) + OIr (aq) ~ SO.'- (aq) + H20(l), the conjugate acid-base pairs are

Q.29

(A) HSO.- and SO.2-; H20 and OIr

(C) HSO.- and OIr; SO,2- and H20

Designate the following complexes X, Y

X = [Al(C20.)313-, Y = [V(H20)612.,

(A) X and Yare inert; Z is labile

(C) X is inert; Y and Z are labile

Q.30 In the reaction sequence

o

0+ Qo --"---i.~ [X 1

o X and Y, respectively, are

(A) ~ ~ ~oand~'t°

o 0

(B) HSO,- and H30· ; SO/- and OIr

(D) HSO.- and OIr ; SO/- and H30'

and Z as inert or labile:

Z = [Cr(C20.)313-

(B) X and Z are labile; Y is inert

(D) X is labile; Y and Z are inert

----"'----i.~ [ Y 1

(B) OJ and ~ 0

o 0

(C) ~o and ~o (D) o-n and ~: o 0 0

CY 7/16

2009 CV

Q.31 The major product X (based on the preferred conformation) in the reaction

is

(A) ~ o

(C) CO OH

d5 OH

KH ------1.~ [X 1

(T5; p-toluenesulfonyl)

(B) q o

(D) 05 Q.32 In the reactions

PhCHO [Xl • acetone

O-glucose -===--..... ~ H+

[Y 1

the major products X and Y, respectively, are

(A)

(B)

Ph/\""~ o 0 HO

HO OH

o Ph~,=\;x •. 0 0 r Ph

o HO

Me

Me-\~o HO~

HO OH

and

Me

and Me-\~o HO~

HO OH

Ph~,=\;x.. 0 O. :e><:,=\;x.. ° 0 M (C) r Ph and X e

o 0 ~ HO HO

(D) Ph1~ and ::><::l P-'-°XMe HO OH )..-lo Me

HO


Cy

Ph-==-O o=q

1. I B-O ~ ci

2. CH3COOH

the major product X is

(A) (B)

• [X 1

(C) (D)

8/16

2009 CY

Q.34 Reaction of m-methylanisole with lithium in liquid ammonia and t-butyl alcohol at -33°C generates compound X as the major product. Treatment of the compound X with dilute sulphuric acid produces compound Y as the major product. The compounds X and Y, respectively, are

OMe OMe

(A) D Me

(B) n MeN

OMe OMe

(C) Me~ (D) Me~ Q.35 The number of signals that appear in the broad-band decoupled 13C NMR spectrum of ortho-, meta- and

para-dichlorobenzenes, respectively, are

(A) 3, 4 and 2 (B) 3,3 and 2 (C) 4,4 and 2 (D) 3,4 and 4


NH20H • H2S04

[ Y] ----'=-'---.... [Z] 00 70% 90% [X]

the structure of the major product Z and the overall yield for its formation from the ketone X, are

(B)

H

;+N-f° ~ and63% (A)

. H

;+N-f° ~ and80%

o ):VLN:H ~ and80%

o ~N:H ~ and63% (D) (C)


H ) LDA, -50°C

4>=0 1 PhSeCI • [X]

H202, 50°C [Y] •

2) LDA, -50°C H Mel


Me

d$=o H SePh d$=o (A) ~e~h and (B) Chr~ and

H H H H

Me Me H SePh Me

(C) q:s:~h and <+>=0 (D) Chr~ and <+>=0 H H H H

CY 9/16

2009 CY


PdCI2, CuCI . [X I O2, H20

DMF


o 0 (A) ~CHO 00

1 U and

(C) cYY and ~: Q.39 In the reaction sequence

conc. _---=O-.-~.~ [X I H2S04 • [ Y I

Ph · o + iL N02


(A) and (B)

(C) and Ph~ t\.... . l!J-Y (D)

Ph\..k and ?-JI

o

and

Q.40 In the photochemical reaction

£C~ CHO hv

----.~ [X I MeO A Me CD30D

formation of the compound X can be inferred hy the disappearance of the 'H NMR signal at ['H NMR spectrum of the starting material; Ii 9.7 (lH, s), 7.8 (lH, d, J 8.0 Hz), 7.1 - 6.8 (2H, m), 3.9 (3H, s), 2.5 (3H, s) ppm]

(A) Ii 9.7 ppm

(C) Ii 3.9 ppm

(B) Ii 7.8 ppm

(D) Ii 2.5 ppm

Q.4! The half-life (t'll) for the hydrolysis of an ester varies with the initial concentration of the reactant ([E]o) as follows:

[Elo / 10-2 mol L- ' 5.0 4.0 3.0 t'll / s 240 300 400

The order of the reaction is

(A) 0 (B) 1 (C) 2 (D) 3

CY 10/16

2009 CV

Q.42 The fluorescence lifetime of a molecule in solution is 10 ns. If the fluorescence quantum yield is 0.1, the rate constant of fluorescence decay is

(A) 1 x 109 S-I

(C) I X 10' S-I

(B) I x 108 S-I

(D) 9 x 10' S-I

Q.43 The fundamental vibrational wavenumbers for H2 and h are 4403.2 cm-I and 214.5 cm-\ respectively. The relative population of the first excited vibrational states of these two molecules compared to their respective ground states at 300 K are, respectively:

(A) 6.75 x 10-1 and 3.57 x 10-1

(e) 3.57 x 10-6 and 6.75 x 10-1 (B) 6.75 X 10-10 and 3.57 x 10-1

(D) 3.57 x 10-1 and 6.75 x 10-1

Q.44 The degeneracy of a quantum particle in a cubic box having energy four times that of the lowest energy is

(A) 3 (B) 6 (e) I (D) 4

Q.45 The rotational Raman spectrum of 19F2 shows a series of Stokes Jines at 19230.769 em-I, 19227.238 em-I and 19223.707 em-I. The rotational constant for 19F, in GHz is

(A) 26.484 (B) 52.968 (e) 105.936 (D) 3.531

Q.46 The de Broglie wavelength for a He atom travelling at 1000 ms- I (typical speed at room temperature) is

(A) 99.7 x 10-1' m (B) 199.4 X 10-12 m (e) 199.4 x 10-18 m (D) 99 x 10-6 m

Q.47 Given that the standard molar enthalpies of formation of NO(g) and NO,(g) are, respectively, 90.3 kJ mol-I and 33.2 kJ mol-I, the enthalpy change for the reaction 2NO(g) + O,(g) -+ 2NO,(g) is

(A) 16.6 kJ (B) -57.1 kJ (e) -:-114.2 kJ (D) 57.1 kJ

Q.48 Among the following, the equilibrium which is NOT affected by an increase in pressure is

(B) H2(g) + 1,(5) ~ 2ffi(g)

(C) C(s) + H,O(g) ~ eO(g) + H,(g)

(D) 3Fe(s) + 4H,O(g) ~ Fe30.(S) + 4H,(g)

Q.49 The free energy change (<'>0) of 1 mole of an ideal gas that is compressed isothermally from 1 atrn to 2 aim is

(A) RTln2 (B) -2RT (e) -RTln2 CD) 2RT

cv 11116

2~ cy

Q.50 Two liquids Band C form an ideal solution. In the figure below, the vapour pressure P of this solution is shown as a function of the mole fraction, X. , of component B.

p (atm)

1:-1""1""1"'" o 0.5 1

XB--

Given a state of this vapour-liquid mixture whose overall composition corresponds to point E in the figure, the mole fraction of B in the vapour phase is approximately

(A) 0.25

(C) 0.65


Common Data for Questions 51 and 52 :

(B) 0.53

(0) 0.80

Treatment of W(CO). with I equivalent of Na(C,H,) in THF solution gives the ionic compound M. Reaction of M with glacial acetic acid results in product N. The 'H NMR spectrum of N displays two singlets of relative intensity 5: I. When N is heated, hydrogen gas is evolved and 0 is produced; 0 may also be prepared by refluxing W(CO). with cyclopentadiene and H, is also produced. Treatment of 0 with an equivalent of Br, produces P. (Use the 18 electron rule as your guide).

Q.51 The compounds M and N, respectively, are

Q.52

cv

(A) [(C,H,)W(COh)Na and [(C,H,)W(CO)'H]

(B) [(C,H,)W(CO).)Na and [(C,H,)W(CO).H]

(C) [(C,H,)W(CO)3)Na and [(C,H,)W(CO).Hl

(0) [(C,H,)W(CO).)Na and [(C,H,)W(CO)3H]

The compounds 0 and P, respectively, are

(A) [(C,H,)W(CO)3h and [(C,H,)W(CO)3Br)

(B) [(C,H,)W(CO).l and [(C,H,)W(CO),Br(THF)l

(C) [(C,H,)W(COh(THFhl and [(C,H,)W(CO)3Brl

(0) [(C,H,)W(CO)3h and [(C,H,)W(CO)z13r(THF»)

12116

2009

Common Data for Questions S3 and S4 :

An organic compound X (C,HIOO) exhibited the following spectral data.

IR: 1680 cm-'

'H NMR: Ii 7.8 (2 H, d, J 7.5 Hz), 7.2 (2 H, d, J 7.5 Hz), 2.7 (3 H, s) and 2.4 (3 H, s).

Cy

Compound X on treatment with m-chloroperbenzoic acid produced two isomeric compounds Y (major) and Z (minor).

Q.53 Compounds Y and Z, respectively, are o 0

(A) ~yand Hoff

~oy 0

(B) and ffOMe 1.-:; 0

0 0

(C)

Hoff

and ffOMe

0

~oy (D) ffOHand 1.-:;

1.-:; 0

Q.54 Compounds Y and Z can be differentiated by carrying out basic hydrolysis, because

(A) Y produces 4-methylphenol and Z is unaffected

(B) Y produces 4-methylphenol and Z produces 4-methylbenzoic acid

(C) Y is unaffected and Z produces 4-methylbenzoic acid

(0) Y is unaffected and Z produces 4-methylphenol

Common Data for Questions SS and S6 :

Character table for the point group C2, is given below:

C2, E C2 a,(xz) a,(yz) A, I 1 I I A2 I I -I -I B, I -I I -I B2 I -I -I I

z R,

x, Rv y, R,

x',y',z' xy

xz yz

Q.55 The reducible representation corresponding to the three translational degrees of freedom, r rr, is

(A) 3, I, I, I (B) 3, -I, I, I (C) 3, -I, -I, -I (D) 3, I, -1,-1

,

Q.56 The asymmetric stretching mode of the H20 is shown below. The molecular plane is yz and the symmetry axis of H20 is Z.

This vibration transforms as the irreducible representation

(C) A2 (D) B2 Cy 13/16

2009 Cy

Linked Answer Questions

Statement for Linked Questions 57 and 58 :

Triphosphazene is prepared by reacting X and Y in equimolar ratio at 120 -150°C using appropriate solvents.

Q.57 The reactants X and Y, respectively, are

(A) PCI3; NH3

(C) PCI,; NH.CI

Q.58 The structure of triphosphazene is

(A) CI , CI N-p'-N Cl ...... II N -,

/p- "'~-CI CI CI

(B)

CI, CI N-p'-N-CI 'N' p- -p

C( (;1 -CI

Statement for Linked Questions 59 and 60 :

In the reaction mechanism given below, k EkE I, A. I...... 3. A.3 )

X+y '" k E Z P 2. A.2

(B) PCI,; NH3

(D) PCI,; NH.CI

(C)

'k's represent rate constants, 'EA's represent activation energies, and k2 » k3.

(D)

Q.59 The overall rate constant (ko"r,lI) for the formation of P can be expressed as

(A) k,k31 k2 (B) k,

(C) k, I (k2 + k3) (D) k, I (k2 - k3)

Q.60 The overall activation energy (EA .• ",,",) for the formation ofP can be expressed as

(B) EA"

(D)


Cy 14116

2010

CY : CHEMISTRY

Max,,,,,,,,, Mark,. JOO

Read the followin!: instructions carefully.

I Thi, que,[ioll paper contains 24 pages mcluding blank pages for rough work. Please check "II pages and repon discrepancy. If any.

2. Wnte your registration number, your name and name of the examination centre at the specified location' on the right half of the Optical Re,ponse Sheet (ORS).

3. Using HB pencil. darken the appropriate bubble under each digit of your registration numher and the letters corresponding to your paper code.

4. All questions in this paper are of objeclive type.

5. Questions must be answered on the ORS by darkening the appropriate bubble (marked A. B. C. Dj using HB pencil against the question number on the left hand side of the ORS. For each 'Iuestion darkcn the bubble of the correct anSwcr. In case you wish to change an answer. erase the old answer completely. More than one anSWer bubbled against a q...estion will be treated as an incorrect response.

6. There arc a tOlal of65 questions carrying 100 marks.

7. Queslions Q.I - Q.25 will carT)' I-mark each, arid queslions Q.26 - Q_55 will carry 2-rnark. each.

8. Questions QA8 - Q.51 (2 pairs) are common data questions and question pairs (0.52. 0.53) and (Q.54, Q.55) are linked answer quesuom. The answer to the second question of the linked answer questions depends on the anSwer to the first question of the pair. If the first question in the linked pair is wrongly answered or is un-attempled, lhcn the anSwer to the second question in t1K: pair will not be evaluuted.

9. Questions Q.56 _ Q.65 belong to General Aptitude (GA). Questions Q.56 - 0.60 will carry I-mark ea,h, and questions Q.61 - Q.65 will ,arry 2·marks each. The GA ql.>estions will hegin on a fresh page ,taning from page 15.

10. IJn-a!t~mpted que.lions will carry zero mark..<.

II. Wrong answer, will carry NEGATIVE marks. For 0.1 - Q.25 and Q.56 -Q.60. % mark WIll be deducted for ea,h wrong anSwer. For 0.26 - Q.51 and Q.61 - Q.65. ¥. mark will be deducted for each wrong answer. The question pair' (Q.52. Q.53). and (Q.54, Q.55) are questions ... ith linked answers. There will be negative marks only for wrong anSWer to the first queSlion of the linked answer question pair i.c. for Q.52 and Q.54. +.I mark will he deducted for each wrong answer. There is no negative marking for 0.53 and Q.55.

12. CalculutOl (wjthout data connectivity) is allowed in Ihe examinalion hall.

13. Chan" graph ,heelS or tables are NOT allowed in the exammal10n hall.

14. Rough work can be done on lhe question paper itself. Additionally, blank pages are provided at the end of Ihe question paper for rough work.

Cy ",.

•

2010

I, Physical Constants

(a) Planck Constant, h" 6.626 x lO - .... J s

(b) Avogadro number. N" 6.023 x 10 2.'

(c) Speed of light, c" 3 x 10 g m S-I

Some Useful DIIIII

(d) Gas constant, R == 8.314 J K- 1 molc-1 ,,2 cal K- I mole' I

2. Atomic Numbers

B 5 M"

Mg " F,

P 15 Co

A, 33 Co

Sb 51 Z" Bi 83 Mo

C, 20

25

26

27

29

30

42

Q.l - Q.25 carry one mark each.

Q I The Lewis ,,~idi(y of BF, is less than Uci" even though f1u(}rine is more electronegative than chlmine, It,s due to

(A) Slronger 2p(B )-2p(F) a-bonding

CC) stronger 2p(B )·3p(CI) a·bonding

(Il) >!ronger 2p(B )-2P(F) ,,-bonding

(D) Slronger 2p(B)·3p(CI) It·bonding

Q_2 Pyroxenes are a class of silicate minerals. which c,hibit a polymeric chain stru<;tur~, as shown hel"" ,

P 0 / ]\ /]

~ ~ \:0'l' b b· = Silicon 0 = Oxygen

Its simplest repeat unit is

(B) [SiO,]'- (C) ]Si,O,lo-

0.3 Among the followmg pentachlorides the one which does not e,ist due to the 'inert-pair dfect' is

(A) PCI, (B) BiCis (0 SbC'I, (D) AsCI,

QA Band lhco')' predicts that magoesium is an insulator. Howe,-er. in practice il acts os a ~ond""tor due

" (A) preoetlce of filled 3s orbital

(C) overlap of filled 3. and empty Jp orbital (B) overlap of filled 2p and filled .15 orbital

(D) preoence of unfilled 3p orbital

Q.S The numher of 'framework electron pair" present in the borane cluster [B"H,,}'- i,

(A) 10 (B) II (e) 12 (D) D

Q.6 The r~action hetween IPdCI,J'- and C,II. produces a new compound_ Compared to free C,I-I,. the C·C bond order of the product is

(A) hetween 1 and 2 «(') unaltered

(B) icss than I

(D) greater than 2

0,7 Among 1he following pair of metal ions pre&en( in Nature. (he firs! one functions ~s ~n electrontran,fer agent and the second one catalyl.cs tile hydrolysis reactions_ Tile correct pair i.l

(A) Fe .lnd Zn

«(') Co and Mo

(B) Mg and Fe

(0) Ca and Cu

Q 8 Structurally nickellocene is similar to fcrroecnc, Ni~kdloccne attams stah>lity due '0 the formation of

(A) a m,,"ocation

« ') a """'00";00 (n)adlcation (I)) a dlanion

user

Sticky Note

B

::.0", <"y

Q_9 The absolute conf'guratlons for compound, X and Y. r~'pectiH)I)'. art

"0 M,

" ;:=.-<;

x (Al R. S

Q.iO In the reaction

C",

" (B) S, R

N f'I'lHSO 2M NaOMa

~; 180°C

!he major productlXI is

(A) d

y

(C) R, R (D) S, S

•

(D)

Q.ll Among the following. a pair of resolval>l~ configurational enanliomer, IS gi"en by

(Al cis-1.2-<1nnethy!cyc1oheunc (e) cis·] ,4-dimethykyclohexane

Q.12 In tlte rcacMn

"NO,

the major product [Xl is

• [X]

o (A) 6

r""Y CHO (B) L-J

(ll) ,.,.,. I .J·djmctitylcyclohexane (D) rr~ns-l.3-dimelhykycloltexane

«('J ~" (D)

user

Sticky Note

D

2010 CY

Q 13 The del:reasmg order of isoelectric point for the followmg a-amino acids is Lysme Alanine UIUIJrntc acid

(All>!l>lIl (ej III > 1>11

(I) (II) (III)

(B)II>i>UI (l)1>1II>1I

Q_14 Too decreasing order of the reactivily of the following compounds towards electrophiles is

Q.15

Q Q " , "

(AJ II:> 1:>111 (C)Ui:> 1:>11

In the reaction

heat -'-"-... [X]

the major producljXI is

,A) IB,

0 m

(B) I!:> 1II:>1 (D)I>lI>m

'C) (0)

Q.16 The decre:,.,ng order of acidity of !he marked H of the following molecules is

, (A) l>ll>lIT (C) III >11:>1

" (B) 1II > 1>11 (D)lI >1 >m

m

211101 I:Y

"

Q_17 Tile decreasing order of nucleophihClty for till.: following anions IS

CH,CO,-. CH,O-. C.,H,cf. NO,

(A) Cll,CO,- > CH.D > C.H,O- > NO, (C)CH,O->CJ{,o- >CH,CO,-> NO;

(B) CH,O- > "10; > CJ{,O- > CHlCO, (D)C"H,O >CH,O->NO, >CH,CO,

Q_18 The molaremropy of crystalline CO at absolute ].ero;,

(A) Zero (B) -Rln 2

Q_J9 For an ideal gas

(A) (OPI ef), (Of I oV)p(oV I apJr ~ 0 (9) (aPI ilT)" (ilTl iN)" (aV I OPh '" -I (C) «(}PI ilT), (ilTl oV)p (OV I OPh '" + I (0) (OPI aTl.· (ilTl av)p(avi (}Ph '" +2

(C) Rln 2

Q.20 Among W (work), Q (heat), U ('"temal energy) and S (entropy)

(Al Wand U are path functions but Q and S are ,talC functions (S) W and S are palh functions bUI Q and U arc Slale functions (C) Sand U are palh functions but Q and W are ,talC funclions (D) W and Q are path functions but U and S arc stale functions

(D) 2Rln 2

For eigen funclions VI, ~ II Sin(~) and VI, = II Sin( 21'-") of particle in a I-D box of length Vb\b ·Vb b

b(O"'_t",b)

(AJ ,+" i. normalized and OTlhogonaito ,+"

(B) 'fI, is normalized but not OTlhogonal to ,+"

(C) ,+" is nonnalized and orthogonal 10 '+'1

{OJ ,+" is neither normalized nor orthogonal (0 ,¥,

Q.22 The bond order of C, molecule is

(Al () (B) 1 (C) 2

Q.23 Sulfur can exi<t 1ll four phase<_ The possible number of triple points is

(A) 1 (B) 2 (C) 3

(0) 3

(D) 4

Q.24 The standard reduction potentials at 298 K for single electrodes are gi,en below.

Electrode

From this we can infer that

(A) Zn can reduce both Mg'+ and Fe" (B) Fe can reduce both Mg" and Zn" (n Mg can reduce both Zn" and Fe'+ (I l) Mg can reduce Zn'+ but not Fe'+

Electrode Potent1al (volt)

-2.34

-H76

(,124

2010 CY

Q.25 For lhe pail' of rcawons given below

i) N,(g)+3H,(g)~2NH\(g)

, 3 i,) :;:N,(g)+"2H,(g) NH,lg)

jf at a pal'\icular temperature., KPI and K,~ arc the equilibrium conslants for reaclions i) and ii) respectively [hen,

(A) Kpl =2K",

(C) 2KPI = K"

Q.26 - Q.55 carry two marks eacb.

Q.26 According!O VSEPR model, the shape of [xeOFsr IS

(A) octahedral (B) trigonal bipyramidal (C) square pyramidal (0) pentagonal monopyramidal

Q.27 The number of unpaired electron(s) prescm in the species (Fe(H,O),(NO»)" which is formed during 'hrown ring test' is

(A) 2 (B) 3 (C) 4 (D) 5

Q.28 Fe,O, and Cop, are metal oxides having spinel structure. Considering their CFSEs, the correct slatemcm regarding their structure is

(A) both have nonnal spinel structure (B) both have inverse spinel structure (C) Fe.D. h" nonnal and Co,O. has inverse spinel structure (D) Fe,O. ha., inverse and Co,O. has nonnal spinel structure

Q.29 The mechanism of lhe reaclion between [Fc(CN) 014- and [Fe(bpYhl'· (bpy = 2,2'-bipyridine) is

(A) ouler -'pi>ere electron-transfer (B) inner-sphere electron-transfer (C) self -exchange reaction (D) ligand-e~change followed by electron-transfer

Q.30 The d-d ab<arplion band of [Fe(H,oJ.l" is split due to

(A) presence of octahedral geometry (B) static lahn-Teller distortion (e) dynamic Jahn-Teller dislortion (D) pre,encc of trigonal bipyramidal geometry

Q.3l The cry,tal-fLeld symbol for the ground-slate of IMn(CN),I4- is

{A)'T" (B) 'A" (C)'E.

('y

1010 ry Q.32 In the following rCl!ctions:

•

the rcagemlcondiuons X and Yare

(A) X = SF,; Y = heating at 1250"C (C) X = NH.f'; Y = HCI

" y I -+t=t • ChCHCHCh

(S) X = NaF; Y = heating at 250"C (PI X = CF,SO,H; Y = H,SO.

Q.33 ICoCI.)'- i, a blue coloured complex. Controlled-treatment of this complex with water generales two isomeric light pink coloured complexe, of composition [Co(H,O).Cl,i. Identify the correct poim groups for [CoCl.I).. and two isomeric complexes [Co(H,o).CI,I.

(A) D", and (e '" and C"J (S) T" and (C",. and D",) (e) D ... , and (C" and D.",)


Et~CXC~H the major product [Xl is

(A) (8)

v

;0 Q.35 In the reaclion

OH

x::: ( heat •

:0 " ",SO, OH

the major proou"tlXI is

(A) (e)

L&He

ii. Ii"

[~

o 0

aee(

(D) T d and (e,_ and C4,)

• [X]

(0)

(C) (D)

Oy o

v ,

l~IO

Q.3b In the following reaclion sequence

'" '" A ~"OH

H

i N:)CVPy ii. light

--_. I~ iii. hydrolysis

lhe major product [Xl is

(A) (8)

=e ~e ""DH

''''''OH

" "

(e)

6~ ..

" Q.37 In the reactions

mCP"" IYJ _0-- --_. I"

(he major products, [Xl and (YJ, respectively, are

(A) (.)

,~ ,., ~

" (e) (D)

,,' ~~ <,

(m

·0"

moe ~ and

0 """

,,' ,~

2010

Q_38 In the reaction

N SnCI.

~,----,

the major product [X J i,

IA) (8)


CH.!OH

~o i. Hg(OAc)2IM9OH

OHH;'; .. [X]

HO ii. NaSH. H

(e)

HCI

the major products. IX] and IY]. re,pc~lIvcl)·. are

(A) (II)

,~ ~ ~ ,OiiEt .00

~ "'" M~

(C) IP)

"

(D)

'"" ~ M~

,~o ~ ,~o ,~~ '00 .~£0: O~ O~

OM, OM.

Q.40 The change in emropy when two moles of Argon g~.' Ul"C heated at con.tant volume from 300 K (0 500 K is

(A)-12.74 J K-' mole-' (C) 6_37 J K- ' mole-I

(I,) _6.37 J K-' mole-' (I)) 12.74 J K-' mole-J

------.--- - ---,-:y ,012'

2010 CY

QAI At any temperature T, the [uga"ily ~oetTidcl11 (y) i, given by

/' Z -J , Iny= J7"P

o whcr~ Z i, the compressibility factor. The fugacity ,()emdenl of a real gas govcrned by equation of state P (V - b) = RT wilh b a constant is given by

(A) RT bP

"' (B) ~.,' 1>1'

(el RT

Q.42 The specIfic rate constant of decomposition of a compound is represented by

(2000 Ink 0=5.0--

T The activation energy of decomposition for lhis compound al 300 K i,

(A) 24 keal/mole (B) 12 kcaVmole

QAJ The commutator! ,,'. p.] is equal to

31u' (A)--

2tri

Iu (8(-

2tri

(0 24 callmole (0) 12 callmole

31u' (O(

2!rj

Q.44 An electron of mass . III' l' confined to a One dimensional 00. of length . b'. IF it makes a radiative transition from second ncited state to the ground state. the frequency of the photon emitted is

9h (A) --,

8mb-

2h (D) -

",b'

Q,45 The point group of elF, molecule and its corresponding number of irreducible representations are respectively

(A) C'" and 4 (B) C',.and 4 (0 C. and-, (0) C,.and 3

Q.46 The most populated rotational Slate for Hel (B = 8.5 em") at 300 K is

{A)2 (B) 3 (e) 5 (D) 7

Q.47 The ratio of life times of two states that give rise to line widths of I () CIl" and 0.2 em-' respectively ,;

(A) 1'2 (B) I ; 5 (e) 2. I (0)5:1

Common Data QuestioDll


A six-.;oordmate transition_metal ~omple" is ESR and Mb.shauer active. The effective magnetic moment of this complex is -5.9 B.M.

Q.48 The metal-,on along with it" oxidation <tatc ond the number of unpaired electron present are

(A) Fe(Il) and 4

(el Fe(llI) and 1

Q,49 The complex is

(A) [Mn(H,O).)'+ (B) [Fe(CN),],(C) iFe(H,O),)" (0) iFe(H,O),]'-

(B) Mn(lI) and 5 (l)) Fe(l]]) and 5

, 112.

1"'~

Common Data ro. Questions SO and 51:

An organic "<Jmpound IX] (('"H,.O,) exhibil' the foll<Jwing speclr~1 dalJ IR. _1720cm· L

'H :-IMR: 2.3511. bH). 3.10 (5, 3H), 3.83 {t, 2H).4.42 (I. 2H). 7.07 (., IH). 7 5H (so 2H) The compound IXI with an excess of MeMgBr give> a J'J mixtu,"" of compounds IY] and IZj. The compound IZI exhibit. the following 'H NMR data. 2.0 (bs. IH). 3.30 Is, 3H). 3.56 (t. 2H). 3.70 (I, 2H)

0·50 The compound [X] is

o

(Al (B)

(C) (D)

Q.51 The compound IY] is

(A) (B)

0" 0"

~ "'" ~" +y ,,.., ~" (C) (D)

"y "" /a.Y.OH )::) ,od ~H

. __ ._----

20,"


Statement for !.inked Questions 52 and 53:

In the reactIOn sequence

IVef'olgBr Ph

'x CHO

HSC "

-----.. IX] (major) + IV] (minor)

i. TsCVPy

[~ • rZr ii. NaOEtfEtOH

Q.52 The compound [X] IS

Ph Ph

(A) +H' (B) H,C+ H,C Cf<,

OH OH

Ph CH,

(e) ~~ -I--~ (0) :+ OH CH,

Q.53 The compound [Zj is

M, M,

1(: '~ (A) eo (B) eo "0 M,

"' Ph

(C) reo (D) Mo-{-Mo Mo,

H H

11110

Statement for Linked Questions 54 and 55:

[n the I.! vs. T diagram for different phases of th~ same substance at one atmospheric pre"nre. the lines A. Band C compound to

" " •

• •

" " " " " " • F::E :0

T

Q.54 Based on the above diagram:

B

c

(A) A represents the change in chemical potential as a function of temperamre for the solid pha,e. B for the liquid and C for the gas

(B) A represents the change in chemi,,1 potential as a function of temperature for the liquid phase, B for the gas and C for the solid

(e) A represents the change in chemical poten!ial as a function of temperature for the gas phase. B for the liquid and e for the solid

(D) A represents the change in chemical potentia! as a function of temperature for the gas phase, B for solid and e for the liqUid

Q.55 From the sarne diagram

(A) D repn:sents boiling pomt. E sublimation poim and F melting jXIin! (B) E represems boiling jXIint. D suhhmation point and F mehing point (0 E represems melting point. F sublimation point and D boiling point (D) 0 represents mehing point, F boiling poinl and E ,ublimalion point

'OHl

General Aptitude (GA) Questions

Q.56 - Q.60 carry one mark each.

Q.56 2j persons an: in a room. 15 of them play hockey. 17 of lhem play football and 10 of lhem play both hockey and football. Then lhe number of persons playing neither hockey nor foolball is;

(A) 2 (B) 17 (C) J3 (D) 3

Q,57 Choose the mos/ appropriale word from /h~ optio", given below 10 complete the following selllfnce: If we mana~e to _______ our natural resources, we would leave a better planet for our cblldren.

(A) uphold (8) restrain (C) cherish (0) conserve

Q.58 TM ques/ion below consis/s of a pair ofre/aleel word. followed by four pairs of words. Select the poir that bcM expresses the relalion in /he or,ginol poir. Unemployed: Worker

(A) fallow: land (B) unaware: sleeper (C) wit: jesler (0) renovated: house

Q.59 W/,kh of/he following opri01lS is the dosestln meaning to the word belolll: Cin:uilous

(A) cyclic (B) indirect (C) confusing (D) crooked

Q,60 Choose the most appropria!e word from the options given below 10 compleTe the following ,enlen<'c: His rather casulIl reJIlllrl<s on po6tics ______ bis IacI< of seriousness about the subject.

(A) masked (B) belied (C) betrayed (D) suppressed

Q.61 - Q.65 carry two marks each.

Q.6J Hari (H), Gita (G), Irfan (I) and Saira (S) are siblings (i.e. brolhers and sister~). All were born on I" Ianuary. The age difference between any IWO SUCCeSSlVe siblings (thaI is oom one after another) is bs than 3 years. Given the following raet.:

L Hari 's age + Gita', age > Irf~n'.\ age + Saira's age, n. The age difference belw«n Gila "nd Saira is I year. However. Gita is nOI the

oldest and Saira is not the younge,t. n'- There are no twin"

In what order were they born (oldest firsl)"

(A) HSJG (8) SGHJ (C) IGSH (D) lHSG

,010 cy

Q.62 5 ~killed workers can build a wall m 20 days, 8 semi·skilled workers can bUild a wall in 25 day,; II) Lm,killed workers Can build a wall in 10 days If a team has 2 ,killed, (, semi·skilled and 5 umkillcd workers, how long will illake lO huild the wall?

(AJ 20 days (B) 18 days (e) 16 day, (D) 15 day,

Q_63 Modern warfare has changed from large scale clashes of armies to snppre&Sion of dvilian populalions. Chemical agents that do their work silently appear to be soited to such warfare; and rellrdfully. there exist people in military estahlishments wbo think that chemical agents are u""fullools for their CIIIl5e.

WI,;ch ofthefollow;llg stolemellts best SlImJ up the meonillg of the above possage:

(A) Modem warfare has resulted in civil ,trifc. (B) Chemical agents are useful in modem ..... arfare. (e) D.e of chemical agents in warfare would be undesirable. (D) People in mihtary establishmenlS like 10 usc chemical agents," war_

Q.64 Given digils 2, 2, 3, 3, 3, 4, 4, 4, 4 how many distioct 4 digit numbers greater than 30()() can be formed?

(Al50 (E) 51 (e) 52 (0) 54

Q.65 If 137 + 276" 435 how much is 731 + 6n?

(A) 5:\4 (B) 1403 (e) 1623 (0) 151)


~QIO

Space for Rough Work

17114

rom


10'0


•

., ,~.

lOlO


>(\fl4

1"10 " Space for Rough Work

"

!UIO


:010 CY


•


•

"

2011 Cy

CY: CHEMISTRY



Cy

1. Write your name and registration number in the space provided at the bottom of this page.

2. Take out the Optical Response Sheet (ORS) from this Question Booklet without breaking the seal.

3. Do not open the seal of the Question Booklet until you are asked to do so by the invigilator.

4. Write your registration number, your name and name of the examination centre at the specified locations on the right half of the ORS. Also, using HB pencil, darken the appropriate bubble under each digit of your registration number and the letters corresponding to your test paper code (CY).

5. This Question Booklet contains 20 pages including blank pages for rough work. After opening the seal at the specified time, please check all pages and report discrepancy, if any.

6. There are a total of 65 questions carrying 100 marks. All these questions are of objective type. Questions must be answered on the left hand side of the ORS by darkening the appropriate bubble (marked A, B, C, D) using HB pencil against the question number. For each question darken the bubble of the correct answer. In case you wish to change an answer, erase the old answer completely. More than one answer bubbled against a question will be treated as an incorrect response.

7. Questions Q.l- Q.25 carry I-mark each, and questions Q.26 - Q.55 carry 2-marks each.

8. Questions Q.48 - Q.51 (2 pairs) are common data questions and question pairs (Q.52, Q.53) and (Q.54, Q.55) are linked answer questions. The answer to the second question of the linked answer questions depends on the answer to the first question of the pair. If the first question in the linked pair is wrongly answered or is unattempted, then the answer to the second question in the pair will not be evaluated.

9. Questions Q.56 - Q.65 belong to General Aptitude (GA). Questions Q.56 - Q.60 carry I-mark each, and questions Q.61 - Q.65 carry 2-marks each. The GA questions begin on a fresh page starting from page 14.

10. Unattempted questions will result in zero mark and wrong answers will result in NEGATIVE marks. For Q.l - Q.25 and Q.56 - Q.60, * mark will be deducted for each wrong answer. For Q.26 - Q.51 and Q.61 - Q.65, -% mark will be deducted for each wrong answer. The question pairs (Q.52, Q.53), and (Q.54, Q.55) are questions with linked answers. There will be negative marks only for wrong answer to the first question of the linked answer question pair, i.e. for Q.52 and Q.54, -% mark will be deducted for each wrong answer. There is no negative marking for Q.53 and Q.55.

11. Calculator is allowed whereas charts, graph sheets or tables are NOT allowed in the examination hall.

12. Rough work can be done on the question paper itself. Additionally, blank pages are provided at the end of the question paper for rough work.

I Name

1120

2011

Planck constant, h = 6.626 x 10 -34 J s

Avogadro number, NA = 6.022 x 10 23

Speed of light, c = 3 x 10 8 m s -I

SOME USEFUL DATA

Gas constant, R = 8.314 J K- I mor l = 0.08314 L bar K- I mor l = 2 cal K- I mor l

Boltzmann constant, kB = 1.38 X 10-23 J K-I

Faraday constant, F = 96500 C

1[ = 3.14

Atomic Numbers

B 5 Ti

F 9 V

Al 13 Cr

Si 14 Mn

S 16 Co

CI 17 Cu

As 33 Ru

Xe 54 Pt

Cy

Cy

22

23

24

25

27

29

44

78

2120

2011


Q.l lahn-Teller distortion of CuS04.5H20 acts to

(A) raise symmetry (B) remove an electronic degeneracy (C) cause loss of H20 ligand (D) promote a d-electron to an antibonding molecular orbital

Q.2 Among the following, the group of molecules that undergoes rapid hydrolysis is

(A) SF6, AlzCI6, SiMe4 (C) BCh, SiCI4, PCl5

(B) BCh, SF6, SiCl4 (D) SF6, AlzCI6, SiCl4

Q.3 The reaction of solid XeF2 with AsF5 in 1: 1 ratio affords

(A) XeF4 and AsF3 + -

(C) [XeF] [AsF6]

Q.4 A well known naturally occurring organometallic compound is

(A) vitamin B12 coenzyme (C) cytochrome P-450

(B) chlorophyll (D) myoglobin

Q.5 The complex that exists as a pair of enantiomers is

(A) trans-[ Co(H2NCH2CH2NH2)2CI2] +

(C) [Pt(PPh3)(CI)(Br)(CH3)f

Q.6 The region of electromagnetic spectrum employed in the electron spin resonance (ESR) spectroscopy is

(A) radiowave (B) microwave (C) infrared (D) visible

Q.7 The red color of oxyhaemoglobin is mainly due to the

(A) d-d transition (B) metal to ligand charge transfer transition (C) ligand to metal charge transfer transition (D) intraligand 1t-1t* transition

Q.8 The band structure in an n-type semiconductor is

II '--------III '------' ::=1.· .;; ••• ;; .••• :;: ••.. :;: ••. ;:: •... ;; .. ·~.·.I

I II III IV

(A) I (B) II (C) III (D) IV

Cy

Cy

3120

user

Sticky Note

D

user

Sticky Note

A

user

Sticky Note

D

user

Sticky Note

C

user

Sticky Note

A

user

Sticky Note

C

user

Sticky Note

B

user

Sticky Note

B

2011


Q II o

the major product [X] is

(A)

o (Bl(l S OAc

Q.lO In the following reaction sequence


(A)

(C)

o Me NH4

Me

Me

A~O/NaOAc

Heat

o

(B)

(D)

[X]

(D)

i) NH20H.HC~ [x]

ii) ArS02C1, Py iii) Heat iv) H20

Q.ll The diene which undergoes Diels-Alder reaction with maleic anhydride is

(A) (B)

Cy

6 (C)~

VV (D)

Q II o

Me

Cy

o

4120

user

Sticky Note

B

user

Sticky Note

A

user

Sticky Note

A

2011 CY

Q.12 The sequence of an mRNA molecule produced from a DNA template strand with the composition

5'-AGCTACACT -3' is

(A) 5'-AGUGUAGCU-3' (B) 5'-UCGAUGUGA-3' (C) 5'-AGTGTAGCT-3' (D) 5'-TCGATGTGA-3'


Me~0Y1rMe Et 0 0

Heat [X]


(A) Et~Me

(B) Et~Me

Me 0 Me 0

(C) Me~Me

(D) Et 0

Me~Me Et 0

Q.14 The structure of the dipeptide Ala-Pro derived from the natural amino acids is

(A) (B)

(C) (D)


Me i) 2 eq. n-BuLi

&N_t(TS -78°C to 0 °c [Xl • ii) DMF

H


(A) &CHO (B) 0 (C) Me (D)

Me--Q-CHO o-CHO

CY

Me

Q CHO

5/20

user

Sticky Note

B

user

Sticky Note

B

user

Sticky Note

A

user

Sticky Note

C

2011


Me

m H+ .. [X]

Me the major product [X] is

(A) Me (B) Me

~ ~ HO .0

Me OH Me

(C) Me Me (D) Me Me

¢6 ill HO .0 OH

Q.17 For a given first order reaction, the reactant reduces to 1I4th its initial value in 10 minutes. The rate constant of the reaction is

(A) 0.1386 min- I (B) 0.0693 min- I

(C) 0.1386 mol L- I min- I (D) 0.0693 mol L- I min- I

Q.18 The freezing point constant for water is 1.86 K (mol kg-iri. The change in freezing point when 0.01 mol glucose is added to 1 kg water is

(A) 1.86 K (C) 0.186 K

(B) - 1.86 K

(D) - 0.0186 K

Q.19 On the pressure-temperature diagram for a one-component system, the point where the solid-liquid and the liquid-gas curves intersect is

(A) triple point (C) melting point

(B) critical point (D) boiling point

Q.20 The wave function for a Harmonic oscillator described by Nxexp( -ax2 /2) has

(A) one maximum only (B) one maximum, one minimum only (C) two maxima, one minimum only (D) two maxima, two minima only

CY

Cy 6/20

2011 CY

Q.21 If an arbitrary wave function is used to calculate the energy of a quantum mechanical system, the value calculated is never less than the true energy.

The above statement relates to

(A) perturbation theory (B) variation principle (C) Heisenberg's uncertainty principle (D) quantization of energy

Q.22 The point group symmetry of the given planar shape is

Q.23 (~~),

Q.24

(A) V (B) S

i S ::s "0 ;>

(C)-S

~ 1 , i !

-----1 , i i

Temperature ~

(D)-V

According to the Ehrenfest classification of phase transitions, the above diagram refers to

(A) Zeroth order phase transition (B) First order phase transition (C) Second order phase transition (D) A transition

Q.25 According to conventional transition state theory, for elementary bimolecular reactions, the molar entropy of activation llS°j: is

CY

(A) positive (B) zero (C) negative (D) positive for endothermic and negative for exothermic reactions

7/20

2011


Q.26 The crystal field stabilization energy (CFSE) value ,for [Ti(H20)6]3+ that has an absorption maximum at 492 nm is

(A) 20,325 cm-1 (B) 12,195 cm-1 (C) 10,162 cm-1 (D) 8,130 cm-1

Cy

Q.27 For Et2AlX (X = PPh2-, Ph-, cr and fr), the tendency towards dimeric structure follows the order

(A) PPh2- > cr > fr > Ph(C) Ph- > fr> cr > PPh2-

(B) cr > PPh2- > H- > Ph(D) fr > Ph- > PPh2- > cr

Q.28 In the isoelectronic series, vol-, CrOl- and Mn04-, all members have intense charge transfer (CT) transitions. The INCORRECT statement is

(A) CT transitions are attributed to excitations of electrons from ligand (0') to metal (e) (B) Mn04- exhibits charge transfer at shortest wavelength among the three (C) The wavelengths of transitions increase in the order vol-< CrOl- < Mn04-(D) The charge on metal nucleus increases in the order vol- < CrO/- < Mn04-

Q.29 The increasing order of wavelength of absorption for the complex ions: i) [Cr(NH3)6]3+, ii) [CrCI6]3-, iii) [Cr(OH2)6]3+, iv) [Cr(CN)6]3-, is

(A) iv < ii < i < iii (B) iv < iii < ii < i (C) iv < i < iii < ii (D) ii < iii < i < iv

Q.30 The total number of metal-metal bonds in RU3(CO)12 and C04(COh2, respectively, is

(A) 3 and 6 (B) 4 and 5 (C) zero and 4 (D) 3 and 4

Q.31 According to VSEPR theory the shapes of [SF2Clt and [S204]2- should be

(A) trigonal planar for [S204f- and trigonal pyramidal for [SF2Clt (B) both trigonal planar (C) trigonal pyramidal for [S20 4]2- and trigonal planar for [SF2CW (D) both trigonal pyramidal

Q.32 The product of the reaction between CH3Mn(CO)s and J3CO is

(A) (CH3 J3CO)Mn(CO)s (B) (CH3CO)Mn(COMI3CO) (C) (13CH3CO)Mn(CO)s (D) CH3Mn(CO)4

Q.33 The correct pair of IH and 31p NMR spectral patterns for C(H)(F)(PClz)2 is

(A) (B) (C)

IH 31p lH 31p

Cy

(D)

8120

2011 CY


0

6 NaCN (cat.) [X] + Ph-CHO »-

DMF


(A) (B) (C) (D) 0 0

0 OH

~Ph 0 OH

~Ph ~Ph li'Ph

0 0


~ i) 8e02 / HOAc

1.0 ... Me • [Xl ii) NaOH

iii) H30+


(A) (B) 0

~ 0=6 I Me 1.0 b OH

(C) (D)

~ 1.0 I Me cg b C02H


Br

~ BU38nH, AIBN

• I xl Toluene, heat


(Al ?u (B) (C) (D)

Me C0) 0-0 CD

Me

cy 9120

2011 CY

Q.37 The most appropriate sequence of reactions for carrying out the following conversion

co is

--" Q:> (A) (i) Peracid; (ii) H+; (iii) Zn / dil. HCI (B) (i) Alkaline KMn04; (ii) NaI04; (iii) Nzf4 / KOH (C) (i) Alkaline KMn04; (ii) H+; (iii) Zn / dil. HCI (D) (i) 0 3 / MezS; (ii) NaOEt; (iii) N2f4 / KOH

Q.38 In the following reaction sequence

0

6 + Q H


(B) 0

Ai' ~~C'

i) PTSA. C6H6• heat

ii) CHCI3• NaOH

iii) H30+

(C) 0

CrZH

..

(D)

[X]

Q.39 In the following conversion

Cy

i) CU~Me)2Li


(A) o

"\\~C02Me

Me

OSiMe2Bu! . nBu3P. THF [X]

(B) o

MXO"'~C02Me Me 0'\'" "',/~Me

OSiMe2Bd

(D) 0

Me

10/20

2011


Q.41


(B)

i) KOBd

ii) Raney Ni EtOH

(C)

•

(Al itf)" Me am o~ o : Me Me Me

In the reaction

HOAc, KOAc Optically pure (+ )-trans-2-acetoxycyclohexyl tosylate !l


(A) racemic trans-l,2-cyclohexanediol diacetate

(B) optically active trans-l,2-cyclohexanediol diacetate

(C) racemic cis-l ,2-cyclohexanediol diacetate

(D) optically active cis-l,2-cyclohexanediol diacetate

Q.42 The activity of water at 11 bar and 298 K is

(A) 1.101 (B) 1.007 (C) 0.998

Q.43 For the process 1 Ar (300 K, 1 bar) ---+- 1 Ar (200 K, 10 bar)

assuming ideal gas behavior, the change in molar entropy is

(A) -27.57 J K-l mor l (B) +27.57 J K-1 mor l

(C) -24.20 J K-l mor l (D) +24.20 J K-l mol-I

Cy

[ xl

(D)

:1p Me

) [Xl

(D) 0.898

Q.44 The wave function for a quantum mechanical particle in a I-dimensional box of length 'a' is given

Cy

A . trx

by If/ = sma

The value of 'A' for a box of length 200 nm is

(B) 1O.J2 (nm)"2 (C) .J2 /10 (nmr"2 (D) 0.1 (nmr"2

11120

2011 Cy

Q.45 For 1 mole of a monoatomic ideal gas, the relation between pressure (P), volume (V) and average molecular kinetic energy ( "E) is

N"E (A) p =_A_

V

N"E (B) p=_A_

3V

2N -(C) =~

P 3V (D) = 2NA

p 3V"E

Q.46 For a 1 molal aqueous NaCl solution, the mean ionic activity coefficient (y±) and the Debye

Hiickel Limiting Law constant (A) are related as

(A) log y± = J2 A

(C) y± = let

Q.47 For the concentration cell

(B) log y± = -J2 A

(D) y± = lO-A

M I M\aq, 0.01 mol dm-3) II M+(aq, 0.1 mol dm-3

) I M the EMF (E) of the cell at a temperature (T) equals

RT (A) 2.303 -

F

RT (B) -2.303 -

F

(C) E~+ 1M + 2.303 RT F

RT (D) EO + - 2.303 -

M 1M F



A hypothetical molecule XY has the following properties

Reduced mass: 2 x 10-26 kg X-Y bond length: 100 pm Force constant of the bond: 8 x 102 N.m-1

Q.48 The frequency of radiation (in cm-1 units) required to vibrationally excite the molecule from v = 0 to v = 1 state is

(A) 3184.8 (B) 2123.2 (C) 1061.6 (D) 840.0

Q.49 The frequency of radiation (in cm-1 units) required to rotationally excite the molecule from J = 0 to J = 1 state is

(A) 1.4 (B) 2.8 (C) 3.2 (D) 3.6


Na2HP04 and NaH2P04 on heating at high temperature produce a chain sodium pentaphosphate quantitatively.

Q.50 The ideal molar ratio of Na2HP04 to NaH2P04 is

(A) 4: 1 (B) 1:4 (C) 3:2 (D) 2:3

Q.51 The total charge on pentaphosphate anion is

(A) -5 (B) -3 (C)-7 (D)-9

Cy 12120

2011


Statement for Linked Answer Questions 52 and 53:

The decomposition of ozone to oxygen 203 (g) ~ 302(g) occurs by the mechanism

(i) M(g) + 0 3 (g) k, ) 02 (g) + O(g) + M(g), Ea .,

(ii) 02 (g) + O(g) + M(g) k2) M(g) + 0 3 (g), Ea ,2

(iii) O(g) + 0 3 (g) k3) 202 (g), Ea•3

where, M is the catalyst molecule. k;' s are rate constants and Ea,;' s the activation energies for the elementary steps.

Cy

Q.52 Under the steady state approximation for the intermediates, the rate of decomposition of ozone, d[03] .

---,IS dt

(A) 2klk 3[03]2[M]

k2[02][M] + k J03]

(C) 2k2k 3[03][M]

k2[02][M] + k 3[03] (D) 2k,k 2[03f[M]

k 2 [Oz][M]- k 3[03]

Q.53 Assuming k 3[°3]» k 2 [02][M] , the activation energy of the overall reaction is

(D) Ea ,1


A ketone on treatment with bromine in methanol gives the corresponding monobromo compound [X] having molecular formula C5H9BrO. The compound [X] when treated with NaOMe in MeOH produces [V] as the major product. The spectral data for compound [X] are: IH NMR: (5 1.17 (d, 6H), 3.02 (m, IH), 4.10 (s, 2H); I3C NMR: (5 17,37,39,210.

Q.54 The compound [X] is

(A) (B) 0

(C) (D) 0

MeY'lrMe BrYMe

Me Me Me~Br BrXyMe

Br 0 Me 0 Me

Q.55 The major product [V] is

(A) (B) 0

(C) 0 (D)

Me~Me Me00Me MeOYMe

MeyyoMe

0 Me Me Me Me 0

Cy 13120

2011 Cy



Q.56 The question below consists of a pair of related words followed by four pairs of words. Select the pair that best expresses the relation in the original pair: Gladiator: Arena

(A) dancer: stage (B) commuter: train (C) teacher: classroom (D) lawyer: courtroom

Q.57 Choose the most appropriate word from the options given below to complete the following sentence: Under ethical guidelines recently adopted by the Indian Medical Association, human genes are to be manipulated only to correct diseases for which treatments are unsatisfactory.

(A) similar (B) most (C) uncommon (D) available

Q.58 Choose the word from the options given below that is most nearly opposite in meaning to the given word: Frequency

(A) periodicity (B) rarity (C) gradualness (D) persistency

Q.59 Choose the most appropriate word from the options given below to complete the following sentence: It was her view that the country's problems had been ------- by foreign technocrats, so that to invite them to come back would be counter-productive.

(A) identified (B) ascertained (C) exacerbated (D) analysed

Q.60 There are two candidates P and Q in an election. During the campaign, 40% of the voters promised to vote for P, and rest for Q. However, on the day of election 15% of the voters went back on their promise to vote for P and instead voted for Q. 25% of the voters went back on their promise to vote for Q and instead voted for P. Suppose, P lost by 2 votes, then what was the total number of voters?

(A) 100 (B) 110 (C) 90 (D) 95


Q.61 The horse has played a little known but very important role in the field of medicine. Horses were injected with toxins of diseases until their blood built up immunities. Then a serum was made from their blood. Serums to fight with diphtheria and tetanus were developed this way.

Cy

It can be inferred from the passage, that horses were

(A) given immunity to diseases (B) generally quite immune to diseases (C) given medicines to fight toxins (D) given diphtheria and tetanus serums

14120

2011 CY

Q.62 The sum of n terms of the series 4+44+444+ .... is

(A) (4/81) [1On+l_ 9n - 1]

(B)(4/81) [1On-

l_ 9n - 1]

(C) (4/81) [1On+'_ 9n - 10] (D)(4/81) [1On -9n-1O]

Q.63 Given that fey) = I y 1/ y, and q is any non-zero real number, the value of I f(q) - f(-q) I is

Q.64

(A) 0 (B) -1 (C) 1 (D) 2

Three friends, R, Sand T shared toffee from a bowl. R took 1I3rd of the toffees, but returned four to the bowl. S took 1I4th of what was left but returned three toffees to the bowl. T took half of the remainder but returned two back into the bowl. If the bowl had 17 toffees left, how many toffees were originally there in the bowl?

(A) 38 (B) 31 (C) 48 (D) 41

Q.65 The fuel consumed by a motorcycle during a journey while traveling at various speeds is indicated in the graph below.

CY

c:: ~ 0

"" c. CD E

~ c. (J) (J)

c:: ~ 0 a; C,)

Q5 E ~ 0

u.. ~

120 .-------------------------------------------~

90

60

30

o +-----~------_,------~------~----~------~ o 15 30 45

Speed (kilometres per hour)

60 75 90

The distances covered during four laps of the journey are listed in the table below

Distance Average speed Lap (kilometres) (kilometres per hour)

p 15 15 Q 75 45 R 40 75 S 10 10

From the given data, we can conclude that the fuel consumed per kilometre was least during the lap

(A) P (B) Q (C) R (D) S


15120

2012 CHEMISTRY – CY

CY 1/20

CY: CHEMISTRY Duration: Three Hours Maximum Marks: 100


1. Do not open the seal of the Question Booklet until you are asked to do so by the invigilator.

2. Take out the Optical Response Sheet (ORS) from this Question Booklet without breaking the seal and read the instructions printed on the ORS carefully.

3. On the right half of the ORS, using ONLY a black ink ball point pen, (i) darken the bubble

corresponding to your test paper code and the appropriate bubble under each digit of your registration number and (ii) write your registration number, your name and name of the examination centre and put your signature at the specified location.

4. This Question Booklet contains 20 pages including blank pages for rough work. After you are

permitted to open the seal, please check all pages and report discrepancies, if any, to the invigilator.

5. There are a total of 65 questions carrying 100 marks. All these questions are of objective type. Each question has only one correct answer. Questions must be answered on the left hand side of the ORS by darkening the appropriate bubble (marked A, B, C, D) using ONLY a black ink ball point pen against the question number. For each question darken the bubble of the correct answer. More than one answer bubbled against a question will be treated as an incorrect response.

6. Since bubbles darkened by the black ink ball point pen cannot be erased, candidates should darken

the bubbles in the ORS very carefully.

7. Questions Q.1 – Q.25 carry 1 mark each. Questions Q.26 – Q.55 carry 2 marks each. The 2 marks questions include two pairs of common data questions and two pairs of linked answer questions. The answer to the second question of the linked answer questions depends on the answer to the first question of the pair. If the first question in the linked pair is wrongly answered or is unattempted, then the answer to the second question in the pair will not be evaluated.

8. Questions Q.56 – Q.65 belong to General Aptitude (GA) section and carry a total of 15 marks.

Questions Q.56 – Q.60 carry 1 mark each, and questions Q.61 – Q.65 carry 2 marks each.

9. Unattempted questions will result in zero mark and wrong answers will result in NEGATIVE marks. For all 1 mark questions, ⅓ mark will be deducted for each wrong answer. For all 2 marks questions, ⅔ mark will be deducted for each wrong answer. However, in the case of the linked answer question pair, there will be negative marks only for wrong answer to the first question and no negative marks for wrong answer to the second question.

10. Calculator is allowed whereas charts, graph sheets or tables are NOT allowed in the examination hall.

11. Rough work can be done on the question paper itself. Blank pages are provided at the end of the

question paper for rough work.

12. Before the start of the examination, write your name and registration number in the space provided below using a black ink ball point pen.

Name

Registration Number CY


CY 2/20

Some Useful Data

1. At T = 298 K, 2.303 0.0591RTF

2. Atomic Numbers H 1 B 5 C 6 N 7 O 8 P 15 Ca 20 Cr 24 Mn 25 Fe 26 Co 27 Ni 28 Zn 30 Ru 44 3. Atomic weights (to the nearest integer) H 1 C 12 N 14 O 16 Ca 40


CY 3/20

Q. 1 – Q. 25 carry one mark each Q.1 In the proton decoupled 13C NMR spectrum of 7-norbornanone, the number of signals obtained is

(A) 7 (B) 3 (C) 4 (D) 5 Q.2 Identify the most probable product in the given reaction

(A)

(B)

(C)

(D)

Q.3 In the cyclization reaction given below, the most probable product formed is

(A) (B) (C) (D) Q.4 If Δy and Δpy are the uncertainties in the y-coordinate and the y component of the momentum of a

particle respectively, then, according to uncertainty principle ΔyΔpy is (2h

and h is Planck’s

constant)

(A) (B) > 2 (C) > (D) 2 Q.5 The average length of a typical α-helix comprised of 10 amino acids is

(A) 10 Å (B) 15 Å (C) 36 Å (D) 54 Å Q.6 Number of thymine residues in a 5000 kb DNA containing 23% guanine residues is

(A) 2.70 × 106 (B) 2.70 × 107 (C) 1.35 × 106 (D) 1.35 × 107

user

Sticky Note

B

user

Sticky Note

C

user

Sticky Note

D

user

Sticky Note

D(10*5*6/3.6) TURN=10/3.6 LENGTH=(10*5*6/3.6) 54A 0

user

Sticky Note

C

user

Sticky Note

c


CY 4/20

Q.7 Shown below is a Hammett plot obtained for the reaction

The change in slope of the plot indicates that

(A) the reaction does not follow linear free energy relationship (B) electrons are being withdrawn from the transition state in the mechanism (C) electrons are being donated to the transition state in the mechanism (D) the mechanism of the reaction is changing

Q.8 The ratio of relative intensities of the two molecular ion peaks of methyl bromide (CH3Br) in the mass spectrum is

(A) M+ : (M+2)+ = 1:3 (B) M+ : (M+2)+ = 3:1 (C) M+ : (M+2)+ = 1:1 (D) M+ : (M+2)+ = 1:2

Lo

g k

(A

r-C

OC

l)

hydr

olys

is)

user

Sticky Note

D

user

Sticky Note

C


CY 5/20

Q.9 A disaccharide that will not give Benedict’s test and will not form osazone is

(A) maltose (B) lactose (C) cellobiose (D) sucrose

Q.10 Choose the allowed transition

(A) 1g+ 3u

+ (B) 1g+ 3u

¯ (C) 1g+ 1u

+ (D) 1g+ 1u

¯

Q.11 The angular part of the wavefunction for the electron in a hydrogen atom is proportional to

2 2sin cos ie . The values of the azimuthal quantum number ( l ) and the magnetic quantum number ( m ) are, respectively

(A) 2 and 2 (B) 2 and –2 (C) 3 and 2 (D) 3 and –2 Q.12 Let C

x and Cz denote the wavefunctions of the 2px and 2pz orbitals of carbon, respectively, and

Ox and O

z represent the wavefunctions of the 2px and 2pz orbitals of oxygen, respectively. If

1c and 2c are constants used in linear combinations and the CO molecule is oriented along the z axis, then, according to molecular orbital theory, the π-bonding molecular orbital has a wavefunction given by

(A) 1 2C Oz xc c (B) 1 2

C Oz zc c

(C) 1 2C Ox zc c (D) 1 2

C Ox xc c

Q.13 The bond that gives the most intense band in the infrared spectrum for its stretching vibration is

(A) C─H (B) N─H (C) O─H (D) S─H Q.14 If xA and xB are the respective mole fractions of A and B in an ideal solution of the two and TA, TB,

T are the fusion temperatures of pure A, pure B and the ideal solution respectively, then

(A) ( ) 1 11 expofus B

BB

Hx

R T T

(B) ( ) 1 11 expofus A

BA

Hx

R T T

(C) ( ) 1 11 expofus B

BB

Hx

R T T

(D) ( ) 1 11 expofus A

BA

Hx

R T T

Q.15 For a reaction involving two steps given below

assume that the first step attains equilibrium rapidly. The rate of formation of P is proportional to

(A) [G]1/2 (B) [G] (C) [G]2 (D) [G]3/2

user

Sticky Note

D

user

Sticky Note

C

user

Sticky Note

A Angular moment=Sin^l(theta) Cos(theta)exp(im*phi)

user

Sticky Note

D

user

Sticky Note

C

user

Sticky Note

B

user

Sticky Note

D FIRST DETERMINE CONC OF H THEN PUT IN THE RATE EQUATION W R T PRODUCT


CY 6/20

Q.16 A metal chelate that can be used for separation and quantitative analysis of aluminium ions by gas chromatography is

(A) EDTA (B) ethylene glycol (C) dinonyl phthalate (D) trifluoroacetylacetone

Q.17 The enthalpies of hydration of Ca2+, Mn2+ and Zn2+ follow the order

(A) Mn2+ > Ca2+ > Zn2+ (B) Zn2+ > Ca2+ > Mn2+ (C) Mn2+ > Zn2+ > Ca2+ (D) Zn2+ > Mn2+ > Ca2+

Q.18 The number of terminal carbonyl groups present in Fe2(CO)9 is

(A) 2 (B) 5 (C) 6 (D) 3 Q.19 Among the following substituted silanes, the one that gives cross-linked silicone polymer upon

hydrolysis is

(A) (CH3)4Si (B) CH3SiCl3 (C) (CH3)2SiCl2 (D) (CH3)3SiCl Q.20 The plot of T versus T (where is molar magnetic susceptibility and T is the temperature) for a

paramagnetic complex which strictly follows Curie equation is

(A)

(B)

(C)

(D)

Q.21 Among the following donors, the one that forms most stable adduct with the Lewis acid B(CH3)3 is

(A) 4-methylpyridine (B) 2,6-dimethylpyridine (C) 4-nitropyridine (D) 2,6-di-tert-butylpyridine

Q.22 The complex with inverse-spinel structure is

(A) Co3O4 (B) Fe3O4 (C) MgAlO4 (D) Mn3O4

user

Sticky Note

D

user

Sticky Note

D

user

Sticky Note

C

user

Sticky Note

B

user

Sticky Note

C

user

Sticky Note

A

user

Sticky Note

B


CY 7/20

Q.23 The IUPAC nomenclature of Na[PCl6] is

(A) sodium hexachlorophosphine(V) (B) sodium hexachlorophosphate(V) (C) sodium hexachlorophosphine (D) sodium hexachlorophosphite(V)

Q.24 An intermediate formed during the hydroformylation of olefins using Co2(CO)8 as catalyst is

(A) HCo(CO)6 (B) H4Co(CO)3 (C) H2Co(CO)4 (D) HCo(CO)4 Q.25 The order of polarity of NH3, NF3 and BF3 is

(A) NH3 < NF3 < BF3 (B) BF3 < NF3 < NH3 (C) BF3 < NH3 < NF3 (D) NF3 < BF3 < NH3


Q.26 From a carboxymethyl-cellulose column at pH 6.0, arginine, valine and glutamic acid will elute in

the order

(A) arginine, valine, glutamic acid (B) arginine, glutamic acid, valine (C) glutamic acid, arginine, valine (D) glutamic acid, valine, arginine

Q.27 Symmetry operations of the four C2 axes perpendicular to the principal axis belong to the same

class in the point group(s)

(A) D4 (B) D4d (C) D4h (D) D4h and D4d

Q.28 At 298 K, the EMF of the cell

Pt│H2(1 bar)│H+(solution)║Cl─ │Hg2Cl2│Hg

is 0.7530 V. The standard potential of the calomel electrode is 0.2802 V. If the liquid junction potential is zero, the pH of the solution is

(A) 4.7 (B) 7.4 (C) 8.0 (D) 12.7

user

Sticky Note

B

user

Sticky Note

D

user

Sticky Note

B

user

Sticky Note

D

user

Sticky Note

A

user

Sticky Note

C


CY 8/20

Q.29 The wavefunction of a 1-D harmonic oscillator between x and x is given by 22 2( ) (2 1) xx N x e . The value of N that normalizes the function ( )x is

(Given: 22 1 3 5 (2 1)

2n x

n

nx e dx

)

(A)

121

8

(B)

121

3

(C)

121

2

(D)

121

4

Q.30 Consider the reaction

H2 + C2H4 C2H6

The molecular diameters of H2 and C2H4 are 1.8 Å and 3.6 Å respectively. The pre-exponential factor in the rate constant calculated using collision theory in 3 1 1( )m mole s is approximately

(For this reaction at 300 K,

12

278 1.11 10BA

k T N

m(mole)─1 s─1, where the symbols have

their usual meanings)

(A) 82.5 10

(B) 142.5 10 (C) 179.4 10 (D) 239.4 10

Q.31 The molecular partition function of a system is given by

33

3 22

2

8( ) B Bk T mk Tq Thc h

, where the symbols have their usual meanings.

The heat capacity at constant volume for this system is

(A) 3R (B) 6R (C) 9R/2 (D) 3R/2

user

Sticky Note

A


CY 9/20

Q.32 Consider the phase diagram given below. At the intersection point Q the phases that are in equilibrium are

(A) solid A, solid B and solid AB2 (B) solid A, solid AB2 and liquid (C) solid B, solid AB2 and liquid (D) solid A, solid B, solid AB2 and liquid

Q.33 Identify the product from the following reaction

(9-BBN = 9-Borabicyclo[3•3•1]nonane)

(A)

(B)

(C)

(D)

Q

Tem

pera

ture

Composition A B AB2

Liquid

user

Sticky Note

A

user

Sticky Note

C


CY 10/20

Q.34 The product from the following reaction is

(A)

(B)

(C)

(D)

Q.35 The acid catalyzed cyclization of 5-ketodecan-1,9-diol is given below

The most predominant spiroketal is

(A)

(B)

(C)

(D)

Q.36 For a face centered cubic lattice, the Miller indices for the first Bragg’s peak (smallest Bragg angle)

are

(A) 0 0 2 (B) 1 1 1 (C) 0 0 1 (D) 1 1 0 Q.37 For the titration of a 10 mL (aq) solution of CaCO3, 2 mL of 0.001 M Na2EDTA is required to

reach the end point. The concentration of CaCO3 (assume molecular weight of CaCO3 = 100) is

(A) 5 10–4 g/mL (B) 2 10–4

g/mL (C) 5 10–5

g/mL (D) 2 10–5 g/mL

user

Sticky Note

A

user

Sticky Note

B


CY 11/20


the product formed is

(A)

(B)

(C)

(D)

Q.39 In the reaction given below, identify the product

(A)

(B)

(C)

(D)

Q.40 Consider the following pairs of complexes

[CoF(NH3)5]2+ and [Cr(OH2)6]2+ [Co(NH3)5 (OH2)]3+ and [Cr(OH2)6]2+ [Co(NH3)6]3+ and [Cr(OH2)6]2+

[CoI(NH3)5]2+ and [Cr(OH2)6]2+

The electron transfer rate will be fastest in the pair

(A) [CoF(NH3)5]2+ and [Cr(OH2)6]2+ (B) [Co(NH3)5 (OH2)]3+ and [Cr(OH2)6]2+

(C) [Co(NH3)6]3+ and [Cr(OH2)6]2+ (D) [CoI(NH3)5]2+ and [Cr(OH2)6]2+


CY 12/20

Q.41 The extent of Mössbauer quadrupole splitting of iron follows the order

(A) FeCl2•4H2O > K2[Fe(CN)5(NO)] > FeCl3•6H2O (B) K2[Fe(CN)5(NO)] > FeCl2•4H2O > FeCl3•6H2O (C) FeCl3•6H2O > K2[Fe(CN)5(NO)] > FeCl2•4H2O (D) FeCl2•4H2O > FeCl3•6H2O > K2[Fe(CN)5(NO)]

Q.42 Hemoglobin is an oxygen carrying protein. The correct statement about oxy-hemoglobin is that

(A) the metal is low-spin in +3 oxidation state while dioxygen is in O2─ form

(B) the metal is high-spin in +3 oxidation state while dioxygen is in O2─ form

(C) the metal is low-spin in +3 oxidation state while dioxygen is in neutral form (D) the metal is high-spin in +3 oxidation state while dioxygen is in neutral form

Q.43 If a mixture of NaCl, conc. H2SO4 and K2Cr2O7 is heated in a dry test tube, a red vapour (P) is

formed. This vapour (P) dissolves in aqueous NaOH to form a yellow solution, which upon treatment with AgNO3 forms a red solid (Q). P and Q are, respectively

(A) CrO2Cl2 and Ag2Cr2O7 (B) Na2[CrOCl5] and Ag2CrO4 (C) Na2[CrOCl5] and Ag2Cr2O7 (D) CrO2Cl2 and Ag2CrO4

Q.44 For the following reaction

2MnO4

─ + 5H2C2O4 + 6H+ 2Mn2+ + 8H2O + 10CO2 E(MnO4

─/Mn2+) = +1.51 V and E(CO2/H2C2O4) = ─ 0.49 V. At 298 K, the equilibrium constant is

(A) 10500 (B) 10338 (C) 1038 (D) 10833 Q.45 The ground states of high-spin octahedral and tetrahedral Co(II) complexes are, respectively

(A) 4T2g and 4A2 (B) 4T1g and 4A2 (C) 3T1g and 4A2 (D) 4T1g and 3T1

Q.46 The INCORRECT statement about Zeise’s salt is

(A) Zeise’s salt is diamagnetic (B) The oxidation state of Pt in Zeise’s salt is +2 (C) All the Pt─Cl bond lengths in Zeise’s salt are equal (D) C─C bond length of ethylene moiety in Zeise’s salt is longer than that of free ethylene molecule

Q.47 The number of possible isomers for the square planar mononuclear complex [(NH3)2M(CN)2] of a

metal M is

(A) 2 (B) 4 (C) 6 (D) 3


CY 13/20


Common Data for Questions 48 and 49: Consider the reaction sequence shown below:

TsCl = p-toluenesulfonyl chloride

Q.48 The oxidant X used in step 1 is (A) CrO3

(B) OsO4

(C) NaIO4

(D) m-CPBA followed by NaOH

Q.49 The product is

(A)

(B)

(C)

(D)


CY 14/20

Common Data for Questions 50 and 51: Consider the E1 reaction of tert-amyl halides from the energy profile given below.

Q.50 In the above reaction, X = Cl, Br or I. Based on the graph, identify the alkyl halides (R-X) as S1, S2 and S3

(A) S1 = R-Cl, S2 = R-Br and S3 = R-I

(B) S1 = R-I, S2 = R-Br and S3 = R-Cl

(C) S1 = R-Cl, S2 = R-I and S3 = R-Br (D) S1 = R-I, S2 = R-Cl and S3 = R-Br Q.51 Identify product P1 and its yield relative to P2

(A) P1 is M and is the major product

(B) P1 is N and is the minor product

(C) P1 is N and is the major product

(D) P1 is M and is the minor product

S3

S2

S1

P1

P2

Reaction coordinate

Ener

gy


CY 15/20


Statement for Linked Answer Questions 52 and 53: A 20491 cm─1 laser line was used to excite oxygen molecules (made of 16O only) to obtain the rotational Raman spectrum. The resulting rotational Raman spectrum of oxygen molecule has the first Stokes line at 20479 cm─1.

Q.52 The rotational constant (usually denoted as B) for the oxygen molecule is (A) 1.2 cm─1 (B) 2.0 cm─1 (C) 3.0 cm─1 (D) 6.0 cm─1

Q.53 The next rotational Stokes line is expected at

(A) 20467 cm─1 (B) 20469 cm─1 (C) 20471 cm─1 (D) 20475 cm─1

Statement for Linked Answer Questions 54 and 55: Hückel molecular orbital theory can be applied to the allene radical CH2═CH─ĊH2

Q.54 The secular determinant (where , and E have their usual meanings) is given by

(A)

0

0

EE

E

(B)

0 0

00

EE

E

(C)

00

0 0

EE

E

(D)

0

0

EE

E

Q.55 The possible values of E are

(A) 2 , , 2 (B) 2 2 , , 2 2 (C) , , (D) 2 , , 2


CY 16/20

General Aptitude (GA) Questions (Compulsory)

Q. 56 – Q. 60 carry one mark each.

Q.56 If (1.001)1259 = 3.52 and (1.001)2062 = 7.85, then (1.001)3321 =

(A) 2.23 (B) 4.33 (C) 11.37 (D) 27.64 Q.57 One of the parts (A, B, C, D) in the sentence given below contains an ERROR. Which one of the

following is INCORRECT? I requested that he should be given the driving test today instead of tomorrow.

(A) requested that (B) should be given (C) the driving test (D) instead of tomorrow

Q.58 Which one of the following options is the closest in meaning to the word given below?

Latitude

(A) Eligibility (B) Freedom (C) Coercion (D) Meticulousness Q.59 Choose the most appropriate word from the options given below to complete the following

sentence:

Given the seriousness of the situation that he had to face, his ___ was impressive.

(A) beggary (B) nomenclature (C) jealousy (D) nonchalance Q.60 Choose the most appropriate alternative from the options given below to complete the following

sentence:

If the tired soldier wanted to lie down, he ___ the mattress out on the balcony.

(A) should take (B) shall take (C) should have taken (D) will have taken

Q. 61 - Q. 65 carry two marks each.

Q.61 One of the legacies of the Roman legions was discipline. In the legions, military law prevailed and discipline was brutal. Discipline on the battlefield kept units obedient, intact and fighting, even when the odds and conditions were against them. Which one of the following statements best sums up the meaning of the above passage?

(A) Thorough regimentation was the main reason for the efficiency of the Roman legions even in adverse circumstances.

(B) The legions were treated inhumanly as if the men were animals. (C) Discipline was the armies’ inheritance from their seniors. (D) The harsh discipline to which the legions were subjected to led to the odds and conditions being

against them.


CY 17/20

Q.62 A and B are friends. They decide to meet between 1 PM and 2 PM on a given day. There is a

condition that whoever arrives first will not wait for the other for more than 15 minutes. The probability that they will meet on that day is

(A) 1/4 (B) 1/16 (C) 7/16 (D) 9/16 Q.63 The data given in the following table summarizes the monthly budget of an average household.

Category Amount (Rs.) Food 4000 Clothing 1200 Rent 2000 Savings 1500 Other expenses 1800

The approximate percentage of the monthly budget NOT spent on savings is

(A) 10% (B) 14% (C) 81% (D) 86% Q.64 There are eight bags of rice looking alike, seven of which have equal weight and one is slightly

heavier. The weighing balance is of unlimited capacity. Using this balance, the minimum number of weighings required to identify the heavier bag is

(A) 2 (B) 3 (C) 4 (D) 8 Q.65 Raju has 14 currency notes in his pocket consisting of only Rs. 20 notes and Rs. 10 notes. The total

money value of the notes is Rs. 230. The number of Rs. 10 notes that Raju has is

(A) 5 (B) 6 (C) 9 (D) 10



CY 18/20



CY 19/20



CY 20/20


2013 CHEMISTRY– CY

CY 1/13

CY:CHEMISTRY Duration: Three Hours Maximum Marks:100 Please read the following instructions carefully: General Instructions:

1. Total duration of examination is 180 minutes (3 hours).

2. The clock will be set at the server. The countdown timer in the top right corner of screen will display the remaining time available for you to complete the examination. When the timerreaches zero, the examinationwill end by itself. You will not be required to end or submit your examination.

3. The Question Palettedisplayed on the right side of screen will show the status of each question using

one of the following symbols:

You have not visited the question yet.

You have not answered the question.

You have answered the question.

You have NOT answered the question, but have marked the question for review.

You have answered the question, but marked it for review.

The Marked for Review status for a question simply indicates that you would like to look at that question again. If a question is answered and Marked for Review, your answer for that question will be considered in the evaluation.

Navigating to a Question

4. To answer a question, do the following: a. Click on the question number in the Question Palette to go to that question directly. b. Select an answer for a multiple choice type question. Use the virtual numeric keypad to enter

a number as answer for a numerical type question. c. Click on Save and Nexttosave your answer for the current question and then go to the next

question. d. Click on Mark for Review and Nextto save your answer for the currentquestion, mark it for

review, and then go to the next question. e. Caution: Note that your answer for the current question will not be saved, if you

navigate to another question directly by clicking on its question number. 5. You can view all the questions by clicking on the Question Paper button.Note that the options for

multiple choice type questions will not be shown. Answering a Question

6. Procedure for answering a multiple choice type question: a. To select your answer, click on the button of one of the options b. To deselect your chosen answer, click on the button of the chosen option again or click on the

Clear Response button c. To change your chosen answer, click on the button of another option d. To save your answer, you MUST click on the Save and Nextbutton


CY 2/13

e. To mark the question for review, click on the Mark for Review and Nextbutton. If an answer is selected for a question that is Marked for Review, that answer will be considered in the evaluation.

7. Procedure for answering a numerical answer type question:

a. To enter a number as your answer, use the virtual numerical keypad b. A fraction (eg.,-0.3 or -.3) can be entered as an answer with or without ‘0’ before the decimal

point c. To clear your answer, click on the Clear Response button d. To save your answer, you MUST click on the Save and Nextbutton e. To mark the question for review, click on the Mark for Review and Nextbutton. If an

answer is entered for a question that is Marked for Review, that answer will be considered in the evaluation.

8. To change your answer to a question that has already been answered, first select that question for

answering and then follow the procedure for answering that type of question.

9. Note that ONLY Questions for which answers are saved or marked for review after answering will be considered for evaluation.


CY 3/13

Paper specific instructions:

1. There are a total of 65 questions carrying 100 marks.Questions are of multiple choice type or numerical answer type. A multiple choice type question will have four choices for the answer with only one correct choice. For numerical answer type questions, the answer is a number and no choices will be given. A number as the answer should be entered using the virtual keyboard on the monitor.

2. Questions Q.1 – Q.25 carry 1mark each. Questions Q.26 – Q.55 carry 2marks each. The 2marks questions include two pairs of common data questions and two pairs of linked answer questions. The answer to the second question of the linked answer questions depends on the answer to the first question of the pair. If the first question in the linked pair is wrongly answered or is not attempted, then the answer to the second question in the pair will not be evaluated.

3. Questions Q.56 – Q.65 belong to General Aptitude (GA) section and carry a total of 15 marks. Questions Q.56 – Q.60 carry 1mark each, and questions Q.61 – Q.65 carry 2marks each.

4. Questions not attempted will result in zero mark. Wrong answers for multiple choice type questions will result in NEGATIVE marks. For all 1 mark questions, ⅓ mark will be deducted for each wrong answer. For all 2 marks questions, ⅔ mark will be deducted for each wrong answer. However, in the case of the linked answer question pair, there will be negative marks only for wrong answer to the first question and no negative marks for wrong answer to the second question. There is no negative marking for questions of numerical answer type.

5. Calculator is allowed. Charts, graph sheets or tables are NOT allowed in the examination hall.

6. Do the rough work in the Scribble Pad provided.

USEFUL DATA - CY CHEMISTRY

COMMON DATA

Planck constant : 6.626 × 10–34 J s

Avogadro number : 6.022 × 1023mol–1

Speed of light : 3 × 108 m s–1

Gas constant : 8.314 J K–1mol–1

: 0.08314 L bar K–1mol–1

: 2 cal K–1mol–1

Boltzmann constant : 1.38 × 10–23 J K–1

Faraday constant : 96500 Cmol–1

: 3.14

Trouton’s rule : ∆Svap = 87 J K–1mol–1

Atomic Numbers: Ca : 20 V : 23 Cr : 24 Mn : 25 Fe : 26 Mo : 42 Xe : 54 Rn : 86


CY 4/13

Q. 1 – Q. 25carry one mark each.

Q.1 The point group symmetry ofCH2=C=CH2 is

(A) D2h (B) C2h (C) C2v (D) D2d

Q.2 Two trial wave functions 1 1c x a x and 222 1 2c x a x c x a x give ground state

energies E1 and E2, respectively, for themicroscopic particle in a 1-D boxby using the variation method. If the exact ground state energy is E0, the correct relationship between E0, E1 and E2 is

(A) E0 = E1 = E2 (B) E0< E1< E2 (C) E0< E2< E1 (D) E0> E2 = E1 Q.3 The ground state energies of H atom and H2 molecule are –13.6 eV and –31.7 eV, respectively. The

dissociation energy of H2 is _______ eV.

Q.4 A 2 L vessel containing 2 g of H2gas at 27 °C is connected to a 2 L vessel containing 176 g of CO2 gas at 27 °C. Assuming ideal behavior of H2 and CO2, the partial pressure of H2 at equilibrium is ________ bar.

Q.5 Consider the reaction 22 2C s O g CO g at equilibrium. The equilibrium can be shifted towards the forward direction by

(A) increasing the amount of carbon in the system. (B) decreasing the volume of the system. (C) decreasing the pressure of the system. (D) increasing the temperature of the system.

Q.6 A sparingly soluble electrolyte M2X ionizes as 2

2 2M X M X The solubility product (Ksp), molal solubility (S) and mean molal activity coefficient () are related by

(A) 2 2SPK S (B) 3 3

SPK S (C) 3 24SPK S (D) 3 34SPK S Q.7 For the first order consecutive reaction P Q R,

under steady state approximation to [Q], the variations of [P], [Q] and [R] with timeare best represented by

(A)

(B)

(C)

(D)

Q.8 At 273 K and 10 bar,the Langmuir adsorption of a gas on a solid surface gave the fraction of

surface coverage as0.01. The Langmuir adsorption isotherm constant is _________ bar–1. (Give the answer to the third decimal place)

Q.9 Conversion of boron trifluoride to tetrafluoroborate accompanies

(A) increase in symmetry and bond elongation (B) increase in symmetry and bond contraction (C) decrease in symmetry and bond contraction (D) decrease in symmetry and bond elongation

user

Sticky Note

D

user

Sticky Note

C

user

Sticky Note

4.5eV

user

Sticky Note

C

user

Sticky Note

D

user

Sticky Note

C

user

Sticky Note

.001


CY 5/13

Q.10 The correct statement with respect to the bonding of the ligands, Me3N and Me3P with the metal ions Be2+ and Pd2+ is,

(A) the ligands bind equally strong with both the metal ions as they are dicationic (B) the ligands bind equally strong with both the metal ions as both the ligands are pyramidal (C) the binding is stronger for Me3N with Be2+ and Me3P with Pd2+ (D) the binding is stronger for Me3N with Pd2+ and Me3P with Be2+

Q.11 A crystal has the lattice parameters a ≠ b ≠ c and = = = 90o. The crystal system is

(A) tetragonal (B) monoclinic (C) cubic (D) orthorhombic Q.12 The by-product formed in the characteristic reaction of (CO)5Cr=C(OMe)(Me) with MeNH2 is

(A) CO (B) MeOH (C) MeCHO (D) MeCONH2 Q.13 The catalyst and co-catalyst used in the Wacker process, respectively, are

(A) PdCl2and Cu (B) CuCl2and [PdCl4]2– (C) Pdand CuCl (D) [PdCl4]2–and CuCl2

Q.14 Oxymyoglobin Mb(O2) and oxyhemoglobinHb(O2)4, respectively, are

(A) paramagnetic and paramagnetic (B) diamagnetic and diamagnetic (C) paramagnetic anddiamagnetic (D) diamagnetic and paramagnetic

Q.15 Hapticity of cycloheptatrienein Mo(C7H8)(CO)3is _______.

Q.16 The number of oxygen molecule(s) that a molecule of hemerythrin can transport is _______.

Q.17 The maximum number of stereoisomers possible for the compound given below is _____.

Me

NO2 NO2

MeMe

O

Q.18 The correct sequence of the amino acids present in the tripeptide given below is

H2NHN

NH

OH

MeMe

OOH

OMe OH

O

(A) Val-Ser-Thr (B) Val-Thr-Ser (C) Leu-Ser-Thr (D) Leu-Thr-Ser Q.19 Among the compounds given in the options A-D, the one that can be used as a formyl anion

equivalent (in the presence of a strong base) is

(A) ethylene (B) nitroethane (C) 1,3-dithiane (D) 1,4-dithiane

user

Sticky Note

C

user

Sticky Note

user

Sticky Note

B

user

Sticky Note

D

user

Sticky Note

B

user

Sticky Note

6

user

Sticky Note

1

user

Sticky Note

A

user

Sticky Note

C


CY 6/13

Q.20 The major product formed in the reaction given below is

O

1. Me2CuLi, Et2O

2. H3O+

HO Me

(A)

Me OH

(B)

O

Me

(C)

O

Me

(D)


1. NaOH, Br2

2. H3O+NH

O

O

(A)NH2

COOH (B)

Br

CONH2

(C)COOH

CONH2

(D) O

O

O Q.22 The pericyclic reaction given below is an example of

OH

HO

(A) [1,3]-sigmatropic shift (B) [1,5]-sigmatropic shift (C) [3,5]-sigmatropic shift (D) [3,3]-sigmatropic shift

Q.23 The major product formed in the reaction of quinoline with potassium amide (KNH2) in liquid

ammonia is

(A)NH

(B)N NH2

(C)N

(D)

N

H2N

Q.24 The number of signals that appear in the proton decoupled 13C NMR spectrum of benzonitrile

(C7H5N) is ________.

Q.25 Among the compounds given in the options A-D, the one that exhibits a sharp band at around 3300 cm–1 in the IR spectrum is

(A) 1,2-butadiene (B) 1,3-butadiene (C) 1-butyne (D) 2-butyne

user

Sticky Note

D

user

Sticky Note

A Hoffman rearrangement reaction

user

Sticky Note

D

user

Sticky Note

B

user

Sticky Note

5

user

Sticky Note

C


CY 7/13


Q.26 In the metathesis reaction given below, 4.32 g of the compound X was treated with 822 mg of the catalyst Y to yield 2.63 g of the product Z. The mol% of the catalystY used in this reaction is ___. [Atomic weights of Ru = 101; P = 31; Cl = 35.5].

MeO MeOPR3

Ru

PR3Cl

Cl

Ph

(R = cyclohexyl)

+

X ZY

Q.27 An organic compound Q exhibited the following spectral data:

IR: 1760 cm-1 1H NMR: (ppm): 7.2 (1H, d, J = 16.0 Hz), 5.1 (1 H, m), 2.1 (3 H, s), 1.8 (3H, d, J = 7.0 Hz) 13C NMR: (ppm): 170 (carbonyl carbon). Compound Q is

(A)

Me

O

O

Me

(B)

Me

O

O

Me

(C)

MeO

Me

O

(D)

Me

OMe

O

Q.28 The major product formed in the Beckmann rearrangement of the compound given below is

Me

Me Ph

NOH

H1. TsCl pyridine2. H3O+

(A)

Me Ph

NHMeHO

(B)

Me Ph

NHMeHO

(C)

HN

Me Ph

O

H Me

(D)

HN

Me Ph

O

H Me


O2N

Me

OMe

OH

HO

conc. H2SO4

(A)

OO2N

OMe

Me

(B)

OMeO

NO2

Me

(C)

OMe

NO2

OMe

(D)

O

Me

NO2

MeO

user

Sticky Note

4.4%

user

Sticky Note

A

user

Sticky Note

D

user

Sticky Note

A


CY 8/13


NH2 NaNO2, aq. HCl0-5 oC

(A) NO2

(B)

OH

(C)

NO2

(D)OH

Q.31 The major product(s) formed in the reaction sequence given below is(are)

Me3Si

Br

Ph 1. Mg, dry Et2O

3. aq. H2SO4

2. PhCHO

(A) PhPh and PhPh

(B) Ph

Phand

PhPhSiMe3

SiMe3

(C)Ph

PhO

(D) PhSiMe3

OH

Ph Q.32 Match the compounds in the column I with the photochemical reactions that they can undergo

given in the column II

I II

(i)

(ii)

(iii)

(q) Paterno-Buchi reaction

(p) oxa-di--methane rearrangement

(r) intramolecular [2+2]-cycloaddition

(s) photoenolisation

O

O

Me

Me

H

H

O

(A) (i)-(q); (ii)-(s); (iii)-(p) (B) (i)-(r); (ii)-(p); (iii)-(s)

(C) (i)-(p); (ii)-(r); (iii)-(q) (D) (i)-(r); (ii)-(q); (iii)-(s)

Q.33 22xe is an eigen function of the operator

2

2

2

16xdxd

. The corresponding eigen value is

(A) + 4 (B) – 4 (C) + 2 (D) – 2 Q.34 The infrared spectrum of HCl gas shows an absorption band centered at 2885 cm–1. The zero point

energy of HCl molecule under harmonic oscillator approximation is

(A) 2.8665 × 10–22 J (B) 2.8665 × 10–20 J

(C) 5.7330 × 10–22 J (D) 5.7330 × 10–20 J

user

Sticky Note

D

user

Sticky Note

A

user

Sticky Note

B


CY 9/13

Q.35 For the reaction 2 4 22X O l XO g at 298 K, given the values, ∆U = 9 kJ and ∆S = 84 J K–1, ∆G is

(A) –11.08 kJ (B) +11.08 kJ (C) –13.55 kJ (D) +13.55kJ Q.36 The change in enthalpy when 3 mol of liquid benzene transforms to the vapor state at its boiling

temperature (80 °C) and at 1 bar pressure is _____________ kJ.

Q.37 The moment of inertia of a homonuclear diatomic molecule is 7.5 × 10–45 kg m2. Its rotational partition function at 500 K is _____________ .

Q.38 For a reaction of the type 1

2

k

kX Y , the correct rate expression is

([X]0 and [X] correspond to the concentrations of X at time t=0 andt = t, respectively)

(A) 1 1 20

d Xk X k k X

dt (B)

1 2 2 0

d Xk k X k X

dt

(C) 1 2 10

d Xk k X k X

dt (D)

1 2 1 0

d Xk k X k X

dt

Q.39 The temperature dependence of partition functions are as follows:

32

translationq T 0vibrationq T

rotationq T (linear molecule) 3

2rotationq T (non-linear molecule)

According to the conventional transition state theory (CTST), the temperature dependence of the Arrhenius pre-exponential factorfor a reaction of the type given below is

linear molecule + linear molecule non-linear transition state products

(A) 1T (B) 0T (C) 1T (D) 2T

Q.40 Decarbonylation reaction of [cis-(CH3CO)Mn(13CO)(CO)4] yields X,Y and Z, where

X =[(CH3)Mn(CO)5]; Y = [cis-(CH3)Mn(13CO)(CO)4]; Z = [trans-(CH3)Mn(13CO)(CO)4] The molar ratio ofthe products(X : Y : Z) in this reaction is

(A) 1 : 1 : 1 (B) 1 : 2 : 1 (C) 1 : 1 : 2 (D) 2 : 1 : 1 Q.41 According to polyhedral electron count rule, the structure of Rh6(CO)16is

(A) closo (B) nido (C) arachno (D) hypho Q.42 The increasing order of melting points of the halides NaCl, CuClandNaF is

(A) CuCl<NaCl<NaF (B) NaF<NaCl<CuCl

(C) NaF<CuCl<NaCl (D) CuCl<NaF<NaCl Q.43 The correct electronic configuration and spin only magnetic moment of Gd3+ (at.no. 64) are

(A) [Xe]4f7 and 7.9 BM (B) [Xe]4f7 and 8.9 BM

(C) [Xe]4f65d1 and 7.9 BM (D) [Rn]5f7 and 7.9 BM Q.44 Among the following octahedral complexes, the one that has the highest enthalpy of hydration is

(A) [Ca(H2O)6]2+ (B)[Mn(H2O)6]2+ (C) [V(H2O)6]2+ (D) [Cr(H2O)6]2+


CY 10/13

Q.45 A metal crystallizes in face-centered cubic lattice with a lattice parameter of 4.20 Å. The shortest atom to atom contact distance in the lattice is

(A) 4.20 Å (B) 2.97 Å (C) 2.42 Å (D) 2.10 Å Q.46 Polarographic method of analysis to obtain individual amounts of Cu2+ and Cd2+ in a given mixture

of the two ions (Cu2+ and Cd2+) is achieved by measuring their

(A) half-wave potentials (B) migration currents (C) decomposition potentials (D) diffusion currents

Q.47 The ground state term of [Ni(H2O)6]2+is

(A) 3T1g (B) 3T2g

(C) 3A2g (D) 4T1g



N,N-Dimethylformamide (DMF) gives different patterns of signals for the methyl protons whenits1H NMR spectrum is recorded at different temperatures.

Q.48 Match the patterns of the NMR signals given in column I with temperatures given in the columnII.

I

II (i) Two singlets,for three protons each, at 2.87 and 2.97 ppm (x) 25 °C

(ii) One sharp singlet for six protons at 2.92 ppm (y) 120 °C

(iii) One broad signal for six protons (z) 150 °C

(A) (i)-(x); (ii)-(y); (iii)-(z) (B) (i)-(x); (ii)-(z); (iii)-(y)

(C) (i)-(z); (ii)-(x); (iii)-(y) (D) (i)-(z); (ii)-(y); (iii)-(x) Q.49 Based on the above data, the calculateddifference in the frequencies of the two methylsinglets, if

the spectrum is recorded on a 300 MHzspectrometer, is _________ Hz.


Heating a mixture of ammonium chloride and sodium tetrahydridoborate gives one liquid product(X), along with other products, under ambient conditions.

Q.50 Compound X is (A) NH4[BH4] (B) [(NH3)2BH2][BH4]

(C) N3B3H6 (D) N3B3H12 Q.51 Compound X is an example of

(A) ionic liquid (B) saturated heterocycle

(C) molecular cage (D) unsaturated heterocycle


CY 11/13

Linked Answer Questions52 and 53:

Q.52 The major product X formed in the reaction given below is

HO OH

OH

OH

2,2-dimethoxypropanep-toluenesulfonic acid

(catalytic)

X

(A)HO

OH

O

OMe

Me

(B)HO

OH

O

O

Me

Me

(C)OH

OH

OO

Me Me

(D) OOMe

Me

OH

HO

Q.53 Oxidation of the product X, obtained in the above reaction, with active manganese dioxide,

followed by acidic hydrolysis gives

(A)

HO

OH

OH

OH

(B)O

OH

OH

OH

(C) OH

O

OHHO

(D)

HO

OH

O

OH


The standard half-cell reduction potential of 3 ( ) |Fe aq Fe is – 0.036 V and that of

3( ) | ( ) |OH aq Fe OH s Fe is – 0.786 V.

Q.54 For the determination of solubility product (KSP) of 3Fe OH , the appropriate cell representation and its emfare, respectively, (A) 3

3( ) | ( ) ( ) , 0.750Fe Fe OH s OH aq Fe aq Fe V

(B) 33

( ) ( ) | ( ) , 0.750Fe Fe aq OH aq Fe OH s Fe V

(C) 33

( ) | ( ) ( ) , 0.750Fe Fe OH s OH aq Fe aq Fe V

(D) 33

( ) ( ) | ( ) , 0.822Fe Fe aq OH aq Fe OH s Fe V Q.55 The value of loge SPK for 3

Fe OH at 298 K is

(A) – 38.2 (B) + 87.6 (C) – 96.0 (D) – 87.6


CY 12/13



Q.56 If 3 ≤ 푋 ≤ 5 and 8 ≤ 푌 ≤ 11 then which of the following options is TRUE?

(A) ≤ ≤

(B) ≤ ≤

(C) ≤ ≤

(D) ≤ ≤

Q.57 The Headmaster ___________ to speak to you. Which of the following options is incorrect to complete the above sentence?

(A) is wanting (B) wants (C) want (D) was wanting

Q.58 Mahatama Gandhi was known for his humility as

(A) he played an important role in humiliating exit of British from India. (B) he worked for humanitarian causes. (C) he displayed modesty in his interactions. (D) he was a fine human being.

Q.59 All engineering students should learn mechanics, mathematics and how to do computation.

I II III IV Which of the above underlined parts of the sentence is not appropriate?

(A) I (B) II (C) III (D) IV Q.60 Select the pair that best expresses a relationship similar to that expressed in the pair:

water: pipe::

(A) cart: road (B) electricity: wire (C) sea: beach (D) music: instrument


CY 13/13


Q.61 Velocity of an object fired directly in upward direction is given by 푉 = 80 − 32푡, where 푡 (time) is in seconds. When will the velocity be between 32 m/sec and 64 m/sec?

(A) (1, 3/2) (B) (1/2, 1)

(C) (1/2, 3/2) (D) (1, 3) Q.62 In a factory, two machines M1 and M2 manufacture 60% and 40% of the autocomponents

respectively. Out of the total production, 2% of M1 and 3% of M2 are found to be defective. If a

randomly drawn autocomponent from the combined lot is found defective, what is the probability

that it was manufactured by M2?

(A) 0.35 (B) 0.45 (C) 0.5 (D) 0.4 Q.63 Following table gives data on tourists from different countries visiting India in the year 2011.

Country Number of

Tourists USA 2000

England 3500 Germany 1200

Italy 1100 Japan 2400

Australia 2300 France 1000

Which two countries contributed to the one third of the total number of tourists who visited India in 2011?

(A) USA and Japan (B) USA and Australia (C) England and France (D) Japan and Australia

Q.64 If |−2푋 + 9| = 3 then the possible value of |−푋|− 푋 would be:

(A) 30 (B) -30 (C) -42 (D) 42 Q.65 All professors are researchers

Some scientists are professors Which of the given conclusions is logically valid and is inferred from the above arguments:

(A) All scientists are researchers (B) All professors are scientists (C) Some researchers are scientists (D) No conclusion follows


GATE 2014: General Instructions during Examination

1. Total duration of the GATE examination is 180 minutes. 2. The clock will be set at the server. The countdown timer at the top right corner of

screen will display the remaining time available for you to complete the examination. When the timer reaches zero, the examination will end by itself. You need not terminate the examination or submit your paper.

3. Any useful data required for your paper can be viewed by clicking on the Useful Common Data button that appears on the screen.

4. Use the scribble pad provided to you for any rough work. Submit the scribble pad at the end of the examination.

5. You are allowed to use a non-programmable type calculator, however, sharing of calculators is not allowed.

6. The Question Palette displayed on the right side of screen will show the status of each question using one of the following symbols:

The Marked for Review status for a question simply indicates that you would like to look at that question again. If a question is answered, but marked for review, then the answer will be considered for evaluation unless the status is modified by the candidate.

Navigating to a Question :

7. To answer a question, do the following: a. Click on the question number in the Question Palette to go to that question

directly. b. Select an answer for a multiple choice type question by clicking on the bubble

placed before the 4 choices, namely A, B, C and D. Use the virtual numeric keypad to enter a number as answer for a numerical type question.

c. Click on Save & Next to save your answer for the current question and then go to the next question.

d. Click on Mark for Review & Next to save your answer for the current question and also mark it for review, and then go to the next question.

Caution: Note that your answer for the current question will not be saved, if you navigate to another question directly by clicking on a question number without saving the answer to the previous question.

You can view all the questions by clicking on the Question Paper button. This feature is provided, so that if you want you can just see the entire question paper at a glance.

Answering a Question :

8. Procedure for answering a multiple choice (MCQ) type question: a. Choose one answer from the 4 options (A,B,C,D) given below the question,

click on the bubble placed before the chosen option. b. To deselect your chosen answer, click on the bubble of the chosen option again

or click on the Clear Response button. c. To change your chosen answer, click on the bubble of another option. d. To save your answer, you MUST click on the Save & Next button.

9. Procedure for answering a numerical answer type question: a. To enter a number as your answer, use the virtual numerical keypad. b. A fraction (e.g. -0.3 or -.3) can be entered as an answer with or without '0'

before the decimal point. As many as four decimal points, e.g. 12.5435 or 0.003 or -932.6711 or 12.82 can be entered.

c. To clear your answer, click on the Clear Response button. d. To save your answer, you MUST click on the Save & Next button

10. To mark a question for review, click on the Mark for Review & Next button. If an answer is selected (for MCQ) or entered (for numerical answer type) for a question that is Marked for Review, that answer will be considered in the evaluation unless the status is modified by the candidate.

11. To change your answer to a question that has already been answered, first select that question for answering and then follow the procedure for answering that type of question.

12. Note that ONLY Questions for which answers are saved or marked for review after answering will be considered for evaluation.

Choosing a Section :

13. Sections in this question paper are displayed on the top bar of the screen. Questions in a Section can be viewed by clicking on the name of that Section. The Section you are currently viewing will be highlighted.

14. A checkbox is displayed for every optional Section, if any, in the Question Paper. To select the optional Section for answering, click on the checkbox for that Section.

15. If the checkbox for an optional Section is not selected, the Save & Next button and the Mark for Review & Next button will NOT be enabled for that Section. You will

only be able to see questions in this Section, but you will not be able to answer questions in the Section.

16. After clicking the Save & Next button for the last question in a Section, you will automatically be taken to the first question of the next Section in sequence.

17. You can move the mouse cursor over the name of a Section to view the answering status for that Section.

Changing the Optional Section :

18. After answering the chosen optional Section, partially or completely, you can change the optional Section by selecting the checkbox for a new Section that you want to attempt. A warning message will appear along with a table showing the number of questions answered in each of the previously chosen optional Sections and a checkbox against each of these Sections. Click on a checkbox against a Section that you want to reset and then click on the RESET button. Note that RESETTING a Section will DELETE all the answers for questions in that Section. Hence, if you think that you may want to select this Section again later, you will have to note down your answers for questions in that Section. If you do not want to reset the Section and want to continue answering the previously chosen optional Section, then click on the BACK button.

19. If you deselect the checkbox for an optional Section in the top bar, the following warning message will appear: "Deselecting the checkbox will DELETE all the answers for questions in this Section. Do you want to deselect this Section?” If you want to deselect, click on the RESET button. If you do not want to deselect, click on the BACK button.

20. You can shuffle between different Sections or change the optional Sections any number of times.

GATE 2014 Examination

CY: Chemistry

Duration: 180 minutes Maximum Marks: 100


1. To login, enter your Registration Number and password provided to you. Kindly go through the various symbols used in the test and understand their meaning before you start the examination.

2. Once you login and after the start of the examination, you can view all the questions in the question paper, by clicking on the View All Questions button in the screen.

3. This question paper consists of 2 sections, General Aptitude (GA) for 15 marks and the subject specific GATE paper for 85 marks. Both these sections are compulsory. The GA section consists of 10 questions. Question numbers 1 to 5 are of 1-mark each, while question numbers 6 to 10 are of 2-mark each. The subject specific GATE paper section consists of 55 questions, out of which question numbers 1 to 25 are of 1-mark each, while question numbers 26 to 55 are of 2-mark each.

4. Depending upon the GATE paper, there may be useful common data that may be required for answering the questions. If the paper has such useful data, the same can be viewed by clicking on the Useful Common Data button that appears at the top, right hand side of the screen.

5. The computer allotted to you at the examination center runs specialized software that permits only one answer to be selected for multiple-choice questions using a mouse and to enter a suitable number for the numerical answer type questions using the virtual keyboard and mouse.

6. Your answers shall be updated and saved on a server periodically and also at the end of the examination. The examination will stop automatically at the end of 180 minutes.

7. In each paper a candidate can answer a total of 65 questions carrying 100 marks. 8. The question paper may consist of questions of multiple choice type (MCQ) and numerical answer

type. 9. Multiple choice type questions will have four choices against A, B, C, D, out of which only ONE is the

correct answer. The candidate has to choose the correct answer by clicking on the bubble (⃝) placed before the choice.

10. For numerical answer type questions, each question will have a numerical answer and there will not be any choices. For these questions, the answer should be enteredby using the virtual keyboard that appears on the monitor and the mouse.

11. All questions that are not attempted will result in zero marks. However, wrong answers for multiple choice type questions (MCQ) will result in NEGATIVE marks. For all MCQ questions a wrong answer will result in deduction of⅓ marks for a 1-mark question and ⅔ marks for a 2-mark question.

12. There is NO NEGATIVE MARKING for questions of NUMERICAL ANSWER TYPE.

13. Non-programmable type Calculator is allowed. Charts, graph sheets, and mathematical tables are NOT allowed in the Examination Hall. You must use the Scribble pad provided to you at the examination centre for all your rough work. The Scribble Pad has to be returned at the end of the examination.

Declaration by the candidate: “I have read and understood all the above instructions. I have also read and understood clearly the instructions given on the admit card and shall follow the same. I also understand that in case I am found to violate any of these instructions, my candidature is liable to be cancelled. I also confirm that at the start of the examination all the computer hardware allotted to me are in proper working condition”.

GATE 2014 SET- 1 General Aptitude -GA

GA 1/2


Q.1 A student is required to demonstrate a high level of comprehension of the subject, especially in the social sciences. The word closest in meaning to comprehension is

(A) understanding (B) meaning (C) concentration (D) stability Q.2 Choose the most appropriate word from the options given below to complete the following

sentence. One of his biggest ______ was his ability to forgive.

(A) vice (B) virtues (C) choices (D) strength Q.3 Rajan was not happy that Sajan decided to do the project on his own. On observing his

unhappiness, Sajan explained to Rajan that he preferred to work independently. Which one of the statements below is logically valid and can be inferred from the above sentences?

(A) Rajan has decided to work only in a group. (B) Rajan and Sajan were formed into a group against their wishes. (C) Sajan had decided to give in to Rajan’s request to work with him. (D) Rajan had believed that Sajan and he would be working together.

Q.4 If y = 5x2 + 3, then the tangent at x = 0, y = 3

(A) passes through x = 0, y = 0 (B) has a slope of +1 (C) is parallel to the x-axis (D) has a slope of −1

Q.5 A foundry has a fixed daily cost of Rs 50,000 whenever it operates and a variable cost of Rs 800Q,

where Q is the daily production in tonnes. What is the cost of production in Rs per tonne for a daily production of 100 tonnes?

Q. 6 – Q. 10 carry two marks each.

Q.6 Find the odd one in the following group: ALRVX, EPVZB, ITZDF, OYEIK

(A) ALRVX (B) EPVZB (C) ITZDF (D) OYEIK Q.7 Anuj, Bhola, Chandan, Dilip, Eswar and Faisal live on different floors in a six-storeyed building

(the ground floor is numbered 1, the floor above it 2, and so on). Anuj lives on an even-numbered floor. Bhola does not live on an odd numbered floor. Chandan does not live on any of the floors below Faisal’s floor. Dilip does not live on floor number 2. Eswar does not live on a floor immediately above or immediately below Bhola. Faisal lives three floors above Dilip. Which of the following floor-person combinations is correct?

Anuj Bhola Chandan Dilip Eswar Faisal (A) 6 2 5 1 3 4 (B) 2 6 5 1 3 4 (C) 4 2 6 3 1 5 (D) 2 4 6 1 3 5

GATE 201

4

user

Sticky Note

A

GATE 2014 SET- 1 General Aptitude -GA

GA 2/2

Q.8 The smallest angle of a triangle is equal to two thirds of the smallest angle of a quadrilateral. The ratio between the angles of the quadrilateral is 3:4:5:6. The largest angle of the triangle is twice its smallest angle. What is the sum, in degrees, of the second largest angle of the triangle and the largest angle of the quadrilateral?

Q.9 One percent of the people of country X are taller than 6 ft. Two percent of the people of country Y

are taller than 6 ft. There are thrice as many people in country X as in country Y. Taking both countries together, what is the percentage of people taller than 6 ft?

(A) 3.0 (B) 2.5 (C) 1.5 (D) 1.25 Q.10 The monthly rainfall chart based on 50 years of rainfall in Agra is shown in the following figure.

Which of the following are true? (k percentile is the value such that k percent of the data fall below that value)

(i) On average, it rains more in July than in December (ii) Every year, the amount of rainfall in August is more than that in January (iii) July rainfall can be estimated with better confidence than February rainfall (iv) In August, there is at least 500 mm of rainfall

(A) (i) and (ii) (B) (i) and (iii) (C) (ii) and (iii) (D) (iii) and (iv)

END OF THE QUESTION PAPER GATE 201

4

GATE 2014 CHEMISTRY – CY

CY 1/10

USEFUL DATA – CY CHEMISTRY

COMMON DATA Gas constant : 8.314 J K−1 mol−1 : 0.083 L bar K−1 mol−1 Faraday constant : 96500 C mol−1 2.303RT/F at 300 K : 0.06 V NA : 6.02 × 1023 Atomic numbers : B = 5, N = 7, Mg = 12, S = 16, Ti = 22, V = 23, Cr = 24, Mn = 25 Fe = 26, Co = 27, Ni = 28, Cu = 29, Rh = 45, Ta = 73

CY (GATE 2

014)


CY 2/10


Q.1 The maximum non-PV work that a system can perform at constant P is

(A) ∆H (B) ∆G (C) ∆S (D) ∆A Q.2 Consider the reaction:

A + B C The unit of the thermodynamic equilibrium constant for the reaction is

(A) mol L−1 (B) L mol−1 (C) mol2 L−2 (D) dimensionless Q.3 The number of IR active vibrational normal modes of CO2 is ______________

Q.4 The number of C2 axes in CCl4 is ______________

Q.5 The value of the magnetic quantum number of a px orbital is

(A) −1 (B) 0 (C) +1 (D) undefined Q.6 The molecular partition function for a system in which the energy levels are equispaced by ε , is

(A)

(B)

(C) (D)

Q.7 A monoatomic gas, X, adsorbed on a surface, follows Langmuir adsorption isotherm. A plot of the

fraction of surface coverage, θ, against the concentration of the gas [X], for VERY LOW concentration of the gas, is described by the equation

(A) (B) 1

(C) (D)

Q.8 At a given temperature and pressure, the ratio of the average speed of hydrogen gas to that of

helium gas is approximately ______________

Q.9 An example of nido-borane from the following is

(A) B4H10 (B) B6H10 (C) B6H12 (D) B8H14

Q.10 The geometries of Ni(CO)4 and [NiCl4]

2−, respectively, are

(A) tetrahedral and square planar (B) square planar and tetrahedral (C) tetrahedral and tetrahedral (D) square planar and square planar

Q.11 The number of S−S bonds in H2S5O6 is ______________

Q.12 In atomic absorption spectroscopy, the atomization process utilizes

(A) flame (B) electric field (C) magnetic field (D) electron beam Q.13 At room temperature, the number of singlet resonances observed in the 1H NMR spectrum of

Me3CC(O)NMe2 (N,N-dimethyl pivalamide) is ______________

CY (GATE 2

014)


CY 3/10

Q.14 Amongst the following, the metal that does NOT form homoleptic polynuclear metal carbonyl is

(A) Mn (B) Fe (C) Cr (D) Co Q.15 The reaction of [Cp2TaMe2]I (Cp = C5H5

−) with NaOMe yields

(A) [Cp2Ta(OMe)2]I (B) [Cp2Ta(Me)OMe]I (C) Cp2Ta(Me)=CH2 (D) Cp2Ta(OMe)=CH2 Q.16 The complexes [Co(H2O)4Cl2]NO2 and [Co(H2O)4Cl(NO2)]Cl are

(A) linkage isomers (B) positional isomers (C) ionization isomers (D) optical isomers

Q.17 The major product of the following reaction is

(A)

(B) (C) (D)

Q.18 Amongst the following, the structure of guanosine is

(A)

(B)

(C)

(D)

Q.19 The correct order of IR stretching frequency of the C=C in the following olefins is

(A) I > II > III (B) II > III > I (C) III > II > I (D) III > I > II Q.20 The correct order of the rate of solvolysis for the following chlorides in acetic acid is

(A) II > I > III (B) III > II > I (C) III > I > II (D) I > III > II

CY (GATE 2

014)


CY 4/10

Q.21 Formation of the product in the following photochemical reaction involves

PhPh

Oh Ph

Ph

O

H

H

(A) di-π-methane rearrangement (B) Paterno-Buchi reaction (C) [2,3]-sigmatropic rearrangement (D) Norrish type I reaction

Q.22 The correct order of stability for the following conformations of cyclohexane is

(A) I > II > III (B) I > III > II (C) II > I > III (D) III > I > II Q.23 The major product formed in the following reaction is

(A)

(B) (C)

(D)

Q.24 The overall yield (in %) for the following reaction sequence is ______________

Q.25 The most suitable reagent combination to effect the following conversion is

O

BzO

OBn

OH

O

BzO

OBn

(A) i. NaH, CS2, then MeI; ii. Bu3SnH, AIBN, C6H6, reflux (B) i. I2, PPh3, imidazole; ii. H2, 10% Pd-C, AcOH, high pressure (C) i. Me3SiCl, pyridine, DMAP; ii. Bu3SnH, AIBN, C6H6, reflux (D) i. MsCl, pyridine, DMAP; ii. LiAlH4, THF, reflux

Q. 26 – Q. 55 carry two marks each.

Q.26 ψ 6 ⁄ cos , is a proposed hydrogenic wavefunction, where Z = Atomic number, r = radial distance from the nucleus, θ = azimuthal angle, N is a constant. The INCORRECT statement about ψ is

(A) ψ = 0 in the xy-plane (B) two radial nodes are present in ψ (C) one angular node is present in ψ (D) the size of the orbital decreases with increase in atomic number

Q.27 The van der Waals constants a and b of CO2 are 3.64 L2 bar mol−2 and 0.04 L mol−1, respectively.

The value of R is 0.083 bar dm3 mol−1 K−1. If one mole of CO2 is confined to a volume of 0.15 L at 300 K, then the pressure (in bar) exerted by the gas, is ______________

CY (GATE 2

014)

GATE 2014

CY

Q.28 A pthe

(A)(B)(C)(D)

Q.29 A p

is fto b1 M

Q.30 Mo

atom

Q.31 The

ene

Q.32 A C

abs

Q.33 Of

tem

(A)

Q.34 The

273

Q.35 Sup

1ψand

2ψThe

Q.36 BC

ano

(A)(B)(C)(D)

plot of osmotplot

) increases w) increases w) decreases w) decreases w

platinum elecfound to be 0be equal to u

M, is _______

olybdenum crmic mass of

e ratio of moergy (in kJ m

Carnot enginsolute temper

the followinmperature (T)

)

e enthalpy of3 K is 44.83

ppose ψ1 and

30.12 sψ= +

d

30.12 sψ= −

e angle (in de

Cl3 and NH4Cother compou

) X = B3N3H) X = B3N3H9

) X = B3N3H3

) X = B3N3Cl

tic pressure a

with increase with increase with decreasewith increase

ctrode is imm0.77 V againsunity, the pote________

rystallizes inf molybdenum

olecules distrmol−1) of the t

ne operates atrature of inpu

ng plots, the c) for a pure su

(B

f fusion of ickJ mol−1. Th

d ψ2, are two

3 0.63xpψ+ +

3 0.63xpψ−

egrees) betw

Cl were heateund Y. Com

3Cl3 and Y =9Cl3 and Y =3Cl3 and Y =l6 and Y = B

against conce

in temperatuin molar mas

e in concentrain temperatu

mersed in a sst SHE. Undeential of the

n a bcc structm to be 96, it

ributed betwetwo states is

t 55% efficieut steam is _

correct repreubstance is (

B)

ce at 273 K ishe enthalpy o

o hybrid orbit

3 0.77ypψ+

3 0.77ypψ−

ween them is

ed at 140 oC tmpounds X an

= B3N3H6 = B3N3H6 = B3N3H12

3N3H6

entration (g L

ure ss of the polyation of the pure

olution contaer standard celectrode, w

ture with units density (in

een two state__________

ency. If the te___________

sentation of (s, l and g d

(

s 6.01 kJ moof sublimatio

tals:

__________

to give compnd Y are

L−1) of a poly

ymer polymer

aining 0.1 Mconditions an

when the conc

t cell dimensn kg m−3) is _

es is 9.22 × 1_____

emperature o____

chemical podenote solid,

(C)

ol−1 and the enn (in kJ mol−

_____

pound X, wh

ymer is cons

M Fe2+ and 0.nd considerincentration of

sions of 0.31___________

106 at 300 K.

of reject steam

tential (µ) agliquid and ga

nthalpy of va−1) of ice at 2

hich when tre

CHE

structed. The

1 M Fe3+. Itsng activity cof Fe3+ is incre

4 nm. Consi____

The differen

m is 105 oC,

gainst absoluas phases, re

(D)

aporization o273 K, is ___

eated with Na

EMISTRY – CY

5/10

e slope of

s potential oefficients eased to

idering the

nce in

then the

ute espectively)

of water at _________

aBH4 gave

Y

0

CY (GATE 2

014)


CY 6/10

Q.37 The number of microstates in term 1G is ______________

Q.38 The set of protons (underlined) in CH3CH2CH2OCH3 that would exhibit different splitting patterns

in high (500 MHz) and low (60 MHz) field 1H NMR, is

(A) CH3CH2CH2OCH3 (B) CH3CH2CH2OCH3 (C) CH3CH2CH2OCH3 (D) CH3CH2CH2OCH3

Q.39 Amongst the following, the complex ion that would show strong Jahn-Teller distortion is

(A) [Cr(H2O)6]2+ (B) [Ti(H2O)6]

3+ (C) [Co(H2O)6]2+ (D) [Fe(H2O)6]

2+ Q.40 Amongst the following, the metal carbonyl species having the highest νCO stretching frequency is

(A) [Mn(CO)6]+ (B) Cr(CO)6 (C) [V(CO)6]

− (D) [Fe(CO)4]2−

Q.41 The correct order of thermal stability for the given compounds is

(A) TiMe4 > Ti(CH2CMe3)4 > TiEt4 (B) TiEt4 > Ti(CH2CMe3)4 > TiMe4 (C) TiMe4 > TiEt4 > Ti(CH2CMe3)4 (D) Ti(CH2CMe3)4 > TiMe4 > TiEt4

Q.42 Amongst the following, the complex ion that is expected to show the highest magnetic moment at

room temperature is

(A) [Ni(CN)4]2− (B) [Fe(CN)6]

3− (C) [Cu(H2O)6]2+ (D) [Co(CN)6]

3− Q.43 MnCr2O4 is

(A) normal spinel with total CFSE of −15.5 Dq (B) inverse spinel with total CFSE of −15.5 Dq (C) normal spinel with total CFSE of −24 Dq (D) inverse spinel with total CFSE of −24 Dq

Q.44 Mg2+ is preferred in photosynthesis by chlorophyll because

(A) it has strong spin-orbit coupling (B) it has weak spin-orbit coupling (C) it is a heavy metal (D) it binds strongly with chlorophyll

Q.45 In Monsanto acetic acid process shown below, the role of HI is

(A) to covert CH3OH to a stronger nucleophile (CH3O−)

(B) to reduce the Rh(I) catalyst to a Rh(0) species (C) to reduce a Rh(III) active species to a Rh(I) species in the catalytic cycle (D) to convert CH3OH to CH3I

CY (GATE 2

014)


CY 7/10

Q.46 Formation of the ketone II from the diazoketone I involves

(A) generation of carbene and a [2,3]-sigmatropic rearrangement (B) generation of carbene and an electrocyclic ring closing reaction (C) generation of ketene and a [2+2] cycloaddition (D) generation of ketene and a [3,3]-sigmatropic rearrangement

Q.47 The major products X and Y formed in the following reaction sequence are

(A)

(B)

(C)

X = Y =

PhS

Me Me

CO2Me OH

(D)

CY (GATE 2

014)


CY 8/10

Q.48 The major products X and Y formed in the following reactions are

(A)

(B)

(C)

(D)


(A)

(B)

(C)

(D)

CY (GATE 2

014)


CY 9/10

Q.50 The product of the following reaction gave 6 line 13C NMR spectrum with peaks at δ 175, 52, 50, 46, 37, 33 ppm. The structure of the product is

(A)

(B)

(C)

(D)

Q.51 The major product formed in the following reaction is

(A)

(B)

(C)

(D)


(A)

(B)

(C)

X = Y =OH

NO2 O

(D)

CY (GATE 2

014)


CY 10/10


CO2H

NH2HO

X YMeOH

H2SO4

Cbz-Cl(1 equiv.)

aq. NaHCO3

(A)

(B)

(C)

(D)

Q.54 Given the fact that 1,3-butadiene has a UV absorption of 217 nm, the absorption wavelength (in

nm) for the conjugated system shown below is ______________

(Use these absorption values for auxochromic groups: alkyl: +5; exo-cyclic double bond: +5; every additional conjugated C=C: +30)

Q.55 The m/z value of the detectable fragment formed by McLafferty like rearrangement of the following

compound in mass spectrometer is ______________


CY (GATE 2

014)

Section Q. No. Key / Range Marks Section Q. No. Key / Range Marks

GA 1 A 1 CY 24 56 to 58 1

GA 2 B 1 CY 25 A 1

GA 3 D 1 CY 26 B 2

GA 4 C 1 CY 27 60 to 66 2

GA 5 1300 to 1300 1 CY 28 A 2

GA 6 D 2 CY 29 0.81 to 0.85 2

GA 7 B 2 CY 30 10000 to 10500 2

GA 8 180 to 180 2 CY 31 38 to 42 2

GA 9 D 2 CY 32 830 to 850 2

GA 10 B 2 CY 33 A 2

CY 1 B 1 CY 34 50 to 52 2

CY 2 D 1 CY 35 175 to 185 2

CY 3 3 to 3 1 CY 36 A 2

CY 4 3 to 3 1 CY 37 9 to 9 2

CY 5 D 1 CY 38 B 2

CY 6 D 1 CY 39 A 2

CY 7 A 1 CY 40 A 2

CY 8 1.4 to 1.5 1 CY 41 D 2

CY 9 B 1 CY 42 B 2

CY 10 C 1 CY 43 C 2

CY 11 4 to 4 1 CY 44 B 2

CY 12 A 1 CY 45 D 2

CY 13 3 to 3 1 CY 46 D 2

CY 14 C 1 CY 47 A 2

CY 15 C 1 CY 48 B 2

CY 16 C 1 CY 49 A 2

CY 17 C 1 CY 50 C 2

CY 18 D 1 CY 51 C 2

CY 19 C 1 CY 52 A 2

CY 20 B 1 CY 53 B 2

CY 21 A 1 CY 54 282 to 282 2

CY 22 B 1 CY 55 41 to 41 2

CY 23 C 1

GATE 2014

Answer Keys for CY ‐ Chemistry

Paper Question no. Key Paper Question no. KeyCY 1 B CY 36 ACY 2 C CY 37 DCY 3 C CY 38 DCY 4 A CY 39 ACY 5 D CY 40 BCY 6 B CY 41 ACY 7 D CY 42 BCY 8 A CY 43 ACY 9 B CY 44 DCY 10 A CY 45 CCY 11 A CY 46 DCY 12 A CY 47 ACY 13 B CY 48 CCY 14 A CY 49 BCY 15 C CY 50 DCY 16 B CY 51 CCY 17 A CY 52 ACY 18 D CY 53 DCY 19 A CY 54 DCY 20 B CY 55 BCY 21 B CY 56 DCY 22 C CY 57 DCY 23 A CY 58 BCY 24 B CY 59 CCY 25 C CY 60 ACY 26 D CY 61 ACY 27 A CY 62 CCY 28 B CY 63 DCY 29 C CY 64 CCY 30 A CY 65 BCY 31 DCY 32 BCY 33 CCY 34 DCY 35 C

GATE 2011 - Answer Key - Paper : CY

For IIT-JAM, JNU, GATE, NET, NIMCET and Other Entrance Exams

Website: www.vpmclasses.com Phone: 0744-2429714 Mobile: 9950679922 Email: [email protected] Address: 1-C-8, SFS, TALWANDI, KOTA, RAJASTHAN

GATE 2010 CHEMISTRY ANSWER KEY

By

VPM CLASSES

1 B 18 C 35 A 52 C 2 B 19 B 36 C 53 C 3 B 20 D 37 B 54 D 4 C 21 C 38 A 55 D 5 D 22 C 39 C 56 D 6 A 23 D 40 D 57 D 7 A 24 C 41 D 58 A 8 B 25 B 42 A 59 B 9 B 26 D 43 A 60 C 10 B 27 B 44 C 61 B 11 D 28 D 45 B 62 D 12 B 29 A 46 B 63 C 13 A 30 C 47 B 64 B 14 D 31 A 48 D 65 C 15 C 32 B 49 D 16 C 33 B 50 B 17 C 34 A 51 B

15/02/2015 www.gatecounsellor.com/gatepapersolutions/GATE2012Solution/GATE2012Solutions.php?dept=cy&[email protected]…

http://www.gatecounsellor.com/gatepapersolutions/GATE2012Solution/GATE2012Solutions.php?dept=cy&[email protected] 1/2

NA: Not AnsweredW: Wrong C: Correct

Calculate Marks Reset Form

Answer Key

Q. A. C W NA Q. A. C W NA Q. A. C W NA Q. A. C W NA

1. B 2. C 3. C 4. D

5. B 6. C 7. D 8. C

9. D 10. C 11. A 12. D

13. C 14. B 15. D 16. D

17. D 18. C 19. B 20. C

21. A 22. B 23. B 24. D

25. B 26. D 27. A 28. C

29. C 30. A 31. A 32. C

33. A* 34. A 35. A 36. B

37. D 38. A 39. C 40. D

41. B 42. A 43. D 44. B

45. B 46. C 47. A 48. B

49. D 50. B* 51. D 52. B

53. C 54. A 55. A 56. D

57. B 58. B 59. D 60. C

61. A 62. C 63. D 64. A

65. A

GATE 2011 Result Analysis See last year GATE Rank and GATE Score variation with marks.

Share it for others:

114 people recommend this. Be the first of your friends.Recommend

Discuss your queries regarding GATE paper solution, Click here...

Descriptive Solution has been sent on your email ID:[email protected]

If you do not receive email, please download it from here, Click here...

Prepared by

GATECounsellor

GATE 2012 Solutions

CHEMISTRY

http://gatecounsellor.com/2012/GATE2012Solution/detailedsolution/GATE2012Solution_CY.pdf

http://gatecounsellor.com/2011/analysis/GATE2011ResultAnalysis.php

http://forum.gatecounsellor.com/viewtopic.php?f=147&t=1526

15/02/2015 www.gatecounsellor.com/gatepapersolutions/GATE2012Solution/GATE2012Solutions.php?dept=cy&[email protected]…

http://www.gatecounsellor.com/gatepapersolutions/GATE2012Solution/GATE2012Solutions.php?dept=cy&[email protected] 2/2

Anil KumarMSc,IITKOrganic Chemistry

Koustuv RayBTech,IITKNA

Gurmeet SinghMSc,IITKOTM, Inorganic

Anmol KumarPhD,IITKPhysical Chemistry

Gurmeet SinghPhD,IITKSpectroscopy, Physical, Inorganic, Organic, OTM

Syllabus for Chemistry (CY)

PHYSICAL CHEMISTRY

Structure: Quantum theory: principles and techniques; applications to a particle in a box, harmonic

oscillator, rigid rotor and hydrogen atom; valence bond and molecular orbital theories, Hückel

approximation; approximate techniques: variation and perturbation; symmetry, point groups;

rotational, vibrational, electronic, NMR, and ESR spectroscopy

Equilibrium: Kinetic theory of gases; First law of thermodynamics, heat, energy, and work; second law of

thermodynamics and entropy; third law and absolute entropy; free energy; partial molar quantities;

ideal and non-ideal solutions; phase transformation: phase rule and phase diagrams – one, two, and

three component systems; activity, activity coefficient, fugacity, and fugacity coefficient; chemical

equilibrium, response of chemical equilibrium to temperature and pressure; colligative properties;

Debye-Hückel theory; thermodynamics of electrochemical cells; standard electrode potentials:

applications – corrosion and energy conversion; molecular partition function (translational, rotational,

vibrational, and electronic).

Kinetics: Rates of chemical reactions, temperature dependence of chemical reactions; elementary,

consecutive, and parallel reactions; steady state approximation; theories of reaction rates – collision

and transition state theory, relaxation kinetics, kinetics of photochemical reactions and free radical

polymerization, homogeneous catalysis, adsorption isotherms and heterogeneous catalysis.

INORGANIC CHEMISTRY

Main group elements: General characteristics, allotropes, structure and reactions of simple and

industrially important compounds: boranes, carboranes, silicones, silicates, boron nitride, borazines

and phosphazenes. Hydrides, oxides and oxoacids of pnictogens (N, P), chalcogens (S, Se & Te) and

halogens, xenon compounds, pseudo halogens and interhalogen compounds. Shapes of molecules and

hard- soft acid base concept. Structure and Bonding (VBT) of B, Al, Si, N, P, S, Cl compounds. Allotropes

of carbon: graphite, diamond, C60. Synthesis and reactivity of inorganic polymers of Si and P.

Transition Elements: General characteristics of d and f block elements; coordination chemistry: structure

and isomerism, stability, theories of metal- ligand bonding (CFT and LFT), mechanisms of substitution

and electron transfer reactions of coordination complexes. Electronic spectra and magnetic properties

of transition metal complexes, lanthanides and actinides. Metal carbonyls, metal- metal bonds and

metal atom clusters, metallocenes; transition metal complexes with bonds to hydrogen, alkyls, alkenes

and arenes; metal carbenes; use of organometallic compounds as catalysts in organic synthesis.

Bioinorganic chemistry of Na, K. Mg, Ca, Fe, Co, Zn, Cu and Mo.

Solids: Crystal systems and lattices, miller planes, crystal packing, crystal defects; Bragg’s Law, ionic

crystals, band theory, metals and semiconductors, Different structures of AX, AX2, ABX3 compounds,

spinels.

Instrumental methods of analysis: Atomic absorption and emission spectroscopy including ICP-AES, UV-

visible spectrophotometry, NMR, mass, Mossbauer spectroscopy (Fe and Sn), ESR spectroscopy,

chromatography including GC and HPLC and electro-analytical methods (Coulometry, cyclic

voltammetry, polarography – amperometry, and ion selective electrodes).

Downloaded from www.gate2015online.in

ORGANIC CHEMISTRY

Stereochemistry: Chirality of organic molecules with or without chiral centres. Specification of

configuration in compounds having one or more stereogeniccentres. Enantiotopic and diastereotopic

atoms, groups and faces. Stereoselective and stereospecific synthesis. Conformational analysis of

acyclic and cyclic compounds. Geometrical isomerism. Configurational and conformational effects on

reactivity and selectivity/specificity.

Reaction mechanism: Methods of determining reaction mechanisms. Nucleophilic and electrophilic

substitutions and additions to multiple bonds. Elimination reactions. Reactive intermediates-

carbocations, carbanions, carbenes, nitrenes, arynes, free radicals. Molecular rearrangements involving

electron deficient atoms.

Organic synthesis: Synthesis, reactions, mechanisms and selectivity involving the following- alkenes,

alkynes, arenes, alcohols, phenols, aldehydes, ketones, carboxylic acids and their derivatives, halides,

nitro compounds and amines. Use of compounds of Mg, Li, Cu, B and Si in organic synthesis. Concepts

in multistep synthesis- retrosynthetic analysis, disconnections, synthons, synthetic equivalents,

reactivity umpolung, selectivity, protection and deprotection of functional groups.

Pericyclic reactions: Electrocyclic, cycloaddition and sigmatropic reactions. Orbital correlation, FMO and

PMO treatments.

Photochemistry: Basic principles. Photochemistry of alkenes, carbonyl compounds, and arenes.

Photooxidation and photoreduction. Di-π- methane rearrangement, Barton reaction.

Heterocyclic compounds: Structure, preparation, properties and reactions of furan, pyrrole, thiophene,

pyridine, indole and their derivatives.

Biomolecules: Structure, properties and reactions of mono- and di-saccharides, physicochemical

properties of amino acids, chemical synthesis of peptides, structural features of proteins, nucleic acids,

steroids, terpenoids, carotenoids, and alkaloids.

Spectroscopy: Principles and applications of UV-visible, IR, NMR and Mass spectrometry in the

determination of structures of organic molecules.

GATE 2013 : Answer keys for CY - Chemistry

Paper Q.No Key(s)/Value(s) Paper Q.No Key(s)/Value(s)

CY 1 D CY 36 90 to 95

CY 2 C CY 37 4500 to 4800

CY 3 4.4 to 4.6 CY 38 B

CY 4 6 to 6.5 CY 39 A

CY 5 C CY 40 B

CY 6 D CY 41 A

CY 7 C CY 42 A

CY 8 0.0009 to 0.0011 CY 43 A

CY 9 A CY 44 C

CY 10 C CY 45 B

CY 11 D CY 46 D

CY 12 B CY 47 C

CY 13 D CY 48 B

CY 14 B CY 49 30

CY 15 6 CY 50 C

CY 16 1 CY 51 D

CY 17 4 CY 52 C

CY 18 A CY 53 C

CY 19 C CY 54 B

CY 20 D CY 55 D

CY 21 A CY 56 B

CY 22 D CY 57 C

CY 23 B CY 58 C

CY 24 5 CY 59 D

CY 25 C CY 60 B

CY 26 4.99 to 5.01 CY 61 C

CY 27 A CY 62 C

CY 28 D CY 63 C

CY 29 A CY 64 B

CY 30 D CY 65 C

CY 31 A

CY 32 B

CY 33 B

CY 34 B

CY 35 A

Education

10 years gate solved papers CHEMISTRY(Upto 2014)