SET13-Chem(B)-D

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Test Booklet Series

PAPER–III Test Booklet No.

OMR Sheet No.

CHEMICAL SCIENCESTime : 2 Hours 30 minutes Maximum Marks: 150

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1. Write your roll number in the space provided on the top of this page and roll number with subjectcode on the OMR Sheet attached with this booklet. Also write your OMR Sheet number in the spaceprovided above.

2. This paper consists of seventyfive multiple choice type questions. Answer all the questions. Eachquestion carries two marks.

3. Each question has four alternative responses marked (A), (B), (C) and (D). You have to select onlyone correct response and mark it in the OMR Sheet with blue/black ball pen.

Example: A B C D

Here (C) is the correct response.

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B

1312

B-3 1312–III

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CHEMICAL SCIENCES

PAPER III

1. Given three operators A, B and C , the followingexpression

[A, [B, C ]] + [B, [C , A]] + [C , [A, B]] will be equal to

(A) 1(B) –1(C) i(D) 0

2. The covariance of two qualities x and y is givenby,

C(x, y) = <xy> – <x> <y>.

If y = M1x + M2, the value of C(x, y) will satisfy(A) C(x, y) > 0 for any M1, M2

(B) C(x, y) < 0 for any M2

(C) C(x, y) = 0 for any M1, M2

(D) C(x, y) > 0 for any M1 > 0

3. The integralsI1 = <Ψ2p+ ⎢z ⎢Ψ2p–>

and I2 = <Ψ2p+ ⎢z ⎢Ψ2p0>

appear in Stark effect. Values of these integrals are(A) I

1 ≠ 0, I

2 = 0

(B) I1 ≠ 0, I2 ≠ 0(C) I

1 ≠ 0, I

2 ≠ 0

(D) I1 = 0, I2 = 0

4. An operator satisfies Â3 = Â. The possibleeigenvalues of  are

(A) 0, ± i(B) 1, ± i(C) ± 1, i(D) 0, ± 1

5. The IUPAC name of the compound

(A) 3–Bromo–3′–Chloro–1, 1′–bicyclobutane(B) 1–Bromo-1′–chloro–4, 4′–bicyclobutane(C) 4(4′–chlorocyclobutyl)–1–bromocyclobutane(D) 4(4′–bromocyclobutyl)–1–chlorocyclobutane

Br Br

6. Mono-formylation of compound I gives:

(A)

(B)

(C)

(D)

NH O

⎯⎯⎯⎯→DMFPOCl3

NH O

CHO

NH O

CHO

NH

OHC

NH O CHO

O

7. In Photosynthesis, oxygen comes from(A) soil(B) atmosphere(C) water(D) CO2

1312–III B-4

8. With respect to the following two reactions, thecorrect statements about their stereochemical nature is

[KHMDS = Potassium hexamethyldisilazide]

(A) P and Q are the same(B) P and Q are optically inactive(C) P and Q are diastereomers(D) P and Q are enantiomers

OHMe

OH

Me⎯⎯⎯⎯→1. KHMDS

2. EtBrQ

⎯⎯⎯⎯→1. KHMDS

2. EtBrP

O

O

9. An organic compound having the molecularformula C6H11ClO3 exhibits the following peaks in its1H–NMR Spectrum:

δ 4·21 (2H, q, J = 7·0 Hz); 4·35 (2H, t, J = 7·5 Hz);1·5-2·5 (4-H, m); 1·25 (3-H, t, J = 7·5z)

The structure of the compound is:

(A)

(B)

(C)

(D)

Cl O

O

Cl

O

O CH3

O CH3

OCl

Cl

O

O

10. The reaction

HgF2 + BeI2 → BeF2 + HgI2

(A) is endothermic and does not satisfy HSABprinciple

(B) is endothermic but satisfies the HSABprinciple

(C) is exothermic but does not satisfy HSABprinciple

(D) is exothermic and satisfies the HSABprinciple

11. The reagents I and II in the following cyclopro-panation reactions are

(A) I is Me3Si I, KOBut; II is CH2I2, Zn–Cu

(B) I is CH2I2, Zn–Cu; II is Me3Si I, KOBut

(C) I is Me3SOI, KOBut; II is CH2I2, Zn–Cu

(D) I is CH2I2, Zn–Cu; II is Me3SOI, KOBut

⊕ s

⊕ s

⊕ s

⊕ s

O OH O

CH3

OH

⎯→⎯→I II

CH3

CH3

OH O

12. In the 13C–NMR spectrum of CDCl3 themultiplicity of the peak will be

(A) singlet(B) doublet(C) triplet of ~ 1 : 2 : 1 intensity(D) triplet of ~ 1 : 1 : 1 intensity

13. CO2 is a gas but SiO2 is a hard solid, because(A) the molecular weight of CO2 is smaller than

that of SiO2

(B) C atom has more allotropic form than Si(C) CO2 is a volatile molecule, but not SiO2

(D) Unlike CO2, SiO2 is not a discrete molecule,rather there is infinite network of Si....O....Sispecies

14. Identify the reaction which involves theconversion of cis-diols to cis-olefins by the formation ofcyclic thionocarbonates with subsequent elimination ofsulphur and generation of a carbene intermediate

(A) Dieckmann Reaction(B) Corey—Winter Synthesis(C) Ramberg—Bücklund Reaction(D) Eschenmoser—Tanabe Ring Cleavage

B-5 1312–III

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16. The true basicity order of the pair of compounds(NH3, NF3) and (PH3, PF3) are

(A) NH3 > NF3 and PF3 < PH3

(B) NF3 > NH3 and PF3 < PH3

(C) NH3 < NF3 and PF3 > PH3

(D) NH3 > NF3 and PF3 > PH3

17. Thiophene, an aromatic compound, on reductionwith H2 in the presence of Raney nickel gives

(A) Tetrahydrothiophene(B) Sulphone(C) Butane(D) Isobutane

18. Overall yield of the following conversion is

A B C D

(A) 70%(B) 60%(C) 33·6%(D) 63·3%

⎯⎯→80% ⎯⎯→60% ⎯⎯→70%

19. “NaCl has higher melting point than KCl3”. The

reason is(A) NaCl is more ionic than KCl(B) the Van-der-Walls force between Na+ and

Cl– is greater than that between K+ & Cl–

(C) the lattice energy of NaCl is higher than thatof KCl

(D) the statement is not correct

20. Which of the following compounds are anti-aromatic?

(1)

(2)

(3)

(4)

(A) 1 and 2(B) 2 and 3(C) 3 and 4(D) 1 and 4

⊕

N

⊕

15. In a 400 MHz 1H–NMR spectrum, an organiccompound exhibited a double doublet, the four lines ofwhich appeared at δ2·42, 2·40, 2·39 and 2·37. Thecoupling constants are

(A) 8·0 Hz and 20·0 Hz(B) 12·0 Hz and 20·0 Hz(C) 6·8 Hz and 10·0 Hz(D) 8·0 Hz and 12·0 Hz

21.

The product ‘X’ of the above reaction is

(A)

(B)

(C)

(D)

⎯⎯→ X

22. Photosynthesis is a process is which(A) CO2 is reduced to carbohydrate(B) NADPH is reduced to NAD(C) ATP is generated(D) oxidative phosphorylation occurs

23. Toluene on oxidation with chromyl chlorideproduces

(A) Benzoic acid(B) Benzaldehyde(C) Chlorobenzene(D) None of the above

1312–III B-6

24.

is an example of(A) Michael Reaction(B) Claisen Rearrangement(C) Ene Reaction(D) Dipolar Cycloaddition

O O

H

⎯⎯⎯⎯⎯⎯⎯→CH

3AlCl

2

25. Out of C, N, O and S atoms, the smallest sizeis of

(A) O(B) N(C) C(D) S

26.

The above reaction is an example of(A) Sarett oxidation(B) Collins oxidation(C) Swern oxidation(D) Dess-Martin oxidation

OH

⎯⎯⎯⎯→CrO

3

C5H

5N

O

27.

The major product is

(A)

(B)

(C)

(D)

⎯⎯⎯⎯⎯⎯⎯⎯⎯→(i) (–) diethyltartrate

(ii) t-BuO OH

(iii) Ti (OiPr)4

CH2Cl2,– 20°COH

OH

O

OH

O

OHO

OHO

29. The reaction that through carbocation is(A) Friedel-Crafts Reaction(B) Wittig Reaction(C) Wolff-Kishner Reaction(D) Grignard Reaction

28. The molecule O3 is(A) linear and diamagnetic(B) linear and paramagnetic(C) bent and paramagnetic(D) bent and diamagnetic

30. II

(A) I is M; II is N(B) I is N; II is M(C) I is O; II is P(D) I is P; II is O

OH

O

H+⎯⎯⎯⎯⎯⎯⎯→

OHOHO

HO OH ⎯⎯⎯⎯⎯⎯⎯→P–TsOH

MeO OMe

I

OHO

OH

OHO

OO

OOH

OO

OH

OHOO

O

OH

O

OHOHO

HOO

M N O

P

O

31. On irradiation with high-energy γ rays, 4Be9 yields(A)

3Li7 and

1H2

(B) 3Li7, 1H1 and a neutron

(C)4Be8 and a neutron

(D) 3Li7, two neutrons and a positron

B-7 1312–III

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32.

Name the above reaction.(A) Wittig Reaction(B) Willgerodt-Kindler Reaction(C) Weiss Reaction(D) Weinreb Amide Reaction

O

S⎯⎯⎯⎯→HN

S8

R

R'N

R

R'

Thioamide

33. Which one of the following is a neem productused as insect repellant?

(A) Azadirachtin(B) Parathione(C) Rotenon(D) Endrin

34. If 1, 2, and 3 represent the gaps between t29

and eg levels of [CO(N2O)6]+3, [CO(NH3)6]

+3 and[CO(CN)6]

–3 respectively, then the following inequalityholds

(A) 3 < 2 < 1

(B) 3 < 1

< 2

(C) 1 < 2 < 3

(D) 2 < 1 < 3

35. The correct reagent combination in the reactionsequence:

(A) (i) Ph3PCH2OMeCl, n-BuLi; (ii) H3O;(iii) NaBH4, MeOH

(B) (i) Me3SiCH2OMe, KOBut; (ii) dil HCl;(iii) NaBH4,

EtOH

(C) (i) NH2NHTs; (ii) NaOEt;(iii) ClCO2Me

(D) (i) NH2NHTs; (ii) nBuLi-2 equiv;(iii) HCHO

O

OH⎯⎯⎯⎯→

⊕ s ⊕

36. Green House Effect refers to(A) Cooling of Earth(B) Trapping of UV rays(C) Production of Cereals(D) Warming of Earth

37. Four ways of distinguishing the complex[CO(NH3)4Cl2)Cl from [CO(NH3)4]Cl3 are given as

A : measurement of electrical conductivityB : study of the number of possible isomersC : boiling with a strong AgNO3 solutionD : treatment with concentrated HCl solution

Of these, the correct ways are(A) A and B(B) A and C(C) B and C(D) C and D

38. Identify the products I and II in the followingreaction sequence:

(A) I is ; II is

(B) I is ; II is

(C) I is ; II is

(D) I is ; II is

HO

(i) PPh3, DEAD

Me(ii) Me

2Si Br

I⎯⎯⎯⎯⎯⎯→

Et3N

AIBN⎯⎯⎯⎯⎯⎯→

Reflux

nBu3SnH

II

O OSiMe2

Br

HSiMeMe

O OMe

2Si Br

HSi

MeMe

O OSi

HSi

MeMe

BrMeMe

O O HSi

OMeMe

BrMe2Si

1312–III B-8

39. Which of the following is used as a local anaestheticagent?

(A) Diazepam(B) Procaine(C) Mescaline(D) Seconal

40. Paramagnetic susceptibility is proportional to(A) T2

(B) T–2

(C) T–1

(D) T

41. The structure of the major product of the followingphoto-rearrangement is:

(A) (C)

(B) (D)

OCN

H3C CO

2Me

⎯⎯⎯⎯→hυ

OHCN

CO2Me

CH3

OHCN

H3C

CO2Me

OCN

H3C

CO2Me

H

OCN

H

CH3

CO2Me

42. The hardest material found in nature is_______.(A) steel(B) topaz(C) diamond(D) quartz

43. Acid rain is defined as any precipitation with(A) pH < 7·0(B) pH < 6·5(C) pH < 6·0(D) pH < 5·6

44.

Name the reaction involved in the above sequence.(A) Beirut Reaction(B) Michael Addition(C) Barton Reaction(D) Shapiro Reaction

O

⎯⎯⎯⎯→ButOK

O ButOHO O

CO2Et

45. Borazine is isoelectronic with benzene. Theydiffer, however, in

(A) addition, substitution and hydrogenationreactions

(B) addition and substitution reactions only(C) substitution and hydrogenation reactions

only(D) addition and hydrogenation reactions only

46. The pair of gaseous molecules/ions havingtetrahedral structure is

(A) SeCl4, XeF4

(B) ICl4

–, PH+4

(C) SnCl4, ICl–4

(D) SnCl4, PH+4

47. Name the reaction which involves the followingsequence via destruction of aromaticity:

(A) Marwein-Pondorf-Verley Reduction(B) Wolf- Kishner Reduction(C) Birch Reduction(D) Clemmensen Reduction

OMe

Me

⎯⎯⎯⎯→t-BuOH

OMe

Me

⎯⎯⎯⎯→dil.H2SO4

O

MeNa or Liin liquidNH

3

48. It is possible to distinguish between opticalisomers by

(A) infra-red spectroscopy(B) mass spectrometry(C) melting point determination(D) polarimetry

B-9 1312–III

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49. If a small piece of Na is dropped in liquifiedammonia an intense blue colour is developed. Thefollowing statement is wrong:

(A) Any alkali metal gives the same colour.(B) The solution becomes paramagnetic.(C) Interaction between solvent and electron is

weak.(D) Density of the solution is much higher than

that of pure ammonia.

50. The reaction of 2-methylfuran with DMF—POCl3would give

(A) (C)

(B) (D)

CH2CHO

O CH3OHC

OCH

3

O CH3

OHC

CHO

O

51. A multi electron atom has sp2 optical electronicconfiguration. The quantum numbers for the resultantorbital momentum of the three electrons are

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

52. The ground state of NO2 has A1 (C2ν) symmetry.The electric dipole moment operator transforms asx(B

1), y(B

2) and z(A

1). The electric dipole transition to

B1 is allowed by x polarized light since

(A) A1× B

2 = B

2

(B) B1× B2 = A1

(C) B2× B

2 = A

1

(D) A2× B1 = B2

E C2 σν(xz)

A1 1 1 1 1 Z

A2 1 1 –1 –1 Rz

B1 1 –1 1 –1 x, Ry

B2 1 –1 –1 1 y, Rx

C2ν σν(yz)

53. Which of the following electronic transition ofdiatomic molecules is allowed?

(A) 1Σg+ → 3Σu

+

(B) 3Σg → 3

u

(C) 3Σg → 3Πu

(D) 1Πu → 1Σ

u

54. Magnitude of nuclear spin angular momentum ofa nuclei is √2 £ units. The value of I is

(A) 1(B) 2

(C)

(D)

1–23–2

55. One of the major limitations of Lindemann theoryfor unimolecular reaction stems from the predicted

(A) lower rate constant value of molecularenergization process

(B) higher rate constant value of molecularenergization process

(C) lower rate constant value of productformation from energized molecules

(D) higher rate constant value of productformation from energized molecules

56. Pauli spin matrices σx, σy and σz obeyσx

2 = σy2 = σz

2 = I. Give further that σxσy= iσz and[σx, σy]+ = 0, the correct relation for σz σx will be

(A) σz σx = – iσy

(B) σz σx = σy

(C) σz σx = –σy

(D) σz σx = iσy

57. Consider 1 mole of argon in a closed vessel. Tothis system 49·8J heat is supplied. The temperaturechange of the system will be

(A) 6° increase(B) 2·5° increase(C) 4° increase(D) 3° increase

1312–III B-10

58. The radius of a colloidal particle is decreasedfrom 10nm to 5nm. Then the pressure difference acrossthe surface of the colloid will

(A) decrease by a factor of 2(B) increase by a factor of 4(C) increase by a factor of 2(D) remain constant

59. The inverse of relaxation time (τ–1) of thefollowing recombination reaction is

H+ + OH– H2O

(A) 4kf [H+] + kb

(B) kf + kb

(C) kf ([H+] + [OH–]) + kb

(D) kf (4[H+] [OH–] + [H+]2) +kb

kf

kb

60. The second-order energy-correction term for theground state of any system under any perturbation is

(A) always positive(B) always negative(C) arbitrary in sign but real(D) generally complex

62. G is the Gibbs free energy. H is the enthalpy and

T is the temperature. The term is equal to

(A)

(B)

(C)

(D)

∂( G/T)∂Τ ][

P HT2

– HT2

HRT2

– HRT2

64. Given the 2-particle exchange operator as,

P Ψ(1, 2) = Ψ(2, 1),the state Φ = (I – P ) Ψ(1, 2) is a(A) symmetric function(B) antisymmetric function(C) function of mixed symmetry(D) function that is not an eigenfunction of P

63. One of the symmetry adopted molecular wavefunctions (Φ) of cyclopropenyl group is given byC (2Ψ

1 – Ψ

2 – Ψ

3), where Ψ

1, Ψ

2 and Ψ

3 are pπ atomic

orbitals. If all the four functions are orthonormal, thevalue of C is

(A)

(B)

(C)

(D)

1√2121

√31

√6

65. A true statement about phase transitions is(A) any phase transition involves a latent heat(B) a first-order phase transition involves a latent

heat(C) Clapeyron’s equation applies to any phase

transition process(D) heat capacity changes continuously during

any phase transition

66. The pH of 0·10 mol L–1 sodium acetate solutionis equal to (pKa of acetic acid is 4·75)

(A) 4·12(B) 6·50(C) 9·38(D) 8·88

61. The plot of chemical potential (μ) of benzeneversus pressure (P) will appear like

(A)

(B)

(C)

(D)

μ

P

μ

P

P

μ

P

μ

B-11 1312–III

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67. Force constant matrix associated with vibrationof water molecule is given below (bond deformations:

d1, d

2; angle deformation: θ):

The stretching and bending force constants, respectively,are

(A) fdd and fθ

(B) fd and fdθ

(C) fdd and fdθ

(D) fd and fθ

d1 d2 θd1 fd fdd fdθ

d2 fdd fd fdθ

θ fdθ fdθ fθ

68. Which of the following cyllic integrals mustvanish?

(A)

(B) pdV

(C)

(D) (pdV + Vdp)

dqT2∫

∫dq∫

∫

69. Out of the following, the correct form of theGibbs-Duhem equation is (a is the activity and x is themole fraction)

(A) x1dlna1 = x2d lna2

(B) x1dlna

2 = x

2d lna

1

(C) x1dlna2 = –x2dlna2

(D) x1dlna

1 = –x

2dlna

2

70. The standard enthalpy of a reaction for which theequilibrium constant is halved by increasing thetemperature from 300 to 400 K, is nearly equal to

(A) 7 kJ mol–1

(B) 700 J mol–1

(C) –7 kJ mol–1

(D) –700 J mol–1

71. Half-life of a reaction decreases linearly withincrease in initial concentration of reactant. Then thereaction is

(A) zero order(B) first order(C) second order(D) third order

72. When a solute gets dissolved in a solvent, thechemical potential of the solvent

(A) increases(B) decreases(C) increases only for endothermic processes(D) increases only for exothermic processes

73. N2 is kept in a cylinder with piston. The volumeof N2 is varied isothermally by moving the piston. Thechange that occurred in the value of the total partitionfunction of N

2 is due to

(A) dependence of rotational partition functionon volume

(B) dependence of translational partitionfunction on volume

(C) dependence of vibrational partition functionon volume

(D) dependence of rotational, translational andvibrational partition functions on volume

74. The electrical conductivity of a metal(A) increases exponentially with temperature(B) temperature independent(C) increases fully with temperature(D) decreases with temperature

75. The uncompetitive enzyme inhibition reaction isidentified by the Lineweaver-Burk plots (at variousinhibitor concentrations), where

(A) the slopes vary linearly with inhibitorconcentrations but intercept remains constant

(B) the intercept vary linearly with inhibitorconcentrations but slope remains constant

(C) both slopes and intercepts vary linearly withinhibitor concentrations

(D) both slope and intercept remain constant

ROUGH WORK

1312–III A-12

ROUGH WORK

A-13 1312–III

ROUGH WORK

1312–III A-14

ROUGH WORK

A-15 1312–III

ROUGH WORK

1312–III A-16