Chemical Sciences Paper I(PART 'B')

41. Complexes of which of the following metals are used in the treatment of rheumatoid arthritis: 1. 2. 3. 4. 42. Gold Ruthenium Iron Copper

Non-heme iron-sulfur proteins are involved in: 1. 2. 3. 4. Electron transfer. Proton transfer. Both electron and proton transfer Oxygen transfer.

43.

Active catalytic species for hydroformylation is 1. 2. 3. 4. RuCl 2(PPh

3) 3

44.

HCo(CO)3 RhCl(PPh 3 3) K 2PtCl6 The unit of molar absorptivity is: 1. 2. 3. 4. L mol -1 cm-1 -1 L -1 mol cm L mol cm L mol cm
-1

45.

Gelatin is added during polarographic measurements to: 1. 2. 3. 4. reduce streaming motion of falling mercury drop increase Id increase E1/2 eliminate residual current

46.

The element that shows both +3 and +4 oxidation states is: 1. 2. 3. 4. Cerium Promethium Gadolinium Holmium

47.

The number of 3c, 2e BHB bonds present in B 4H 10 is

1. 2. 3. 4. 48.

2 3 4 0

In BrF 3 as a solvent SnF 4 and KF behave as 1. 2. 3. 4. acid and base, respectively base and acid, respectively acids bases
*

49.

The effective nuclear charge (Z ) for the 1s electron of O according to 8 Slater's rules is nearly 1. 2. 3. 4. 4.55 3.45 7.65 5.45

50.

+ Among the species O , 2O and O , the order of first ionization energy is 2 2

1. 2. 3. 4. 51.

O 2 < O 2 < O2 O2 < O 2 < O2 + O2 < O 2 + < O2 + O2 < O 2 < O2

CO bond order is lowest in 1. 2. 3. 4. uncoordinated CO CO bonded to one metal CO bridging two metals CO bridging three metals

52.

The most unstable species among the following is

1. 2. 3. 4.

Ti(C 2H 5

4)

Ti(CH 2Ph)4 Pb(CH 3 4) Pb(C 2H 5 4)

53.

In which of the following species quadrupole bonding is involved?

1. 2. 3. 4. 54.

Mo 2(NMe
6)

Mn 2(CO)10 2Re 2Cl8 Fe 2(CO)9

In which one of the following pairs the species have similar geometry?

1. 2. 3. 4. 55.

CO 2 and SO2 NH 3 and BH3 22CO3 and SO3 2SO4 and ClO4 -

On oxidative addition of O 2 to Ir(CO)Cl(PPh 3 2) , the oxidation state and coordination number of Ir changes, respectively, by 1. 2. 3. 4. 1 and 3 2 and 2 3 and 1 2 and 3

56.

In linear metal nitrosyls NO acts as a/an: 1. 2. 3. 4. One electron donor Two electron donor Three electron donor Four electron donor

57.

Among the following molecules, the dipole moment is the highest for 1. 2. 3. 4. NH3 trans-[PtCl 2(NH 3 BF3 NF3

2)

58.

An element 'X' emits successively two particles, one particle, one positron and one neutron. The mass and atomic numbers of the element are decreased by, respectively, 1. 2. 3. 4. 4 and 1 5 and 1 3 and 2 3 and 1

59.

The 1 NMR spectrum of ( -C5H )5 Fe5 recorded at room temperature has H 2 1. 2. 3. 4. One singlet One multiplet Two singlets Two multiplets
2+ 2 7 2-

60.

In the estimation of Fe by Cr O indicator, H 3PO 4 is added to 1. 2. 3. 4.

using barium diphenylamine sulfonate as

maintain the pH of the medium decrease the Fe 2+/3+ potential increase the oxidizing power of Cr 2O7 stabilize the indicator

2-

61.

The polymeric species (SN) n is a / an 1. 2. 3. 4. three dimensional conductor two dimensional conductor insulator one dimensional conductor

62.

Among feldspar, muscovite mica and zeolite, 1. 2. 3. 4. all are three dimensional silicates feldspar and zeolite are three dimensional, while muscovite mica is layered feldspar is three dimensional, while zeolite and muscovite mica are layered all are layered silicates
max

63.

The molar absorptivity at 1. 2. 3. 4. [Mn(H O) ] 2 6 [Cr(H O) ] 2 6 [Co(H O) ] 2 6 [Fe(H O) ] 2 6

2+ 2+ 2+ 2+

is minimum for

64.

The acid catalyzed hydrolysis of trans-[Co(en) AX] also due to the formation of 1. 2. 3. 4. square pyramidal intermediate trigonal bipyramidal intermediate pentagonal bipyramidal intermediate face capped octahedral intermediate

can give cis- product

n+

65.

The total number of lines expected in H NMR spectrum of HPF is (I = 1/2 2 for both 19 and 31P) F 1. 2. 3. 4. six four five three
2+

66.

2+ In the inner sphere reduction of [Co(NH ) Cl]3 5with [Cr(OH ) )] , the 6 2 chloride

1. 2. 3. 4. 67.

bridges the metal centres only mediates electron transfer only bridges and mediates electron transfer both does not play any role

The number of faces and edges in IF 7 polyhedron are, respectively 1. 2. 3. 4. 15 and 15 10 and 15 10 and 10 15 and 10

68.

Among N 2, N 3 , azobenzene and hydrazine, the shortest and longest N-N distances are found, respectively, in 1. 2. 3. 4. N 3 and hydrozine N 2 and azobenzene N 3 and azobenzene N 2 and hydrazine

69.

+ O 2 can be converted to O 2 by using

1. 2. 3. 4. 70.

PtF6 KF Na 2S 2O3 Br2

Only one absorption band is observed in visible region of spectrum of 1. 2. 3. 4. [Ni(H O) ] 2+ 2 6 [Ti(H O) ] 3+ 2 6 [Fe(CN) ]6 4VO4
3-

71.

CFSE of transition metal complexes can be determined by 1. 2. 3. 4. UV-visible spectroscopy IR spectroscopy Microwave spectroscopy NMR spectroscopy

72.

33Which two among [Fe(CN) ] ,6 [FeF ] , [Cu(bpy) ] (bpy2+ 2,2'-bipyridine) 6 2 = and [Mn(acac) 3] (acac = acetylacetonate anion) show the same spin-only magnetic moment?

1. 2. 3. 4. 73.

[Fe(CN) ]6 and [FeF ] 6 [Fe(CN) ]6 3-and [Cu(bpy) ] 2 [FeF 6 3- [Mn(acac) ] 3 ] and [Cu(bpy) ]2 2+ [Mn(acac) ] and

3-

3-

2+

In aqueous medium a mixture of KI and I 2 converts thiosulfate to 1. 2. 3. 4. SO6

4 222-

SO
2

S O 4 2-

46

74.

SO 2 An exothermic reaction will necessarily follow the condition 1. 2. 3. 4. < 0 > 0 = 0 S= 0

75.

The unit of rate constant (k) for a zero-order reaction is 1. 2. 3. 4. s L mol -1s -1 s mol L -1s -1
-1

76.

Heating is observed when N 2 gas at 200 atm is expanded at T > 600 K. It is because 1. 2. 3. 4. inversion temperature is smaller than 600 K N 2 is a real gas Joule-Thomson coefficient is negative Joule-Thomson coefficient is positive

77.

Increase in disorder is more if 1. 2. 3. 4. heat is absorbed reversibly at higher temperature heat is absorbed reversibly at lower temperature heat absorbed reversibly is independent of temperature heat absorbed reversibly is independent of phase of the system.
g 2 ) (1 u 2 ) (2 g

78.

+ The term symbol of Li 2 with configuration (1

) 1is

1. 2. 3. 4. 79.

+ g

g g + g

Which one of the following equations is used for the calculation of equilibrium constant (K) of an electrochemical cell reaction (n = number of electrons transferred, F = Faraday constant and E = standard redox potential)? 1. 2. 3. 4. ln K = (nFE / RT ) ln K = (nFE / RT ) ln K = (RT / nFE )
o o o o

80.

ln K = (RT / nFE ) Cubic close packing of n spheres generates the following number of interstitial sites 1. 2. 3. 4. 2n octahedral and n tetrahedral sites n octahedral and n tetrahedral sites 2n octahedral and 2n tetrahedral sites n octahedral and 2n tetrahedral sites

81.

The point group symmetry of the molecule CH 2Cl 2 is 1. 2. 3. 4. C2h C2v D2h D2d

82.

The point group symmetries of isosceles and equilateral triangles respectively are 1. 2. 3. 4. C
3v

and D2d

D 3h and D2d D 3h and C2v C 3v and C2v

83.

The infrared spectrum of CO 2 exhibits the following number of absorptions: 1. 2. 3. 4. one two three four

84.

The first line in the rotational Raman spectra of a diatomic molecule appears with a Stokes shift of 12 cm . The Stokes shift for the second line is 1. 2. 3. 4. 36 cm 24 cm 18 cm
-1 -1 -1 -1 -1

85.

20 cm Which of the following molecules shows EPR resonance? 1. 2. 3. 4. H 2O O2 H 2O2 CO2

86.

The R branch in the vibrational spectra of AX exhibits a set of equally spaced lines with a separation of 10 cm . The rotational constant of AX is 1. 2. 3. 4. 10 cm 20 cm 5 cm -1 15 cm
-1 -1 -1 -1

87.

Overtones are observed in the vibrational spectra of diatomic molecules when 1. 2. 3. 4. anharmonicity is large anharmonicity is absent vibration and rotational modes are coupled an alternating electric field is applied

88.

Which of the following electronic transitions is disallowed? 1. 2. 3. 4. n

89. T

If the Carnot cycle in entropy-temperature diagram looks as below, D A C B

S then the system rejects heat to the surroundings in going from 1. 2. 3. 4. 90. BA AB DC CD

The correlation coefficient (x, y) for two variables x and y satisfies 1. 2. 3. 4. -1 (x, y) 1 -1 < (x, y) < 1 0 (x, y) 1 0 < (x, y) < 1

91.

When we introduce anharmonicity in the harmonic vibrator model of a diatomic molecule, the energy-level spacing changes from 1. 2. 3. 4. equal to gradually decreasing gradually decreasing to equal equal to gradually increasing gradually increasing to equal

92.

For a one-electron atom with nuclear charge Z, the speed v n of the electron in some n-th stationary orbit satisfies v n 2 Z -1 v n -2 Z v n The optimized variational wavefunction gives Z 1. 2. 3. 4. 1. 2. 3. 4. all properties and energy of same quality properties better than the energy energy better than properties equal kinetic and potential energy values

93.

94.

The commutator [Ly, Lx] has a value equal to 1. 2. 3. 4. zero -iLZ -i LZ - LZ

95.

The following statement is true for any hermitian operator: 1. 2. 3. 4. All eigenvalues are real and non-degenerate All eigenfunctions are real All eigenfunctions are complex All eigenvalues are real

96.

A molecular orbital of a diatomic molecule is defined by 1. 2. 3. 4. n=3 =2 =2 m = 2

97.

The 2p x hydrogenic orbital has the -part in its wavefunction of the form 1. 2. 3. 4. e +i e sin cos
-i

98.

Which of the following statements about valence bond (VB) and molecular orbital (MO) theory is false? 1. 2. 3. 4. The VB uses non-orthogonal basis. The simple MO theory does not include any ionic terms. The VB theory views molecules as composed of atomic cores and bonding valence electrons. The MOs can be delocalized over all the atoms.

99.

If A an operator and A = i d 2 1. 2 dx 2. 3. 4.
2

d dx

, then A 2 is given by

d 2 dx
2

d 2 dx d 2 dx
2 2

100.

If all the energy-levels of a system are given a constant shift by an amount , the entropy of the system 1. 2. 3. 4. does not change at all changes by the amount of decreases increases, but irregularly

101.

An equimolar mixture of two macromolecules of molar masses 10,000 and 30,000 will have the number average molar mass equal to: 1. 2. 3. 4. M n = 10,000 M n = 15,000 M n = 20,000 M n = 25,000

102.

Addition of a positive catalyst to an exothermic reaction 1. 2. 3. 4. increases exothermicity and activation barrier decreases exothermicity, but increases barrier increases exothermicity only decreases activation barrier, but does not change the exothermicity.

103.

The electrical conductivity of a crystalline solid increases with temperature. The solid is a 1. 2. 3. 4. superconductor metal semiconductor semimetal

104.

K sp values for CuS, FeS, PbS and ZnS are 8.5 10 , 6.3 10 , 3.4 10 and 1.6 10 -24respectively. If H S gas is passed through a solution , 2 containing these ions with same molar concentration, the ion that will precipitate first is 1. 2. 3. 4. Pb 2+ 2+ Zn 2+ Fe Cu 2+

-45

-18

-28

105.

The experimental adsorption data of a gas on a solid surface at temperature T exhibits the following variation with pressure. V is the volume of gas adsorbed.

1/V

1/P Which of the following statements is true? 1. 2. 3. 4. 106. Heat of coverage varies linearly with temperature Adsorption is multilayer Heat of adsorption is independent of coverage Complete coverage cannot be determined

The second order Bragg diffraction from the 100 planes of a cubic crystal is equivalent to 1. 2. 3. 4. the second order diffraction from the 200 planes first order diffraction from the 200 planes first order diffraction from the 400 planes first order diffraction from the 100 planes

107.

IUPAC name of the compound given below is

COOH

1. 2. 3. 4.

4-methylcyclohex-4-enecarboxylic acid 4-methylcyclohex-3-enecarboxylic acid 1-methylcyclohexene-4-carboxylic acid 2-methylcyclohexene-5-carboxylic acid

108.

The major product formed in the reaction given below is

CHO i. NH 2OH ii. P 2O5 1. NC

2.

NHCHO

3. 4.

CONH2

CN

109.

Cope rearrangement involves 1. 2. 3. 4. [1,5]-sigmatropic rearrangement [4+2]-cycloaddition reaction [3,3]-sigmatropic rearrangement 6 -electrocyclisation reaction

110.

The major product formed in the reaction given below is

O Cl NH 2NH KOH
2

Cl 1.

2. O 3. NHNH2

COOH 4.

111.

The stereochemical descriptors for the chiral centre and olefin in the compound given below, are
O
2

Me

H HO

1. 2. 3. 4. 112.

4R, 2Z 4S, 2Z 4R, 2E 4S, 2E

A

In the compound given below, the hydrogens H

HA HB OH

and H B are

1. 2. 3. 4. 113.

homotopic enantiotopic diastereotopic isotopic

An organic compound with molecular formula C 3H 6Cl 2 exhibits only one 1 signal in the H NMR spectrum. The compound is 1. 2. 3. 4. 2,2-dichloropropane 1,2-dichloropropane 1,3-dichloropropane 1,1-dichloropropane
max

114.

The order of

in the UV-Vis spectra for the compounds A-C is

1. 2. 3. 4. 115.

A>B>C B>A>C B>C>A C>B>A

The photochemical Paterno-Bchi reaction is a cycloaddition between 1. 2. 3. 4. two >C=C< groups a >C=O and >C=C< groups a >C=N-R and >C=C< groups a >C=S and >C=C< groups

116.

The reaction given below is an example of

O + O O O O O

1. 2. 3. 4. 117.

4s 2 s cycloaddition 2 cycloaddition a 4s s 2 cycloaddition + 2 cycloaddition 4a a + Which one among the dienes A-D will undergo [3,3]-sigmatropic shift upon heating 4a +

1. 2. 3. 4. 118.

A B C D

The LUMO of the ground state buta-1,3-diene is

1.

2.

3.

4.

119.

The major product formed in the reaction given below is

OH OTs EtOH /

1.

OTs

2.

3.

OTs CHO

4.

120.

The transformation given below can be achieved using

O

1. 2. 3. 4. 121.

BH 3.THF followed by H 2O 2 / NaOH alkaline KMnO 4 / NaIO4 pyridinium chlorochromate PdCl 2 / CuCl 2 / O 2 / H 2O

The base peak in the electron impact mass spectrum (EI MS) of acetophenone is 1. 2. 3. 4. 120 105 77 65

122.

In the reaction given below, the orientation of two bromine substituents in the product is
Br Br
2
1 2

Br

1. 2. 3. 4.

equatorial at both C-1 and C-2 equatorial at C-1 and axial at C-2 axial at C-1 and equatorial at C-2 axial at both C-1 and C-2

123.

Cyclohexyl benzyl ether is converted to cyclohexanol using 1. 2. 3. 4. 5% aq. KOH hydrazine hydrate H 2-Pd/C tetrabutylammonium fluoride

124.

Which one among the compounds A-D will have highest dipole moment?
C C A B C D

1. 2. 3. 4. 125.

A B C D

The major products formed in the nitration (HNO 3 / H 2SO 4) of aniline and acetanilide are 1. 2. 3. 4. o-nitroaniline and o-nitroacetanilide m-nitroaniline and p-nitroacetanilide p-nitroaniline and m-nitroacetanilide m-nitroaniline and m-nitroacetanilide

126.

Which one of the following name reactions is an example of atom economy reaction? 1. 2. 3. 4. Wittig reaction Grignard reaction Dieckmann condensation Diels-Alder reaction

127.

The order of nucleophilicity among PhNH 2, EtNH 2 and PhNHNH 2 is 1. 2. 3. 4. PhNHNH 2 > PhNH 2 > EtNH2 EtNH 2 > PhNH 2 > PhNHNH2 PhNHNH 2 > EtNH 2 > PhNH2 EtNH 2 > PhNHNH 2 > PhNH2

128.

The order of acid strengths of CH 3COOH, CF 3COOH and CCl 3COOH is 1. 2. 3. 4. CCl 3COOH > CF 3COOH > CH 3COOH CCl 3COOH > CH 3COOH > CF 3COOH CF 3COOH > CCl 3COOH > CH 3COOH CF 3COOH > CH 3COOH > CCl 3COOH

129.

The major product formed in the reaction given below is

Me Me O i. ozonolysis ii. NaOH

1.

O 2. Me 3. O O

4.

130.

The most suitable reagent to achieve the transformation, given below, is

OH O

HO

HO

1. 2. 3. 4. 131.

CrO 3 / H 2SO4 MnO2 KMnO 4 / H + RuCl 3 / NaIO4

An optically active compound A having molecular formula C 6H 12 on catalytic hydrogenation gives an optically inactive compound (C 6H 14). The compound A is 1. 2. 3. 4. 2-methylpentene 3-methylpentene 3,3-dimethylbutene 4-methylpentene

132.

The reagent suitable for converting oct-4-yne to trans-oct-4-ene is 1. 2. 3. 4. H 2 - Pd/C Pd / CaCO 3 / H2 NaBH4 Na / liq. NH3

133.

Which one of the following is a polar aprotic solvent? 1. toluene 2. carbon tetrachloride 3. N,N-dimethylformamide 4. acetic acid The major product formed in the reaction, given below, is
N OH PCl5 MeO Cl
O

134.

1.
Cl

NH OMe

O NH

2.
MeO

Cl O NH

3.

Cl O NH

Cl

4.

MeO

OMe

135.

The major product formed in the reaction, given below, is

CN i. EtMgBr ii. H O
3 +

1.

CHO O

2.

3.

NH2 CN

4.

136.

The most suitable reagent for carrying out the transformation given below, is
OH

Me

Me

1. 2. 3. 4. 137.

aq. H 2SO4 Hg(OAc) 2 followed by reaction with NaBH 4 / NaOH B 2H 6 followed by reaction with H 2O 2 / NaOH m-CPBA followed by reaction with dil H 2SO4

Natural product abietic acid, given below, is a

COOH

1. 2. 3. 4.

monoterpene sesquiterpene diterpene triterpene

138.

The major product formed in the reaction of ethyl acetoacetate with sodium hydride (1 equivalent) and methyl iodide (1 equivalent) is
O 1. Me 2. O Me OEt 3. MeO O OEt O 4. O O O OEt

139.

The reaction of phenylacetylene with one equivalent of methylmagnesium bromide followed by reaction with benzaldehyde provides
1. OH Ph OH 2. Ph Ph 3. Me Ph HO 4. Ph Me H Ph Ph Me H

140.

Sucrose is a disaccharide consisting of 1. 2. 3. 4. glucose and glucose glucose and galactose glucose and fructose glucose and mannose