MH SET 2013: 1 December, Paper III, Chemical Sciences
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Chemical Science
Paper III
Time Allowed : 2½ Hours] [Maximum Marks : 150
Note : This Paper contains Seventy Five (75) multiple choice questions, each
question carrying Two (2) marks. Attempt All questions.
1. The Bromination of phenol to form tribromophenol :
Phenol(aq.) + 3Br(aq.) → 3HBr(aq.) + 3-bromophenol(aq.)
Change in standard free energy of the system (∆G0) is given as :
1 0 1
(A) ∆G 0 = µBr + µ0C H OH − µ0HBr − µ0TBP
3 2 6 5 3
1 0 1
(B) ∆G 0 = µHBr + µ0TBP − µ0Br − µ0C H OH
3 3 2 6 5
(C) ∆G 0 = 3µ0Br + µ0C H OH − 3µ0HBr − µ0TBP
2 6 5
(D) ∆G 0 = 3µ0HBr + µ0TBP − 3µ0Br − µ0C H OH
2 6 5
2. Consider the equation below :
AgCl(s) + 2NH3(aq.) ←→ Ag(NH ) +(aq.) + Cl–(aq.)
3 2
Increase in Cl– concentration causes equilibrium concentration to change
favoring :
(A) the formation of Ag(NH3)2+(aq.)
(B) a decrease in NH3(aq.) concentration
(C) the formation of AgCl(s)
(D) the decrease in amount of AgCl(s)
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3. For 0.01 Molal AgNO3 solution, the mean activity coefficient (γ±) is given
by expression (assume A = ½) :
2 2
(A) log γ± = (B) log γ± = –
2 2
(C) γ± = 100.05 (D) γ± = 10–0.05
4. For the concentration cell,
Ag|Ag+(0.01 mol dm–3) || Ag+(0.1 mol dm–3)|Ag
EMF of the cell reaction at temperature (T) is equal to :
RT RT
(A) 2.303 (B) −2.303
F F
RT RT
(C) E0 + + 2.303 (D) E0 + − 2.303
Ag /Ag F Ag /Ag F
5. For the enzymolysis with the following mechanism :
k
E + S ←
1
→ X →
k2
E + P
k −1
Applying steady state approximation on the rate law, the concentration of
an intermediate will become :
kE S
[ x ] = k S +1 k0 0 + k
1 0 −1 2
Based on this, the initial rate of a reaction is worked out to be :
k1 k2E0 k1 k2 E0
(A) ν0 = (B) ν0 =
k + k2 k + k1
k1 + −1 k2 + −1
S0 S0
k1 k2E0 k1 k2E0
(C) ν0 = (D) ν0 =
k + k2 k1 + k−1 + k2
k−1 + 1
S0 S0
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6. For the reaction given below, the relaxation time (τ) is found to be 10–9 s.
If 10% of cis-dichloroethene remains at equilibrium, then the value of
k1(s–1) is :
Cl
Cl Cl
Cl
(A) –9 × 10–8 (B) 10–8
(C) 10 8 (D) 9 × 10–8
7. The following are the comparison between bimolecular rate constants predicated
from Collision Theory (CT) and the corresponding experimental values, for
the various gaseous phase reactions :
k(Expt.), k(Collision Theory),
k1
← →
k
−1 L mol–1 s–1 L mol–1 s–1
2NaCl → 2Na + 2Cl 9.4 × 109 5.9 × 1010
2ClO → Cl2 + O2 6.3 × 107 2.5 × 1010
H2 + C2H4 → C2H6 1.24 × 106 7.3 × 1011
These results suggest that CT over-estimates the rate constants. This limitation
of CT is due to :
(A) favorable orientation is needed to be considered for the successful reaction
(B) experimental errors in the measurements
(C) activation energy is involved in the reaction
(D) molecules are assumed as hard sphere
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8. Which of the answers below is the correct short hand representation for the
galvanic cell having the following over all reaction ?
2Fe3+(aq.) + 3Ni(s) ←→ 2Fe(s) + 3Ni2+(aq.)
(A) Fe3+(aq.)|Fe(s) || Ni(s)|Ni2+(aq.)
(B) Fe3+(aq.)|Ni(s) || Fe(s)|Ni2+(aq.)
(C) Ni(s)|Ni2+(aq.) || Fe(s)|Fe3+(aq.)
(D) Ni(s)|Ni2+(aq.) || Fe3+(aq.)|Fe(s)
9. What would happen to the state of a substance represented by this phase
diagram, if the pressure changed from Point ‘A’ to Point ‘B’ (holding temperature
constant) ?
(A) Melting (B) Deposition
(C) Sublimation (D) Freezing
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10. What will be the number of possible arrangements for a hypothetical system
consisting of 5 molecules and 2 quanta ?
(A) 21 (B) 3
(C) 15 (D) 2
11. Nylon is not a :
(A) Co-polymer (B) Condensation polymer
(C) Polyamine (D) Homopolymer
12. A liquid does not wet the surface of a solid if the angle of contact is :
(A) Zero (B) 90°
(C) 30° (D) 120°
13. Radioactive disintegration differs from a chemical change in being :
(A) A unimolecular first order reaction
(B) A spontaneous process
(C) A bimolecular process
(D) A nuclear process
14. Predict the value for the standard constant volume heat capacity (C°v ) of a
closed shell heteronuclear diatomic molecule at high temperature :
5 7
(A) R (B) R
2 2
3 9
(C) R (D) R
2 2
15. The radio carbon dating method was developed by :
(A) A. Yukawa (B) J.J. Thomson
(C) Willard Libby (D) Enrico Fermi
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16. The commutator of [x2, px] is equal to :
hx 2hx
(A) (B)
πi πi
hx2 hx
(C) (D) −
2 πi πi
17. The life time of a state that gives rise to a spectral line of width
0.1 cm–1 is :
(A) 53 nm (B) 53 pm
(C) 33 nm (D) 33 pm
18. The wave function for a particle in a 1-D box of length ‘L’ is given as
πx
ψ = A sin . The value of ‘A’ for a box of length 50 nm is :
L
(A) 5 2 (nm)1/2 (B) 0.2 (nm)–1/2
(C) 0.2 (nm)1/2 (D) 5 /10 (nm)–1/2
19. The quantum state of a particle in a circular path in a plane is given
by :
1 − imφ
ψ m (φ ) = e , m = 0, ± 1, ± 2, .............
2π
When a perturbation H′ = P cos θ is applied (P is a constant), what will be
the first order correction to the energy of the mth state ?
(A) 0 (B) P/(2π)
(C) P/(4π) (D) Pm2/(4π2)
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20. The molecular orbitals of 1, 3-butadiene (not in proper order) are given
below :
(f1, f2, f3, f4 are the 2pz orbitals on carbon atoms.)
ψ1 = 0.372f1 – 0.602f2 + 0.602f3 – 0.372f4
ψ2 = 0.602f1 + 0.372f2 – 0.372f3 – 0.602f4
ψ3 = 0.372f1 + 0.602f2 + 0.602f3 + 0.372f4
ψ4 = 0.602f1 – 0.372f2 – 0.372f3 + 0.602f4
The correct order of the orbitals with increasing energy is :
(A) ψ1 < ψ2 < ψ3 < ψ4 (B) ψ3 < ψ2 < ψ4 < ψ1
(C) ψ3 < ψ4 < ψ1 < ψ2 (D) ψ4 < ψ3 < ψ2 < ψ1
21. The infrared spectrum of a diatomic molecule exhibits transitions at
2143.0 cm–1 and 4260.0 cm–1 corresponding to excitations from the ground
state to first and second vibrational states respectively. The value of the
fundamental frequency, ω e (cm–1) for the molecule is :
(A) 2156 (B) 2169
(C) 2182 (D) 2195
22. The ratio of the translational partition functions of D2 and H2 at the same
temperature and pressure is :
(A) 1.59 (B) 2.83
(C) 2.00 (D) 0.35
23. The Td point group has 24 elements and 5 classes. Given that it has two
three-dimensional irreducible representations, the number of one-dimensional
irreducible representations is :
(A) 1 (B) 6
(C) 2 (D) 3
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24. In which of the following will the energy level separation be maximum ?
(A) A 13C nucleus in a 400 MHz NMR instrument
(B) A 95Mo nucleus in a 600 MHz NMR instrument
(C) A 31P nucleus in a 600 MHz NMR instrument
(D) An unpaired electron in a magnetic field of 0.33 T
25. The 129I Mössbauer spectral data for the compounds I2Cl6 and I2Br2Cl4 are
given below :
Compound Isomer Shift Quadrupole Splitting
(mm/s) (MHz)
I2Cl 6 3.50 3060
I2Br2Cl4 2.82 2920
3.49 3055
The structure of I2Br2Cl4 can be represented as :
(A) (B)
(C) (D)
26. When a KCl crystal is strongly heated, it loses some chlorine. The resulting
structure then has :
(A) F centers (B) Schottky defects
(C) Frenkel defects (D) Metal deficiency defects
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27. PbTiO3 and YBa2Cu3O7 both are having :
(A) Semiconducting property
(B) Superconducting property
(C) Piezoelectric property
(D) Common structural features
2+
28. Magnetic measurements indicate that Co (H 2O)6 has 3 unpaired electrons.
2+
Therefore, the hybridization of the metal orbitals in Co (H 2O) is :
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(A) d2sp3 (B) sp3d2
(C) dsp2 (D) sp2d
29. Which of the statements is false ?
(A) In an octahedral crystal field, the electrons fill the eg level first, followed
by t2g level.
(B) Diamagnetic metal ions cannot have an odd number of electrons.
(C) Low-spin complexes can be paramagnetic.
(D) In high-spin octahedral complexes ∆oct is less than the electron pairing
energy, and is relatively every small.
3+
30. The complex Ti (H 2O) shows an absorption band at 20,000 cm–1. Therefore,
6
the CFSE of this complex is :
(A) 8,000 cm–1 (B) 12,000 cm–1
(C) –8,000 cm–1 (D) –12,000 cm–1
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31. The first excited state configuration of low-spin octahedral d4 system is :
(A) 2E (B) 5T
g 2g
(C) 5E (D) 3T
g 2g
32. Coordinated water molecules of Cd(11) complex can be successively replaced
2−
by Br– finally to result in CdBr4 . In this process, the fourth equilibrium
constant (K4) is observed to be higher than the third one, because :
(A) Equilibrium constant for the last step is always the highest
(B) Three molecules of H2O are released during the fourth step
(C) The aqua Cd2+ complex is octahedral
(D) A Br– anion replaces a neutral (H2O) molecule from the coordination
sphere
33. The reaction :
2+ 2+ 2+ 2+
Co (H O) Cl + Cr (H 2O)6 → Co (H 2O)6 + Cr (H 2O)5 Cl
2 5
is an example of :
(A) isomerization
(B) nucleophilic substitution
(C) inner-sphere electron transfer
(D) outer-sphere electron transfer
34. Reducing ability of the oxyanions of sulphur change as :
(A) S2O32− > SO32− > S2O82− (B) SO32− > S2O82− > S2O32−
(C) SO32− > S2O32− > S2O82− (D) S2O82− > S2O32− > SO32−
35. Match the following class of boranes with their examples :
(a) closo (i) B8H14
(b) nido (ii) (B10H10)2–
(c) arachno (iii) B9H13
(A) (a)—(iii), (b)—(i), (c)—(ii)
(B) (a)—(i), (b)—(iii), (c)—(ii)
(C) (a)—(ii), (b)—(i), (c)—(iii)
(D) (a)—(ii), (b)—(iii), (c)—(i)
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36. The molecule BrF5, interconverts between :
(A) trigonal-bipyramidal and tetrahedral structure
(B) square pyramidal and pentagonal structure
(C) trigonal-bipyramidal and square planar structure
(D) square pyramidal and trigonal-bipyramidal structure
37. Among the following statements :
2n−
(a) Sheet silicates have general formula Si2O5 n
(b) ZrSiO4 is an example for orthosilicate
(c) Si2O76− is a cyclosilicate
(d) BaTiSi3O9 is a pyrosilicate
(A) Only (a) is correct (B) (a), (c) are correct
(C) (a), (b) are correct (D) (b), (c) are correct
38. The type of hybridisation of carbon atoms in graphene sheets is :
(A) only sp2 (B) sp2 and sp3
(C) only sp3 (D) sp and sp2
39. Which of the following ligands will form a stable complex with Ln3+ ions ?
(A) H2O (B) CO
(C) C2 H 4 (D) PPh3
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40. The ligand field bands of lanthanide complexes are generally sharper than
those of transition metal complexes because :
(A) The corresponding transitions are allowed
(B) The bands are more intense
(C) f-orbitals have higher energy than d-orbitals
(D) The interaction of ligands with f-orbitals is less effective than with
d-orbitals
41. The reaction of an alkylbromide with IrCl (CO) (PMe3 )2 is :
(A) oxidative addition (B) substitution
(C) alkylation (D) halogenation
42. M4 carbonyl clusters A and B have CVE count of 60 and 62, respectively.
Therefore the cluster geometrices should be, respectively :
(A) square planar and tetrahedral
(B) tetrahedral and butterfly
(C) square planar and butterfly
(D) tetrahedral and square planar
43. The correct order νCO in the given compounds is :
(A) ( ) ( ) (
Rh η5 —C5H5 (CO) < Rh η5 —C5 F5 (CO) < Rh η5 —C5 Me5 (CO)
2 2 2 )
(B) ( ) ( )
Rh η5 —C5Me5 (CO) < Rh η5 —C5H5 (CO) < Rh η5 —C5F5 (CO)
2 2 2 ( )
(C) ( ) ( ) (
Rh η5 —C5F5 (CO) < Rh η5 —C5 H5 (CO) < Rh η5 —C5 Me5 (CO)
2 2 2 )
(D) ( ) ( )
Rh η5 —C5F5 (CO) < Rh η5 —C5 Me5 (CO) < Rh η5 —C5H5 (CO)
2 2( )
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44. In oxyhaemoglobin, the iron centre is best described as :
(A) high-spin Fe(III) (B) high-spin Fe(II)
(C) low-spin Fe(III) (D) low-spin Fe(II)
45. Iron is stored in the body as :
(A) transferrin (B) haemoglobin
(C) ferritin (D) siderophore
46. In zinc enzymes binding of water to zinc ion induces :
(A) formation of hydronium ion
(B) conformational change in the binding site
(C) ionization of a histidine residue
(D) formation of a zinc bound hydroxide ion
47. Identify the correct response given in column 2 to analyte concentration
measured in the following electroanalytical techniques given in column 1 :
Column 1 Column 2
(a) Coulometry (i) Cathodic current
(b) Polarography (ii) Coulombs
(c) Voltammetry (iii) Conductivity
(d) Conductometry (iv) Cathodic or anodic current
(A) (a)—(i), (b)—(ii), (c)—(iii), (d)—(iv)
(B) (a)—(ii), (b)—(i), (c)—(iv), (d)—(iii)
(C) (a)—(iv), (b)—(i), (c)—(ii), (d)—(iii)
(D) (a)—(ii), (b)—(iv), (c)—(ii), (d)—(iii)
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48. The amount of Al2 (SO4 )3 ·18H2O(MW = 662.42) required to prepare a litre
of 1 M Al solution is :
(A) 331.21 g (B) 662.42 g
(C) 33.121 g (D) 66.42 g
49. Which of the following molecules contains the highest % of sulphur by
mass ?
(A) Na2SO4 (B) Li2SO4
(C) H2SO4 (D) PbSO4
50. On a 20 cm column, the retention times tR of A and B are 16.40 and
17.63 minutes, respectively. The peak width at base lines for A and B are
1.15 and 1.31 minutes, respectively. The column resolution RS is :
(A) 0.10 (B) 0.50
(C) 1.00 (D) 1.50
51. A 10 mg sample containing CaCO 3 and α-Al 2 O 3 was analysed by
thermogravimetry between 30—800°C. A weight loss of 2.2 mg was observed.
The % CaCO3 in the mixture is ................................... .
(Given : M.W. CaCO3 = 100.0)
(A) 50% (B) 45%
(C) 55% (D) 75%
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52. The extraction of uranyl (VI) ion (UO2)2+ from an aqueous solution in
concentrated HCl using ether as solvent is an example of :
(A) neutral metal-chelate extraction
(B) ion-pair association
(C) supercritical fluid extraction
(D) fractional extraction
53. Which of the following is not a criteria for aromaticity ?
(A) Presence of (4n + 2) delocalizable electrons
(B) Diamagnetic character
(C) Strong shielding-de-shielding pattern as a result of induced ring current
(D) Paramagnetic character
54. Which of the following statements is correct regarding fullerene C60 ?
(A) 12,500 Resonating structures are possible for C60
(B) Fullerene C60 is a super aromatic compound
(C) Unsubstituted fullerene C60 can be acylated using Friedel-Crafts
acylation
(D) Fullerene C60 is susceptible to attack by nucleophilic reagents
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55. Predict the stereochemical outcome of the following reaction :
(A)
(B)
(C)
(D)
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56. Study the following reaction sequence, predict the structure of X and choose
the correct description for the same :
(A) Both the steps are non-stereoselective and X is
(B) Both the steps are enantiostereoselective and X is
(C) The first step is diastereoselective as well as
enantioselective and X is
(D) Both the steps are diastereoselective as well as
enantioselective and X is
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57. 2-Bromocyclohexanone on reaction with methoxide gives methyl ester of
cyclopentane carboxylic acid. Give the name of the reaction and the key
intermediate involved in this reaction :
(A) Favorskii rearrangement with a derivative of cyclopropanone
intermediate.
(B) Favorskii rearrangement with a carbocation as an intermediate.
(C) Benzyllic acid rearrangement with carbocation as an intermediate.
(D) Baeyer-Villiger reaction with carbocation as an intermediate.
58. Study the following chemical transformation :
The correct reagents for the above reaction are :
(A) t-BuOOH, Ti(O-i-Pr)4, (–)-DET
(B) t-BuOOH, Ti(O-i-Pr)4, (+)-DET
(C) H2O2
(D) MCPBA
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59. Hammett plot for hydrolysis of ethyl benzoates in 99.9% H2SO4, has two
separate reaction constants, ρ = –3.25 and ρ = 2.0, for electron donating groups
(EDG) and electron withdrawing groups (EWG) respectively.
Which of the following statements correctly summarizes the above
observation ?
(A) For EDG, reaction proceeds by AAC1 and for EWG, reaction proceeds
by AAC2 mechanism
(B) For EDG, reaction proceeds by AAC1 and for EWG, reaction proceeds
by AAL1 mechanism
(C) For EDG, reaction proceeds by AAC1 and for EWG, reaction proceeds
by AAC1 mechanism
(D) For EDG, reaction proceeds by AAL1 and for EWG, reaction proceeds
by AAC1 mechanism
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60. The following are some of the processes used for studying reaction mechanism.
Match them with their specific applications :
(M) Primary Kinetic isotope effect (1) Largely gives information about
RDS
(N) Cross-over experiments (2) Detection of non-isolable sus-
pected intermediate
(O) Trapping of intermediates (3) Helps in distinguishing between
intramolecular and intermole-
cular mechanisms
(P) Kinetic studies (4) Helps to find out whether a
particular bond is cleaved in
the RDS
(A) (M)—(1), (N)—(2), (O)—(3), (P)—(4)
(B) (M)—(2), (N)—(4), (O)—(1), (P)—(3)
(C) (M)—(4), (N)—(3), (O)—(2), (P)—(1)
(D) (M)—(3), (N)—(2), (O)—(1), (P)—(4)
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61. Study the following reaction and identify the process involved :
(A) Thermal 6 pi electron electrocyclic reaction
(B) Photochemical 6 pi electron electrocyclic reaction
(C) (4 pi + 2 pi) electron photochemical cycloaddition reaction
(D) (4 pi + 2 pi) electron thermal cycloaddition reaction
62. Study the following reaction and identify the processes involved :
(A) Claisen rearrangement followed by keto-enol tautomerism
(B) [3, 3] Sigmatropic rearrangement followed by [1, 5]-H-shift
(C) [3, 3] Sigmatropic rearrangement followed by keto-enol tautomerism
(D) [1, 3] Sigmatropic rearrangement followed by keto-enol tautomerism
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63. In Fischer-indole synthesis of 2-phenylindole, starting materials used are :
(A) Phenyl hydrazine and acetophenone
(B) Phenyl hydrazine and benzaldehyde
(C) Phenyl hydrazine and acetone
(D) Phenyl hydrazine and acetaldehyde
64. Match the structures in List I with their correct names in List II :
List I List II
(L) (1) 5-hydroxybenzothiazole
(M) (2) 2-amino pyridine
(N) (3) 2-methyl furan
(O) (4) 2-amino piperidine
(A) (L)—(1), (M)—(2), (N)—(3), (O)—(4)
(B) (L)—(3), (M)—(2), (N)—(4), (O)—(1)
(C) (L)—(3), (M)—(2), (N)—(1), (O)—(4)
(D) (L)—(2), (M)—(3), (N)—(4), (O)—(1)
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65. Lithium isopropylamide (LDA) is a :
(A) Conjugate base of diisopropylamine which is strongly basic and bulky.
(B) Conjugate base of diisopropylamine which is weakly basic and bulky.
(C) Conjugate acid of diisopropylamine which is strongly basic and bulky.
(D) Conjugate base of diisopropylamine which is strongly basic and small
in size.
66. The products formed as X and Y respectively in the following reactions
are :
(A)
(B)
(C)
(D)
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67. Dehydrocholesterol is present in the tissues of the skin, where it is transformed
to vitamin D3 by a sun-light induced photochemical reaction :
.
Choose the correct structure of vit. D3 :
(A)
(B)
(C)
(D)
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68. Which of the following structures is the correct representation of
β-D-glucopyranose ?
(A)
(B)
(C)
(D)
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69. The correct stereochemical structure of the tetrapeptide, Try-Gly-Gly-Phe,
derived from the natural amino acids is :
(A)
(B)
(C)
(D)
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70. The following rearrangement occurs when 2, 5-cyclohexadienone [X] is
irradiated. The name of the rearrangement is :
hν
(A) Barton rearrangement
(B) Photo Fries rearrangement
(C) Dienone-phenol rearrangement
(D) Di-pi-methane rearrangement
71. The following photochemical reaction is :
hν
(A) Norrish type I reaction (B) Photochemical reduction
(C) Paterno-Buchi reaction (D) Norrish type II reaction
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72. Chymotrypsin preferentially cleaves the carbon side of the peptide bond of :
(A) Methionine (B) Proline
(C) Phenyl alanine (D) Alanine
Linked Problem Q. No. 73 and Q. No. 74 :
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 Y as the major product. The
spectral data for the compound X are 1H NMR δ 1.17(d, 6H), 3.02(m, 1H),
4.10(s, 2H); 13C NMR δ 17, 37, 39, 210.
73. The compound [X] is :
(A) (B)
(C) (D)
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74. The major product Y is :
(A) (B)
(C) (D)
75. Compound X and Y exhibit two singlets each in 1H NMR. The expected chemical
shifts are at δ :
(A) 6.9 and 2.1 for X, 7.7 and 3.9 for Y
(B) 6.9 and 3.9 for X, 7.7 and 2.1 for Y
(C) 7.7 and 3.9 for X, 6.9 and 2.1 for Y
(D) 7.7 and 2.1 for X, 6.9 and 3.9 for Y
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ROUGH WORK
32Official key not published for this paper.
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Source: Savitribai Phule Pune University. Question paper published by Savitribai Phule Pune University.