M. Phil ENTRANCE EXAMINATION-2015 SUBJECT: CHEMISTRY Roll Number:……………………….

Signature of the Candidate Date:…………………

Signature of the Invigilator Date:…………………

Full Marks: 100

Time: 2 hours

INSTRUCTIONS 1. Fill in your Roll No. in appropriate space provided in the question Booklet and Answer Sheet. Fill in the subject in the place provided in the Answer Sheet. 2. There are two sections; Section-A & Section-B 3. All the questions in Section-A are of multiple choice type and are compulsory. Each question carries one mark. Write the correct answer among four options. Answering more than one option will be treated wrong. There is no negative mark for wrong answer. 4. There are 15 short answer type questions in Section-B. The candidates are required to answer only 10 questions. Each question carries 5 marks. 5. Do all the rough work on the last page of the answer sheet. 6. The candidate must handover this booklet to the invigilator before leaving the examination hall.

Section-A All questions are compulsory. Each question carries one mark 1.

The pH of a buffer solution containing 0.004 and 0.4 M of acetic acid (pKa = 4.76) and sodium acetate, respectively will be (a) 6.76

2.

3.

(b) Hydrogen atom

(c) Rigid rotator

(d) Harmonic oscillator

A chemical reaction proceeds with decrease in both enthalpy and enthalpy. The reaction will be spontaneous if ΔH = TΔS

(b) 5 t

(d) 2t

(c) 0.5

(d) 0.2

The method of removing excess solute from a colloidal solution is by (b) recrystalization

(c) dialysis

(d) gas chromatography

Root mean square velocity of molecule is 1000 m/s. The average velocity of the molecule is (b) 675.55 m/s

(c) 921.58 m/s

(d) 1221.58 m/s

Which of the following molecule has lowest vibrational stretching frequency? (b)

2

HCl35

(c) 4HCl36

(d) 4HCl37

The zero point energy of a harmonic oscillator (b) zero

(c) 1/4π hω

(d) 2/6π hω

The number of peaks in the ESR spectrum of CH3 radical is (a) 1

13.

(d) H2

(c) 100 t

(b) 0.10

(a) hω/2π 12.

(c) HCl

The ionic strength of 0.1 M aqueous solution of NaCl assuming complete dissociation of the electrolyte is

(a) 4HCl35 11.

(d) Al2(SO4)3

In a first order reaction, if the time taken for completion of 50 % of the reaction is t second the time required for completion of 99.9 % of reaction is

(a) 455.55 m/s 10.

(c) K2SO4

(b) SF6

(a) Distillation 9.

(d) none of these

The molecule active in rotational microwave, infrared absorption as well as rotational Raman spectra is

(a) 0.15 8.

(c) ΔH > TΔS

(b) C6H12O6

(a) 10 t 7.

(b) ΔH < TΔS

0.1 M aqueous solution of which of the following compounds will exhibit the largest depression of freezing point?

(a) CO2 6.

(d) 0.76

(a) Particle in a one dimensional box

(a) KCl 5.

(c) 2.76

The system for which energy E increases quadratically with the quantum number (n) is

(a) 4.

(b) 4.76

(b) 2

(c) 3

(d) 4

The mixing of two ideal gases at 25°C and 1 atm.Which of the following is true (a) ΔG mix = 0

(b) ΔS mix = 0

(c) ΔV mix = 0

(d) ΔH mix = 0

14.

The specific conductance of 0.01 solution KCl is 0.0014 Ohm-1 cm-1 at 25°C. It equivalent conductance is (c) 14

15.

(b) 140

(b) Viscosity (c) Internal energy (b) ΔJ = ±1,

19.

(b)

bcc

(c) fcc

(d) hexagonal

(a) [Cu(NH4)4]2+

(b) [Cu(NH3)2]2+

(c) [Cu(NH3)4]2+

(d) [Cu(NH4)2]2+

A compound shows 1H NMR peak at 240 Hz downfield from TMS peak and operating at 60MHz. The value of τ is (b) 6ppm

(c) 8ppm

(d) 2ppm

How many significant figures are present in the number 0.0025? (a) 5

21.

(d) ΔJ = ±2

The blue complex formed on addition of concentrated NH4OH solution to a Cu2+ salt solution has the structure

(a)4ppm 20.

(c) ΔJ = ±1,0

If reflections from the crystal planes 100, 110, 210, 211 are absent in the diffraction pattern the crystal lattice is (a) Simple cubic

18.

(d) Molar heat capacity

The selection rule for rotational spectra is (a) ΔJ = 0

17.

(d) 0.14

An example of extensive property is (a) Temperature

16.

(c) 1.4

(b) 4

(c) 2

(d) 6

Which of the following amino acids is achiral? (a) Alanine (b) Glycine (c ) Serine (d) Cysteine

22.

Which one of the following alkenes will give optically active product with Br2/CCl4? (a) 1-Butene (b) Propene

23.

25.

(d) Trans-2-butene

Which one of the following carbocations is the most stable?

(a) NC

24.

(c )Cis-2-butene

CH2

(b) HO

(c ) Cl

CH2

CH2

(d) O2N

The shift of an absorption maximum towards longer wave length is known as (a) Hypsochromic effect

(b) Bathochromic effect

(c) Hyperchromic effect

(d) Hypochromic effect

In the given reaction, the product will be: (1) NBS/CCl4 light

?

(2) HOH/K2CO3 Br

(a)

OH

(b)

O

(c)

(d)

COOH

CH2

26.

27.

28.

Claisen-Schmidt reaction takes place between (a)

Aldehyde and aldehyde

(b)

Aromatic aldehyde and ketone

(c)

Ketone and Ketone

(d)

Aromatic aldehyde and compound having active methylene group

Distance between centres of the peaks of doublet is called (a) coupling constant

(b) spin-spin Coupling

(c) spin constant

(d) None

1

13

H- C COSY is termed

(a) HECTOR 29.

32.

35.

37.

(d) D∞h

(b) 2

(c) 3

(d) 0

(b) Composition of a complex

(c) Dissociation constant

(d) No of outer-sphere ligands in a complex

The effective atomic number (EAN) of Fe(CO)5 is (b) 35

(c) 36

(d) 39

On complete decomposition, a 10 volume of hydrogen peroxide liberates _____ time(s) its volume of oxygen at 0oC and 760 mm. (b) 100

(c) one

(d) 20

Identify the atom-economy reaction from the following (a) Grignard reaction

(b) Wittig reaction

(c) Diels-Alder reaction

(d) Friedel-Crafts reaction

The strongest acid among the following is: (a) CH3OH

36.

(c) D2h

(a) Rate of a reaction

(a) 10 34.

(b) C3v

Job’s method of continuous variation is used for determination of

(a) 34 33.

(d) NOISY

The brown ring complex compound is formulated as [Fe(H2O)5NO+]SO4. The oxidation state of iron is (a) 1

31.

(c) Inadequate

What is the point group of CO2 ? (a) C2v

30.

(b) DEPT

(b) CH3NH2

(c) CH3SH

(d) CH3CH2NH2

The compound with lowest boiling point is (a) 2-Methylhexane

(b) 3,3-Dimethylpentane

(c) n-Heptane

(d) Cycloheptane

Identify the most appropriate C-C bond forming reaction involving the carbocation intermediate. (a) Cannizzaro reaction

(b) Favorskii rearrangement

(c) Friedel-Crafts reaction

(d) Benzoin Condensation

38.

Identify the most appropriate product in the reaction of RCOOH with diazomethane. (a) RCH2COOH

(b) RCH2OH

(c) RCOOCH3 39.

(d) RCOCH3

What is the reagent used for the conversion of RCOCH2R’ to RCOCOR’? (a) H2O2

(b) SeO2

(c) OsO4 40.

(d) HNO3/H2SO4

Sucrose on hydrolysis with diluted acids gives (a) D(+)-Glucose and D(-)-Fructose

(b) D(-)-Glucose and D(-)-Fructose

(c) D(+)-Glucose and L(-)-Fructose (d) 2 molecules of D(+)-Glucose 41.

42.

43.

44.

The degree of unsaturation of the fatty acid is determined by: (a) Acid value

(b) Iodine value

(c) Acetyl value

(d) Reichert-Meissl value

Identify the achiral molecule from the following. (a) 2-Amino-2-carboxypropane

(b) Alanine

(c) 2-Phenylpentane

(d) Lactic acid

The conversion of silver salt of the carboxylic acid to alkyl halide is called: (a) Hunsdiecker reaction

(b) Stephen reaction

(c) Ritter reaction

(d) Vilsmeier reaction

The number of geometrical isomers of the complex [Co(NO2)3(NH3)3] is (a) 2

45.

(d) [Ni(CO)4]

(b) polyamine

(c) polyamide

(d) polyester

(b) [Cr(NH3)6]3+

(c) [Fe(CN)6]4-

(d) [Fe(CO)5]

(b) 8

(c) 12

(d) 9

The hormone which helps in the conversion of glucose into glycogen is (a) Insulin

50.

(c) [Cu(NH3)4]Cl2

The coordination number for an atom in a body centred cubic (bcc) unit cell is (a) 6

49.

(b) [Co(NH3)6]Cl3

Which of the following is paramagnetic with a spin of an electron? (a) [Cr(CO)6]

48.

(d) 0

Nylon-66 is a (a) polyalcohol

47.

(c) 4

Which of the following will exhibit maximum ionic conductivity (a)K4[Fe(CN)6]

46.

(b) 3

(b) glucogen

(c) Adrenaline

(d) Zymase

Which of the following is a condensation polymer (a) Polystyrene

(b) Neoprene

(c) PAN

(d) Poly(ethylene glycol phthalate)

Section-B Answer any ten questions within the space provided. Each question carries five marks 1.

2. 3. 4.

5.

The vibrational wavenumbers of the following molecules in their v = 0 state are HCl = 2885 cm-1, DCl = 1990 cm-1, D2 = 2990 cm-1 and HD = 3627 cm-1. Calculate the energy change in kJ/mol of the following reaction HCl + D2→ DCl + HD Calculate the ionic strength of solution obtained by mixing equal volume of 0.1M NaCl and 0.02M AlCl3 solution. Show that pH of a 10-8 M HCl solution in water is in between 6 to 7. A certain system absorbs 2×1016 quanta of light per second. At the end of 20 minutes, it is observed that 0.002 mole of irradiated substance has reacted. What is the quantum yield of the product?

How can you distinguish the following pair of compounds by IR spectroscopy? O

and H3C

CH3

and

COOH

6.

H3C

CH3

O

HO

COCH3

Write the product of the following reaction with mechanism. N(CH3)3I

PhLi ?

7.

An organic compound (C9H10O3) exhibited the following spectral data IR: 3400, 1680 CM-1 : 1H NMR: δ 7.8 (1H, d, J = 8.0 Hz, 7.0 (1H, d, J = 8.0 Hz), 6.5 (1H, s), 5.8 (1H, s, D2O, exchangeable), 3.9 (3H, s), 2.3 (3H, s). Elucidate the structure of the compound.

8.

Calculate λmax of the following compound. R

9.

Complete the following reaction. H3CO HO

CHO (i) Ph P-CH-COOC H 3 2 5

(ii) H3O

+

?

LiAlH4

?

10.

Write down the products and mechanism of the given reactions?

11.

(a) Explain why [Co(CN)5Cl]3- is insensitive to base (NaOH) hydrolysis . (b) Aqueous solution of Co(OH2)63+ is pink while that of CoCl42- is blue. Explain.

12.

Inorganic benzene is isoelectronic with benzene, but it is more reactive than benzene. Explain why?

13.

Explain the Mossbauer spectra of K4[Fe(CN)6].3H2O and K3[Fe(CN)6] on the basis of quadrupole splitting.

14.

Differentiate between Frenkel and Schottky defects with examples

15.

Differentiate between Chemical shift and contact shift in NMR. ************