JMS 2 PAPER 1

PAPER-1
Maximum Marks: 80

Question paper format and Marking scheme: 1. In Section I ( Total Marks: 21), for each question you will be awarded 3 marks if you darken ONLY the bubble corresponding to the correct answer and zero marks if no bubble is darkened. In all other cases, minus one (1) mark will be awarded. 2. In Section II (Total Marks: 16), for each question you will be awarded 4 marks if you darken ALL the bubble(s) corresponding to the correct answer(s) ONLY and zero marks other wise. There are no negative marks in this section. 3. In Section III (Total Marks: 15), for each question you will be awarded 3 marks if you darken ONLY the bubble corresponding to the correct answer and zero marks if no bubble is darkened. In all other cases, minus one (1) mark will be awarded. 4. In Section IV (Total Marks: 28), for each question you will be awarded 4 marks if you darken ONLY the bubble corresponding to the correct answer and zero marks otherwise. There are no negative marks in this section.

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JMS 2 PAPER 1

SECTION I (Total Marks : 21) (Single Correct Answer Type) This section contains 7 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of which ONLY ONE is correct. 1. For the reaction A+B 2C, equal moles of A and B are placed in a container at 250C. At equilibriium, it is found that concentration ratio of [C] to [A] is equal to 2, then value of G0 is equal to (A) 826.29 cal (B) -693.2 cal (C) 277.28 J (D) 596 J (A) A+B 2C Initially, [ A] = [ B ] At equilibrium,

Sol :

[C ] = 2; C = 2 A [ ] [ A]

[ 2 A]2 = 4 A2 = 4 K= [ A][ B ] A2
G 0 = 2.303 RT log K = 2.303 2 298log 4 = 826.29 cal 2. Match the following. Column-I Complete XeF +H O 4 2 hydrolysis Complete XeF +H O 6 2 hydrolysis Column-II HF
XeO 3

(a) (b) (c)

(P) (Q) (R)

SiF 4 XeO F 2 2

(d)

(S)

A) a - R ,S; b - P,S; c - Q; d -P,R B) a- P; b R , S; c Q ,S; d Q ,P C) a- P,Q; b - P,Q; c P ,S; d - R,S D) a - S; b - P,R; c Q , R; d -P

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JMS 2 PAPER 1
Sol. (C)

Complete Hydrolysis 6 XeF + 12 H O 4 Xe + 2 XeO + 24 HF + 3O 4 2 3 2 Complete Hydrolysis XeF + 3H O XeO + 6 HF 6 2 3 Partial Hydrolysis XeOF + H O XeO F + 2 HF 4 2 2 2
2 XeOF + SiO 2 XeO F + SiF 4 2 2 2 4

3.

An organic compound (X) with molecular formula C7H8O is insoluble in aq NaHCO3 but dissolves in NaOH. When treated with Bromine water, X rapidly gives Y, C7H5OBr3. The compounds X and Y respectively are (A) Benzyl alcohol and 2,4,6 Tribromo 3methoxy phenol (B) o-Cresol and 3,4,5 Tribromo 2 methyl phenol (C) m Cresol and 2,4,6 tribromo 3 methyl phenol (D) Benzyl alcohol and 2,4,6 tribromo 3 methyl phenol (C) Compound X (C7H8O) must be a phenolic compound since it is soluble in NaOH and insoluble in
NaHCO3. X on treatment with Br2 water is giving Y with three Br atoms. (C7H5OBr3) So, placement of OH and CH3 must be such that they reinforce each other in electrophilic substitution Therfore, it must be m Cresol. -OH is more activating than -CH3. So, all the o- and para positions wrt OH are substituted.

Sol.

OH
Br 2 H O 2
3

OH
Br Br

CH
Br

CH

m - cresol (X)
4.

(Y)

The oxidative cleavage of Glucose (A) and Fructose (B) with HIO4 leads to the formation of acids, aldehydes and also CO2. The ratio of no of moles of formic acid to formaldehyde formed in case of (A) and (B) are respectively

a) 5:1 , 3:2
Sol. (A)

b) 5:2 , 3:1

c) 3:2 , 5:2

d) 4:2 , 5:1

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JMS 2 PAPER 1

5.

(1) NaOI A B ( 2) H+
O

.Starting compound A is

O
O O

C OH
O
(C)

A)

CH C OH 2 (B)

C CH
O

3
(D)

C CH
O

Sol.

(C)

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JMS 2 PAPER 1
6. An alkali metal hydride (NaH) reacts with diborane in Y to give a tetrahedral compound Z which is extensively used as reducing agent in organic synthesis. Y and Z in the above reaction are (A) C2H6, C2H5Na (B) C2H5OC2H5, NaBH4 (C) NH3, B3N3H6 (D) C3H8, C3H7Na (B)
C H O 2 5 2 2 NaH + B H 2 NaBH 2 6 4 Z) ( (Y )

Sol.

BH

is tetrahedral. (As per VSEPR, it has 4 bonded and 0 lone pairs)

7.

The following canonical structures follow the stability order

N=N
I
+

II

N=N

III

NN

(A) I > II > III (C) II > III > I

Sol. (D)

(B) III > I > II (D) II > I > III

SECTION II (Total Marks : 16) (Multiple Correct Answers Type)

This section contains 4 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of which ONE OR MORE may be correct.
8. Which of the following is/are correct for the characteristics indicated against each (A) NH3 > PH3 > AsH3 > SbH3 (boiling point) (B) BF3 < BCl3 < BBr3 < BI3 (lewis acid strength) (C) H3PO2 > H3PO3 > H3PO4 (acidic strength) (D) HClO < HClO2 > HClO3 < HClO4 (acidic strength) (B,C,D) Boling points order of hydrides of V A group elements is BiH3 > SbH3 > NH3 > AsH3 > PH3

Sol.

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JMS 2 PAPER 1
9. Which of the following statement(s) is/are correct (A) Cuprite and Zincite are oxide ores (B) Magnesite and carnallite are carbonate ores (C) Chalcocite and azurite are ores of copper (D) Felspar and mica contain aluminium. (A,C,D) Cuprite and zincite are Cu2O and ZnO. Magnesite and carnallite are MgCO3 and KCl MgCl2 6H2O Chalcocite and azurite are Cu2S and 2CuCO3 . Cu ( OH)2 Felspar and mica are KAlSi3O8 and K2O 3Al2O3 6SiO2 2H2O 10. Which of the following is/are correct order with respect to the property mentioned. (A) O22 > O2 > O22+ [Paramagnetic moment] (B) (NO) > (NO) > (NO)+ [bond length] (C) H2 > H2+ > He2+ [bond energy] (D) NO2+ > NO2 > NO2 [bond angle] (B,C,D) Correct paramagnetic moment is O2 > O22+ = O22 Acc to MOT, O2 has 2 unpaired e- and the remaining two have 0 unpaired e-s each

Sol.

Sol.

11.

Which of the following statement(s) is /are correct ? 1 (A) Ionisation energy screening effect (B) The ionisation energies of Be and Mg are more than ionisation energy of B and Al respectively. (C) Atomic and ionic raddii of Nb and Ta are almost same (D) Metallic and covalent radii of potassium are 2.3 and 2.03 respectively. (A,B,C,D)

Sol.

(A) As Screening effect increases, effective nuclear charge decreases, thus valence shell electron is loosely bound. Hence I.E decreases. (B) Be and Mg have ns2 configuration (stable configuration) (C) It is due to lanthanide contraction (D) rmetallic > rcovalent (covalent bond formation involves the overlapping of orbitals)

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JMS 2 PAPER 1

SECTION-III (Total Marls : 15)

(Paragraph Type)

This section contains 2 paragraphs. Based upon one of paragraphs 2 multiple choice questions and based on the other paragraph 3 multiple choice questions have to be answered. Each of these questions has four choices (A), (B), (C) and (D) out of which ONLY ONE is correct. Paragraph for Question Nos. 12 and 13 Aqueous solution of A H SO 2 4 White precipitate soluble in ammonium acetate D
Further, aqueous solution of A
K Cr O 2 2 7

White precipitate soluble in excess of NaOH B H O 2 2 Brown precipitate C

.

white precipitate soluble in NH3.

HCl / H S 2

Yellow ppt Black ppt insoluble in NaOH

12.

Sol.

The complex B , which is soluble in excess of NaOH is (A) Na[Cu(OH)4] (B) Na2[Pb(OH)4] (C) Bi(OH)3 (D) Na2SnO2 (B) PbCl + 2 NaOH Pb ( OH )2 +2 NaCl 2 white (A)

Pb ( OH )2 + 2NaOH Na 2 Pb ( OH )4 B) (
13. Aqueous solution of A on treatment with HCl / H2S gives a black ppt. Thus which of the cationic species must not be present in compound A. (A) Hg2+ B) Pb+2 C) Cd2+ D) Bi3+ (C) HgS, PbS and Bi2S3 are black in color whereas CdS is yellow.

Sol.

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JMS 2 PAPER 1

Paragraph for Question Nos. 14 to 16 Benzoic aicd, phenol, toluene and aniline were dissolved in dichloromethane . The solution was then treated with 10% aq.HCl. After that, aqueous layer was collected in container I. Oily layer was further treated with 10% aq NaOH. This time aqueous layer was collected in container II and oily layer was collected in container III. Container I contains
OH

14.

(A)

(B)
NH2

(C) Both A and B Sol. 15. (D) Compound present in container II is

COOH

(D)

OH

(A)

(B)
NH2

(C) Both A and B Sol. 16. (C) Compound present in container III is
NH2

(D)

COOH

(A)
OH

(B)
CH3

(C)

(D)

Sol.

(D)

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JMS 2 PAPER 1
Solutions for Q. No 14 , 15 and 16.

SECTION-IV (Total Marks : 28)

(Integer Answer Type)

This section contains 7 questions. The answer to each of the questions is a single digit integer, ranging from 0 to 9. The bubble corresponding to the correct is to be darkened in the ORS.

17.

Among the following the total number of species which give two more than two types of acids on addition of water is NO2 , N2O, ClO2, NO, Cl2O6, P4O6, P4O10, Cl2.

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JMS 2 PAPER 1
2NO2 + H 2O HNO2 + HNO3 2ClO2 + H 2O HClO2 + HClO3 2ClO3 + H 2O HClO3 + HClO4 Cl2 + H 2O HCl + HClO 18. 20% surface sites are occupied by N2 molecules. Number of surface sites per unit area is 6.023 1014 cm2 and total area of catalyst surface is 1000 cm2 . When catalyst is heated to 300K N2 gas is desorbed and evolved gas occupied, 2.46 cm3 at 0.001 atm. Find the no. of sites ocupied by each molecule of N2. Sol : (2) Total no. of surface sites = 1000 6.023 1014 = 6.023 1017 Total no. of sites occupied = 0.2 6.023 1017 = 2 6.023 1016 No of moles of nitrogen desorbed = n =

0.001x 2.46 x103 0.082 x300

So, no. of nitrogen molecules =

2.46 x106 6.023 1023 = 6.023 1016 24.6 2 x6.023x1016 6.023x1016

no. of sites per molecule of N2 = = 2.

19.

Total number of structural and stereoisomers obtained from monochlorination of methyl cyclohexane is

Sol : (7)

CH Cl 2

CH

CH

CH

CH 3

Cl Cl Cl
(achiral) (achiral) chiral (a pair) chiral (a pair)

Cl

(achiral)

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JMS 2 PAPER 1
20. Sol. In case of [Cu(NH 3 ) 4 ] , 4p subshell contains ----------- unpaired e (1)
2+

` [Cu(NH 3 ) 4 ] NH 3 is a strong field ligand.

2+

21.

10 g of mixture of hexane and ethanol are allowed to react with sodium to give 214.2 mL hydrogen at 27 0C and 760 mm pressure. The percentage of ethanol in the mixture is (8) The given mixture (hexane + ethanol) weighs 10 g. The mixture reacts with Na to give 214.2 mL hydrogen at 27 0C and 760 mm pressure. Only ethanol liberates hydrogen upon reaction with Na and thus,
C2 H 5OH + Na C2 H 5O Na + + 1 / 2 H 2

Sol.

No. of moles of H2 formed PV 1 214.2 = = = 8.69 103 moles RT 1000 0.0821 300 1/2 mole of H2 is formed from 46 g of ethanol
8.69 103 moles are formed from

46 8.69 103 = 0.8 g of C2H5OH. 1/ 2 0.8 100 = 8% of ethanol in mixture = 10

22 Sol.

The number of OH groups in the product obtained by reacting 3-methylbutane-1, 3-diol with TsCl followed by NaBH4 is (1) CH 3 TsCl CH C CH CH OH 3 2 2

OH
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JMS 2 PAPER 1
CH CH 3
4

CH C CH CH BH 3 2 3 CH C CH CH OTs 3 2 2 OH OH Sterically hindered OH group does not react with TsCl.

23. A small piece of white phosphorus was reacted with excess Cl2 gas to yield 68.75 grams of phosphorus trichloride. No of discrete P4 molecules in the sample is (X.Y x 1022) . X is (7) P4 + 6Cl2 4 PCl3 68.75 1 1 1 mole PCl3 = mole PCl3 = moles P4 137.5 2 4 2 1 Number of P4 molecules = 6.023 1023 = 0.75 1023 8

Sol:

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