JMS 3 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 3 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. A current is passed through 2 voltameters connected in series. The first voltameter contains XSO4 (aq.) and second has Y2SO4. The relative atomic masses of X and Y are in the ratio of 2 : 1. The ratio of the mass of X liberated to that of Y liberated is (A) 1 : 1 (B) 1 : 2 (C) 2 : 1 (D) None of the above (A)

Sol.

m=

G.At.wt c t Valency 96500

Ax 2 mx Vx 1 = =2= Ay 1 1 my Vy 1
2. STATEMENT 1 : Sulphide ores are concentrated by froth floatation. STATEMENT 2 : Pine oil act as collector in froth floatation.

(A) Statement 1 is True, Statement 2 is True; Statement 2 is a correct explanation for Statement 1. (B) Statement 1 is True, Statement 2 is True; Statement 2 is NOT a correct explanation for Statement 1. (C) Statement 1 is True, Statement 2 is False. (D) Statement 1 is False, Statement 2 is True.
Sol. (B)

Froth floatation is used for removing gangue ( impurities ) from sulphide ores. In this process, a suspension of the powdered ore is made with water and to this collectors and froth stabilisers are added. Collectors (e. g., pine oils, fatty acids, xanthates) enhance non-wettability of the mineral particles Froth stabilizers (e. g., cresols, aniline) stabilise the froth.

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JMS 3 PAPER 1
3. Which of the following Corey-house synthesis will give poor yield ? (A)

CuLi
+ CH I 3

CH

2
(B)

(
(C)

3 CH CH CuLi+CH C Br 3 2 2 3 CH 3

CH

3 CH CH C CH 3 2 3 CH 3

CH

( CH3 )2 CuLi+CH3 Br

CH CH 3 3

(D)

( CH3 CH2 CH )2 CuLi+CH3 CH2 Br

H C 3

CH CH CH CH CH 3 3 2 3
CH 3

Sol :

(B) Corey-House synthesis proceeds through nucleophilic substitution bimolecular (SN2) mechanism. So, it gives best result with primary halide.Alkyl halide used in B is tertiary . So , it gives poor yield .

4.

Among the following, the one formed by condensation polymerization is (A) Teflon (B) Polystyrene (C) PVC (D) Dacron (D) Dacron ot Terylene is a condensation polymer. Teflon, Polystyrene and PVC are formed by addition polymerization Condensation polymers are formed by repeated condensation reaction between two different bifunctional or tri-functional monomeric units. In these polymerisation reactions, the elimination of small molecules such as water, alcohol, hydrogen chloride, etc. take place. Addition polymers are formed by the repeated addition of monomer molecules possessing double or triple bonds, Monomer of Teflon is Tetra fluoro ethylene, that of polystyrene is Ethenyl benzene or vinyl benzene That of PVC is vinyl chloride or Chloroethene and that of Dacron are Hexamethylene diamine and adipic acid

Sol.

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JMS 3 PAPER 1
5. The end product of the following reaction is

A
OHC

OH

B)
OHC

OH Cl

OH

D
Cl
OHC

OH Cl

OHC NH2

NC

NH2

CHO

Sol.

(D) Reimer-tiemann reaction as well as carbene addition

6.

ColumnI a) 3 CuO + 2NH3 b) PH4I + NaOH c) Ba(N3)2 d) 2H3PO2

Column II p) PH3 q) Metal r) H3PO4 s) Nitrogen t) H2O

A) a-s,t ; b-p,s ; c-q,s,t ; d-p,r B) a-q,t ; b-q,t ; c-p,q,s ; d-t,r C) a-q,s,t ; b-p,q,t ; c-p,s ; d-p,q,r D) a-q,s,t ; b-p,t ; c-q,s ; d-p,r Sol. (D) 3CuO + 2 NH 3 3Cu + N 2 + 3H 2O PH 4 I + KOH KI + PH 3 + H 2O
Ba ( N 3 )2 Ba + 3N 2
2H 3 PO2 H 3 PO4 + PH 3

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JMS 3 PAPER 1
7. Arrange following Amines for rate of reaction with CHCl3 + KOH (Hoffmann isocynide test)

NH2

NH2

NH2

NH2

(P)

CH3

(Q)

NO2

(R) (C) S > P > Q > R

(S) (D) S > Q > R > P

(A) S > P > R > Q Sol.

(B) Q > R > P > S

(A) Kb of amines Rate of reaction. (See the mechanism of carbyl amine reaction) Greater the kb , lesser the Pkb , greater is the basic nature Pkb values of given compounds S (3.36) P (8.88) R (9.42) Q (12.98) 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 form only one oxime on reaction with NH2OH solution.

(A) I Sol.

(B) II

(C) III

(D) IV

(B , C) I and IV give two oximes as the carbonyl group has different gro
O-H C = O+H NOH 2
H H

ups attached to it

C=N
H

C=N O-H

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JMS 3 PAPER 1
II and III give only one oxime as the carbonyl group has only one or same type of groups attached to it
O-H
+ H NOH 2

=N

9.

In the structure given below

H H H H C C = C C H

C H

(A) one carbon is in zero oxidation state (C) Two carbons are in 2 state Sol. (A,C,D)

(B) one c is in 4 state (D) Two carbons are in 1 state

Individual oxidation state = Actual valency No of e- belonging to it after bonding e- belong to more electronegative atom after bonding If difference in electronegativity is 0 , both the bonded atoms get equal share of bonded e-

10. From the following diagram, the potentials Eo1 and Eo2 are

A) 1.496 V

B)1.392 V

C)1.425 V

D) 1.532 V

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JMS 3 PAPER 1
Sol. (A,C) For E20 : BrO3 + 2 H 2O + 4e BrO + 4OH ; G10 BrO + H 2O + e 1 Br2 + 2OH ; G 20 2

1 Br2 + e Br ;G 30 2 BrO3 + 3H 2O + 6e Br + 6OH ; G 0

G 0 = G10 + G 2 0 + G 30 6FE 0 = [4 F(1.47)] + [1F(1.6)] + [1F(1.07)] 6 E 0 = 5.88 + 1.6 + 1.07 E 0 = 1.425V

For E10 :

BrO3 + 2 H 2O + 4e BrO + 4OH ; G10 BrO + H 2O + e 1 Br2 + 2OH 2 1 BrO3 + 3H 2O + 5e Br2 + 6OH ; G 0 2

G 0 = G10 + G 2 0 5FE 0 = [4F(1.47)] + [1F(1.6)] E 0 = 1.496V

11.

Which of the following reactions give product having two-D atoms at trans position?
(A)
CH
D D

3
Br Br

Zn alcohol

CH

(B) (C)

Na C H C C CH 2 5 3 liq. ND 3

CH COOD 3

(D)

D 2 C H C C CH 2 5 3 Lindlar catalyst

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JMS 3 PAPER 1
Sol. (A , B) I) Dehalogenation (E2) Trans Anti - Meso (TAM)
CH
D D

3
Br Br E2
anti-elimination

C= C
D

3 (meso)

CH

CH

(trans)

II) Birch reduction Anti addition

III) Syn addition

D D

. IV) Lindlars catalyst Syn addition

CH 3
C= C D
D

C H 2 5

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JMS 3 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 to 13 In qualitative analysis, III group includes Fe3+, Al3+ and Cr3+ . III group reagent is NH4OH in presence of NH4Cl. NH4Cl is added to suppress the ionisation of NH4OH so that only the III group radicals are precipitated as their insoluble hydroxide and not the IV and V group radicals as the solubility products of their hydroxides are much higher. Before adding group reagent to the filterate of II group, one drop of concentrated HNO3 (oxidising agent) is added and the contents are boiled for 2-3 minutes and then cooled because the solubility product of Fe(OH)2 is very high as compared to Fe(OH)3. When a light bluish green crystalline compound containing cations of IIIrd group and zero group is analysed, it responds to following tests /reactions. Its aqeous solution gives a reddish brown precipitate with alkaline solution of potassium tetraiodomercurate (II) Its aqueous solution after boiling with conc. HNO3 gives a reddish brown ppt. with sodium hydroxide. Solution of reddish brown ppt. in dil. HCl gives blood red colouration with ammonium sulphocyanide and prussian blue with potassium ferrocyanide. Its very dilute solution gives white ppt. with (CH3COO)2 Pb solution and white ppt. is only soluble in hot ammonium acetate.

(a) (b) (c) (d)

12. Identify the correct statement : A) NH4Cl is added along with NH4OH so that only III group cations can be precipitated as their hydroxides B) In place of NH4Cl, (NH4)2 SO4 can not be used, as barium ( V group radical) will also be precipitated as BaSO4 along with Al+3 , Fe+3 & Cr+3 C) Aqueous solution of ammonium sulphate also produces white ppt. with BaCl2 solution which is insoluble in conc. HCl. D) All of these Sol. (D) A) It is because , Ksp of hydroxides of Al+3 , Fe+3 & Cr+3 are low and NH4Cl suppresses the ionization of NH4OH B) ( NH 4 )2 SO4 + Ba 2+ BaSO4 ( white) + 2 NH 4 + C) SO4 2 + Ba 2+ BaSO4 ( white) http://www.chemistrycrest.com/ Page 9

JMS 3 PAPER 1
13 The reddish brown precipitate formed in (a) is of A) Mercury amido iodide B) Mercury iodide C) Oxydimercuric ammonium iodide D) Mercury amido iodide and mercury Sol. (C) 2 K 2 HgI 4 + NH 3 + 3KOH NH 2 Hg O Hg I + 7 KI + 2 H 2 0 NH 2 Hg O Hg I , Oxydimercuric ammonium iodide, Iodide of Millons base(Brown ppt) Paragraph for Question Nos. 14 to 16 One of the most important applications of chemical reactions is in the production of energy in the form of useful work. For example in combustion, the heat generated is used to create steam for production of mechanical work, or electrical work from a dry cell or storage battery. The quantity G is called free energy because G represents the maximum quantity of energy released in a process occuring at constant temperature and pressure that is free-or-available to perform useful work. G is a driving force in a chemical change that can be used to perform useful work. 14 . The e.m.f. of a certain cell varies as E = 0.4108 + 0.0032 T, where E is in volts and T is in Kelvin temperature. The H of the following cell reaction is nearly

2CeCl 4 + Zn (S ) 2CeCl3 + ZnCl 2 at 250 C

(A) -79 kJ (C) -49 kJ Sol. (A) G G = H T S ; G = H T T P
G G = H + T T P

(B) -59 kJ (D) -19 KJ

( nFE ) G = H + T T P

( nFE ) nFE = H + T T P ( E ) nFE = H nFT T P

E=

H E +T nF T P E = 0.4108 + 0.0032T
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JMS 3 PAPER 1
E = 0.0032 T P E = 0.4108 + 0.9536 = 1.3644
1.3644 = H + 300 0.0032 2 96500

H = 78.049 J

15.

The enthalpy change of a reaction at 27 C is 15KJ/mole. The reaction is feasible if the entropy change is (A) 15 J mole-1 K-1 (B) - 50 J mole-1 K-1 -1 -1 (D) lesser than 50 J K-1 mole-1 (C) greater than 50 JK moles (C)
G = H T S ; G = 15 KJ 300S

Sol.

If S is > 50 J K-1 mole 1 , then G is ve; So process is feasible

16

The change in free energy observed when four moles of N2 and one mole of O2 (assumed to behave as ideal gases) are mixed at 298K and constant pressure is nearly A) - 6.2 KJ B) 6.2 KJ C) - 3.1 KJ D) 3.1 KJ (A)
S mix = 2.303R n log X i i

Sol.

= 8.314 2.3 ( 4 log 0.8 + log 0.2 ) J K 1

= 20.8JK 1

G = H T S ; mix mix mix for ideal solution, H

G = 298 20.8 mix = - 6198.4 - 6200 J = - 6.2 KJ
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mix

=0

JMS 3 PAPER 1
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. The plot of log (V V) versus t (where V is the volume of nitrogen collected under constant temperature and pressure conditions) for the decomposition of C 6 H 5 N 2 Cl is given at 50C with an amount of C 6 H 5 N 2 Cl equivalent to 58.3 cc N 2 .
1.75 log(V V) 1.0 5 10 15 20 25 30 time(min.)

Rate constant for the reaction in hr 1 in a single significant digit is Sol.

y2 y1 x2 x1 1.75 1.0 slope = 25 0 = 0.03 k = 2.303 (slope) min 1 = 2.303 ( 0.03) min 1 = 0.06909 min 1 = 4.14 hr 1 4 hr 1 slope =

(4)

18.

Total number of DBE present in the product obtained when cyclohexanone reacts with 2,4-DNP is (8) The product is

Sol.

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JMS 3 PAPER 1
C H N O 12 14 4 4

The general formula to calculate DBE of a compound is CaHbNcOd

bc Then DBE = a + 1 2 a = 12, b = 14, c = 14, d = 4

10 14 4 DBE = 12 + 1 = 13 = 13 5 2 2 DBE = 8

19.

Amongst the following the total number of compounds which show positive test towards tollens reagent are Glucose , Fructose , Formaldehyde , Acetaldehyde , Formic acid , Acetic acid (5)
Glucose , Fructose , Formaldehyde , Acetaldehyde , Formic acid give positive test towards tollens test.

Sol.

20.

The structure of B3N3H6 is as follows

H H N H B N H B N B H H

How many derivatives of B3N3H4X2 can be derived from the basic structure, by the replacement of two hydrogen atoms? Sol. (4)
Replacing any two hydrogen atoms of B3N3H6 , 4 derivatives can be obtained

21.

The number of total carbon atoms in the little amount of ester formed during the Kolbes electrolysis of sodium propanoate is (5)
Kolbes electrolysis occurs via free radical mechanism

Sol.

O
Free radicals CH CH C O and CH CH combine to give ester as the side product.

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JMS 3 PAPER 1
22 No of species that contain N = N structural unit in their structures in the following N 2 , N 2O, HN3 , N 2 H 2 , N 2 H 4 , N 2O4 , N 2O5 , H 2 N 2O2 (4)
N 2O, HN3 , N 2 H 2 , H 2 N 2O2 contain N = N bonds.

Sol.

Hydrazoic acid Nitrous oxide

Diazene

Hyponitrous acid

23.

0.5 mole of Borax and 0.2 mole of Boric acid are mixed in 250 ml of water. pH of the solution formed is x. Now the solution is diluted to 1 lit. pH of diluted solution is y. The value of x + y is y ( Ka of boric acid is 2.5 10 ) (consider borax remains normal)
5

Sol :

(6)
pH of an acidic buffer, Boric acid and its salt with strong base,NaOH i.e., borax is

pH = p ka + log

[salt] [acid]
0.5 0.2

pH = (5 log 2.5) + log =5= x

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JMS 3 PAPER 1
On dilution, pH of buffer does not change So, y = 5

x 5 + y = +5 = 6 y 5

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