JMS 4 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 4 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. Correct acidic strength order of the following is
COOH
COOH Cl

COOH CH3

COOH OMe

(A) 3 > 2 > 4 > 1 Sol. (C)

(B) 4 > 2 > 1 > 3

(C) 2 > 3 > 4 > 1

(D) 2 > 1 > 3 > 4

. Except NH2, almost all osubtituted benzoic acids are strong than benzoic acid due to ORTHO EFFECT. Reason : Benzoic acid is resonance hybrid. Carbonyl gp is coplanar with the ring. Ortho subtituent tends to prevent this coplanarity. Therefore, resonance is prevented. So, the O atom of OH group has greater +ve charge resulting in increased acidic strength. 2. Match the following ListI List II (Sol) (Nature) 1) Starch sol P) Lyophilic 2) Gold sol Q) Lyophobic 3) Sulphur R) Multimolecular 4) Natural Rubber S) Macromolecular T) Negatively charged A) 1 - P,T; 2 - R,T; 3 - Q; 4 - S,T B) 1 - P,S,T; 2 - Q,R,T; 3 - R; 4 - P,T C) 1 - S,T; 2 - Q,T; 3 - R; 4 - P,T D) 1 - P,Q,T; 2 - S,R,T; 3 - P,S; 4 - P,T http://www.chemistrycrest.com/ Page 2

JMS 4 PAPER 1
Sol. (B)

Lyophilic :Lyophilic means liquid-loving Eg : gum, gelatine, starch, Rubber in a suitable liquid Lyophobic : Lyophobic means liquid-hating. Eg : metals ( Gold sol) , their sulphides, etc., Multimolecular :On dissolution of a substance, large number of atoms or smaller molecules aggregate together to form species having size in the colloidal range , forming multimolecular colloids. Eg : Gold sol , Sulphur sol Macromolecular : Macromolecules in suitable solvents form solutions in which the size of the macromolecules is in the colloidal range, forming macromolecular colloids. Ex : starch, cellulose, proteins, enzymes ,polythene,nylon, polystyrene, synthetic rubber, etc. Negatively charged : Metals, e.g., copper, silver, gold sols. Metallic sulphides, e.g., As2S3,Sb2S3, CdS sols. Acid dye stuffs, e.g., eosin,congo red sols. Sols of starch, gum, gelatin,clay, charcoal, etc. 3. Compound (A), C5 H10O4 is oxidized by Br2 H 2O to the acid, C5 H10O5 which readily forms a lactone. (A) forms a triacetate with Ac2O and a hydrazone with PhNHNH 2 . A is oxidized by HIO4 when only one molecule of it is consumed. The structure of A is
CHO (CHOH)3 CH2OH

A)

B) CH 2OH
CO

( CHOH )2
CHO

C)
H

CHO C C OH O OH

D)

CH 2OH
HOH 2C CH CH ( OH ) CHO

CH 2OH
Sol. (D) A forms a hydrazone with PhNHNH 2 . So, it may be an aldehyde or ketone A is oxidized by Br2 H 2O to acid which forms a lctone , So it must be an aldehyde A forms a triacetate. So, it must have three OH groups A is oxidized by HIO4 when only one molecule of it is consumed. So it must contain either two OH groups on adjacent carbons or OH or NH2 and carbonyl group So, It must be D because, it has one OH and CHO on adjacent carbons.Remaining have more than One such arrangements

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JMS 4 PAPER 1
4. To 500 ml of 2 M impure H2SO4 sample, NaOH solution 1 M was slowly added & the following plot was obtained. The percentage purity of H2SO4 sample and slope of the curve respectively are
(mol of H + )
1.5 1.0 0.5 vol. of NaOH added (L)

A) 50%, C) 75%, 1 Sol. (C)

1 3

1 3 D) none of these

B) 75%,

500 = 1 , then Mole of H+ = 1 x 2 = 2 1000 But, given mole of H+ = 1.5 1.5 Therefore, % purity = x100 = 75% 2 Required mole of OH- = mole of H+ = 1.5 mole n 1.5 Therefore, vol of NaOH = = = 1.5lit M 1 Slope = tan 1350 = - 1 Mole of H2SO4 = 2 x

5. IP/EA ratio for bromine is in kJ/mol is,

A) 81 B) 93

10 3

. Its electronegativety is 2.8. Its electron affinity on Mullikens scale

C) 162

D) 351

Sol.

(D)
10 EA 3 IP + EA = EN 544 10 EA + EA 3 = EN 544 13 EA 3 = 2.8 544 EA = 351.5

IP =

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JMS 4 PAPER 1

6.

NaOD / D O 2

(A)

(B)

(C)
Sol. (D) It is cannizzaro reaction

(D)

O
Ph CH OD + Ph C O 2

7.

Match the following ColumnI A) Wurtzite structure B)Zinc Blende Structure C)Antifluorite structure D)Rocksalt structure

Column II P) Anions occupy F.C.C lattice Q) Closest packed structure R) Anions occupy HCP lattice S) Cations occupy half/alternate tetrahedral voids

A) B) C) D)
Sol.

A-R,S; B-P, R,S; C-S; D-P, A-Q,R,S; B-P,Q,S; C-P,Q; D-P,Q A-Q, B-P; C-S; D-R A-P,Q,S; B-R,; C-S; D-P,
(B)

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JMS 4 PAPER 1
Wurtzite type structure: Eg: ZnS S -2 occupy lattice points of HCP

Zn +2 occupy half ( or ) alternate TV's

Zinc blende (or) Sphalerite type Eg: ZnS S 2 occupy lattice points of FCC Zn +2 occupy half (or) alternative TVS Anti fluorite type structure: Eg: Na2O Na + all TVs
O-2 lattice points of FCC

Rock salt type structure Eg: NaCl Cl- occupy lattice points of FCC Na + occupy all OVs 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 statements are true. A) The ratio of the velocity of electron in first three Bohr orbits of hydrogen atom is 2:3:6 respectively B) The ratio of magnitude of Total Energy:Kinetic Energy:Potential Energy for any orbit is 1:1:2 C) The wavelength of a green light is 500 nm, then its frequency is 6 x 1014 Hz D) The ratio of de-broglie wavelength of a H atom, He atom and CH4 molecule moving with equal kinetic energy is 4:2:1 Sol. (B, C, D)
A) False z v n
1 1 v1 : v2 ; v3 = 1: : = 6 : 3 : 2 2 3

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JMS 4 PAPER 1
B)

Potential Energy = Kinetic Energy =

ze2 r

ze2 2r ze 2 Total Energy = 2r 1 1 TE : KE : PE = : :1 = 1:1: 2 2 2

C)
C 3 x108 = = = 0.5 x106 = 500 x109 m = 500nm 14 6 x10

D)
= h 2.m.KE 1 1 1 1 1 : : = 1: : = 4 : 2 :1 2 4 1 4 16

H : He : CH 4 =

9.

Among the following orbital interactions, those which represents hyper conjuction interaction.

A)

B)

C)

D)

Sol.

(A, B)
A has ( C), positive charge conjugation B has odd e conjugation

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JMS 4 PAPER 1
10. Which of the following is true about the complex [PtCl2(NH3)(OH2)] ; [Atomic no. of Pt = 78] (i) It will have two geometrical isomeric forms, cis and trans (ii) The hybridisation state of Pt(II) is sp3 (iii) It is a square planar complex (iv) It is a diamagnetic complex (v) It can show hydrate isomerism (vi) It is a tetrahedral complex (A) (i), (iii) (B) (ii),(v) (C) (ii),(vi) (D)(iv) Sol. (A, D) [PtCl2(NH3)(OH2)] shows geometrical isomerism ( Ma2bc type) Pt (II) is 5d8. It forms square planar complex which is diamagnetic The polarimeter readings in an experiment to measure the rate of inversion of cane sugar (1st order reaction) were as follows time (min) : 0 30 angle (degree) : 30 20 15 Identify the true statement (s) log 2 = 0.3, log 3 = 0.48, log 7 = 0.84 The half life of the reaction is 82.7 min The solution is optically inactive at 131 min. The equimolar mixture of the products is dextrorotatory The angle would be 7.5 at half time (A,B, D) 0 30 30 20 15 r r a = 0 ax r r t Half life of the reaction :
k=
=

11.

(A) (B) (C) (D) Sol.

30 ( 15 ) 2.303 log 30 20 ( 15 )

2.0303 45 log = 0.008377 min 1 30 35 0.693 t1/2 = = 82.7 min 0.008377

The solution will be optically inactive ( r = 0 ) :

2.303 45 log t 0 ( 15 ) t = 131.1 min 0.008377 =

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JMS 4 PAPER 1
The angle at half time :

30 ( 15 ) a = = 2 at half time x + 15 aa/2 45 45 = 2 x + 15 = x + 15 2 0 x = 22.5 15 = 7.5 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 A chemist opened a cupboard to find four bottles containing water solutions, each of which had lost its label. Bottles 1, 2, 3 contained colourless solutions, while bottle 4 contained a blue solution. The labels from the bottles were lying scattered in the floor of the cupboard. They were : Copper (II) sulphate, Hydrochloric acid Lead nitrate, Sodium carbonate By mixing samples of the contents of the bottles, in pairs, the chemist made the following observations. Bottle 1 + Bottle 2 White precipitate Bottle 1 + Bottle 3 White precipitate Bottle 1 + Bottle 4 White precipitate Bottle 2 + Bottle 3 Colourless gas evolved Bottle 2 + Bottle 4 No visible reaction Bottle 3 + Bottle 4 Blue precipitate 12. Bottle 3 contains (A) copper (II) sulphate (C) lead nitrate (D) When bottle 1 is mixed with bottle 4, white precipitate is observed, which is (A) PbSO4 (B) PbCO3 (C) PbCl2 (D) Pb(NO3)2 (A) Solutions for Q No 12 to 13 : 12.
Bottle 2 + bottle 3 colourless gas (carbon dioxide) sodium carbonate + acid It suggests that bottle 2 and 3 contain sodium carbonate and HCl.

(B) hydrochloric acid (D) sodium carbonate

Sol. 13.

Sol.

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JMS 4 PAPER 1
Bottle 3 + 4 blue precipitate. It confirms Cu2+ in either of the bottles , considering available sulphate, chloride, nitrate and carbonate. So, the precipitate must be carbonate, Hence, 3 carbonate (sodium carbonate) 4 Cu2+ 2 HCl Left out , 1 - Pb(NO3)2 13. Pb(NO3)2 + Cu SO4 Cu(NO3)2 + PbSO4 Soluble white ppt. Bottle 1 Bottle4 Paragraph for Question Nos. 14 to 16 A is a hydrocarbon with molecular formula C6H10. It reacts with Br2 to give B. With Zn/ethanol B gives A and with alcoholic KOH, B gives C. C, A differ from each other with respect to sites of unsaturation. 14. (A)
CH CH 3

Compound A maybe (B)

(C)

(D)

CH = CH CH CH CH = CH 2 2 2 2
CH 2

Sol. 15.

(B) Which of the following gives a dialdehyde on ozonolysis? (A) only A (B) A and B (C) Only C (D) A and C (D)

Sol.

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JMS 4 PAPER 1
16. Which of the following reactions cannot generate either A or B or C? (A) (B)

H+ OH

CH

H+ OH 2

(C)

OH

P Br 2 OH
Sol. (D) Solutions for Q No 14 to 16 : 14.

(D)

H+ OH

Br 2 (A) Zn ethanol
15.

Br

KOH
alcohol

(B)

Br

(C)

Being cyclo alkenes, both A and C give dialdehydes on ozonolysis, which involves replacement of c = c by two c = o groups. Option (A) :

16.

H+ OH
Option (B) :
CH 2

(C)

OH

H+
(A)

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JMS 4 PAPER 1
Option (C) :

OH

Br Br

P Br 2 OH
Option (D) :

(B)

Not possible because a carbocation is never formed at the vinylic carbon , unless otherwise the leaving group is a super leaving group, - OTf. 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. (No of POP bonds in P4O6) + (No of BOB bonds in borax) (No of SOS bonds in form of SO3) is (8) No of POP bonds in P4O6 = 6

Sol.

No of BOB bonds in borax = 5

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JMS 4 PAPER 1
No of SOS bonds in form of SO3 ( S3O9) = 3

Therefore, it is 6 + 5 3 = 8 18. The total number of optically active alkynes having molecular formula C3FClBrI is Sol. (8)

19.

Among the following diazonium salts, those less reactive than (I) towards coupling reaction are

Sol.

(3)

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JMS 4 PAPER 1
Diazo coupling : Arene diazonium ions are weak electrophiles. They react with highly reactive aromatic compounds i.e., with phenols, & 30 amines to yield azo compounds.This electrophilic aromatic substitution reaction is called Diazo coupling reaction.

+I groups decrease the reactivity of a diazonium cation towards coupling as they decrease electrophilicity -I groups increase the reactivity of a diazonium cation towards coupling as they increase electrophilicity III has no group whereas V and VI have +I groups.Remaining have I groups. 20. No of metals that can be extracted by carbon reduction method is Na, Al, Mg, Sn, Fe, Pb, Zn, Ca (4) The metals which are less electro positive and do not form carbides with carbon are reduced by carbon reduction method Eg : oxides of Sn, Fe, Pb, Zn Ores of Na, Al, Mg, Ca are reduced by electrolytic reduction as their reduction by carbon needs very high temperature and at such high temperature, formation of carbides may occur. 3000 ml sample of H2O2 has 5.6 volume strength. If this sample liberates 5.6 litre of O2 at 1 atm & 273 K, then molarity of resultant H2O2 solutio is 1/x . x is (Assuming no change in volume of H2O2 solution) Sol. (3) Volume strength of H2O2 = 5.6 So, volume of O2 liberated by 3 lit of this is 3 x 5.6 lit Strength of it remaining after liberation of 5.6 lit of O2 = 3 x 5.6 5.6 = 2 x 5.6 Vol of O2 liberated at STP = Vol strength of H2O2 x Vol of H2O2 solution 2 x5.6 New volume strength = 3 Volume strength = Molarity x 11.2 2 x5.6 1 So the molarity of new H 2 O 2 = 3 = M 11.2 3 http://www.chemistrycrest.com/ Page 14

Sol.

21.

JMS 4 PAPER 1
22. Bleaching powder reacts with iodide ion according to the following unbalnced equation OCI + I + H+ I2 + Cl + H2O A 0.6 g sample of bleaching powder requires 35.24 mL of 0.1084 M Na2S2O3 to titrate the liberated iodine. The percentage of Cl in the sample is nearly z. Sum of the digits of z is

Sol : (5) % of aUsing simplified formula, % of % of available Cl =

3.55 x0.1084 x35.24 = 23 0.6

23.

The number of tripeptides formed by three different amino acids are

Sol. (6) Since each amino acid has one N-terminal end and one C-terminal end, therefore, three different amino acids form 2 3 = 6 different tripeptides.
Let the three amino acids be 1 ,2 and 3 1 2 3, 2 3 1, 3 1 2, 3 2 1, 1 3 2, 2 1 3.

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