JMS 4 PAPER - 2

PAPER-2
Maximum Marks: 80

Question paper format and Marking scheme: 1. In Section I (Total Marks: 24), 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: 24), 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. 4. In Section IV (Total Marks: 16), for each question you will be awarded 2 marks for each row in which you have darken ALL the bubble(s) corresponding to the correct answer(s) ONLY and zero marks otherwise. Thus each question in this section carries a maximum of 8 Marks. There are no negative marks in this section. http://www.chemistrycrest.com/ Page 1

JMS 4 PAPER - 2
SECTION I (Total Marks : 24) (Single Correct Answer Type) This Section contains 8 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out of which ONLY ONE is correct. H H | | 1. H for the reaction H C N ( g ) +2H 2 ( g ) H C N H (g) is 150 KJ | H Calculate the bond energy of C N bond. [Given bond energies of C H = 416 KJ mol1;
H H = 436 KJ mol1; C N = 293 KJ mol1; N H = 369 KJ mol1] A) 762 KJ mole1 B) 481 KJ mole1 C) 841 KJ mole1 D) 741 KJ mole1

Sol.

(C)
H H | | H C N ( g ) +2H 2 ( g ) H C N H | H H = [ BE (C H ) + BE (C N ) + 2 BE ( H H )] [ 3BE (C H ) + BE (C N ) + 2 BE ( N H )]

150 = [ 416 + BE (C N ) + 2(436)] [3(416) + 293 + 2(369) ] 150 = 416 + BE (C N ) + 872 2279 150 = BE (C N ) 991 BE (C N ) = 150 + 991 = 841kj / mol
2. Given are two reactions:
CH3OH CH I Rate constant k1 Nu 3 DMF CH I Rate constant k 2 Nu 3

The difference in the value of k1 and k2 is highest when Nu is

(A) Cl
Sol.

(B) Br

(C) NCS

(D) CH 3 S

(A) In DMF, none of these nuclephiles get solvated. But in CH3OH, the negative nuclephiles get solvated. Cl being the smallest, is solvated to the maximum extent. Therefore, in CH3OH , it is the poorest nucleophile. So, the difference between k1 and k2 is highest. Page 2

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JMS 4 PAPER - 2

3.

ColumnI Column II A A) Borax P) BN Q) B2H6 B) B2H6 + H2O C) B2H6 + NH3 R) H3BO3 D) BCl3 + LiAlH4 S) NaBO2 + B2O3 A) A-R; B-S; C-P; D-Q C) A-S; B-R; C-P; D-Q B) A-Q; B-R; C-P; D-S D) A-S; B-P; C-R; D-Q

Sol.

(A)
60 c Na2 B4O7 10 H 2O Na2 B4O7 5 H 2O Na2 B4O7 2 NaBO2 + B2O3 , Glassy mass (Borax bead test)
0

high 'T ' B2 H 6 + ' excess ' NH 3 ( BN ) x (Boron nitride)

B2 H 6 + 6 H 2O 2 H 3 BO3 + 6 H 2 BCl3 + 3LiAlH 4 2 B2 H 6 + 3 AlCl3 + 3LiCl 4. Statement-1 : HIO4 decomposes . 1, 2 glycols but not 1,3 or higher glycols Statement 2 : Only 1, 2 glycol forms cyclic esters which subsequently undergo clevage to form carbonyl compound. (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 (A) Periodic acid cleavage of a 1,2 - glycol involves a cyclic periodate intermediate which involves the following mechanism. It is not possible with 1,3 or higher glycols

Sol.

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JMS 4 PAPER - 2
5. Match the following ColumnI (Organic comp.) A) Column II (Test responded)

NH CH 3

P) Hinsberg test B)
NH 2

CH 2 OH

Q) Victor Meyer test

C)

NH CH 3

CH 2 OH
D)
H 3C N CH 3

R) Yellow oily layer with, NaNO2 + HCl

CH 2 CHO

S) Silver mirror test A) A-P,Q; B-P,R; C-P,Q,S; D-Q,S B) A-P,R; B-P,Q; C-P,Q,R; D-S C) A-P,R,S; B-P,Q; C-P,Q,R,S; D-S D) A-P,Q,S; B-P,Q; C-Q,R; D-P,Q Sol. (B) A is a sec amine B is a pri amine and it also has OH group C is a sec amine and it also has OH group D is a ter amine and it also has an aldehyde group

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JMS 4 PAPER - 2
6. S1 : The graphite is diamagnetic and diamond is paramagnetic in nature. S2 : Graphite acts as a metallic conductor along the layers of carbon atoms and as semi-conductor perpendicular to the layers of the carbon atoms. S3 : Graphite is less denser than diamond S4 : C60 is called as Buckminster fullerene (A) F T T T (B) T F T T (C) F F T T (D) F T T T (A) Both graphite and diamond are diamagnetic. Indicate the correct stereochemical relationship amongst the following monosacharides

Sol.

7.

I) A) B) C) D)

II)

III)

IV)

I and II are anomers; III and IV are epimers I and III are epimers; II and IV are anomers I and II are epimers; III and IV are anomers I and III are anomers; I and II are epimers Sol : (D)

Anomers differ in stereochemistry at 1st carbon. (anomeric carbon) I and III have difference stereochemistry at 1st carbon.So, they are anomers Epimers differ in stereochemistry at carbon other than 1st I and III and II have difference in stereochemistry at 4th carbon. So they are C - 4 epimers.

8.

Match the following I Bauxite II Carnallite III Malachite IV Galena (A) I a, II b, III c, IV d (C) I b, II a, III d, IV c

(a) Lead (b) Copper (c) Magnesium (d) Halls Process (B) I d, II c, III b, IV a (D) I d, II b, III c, IV a

Sol.

(B) Page 5

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JMS 4 PAPER - 2
Bauxite is Al2O3 .2H20.It is of two types. Red bauxite which contains Iron oxide impurities,purified by Baeyers and Halls process and the other one is white bauxite which contains SiO2 impurities, purified by serpeck process Carnallite contains Mg.It is KCl MgCl26H2O Malachite is CuCO3. Cu(OH)2 Galena contains lead.It is PbS SECTION II (Total Marks : 16)
(Multiple Correct Answer(s) 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. 9. Figure displays the plot of the compressibility factor Z verses p for a few gases
IV I III II

Which of the following statements is/are correct for a vander waals gas ? A) The plot I is applicable provided the vander waals constant a is negligible. B) The plot II is applicable provided the vander waals constant b is negligible. C) The plot III is applicable provided the vander waals constants a and b are negligible. D) The plot IV is applicable provided the temperature of the gas is much higher than its critical temperature. Sol. (A, B, C) I shows positive deviation from ideal behavior. So, a is negligible II shows negative deviation from ideal behavior, So, b is negligible III shows ideal behavior. So a and b are negligible Which of the following molecule/s gives only acids on hydrolysis A) PCl3 B) SF4 C)NCl3 (A, B, C, D) PCl3 + 3H 2 0 H 3 PO3 + 3HCl SF4 + 2 H 2 0 SO2 + 4 HF NCl3 + 6 H 2 0 NH 3 + 3HOCl P4O6 + 6 H 2 0 4 H 3 PO3 http://www.chemistrycrest.com/ Page 6

10.

D) P4O6

Sol.

JMS 4 PAPER - 2
11. Given log3 = 0.4771, log2 = 0.3010. To measure the activity of a given radioactive sample, a count rate meter is used. Two recordings separated in time by 1 minute show a count rate ratio of 2.25. The decay constant (min1) of the sample is : (A) 0.83 min1 (B) equal to its t1/2 numerically in min. (D) varying with time (C) 1 min1 (A, B) 1 initial rate k = 2.303 log t final rate 1 k = 2.303 log 2.25 = 2.303 x log(1.5)2 1 = 2 x 2.303 x log1.5 = 0.83 min1 0.693 t1/2 = = 0.83 min 0.83 Identify the set in which product formed is reactant is 1-tert-butyl cyclohexene. correctly matched with given reagent. The

Sol.

12.

Sol. A) B) C) D)

(A, B, C) Syn addition. But, equitorial is more stable with bulky - C(CH3)3. Anti addition Anti addition Syn addition. So, T should be equatorial (axial given) Cis : Both either upper or lower Trans :One upper and one lower Page 7

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JMS 4 PAPER - 2
SECTION-III (Total Marks : 24) (Integer Answer Type) This section contains 6 questions. The answer to each of the questions is a single-digit integer, ranging from 0 to 9. The bubble corresponding to the correct answer is to be darkened in the ORS. 13. pH of 6.66 x 104 M solution of Al(OH)3 is xy . x + y is... Given the first dissociation of Al(OH)3 is complete, second dissociation is 50% and third is insignificant Sol. (2)

+ Al ( OH )3 Al ( OH )2 + OH (Complete dissociation) 6.66 104 M 6.66 104 M

Al ( OH )+ Al ( OH )2 + + OH 2 6.66 104 M

(50% dissociation)

3.33 104 M

Total OH = 6.66 104 + 3.33 104 = 103 pOH = 3; pH = 11

14. Sol. 0.5g of fuming H2SO4(oleum) is diluted with water. This solution is completely neutralized by 26.7 ml of 0.4 N NaOH. The percentage of free SO3 in the sample is nearly Z X 4. z is (5) No of eq of H2SO4 = no of eq of NaOH 26.7 = 0.4 x = 0.01068 1000 Wt of H2SO4 = 0.01068 x 49 = 0.52332 Wt of H2O added = 0.52332 0.5 = 0.02332 H2O + SO3 H2SO4 18 80 0.02332 ? = 0.1036 0.1036 Therefore % of free SO3 = x100 = 20.72 0.5 Page 8

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JMS 4 PAPER - 2

15.

For an ionic compound AX3(s) formed between a metal A and a non-metal X (outermost shell configuration of X = ns2np5). Unit place of enthalpy of formation (magnitude) of AX3(s) in k cal mol1 using following data. (Non-metal X is found to exist in nature as a diatomic gas)
H sublimation
IE1

A(s) = 100 Kcal/mol

A(g) = 60 Kcal/mol

IE 2

A(g) = 150 Kcal/mol

IE3

A(g) = 280 Kcal/mol

Hdiss X2(g) = 80 Kcal/mol He.g X(g) = 110 Kcal/mol HLattice energy A X3(s) = 470 Kcal/mol

Sol.

(0)

For the ionic compound AX3 (s) 3 A( s ) + X 2( g ) AX 3( s ) 2

3 f H = H sub + (H IE1 + H IE 2 + H IE 3 ) + H diss + 3H e. g + H LE 2 3 = 100 + (60 + 150 + 280) + (80) + 3(110) 470 2 = 90

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JMS 4 PAPER - 2
16. Electrolysis of a solution of MnSO4 in aqueous sulphuric acid is a method for the preparation of MnO2. Passing a current of 27A for 24 hours gives 1 kg of MnO2. The current efficiency is n. The unit place value of n is (5)

Sol.

1000 =

87 cx 24 x60 x60 x 2 96500 c = 25.67 amp

25.67 x100 = 95% 27

Therefore current efficiency =

17.

Decomposition of A follows first order kinetics by the following equation.

B(g) + 2C(g) 4A(g) If initially, total pressure was 800 mm of Hg and after 10 minutes it is found to be 650 mm of Hg. What is half-life of A in min ? (Assume only A is present initially)

Sol.

(5)
B(g) 4A(g) 800 800 4p p

t=0 t = 10 min

2C(g) 2p

800 4p + p + 2p = 800 - p = 650 p = 150 Pressure of A = 800 -4 x 150 =200, So, 2 x t1/2 = 10 minutes t1/2 = 5 minutes

18.

Among K2CO3, MgCO3, CaCO3, BeCO3, Na2CO3, BaCO3, SrCO3, the no of carbonates,those more thermally stable than MgCO3 are (5)
Na2CO3, K2CO3 ,CaCO3, SrCO3 ,BaCO3, Thermal stability of alkaline earth metal cabonates increases down the group. So CaCO3, SrCO3 and BaCO3 are more stable than MgCO3 Thermal stability of alkali metal cabonates increases down the group.

Sol.

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JMS 4 PAPER - 2
SECTION-IV (Total Marks : 16) (Matrix-Match Type) This section contains 2 questions. Each question has four statements (A, B, C and D) given in Column I and five statements (p, q, r, s and t) in Column II. Any given statement in Column I can have correct matching with ONE or MORE statement(s) given in Column II. For example, if for a given question, statement B matches with the statements given q and r, then for the particular question, against statement B, darken the bubbles corresponding to q and r in the ORS. 19. Match the reactions mentioned in Column-I with the nature of the reaction/characteristic(s) of the products mentioned in Column-II Column I (A) Column II
strongly heated

H3PO 2
i)H 2 O PCl3 ii)

(p) One of the products is a reductant (q) One of the products is tribasic (r)
(s) (t)

(B) (C) (D)

NO 2 + H 2 O
HNO3 + P4 O10

Dehydration
One of the products has central atom in +5 oxidation state Disproportionation

Sol :

(A p, q,s, t; B p, q,s, t;C p,s, t; D r,s)

A) 3H 3PO2 2H3PO3 + PH3 4H3PO3 3H 3PO 4 + PH3 B) PCl3 + 3H 2O H3PO3 + 3HCl 4H3PO3 3H 3PO 4 + PH3 C) 2NO 2 + H 2O HNO2 + HNO3 D) 4HNO3 + P4O10 4HPO3 + 2N 2 O5

Note : Substance in highest oxidation state acts only as oxidant Substance in lowest oxidation state acts only as reductant Substance in intermediate oxidation state can act as both oxidant and reductant

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JMS 4 PAPER - 2
20. Match the reactions given in Column-I with the facts given in Column-II. (A) Column-I PyH+CrO Cl 3 CH CH CH OH 3 2 2 CH Cl 2 2
2 2 7 CH CH CH OH 3 2 2 H SO , H O 2 4 2 K Cr O

Column-II

(p)

Net result is reduction

A ketone is formed

(B)

(q)

(C)

4 CH CH CH Cl 3 2 ether
CH 3

LiAlH

(r)

Net result is oxidation

(D)

3 3 3 CH CH OH 3 ether CH CH 2 3

PCl

( CH )

COK +

(s)

A hydrocarbon is formed

(t)

An acid is formed

Sol.

A-r; B-r,t; C-p,s; D-s

A)This oxdising agent is PCC ( pyridinium chloro chromate), an agent that does not over oxidise the resulting aldehyde.

B)

K Cr O 2 2 7 CH CH CH OH CH CH COOH 3 2 2 3 2 H SO , H O 2 4 2 C)

This is reduction and a hydrocarbon results.

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JMS 4 PAPER - 2

D)

CH CO K + PCl 3 3 CH CH Cl CH CH OH CH = CH CH CH 3 3 2 2 3 CH C OH (an alkene) 3 3 CH CH CH CH 2 3 2 3

This reaction is not at all a redox reaction. Because at one site, carbon is losing a strong electronegative atom chlorine (getting reduced) and the next adjacent site is losing one hydrogen (getting oxidized). The net result is not a redox reaction. The bulky base gives Hofmann elimination to give but-1-ene.

( ) ( )

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