CHEMISTRY CREST

AIEEE ACHIEVER 1

Maximum Marks: 120

Question paper format and Marking scheme: 1. This question paper has 30 questions of equal weight age. Each question is allotted 4(four) marks for each correct response. 2. (one fourth) of total marks allotted to each question i.e., 1 mark will be deducted for indicating incorrect response 3. No deduction from the total score will be made if no response is indicated for an item in the answer sheet. 4. There is only one correct response for each question. Filling up more than one response in each question will be treated as wrong response and marks for wrong response will be deducted accordingly.

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1.

AIEEE ACHIEVER 1

A solution containing 0.1g of a non-volatile organic substance P (molecular mass 100) in 100 g of benzene raises the boiling point of benzene by 0.20C, while a solution containing 0.1 g of another non-volatile substance Q in the same amount of benzene raises the boiling point of benzene by 0.4 0 C. What is the ratio of molecular masses of P and Q (1) 1 : 2 (2) 2 : 1 (3) 1 : 4 (4) 4 : 1 (2) T = K .m b b w 1000 T = K x B b b mB wA
w 1000 Kb B (Tb ) P mB wA P = (Tb )Q w 1000 Kb B mB wA Q

Sol.

0.11000 0.2 100 100 P = 0.4 0.1 1000 100 mB Q

1 (mB )Q = 2 100 (mB)Q = 50 (mB)P : (MB)Q = 100 : 50 = 2 : 1

2. The correct order of rates of nitration in the following is
D D D

NO2

Cl

D D

II

III

IV

V
2) IV < V < I = III < II 4) I < III < II < V < IV

1) II < III < I < IV < V 3) IV < I = III < V < II

Sol. (2) a) Rate of electrophilic substitution reaction is increased by e-releasing groups or activators and decreased by e- withdrawing groups or deactivators - NO2 is strong deactivator, - Cl is weak deactivator, -CH3 is activator b) Formation of - complex or attack of electrophile on ring is rate determining step. c) No isotopic effect is observed in nitration of benzene

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3.

AIEEE ACHIEVER 1

Consider the following molecular structures of [Pt(NO2)(Py)(NH3) (NH2OH)]+

O2 N Pt H3N Py HOH2N NH2OH

O2N Pt

Py

O2N Pt

Py

O2 N Pt

NH3

NH3

H3N

NH2OH

Py

NH2OH

II

III

IV

Choose the incorrect statement among the following (1) I,II and III are geometrical isomers (2) III and IV are identical structures (3) I ,II and III are diastereoisomers (4) II and IV are enantiomeric pair Sol. (4) It is Mabcd type of complex. I, II and III are geometrical isomers and geometrical isomers are diastereoisomers. III and IV are identical structures. Symmetry is present due to square planar structure. So, no optical isomerism is possible 4. In a fossil 97.56% of initial concentration of C-14 was present when analyzed in the year 2004. The fossil is likely to originate in which of the following battle. (t1/2 for C-14 is 5760 year; use log 12.5/12.195 = 0.01072) (1) Battle of Kalinga 361 BC which turned emperor Ashoka towards Buddhism (2) I battle of Panipat 1526, Babar defeats Ibrahim Lodi (3) II battle of Panipat 1556, Akbar defeats Hemu . (4) Battle of Pyramids 1798, Napoleon defeats Mamelkus in Egypt (4)

Sol.

0.693 = 1.2 104 year 1 5760

t=

2.303

log

C 14

initial

C14 left after time 't '

t=

2.303 100 log 4 1.2 10 97.56

t = 206 years Therefore, it is Battle of pyramids ( 2004- 1798 = 206 ) , during the time of which the fossil must have originated.

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5. (1)
Br

AIEEE ACHIEVER 1

on reaction with NBS in CCl4 gives the major product (2)

CHBr Br

(3)

(4)
CH2Br

Sol.

(4) It follows free radical mechanism.

CH2 CH

Br
Br

(I) and

(II)

Structure II has more number of hyper conjugative structures than I. 6. 1) 3) Sol. Most powerful reducing agent among the following is Pyrophosphoric acid Hypophosphorous acid (3) Greater the no of P-H bonds present, Greater is the reducing nature. It is because, hydrogen atoms bonded to phosphorus are readily available as nascent hydrogens for reduction 1) Pyrophosphoric acid (H4P2O7) No of P H bonds = 0 2) 4) Hypophosphoric acid Orthophosphorous acid

2)

Hypophosphoric acid (H4P2O6)

No of P H bonds = 0

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3) Hypophosphorous acid (H3PO2) No of P H bonds = 2

AIEEE ACHIEVER 1

4)

Orthophosphorous acid(H3PO3)

No of P H bonds = 1

7.

COCl + Cl2 COCl2 + Cl (slow) (1) (3) .. Sol. (3) Rate = k [CO] [Cl2] Rate = k [CO] [Cl2]3/2

For the formation of phosgene from CO(g) and chlorine (g) as , CO( g ) + Cl2 ( g ) COCl2 ( g ) the possible mechanism is Cl2 2Cl (fast) Cl + CO COCl (fast) The rate law expression can be written as
(2) (4) Rate = k [CO]1/2 [Cl2] Rate = k [CO] [Cl2]1/2

Cl2 2Cl (fast)

Kc 1 =

[Cl ]

Cl + CO COCl (fast)
Kc 2 =

Cl 2

(1)

[COCl ] .(2) [Cl ][CO ]

COCl + Cl2 COCl2 + Cl (slow) Hence,

rate = k 1 [Cl2 ][COCl ]

Sub 1 and 2 in the above expression, we get

rate = k 1 [Cl2 ] Kc2 [CO ] Kc1 [Cl2 ]

rate = k .Kc2 . Kc1 [Cl2 ]

1

3/2

[CO ]

k1K c2 K c1 = k , another constant

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8. Glucose on reduction with Na/Hg and water gives ? (1) Sorbitol (2) Fructose (3) Saccharic acid (1)

AIEEE ACHIEVER 1
(4) Gluconic acid

Sol.

9.

The decreasing order of second ionisation enthalpy of Mg, Al, Si is (1) Mg > Al > Si (2) Al > Si > Mg (3) Si > Al > Mg (4) Si > Mg > Al. (2) Order of 1st IE of these elements is Mg > Al < Si For 2nd IE, Imagine, once the first e- is lost, Mg becomes Na, Al becomes Mg and Si becomes Al , for which the order of ionization energies is Na < Mg > Al Therefore, order of 2nd IE of these elements is Al > Si > Mg Two elements X and Y combine to form two compounds XY2 and X3Y2. When 0.1 mole of former weighs 10 grams while 0.05 moles of the latter weighs 9grams. Then the weight of 0.2 moles of X2Y is (1) 11 grams (2) 22 grams (3) 2.2 grams (4) 1.1 grams

Sol.

10.

Sol.

(2) Molar mass of XY2 = ( a + 2b ) =

10 (1) = 100 0.1 9 Molar mass of X 3Y2 = ( 3a + 2b ) = = 180 .(2) 0.05 From 1 and 2, a = 40, b = 30

Theefore, weight of 0.02 moles of X2Y is = 0.2 ( 2 40 + 1 30 ) = 22g

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11. Which is incorrect product (1)
H3C C C CH3

AIEEE ACHIEVER 1

Na / Liq.NH 3 CH3 C C CH 3

H (cis) H

(2)
CH 3 C C CH 3
H2 Pd / BaSO4

H3C C H
CH3

CH3 C H
(cis)

(3)

CH3
Br2

CH3 H Br Br H CH3

Br H

H Br CH3

CH3

cis-But-2-ene

( ) -2, 3-Dibromobutane

(4)

CH3
Br2

CH3 H H Br Br CH3
Meso -2, 3-dibromobutane

H3C

trans-But-2-ene

Sol.

(1)

Na /Liq.NH3 CH3 C C CH3 CH3CH = CHCH3 (Trans)

2)With Lindlars catalyst, it is syn addition 3)CAR ( cis-anti addition-racemic mixture) 4)TAM ( trans anti addition meso compound)

12.

Which of the following pairs have same hybridization about the central atom? (1) SF4/SiF4 (2) NO3 / NF3
2 2 (3) S2 O8 / S2 O 3

(4) BrF5 / IF7

Sol.

(3) Hybrid orbitals = No of bonds + lone pairs Or

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SF4(sp3d) / SiF4(sp3) NO3 (sp2) / NF3 (sp3) S2O82 (sp3) / S2O32 (sp3) BrF5 (sp3d2) / IF7 (sp3d3) 13.

AIEEE ACHIEVER 1

Coagulation values of the electrolytes AlCl3 and NaCl for As 2S3 solution are 0.093 and 52 respectively. How many times nearly AlCl3 has greater coagulating power than NaCl ? (1) 930 (2) 520 (3) 560 (4) 1000

Sol.

(3)

Coagulation power

1 coagulation value Coagulation power of AlCl3 Coagulation value of NaCl = Coagulation power of NaCl Coagulation value of AlCl3

52 0.093 = 559.139 =

14.

The treatment of benzene with isobutene in the presence of sulphuric acid gives : (1) isobutyl benzene (2) tert-butyl benzene (3) n-butyl benzene (4) no reaction (2)

Sol.

15.

The wrong statement about N2O is : (1) It is nitrous oxide (2) It is least reactive oxide of nitrogen (3) It is not a linear molecule (4) It is known as laughing gas (3) N2O is a linear molecule

Sol.

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16.

AIEEE ACHIEVER 1

n containers having volumes v, 2v, 3v..nv containing gaseous moles n, 4n, 9n,..n3 respectively are connected with stopcock at same temperature. If pressure of first container is P, then the final pressure when all the stopcocks are opened is (1) (3)
n ( 2n + 1) P 3

(2) (4)

( 2n + 1) P
3n

( 2n + 1) P
6n

( 2n + 1) P
3

Sol.

(4) Initial, Pv = nRT Final, P(v + 2v + .. nv) = (n + 4n +.. + n3)RT Since 1 +2 +3+ + n =
n ( n + 1) 2 n ( n + 1)( 2n + 1) 6

And 12 +22 +32 + .n2 = 1 + 4 + 9 + + n2 =

P' n ( n + 1) 2 n ( 2n + 1) v=n n ( n + 1)( 2n + 1) 6 RT RT

P 'v =

3 2n + 1 P 'v = Pv 3 ( 2n + 1) P P' = 3

17.
OH OH OH OH OH

NO2 (I)

Cl (II)

Me (III)

OMe (IV)

(V)

Correct order of Acidic strength is (1) I > II > III > IV > V (3) I > II > III > V > IV Sol. (2) I groups increase acidic strength , + I groups decrease acidic strength OMe ( I) (+ R), ( +R > - I ) CH3 (+ I and Hyper congregation) NO2, (strong I and strong - M) - Cl (- I > +R ) visit us at www.chemistrycrest.com Page 9 (2) I > II > V > III > IV (4) I > II > V >IV > III

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18.

AIEEE ACHIEVER 1

In electrolysis of Al2O3 by Hall-Heroult process: (1) cryolite Na3[AlF6] lowers the melting point of Al2O3 and increases its electrical conductivity. (2)Al is obtained at cathode and probably CO2 at anode (3) both (1) and (2) are correct. (4) none of the above is correct. (3) Na3 AlF6 3NaF + AlF3 NaF and AlF3 are ionic in nature. So, undego ionization to give ions , This increases electrical conductivity and decreases melting point C : Al 3+ + 3e Al
A : C + O 2 CO + 2e C + 2O 2 CO2 + 4e

Sol.

19.

At equilibrium N 2O4( g ) 2 NO2( g ) the observed molecular weight of N 2O4 is 80 g mol 1 at 350K. The percentage dissociation of N 2O4 (g) at 350 K is : 1) 10% 2) 15% 3) 20%

4) 18%

Sol.

(2)

Degree of dissociation may be calculated as, =

M m ( n 1) m

where, M = M normal and m = M observed, n = no of moles of products 92 80 12 = = = 0.15 ( 2 1) 80 80

Percentage dissociation = 0.15 x 100 = 15%

20. Arrange following in order of reactivity toward SN1 reaction
Cl Cl Cl Cl

(I)

(II)

(III)

(IV)

(1) I > II > III > IV (3) IV > II > I > III
Sol.

(2) IV > I > II > III (4) IV > III > II > I

(3) IV forms aromatic ion ( Tropyllium cation- cyclo hepta trienyl cation) III form antiaromatic ion (cyclo penta dienyl cation) Cation of II has less strain than Cation of I

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21.

AIEEE ACHIEVER 1

The following acids have been arranged in order of decreasing acid strength. Identify the correct order. ClOH (), BrOH ( IOH ( ), )
(1) > > (2) > > (3) > > (4) > >

Sol.

(1) Acidic character of hypohalous acids increases with increase in the electro negativity of the halogen atom Electrolysis of an acetate solution produces ethane according to the Kolbe reaction : 2CH 3COO C2 H 6 + 2CO2 + 2e What volume of ethane is produced at 270C and 740 mm Hg, if a current of 0.500 A were passed through the solution for 7 h and the electrode reaction is 82% efficient? (1) 2.70 L (2) 5.4 L (3) 1.35L (4) 0.65 L (3) Number of moles of 0.500 7.00 3600 e = 0.82 = 1.071 mole 96500 Two moles of electrons are associated with 1 mole C2 H 6 , thus, 1.071 Volume of C2 H 6 = 22.4. 2 PV PV Under given conditions, using , 1 1 = 2 2 T1 T2 1.071 760 300 V2 = 22.4 = 1.35L. 2 740 273 Which of the following compound gives N-nitrosoamine on reaction with nitrous acid
(1)

22.

Sol.

23.

CH2
N

NH2

(2)

H3C

NH2

(3)
Sol.

(4)

NH

CH3

(4) 20 amines give N-nitroso amines Among given, 1 and 2 are 10 , 3 is 30 and 4 is 20 Which of the following ore can be concentrated by froth floatation process : (1) Epsom salt (2) Silver glance (3) Haematite (4)All (2) Froth floatation method is employed for sulphide ores. Silver glance (Ag2S) is a sulphide ore Page 11

24.

Sol

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25.

AIEEE ACHIEVER 1

The enthalpy of neutralization of a weak monoprotic acid, HA in 1 M solution with a strong base is -55.95 kJ/mol. If the unionized acid requires 1.4 kJ/mol heat for its complete ionization and enthalpy of neutralization of the strong monobasic acid with a strong monoacidic base is -57.3 kJ/mol. Then % ionization of the weak acid in molar solution is (1) 1.2 % (2) 3.57 % (3) 6.07 % (4) 12.01 % (2)
H ( neutralisation ) = H ( ionisation ) +H r ( H + + OH H 2O )

Sol.

55.95 = H1 57.3 H ionisation = 1.35 kJ/mol but a given, 1.4 kJ/mol heat is required for ionization 1.35 So, % of heat utilized by 1 M acid for ionisation = 100 = 96.43% ionized by utilizing heat 1.4 so, % of ionization on its own 100 96.43 = 3.57% 26. Which will not perform iodoform reaction? (1) CH3COCH2CH3 (2) CH3CONH2 (2) Which of the following species will be paramagnetic in nature, if Hund's rule is violated while writing their molecular orbital configuration : (1) O2 (2) C2 (3) B2 (4) N2 -- O2 (16e ) = 1s 2 2 2 s 2 2 s2 2 pz 2 2 p 2 = 2 p 2 2 p 2 = 2 p0
1s x y x y

(3) C6H5COCH3

(4) CH3CHO

Sol. 27.

C2 (12e
.

) =

(Diamagnetic)

1s 2

2s 2 p = 2 p

1s2 2

2 s2

2 x

2 y

B2 (10e ) = 1s 2 2 2 s 2 2 s2 2 p 2 = 2 p0
1s x y

(Diamagnetic) (Diamagnetic)
y

N 2 (15e ) = 1s2 2 2 s2 2 s 2 2 p2 = 2 p2 2 pz 2 2 p1 = 2 p0
1s x x y

(Paramagnetic)

28.

Calcium lactate is a salt of weak acid i.e., lactic acid having general formula Ca ( Lac )2 . Aqueous solution of salt has 0.3 M concentration. pOH of solution is 5.60. If 90 % of the salt is dissociated then what will be the value of pK a ?
(1) 2.8 log ( 0.54 )

(2) 2.8 + log ( 0.54 )

(3) 2.8 + log ( 0.57 )

(4) None of these

Sol.

(1)

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Ca ( Lac ) 2 Ca +2 + 2 Lac Concentration of Lac after dissociation = 2 x 0.3 x 0.9 = 0.54

AIEEE ACHIEVER 1

29.

Identify the reagent in the following reaction

(1) Conc. HCl

Sol. (3)

(2) HCl , ZnCl2

(3) SOCl2

(4) Aqueous KOH

SOCl2 converts pri and sec alcohols to alkyl chlorides usually without rearrangement
30. The ion that cannot be precipitated by both HCl and H2S is (1) Pb2+ (2) Cu+ (3) Ag+ (4)

(4) Sn2+

Sol.

(A), (B) and (C) can be precipitated by HCl as well as H2S as their insoluble chlorides and sulphides respectively Sn2+ can be precipitate only by H2S as its insoluble sulphide (brown). Sn2+ + 2HCl SnCl2 (soluble) + 2H+

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