CONTENTS

CHEMISTRY PAGE No.

1. VOLUMETRIC ANALYSIS 1–9

2. SOLUTION & COLLIGATIVE PROPERTIES 10 – 19

3. CHEMICAL KINETICS 20 – 31

4. ELECTROCHEMISTRY 32 – 41

5. ALCOHOL, ETHER & PHENOL 42 – 55

6. ALKYL HALIDE AND ARYL HALIDE 56 – 71

7. ALDEHYDES AND KETONES 72 – 84

8. CARBOXYLIC ACID AND ITS DERIVATIVES 85 – 101

9. AMINES 102 – 112

10. BIOMOLECULES, POLYMER & EVERYDAY LIFE 113 – 122

11. P-BLOCK ELEMENT (OXYGEN FAMILY, HALOGEN & 123 – 132

INERT GAS)
12. COORDINATION COMPOUND 133 – 143

13. METALLURGY & d-f BLOCK ELEMENT 144 – 154

14. QUALITATIVE ANALYSIS 155 – 165

“ ”
No one can push you up the ladder, unless you are willing to climb
 VOLUMETRIC ANALYSIS
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. In a compound Ax By
(A) mole of A = mole of B = mole of Ax By
(B) equiv of A = equiv of B = equiv of Ax By
(C) y × moles of A = y × mole of B = (x + y) mole of Ax By
(D) y × mole of A = y × mole of B

2. Molecular mass of tribasic acid is W. Its equivalent mass would be

(A) W/2 (B) W/3 (C) W (D) 3W

3. Equivalent wt. of H3PO4 in each of the reaction will be respectively

H3PO4 + OH– H2PO4– + H2O
H3PO4 + 2OH– HPO42– + 2H2O
H3PO4 + 3OH– PO43– + 3H2O
(A) 98, 49, 32.67 (B) 49, 98, 32.67
(C) 98, 32.67, 49 (D) 32.67, 49, 98

4. Equivalent mass of NH3 in the reaction NH3 + H+ NH4+

(A) 17 (B) 17/2 (C) 1.7 (D) 17/3
5. The equivalent mass of crystalline oxalic acid is equal to the equivalent weight of
(A) Na2CO3 (B) HNO3 (C) KOH (D) CH3COOH

6. The equivalent mass of calcium phosphate Ca3(PO4)2 (Mol. wt. = 310) is

(A) 310/2 (B) 310/6 (C) 310/3 (D) 310

7. Equivalent mass of a bivalent metal is 32.7. Molecular mass of its chloride is

(A) 68.2 (B) 103.7 (C) 136.4 (D) 166.3

8. Milli equivalents of a solute in a solution can be given by

(A) Meq. = M × Vin ml (B) Meq. = N × Vin ml
wt.
(C) Meq. = × 1000 (D) (B & C) both
E.wt.

9. How many millilitre of 0.5 N SnCl2 solution will reduce 600 ml of 0.1 N HgCl2 to Hg2Cl2
(A) 120 ml (B) 60 ml (C) 30 ml (D) 240 ml

10. If in a reaction is reduced to NO, the mass of HNO3 absorbing one mole of electrons would be
(A) 12.6 g (B) 21.0 g (C) 31.5 g (D) 63.0 g

11. If in a given reaction NO3 is reduced to NH4 , the mass of NO3 absorbing one mole of
electrons would be
(A) 31.0 g (B) 12.4 g (C) 6.29 g (D) 7.75 g

1
12. For the reaction Br2  OH  Br   BrO3  H2O
What is the equivalent weight of Br2
(A) M/8 (B) M/5 (C) 3M/5 (D) 5M/8.

13. Amount of oxalic acid required to prepare 250mL of N/10 solution (Mol. mass of oxalic
acid = 126) is:
(A) 1.5759 g (B) 3.15 g (C) 15.75 g (D) 63.0 g

14. In the following redox reaction Cu(OH)2(s) + N2H4(aq) — Cu(s) + N2(g)

number of mol of Cu(OH)2 reduced by one mol of N2H4 is -
(A) 1 (B) 2 (C) 3 (D) 4

15. Mixture of 1mol MgCl2 and 2 mol H2SO4 can be neutralized by:
(A) 1 mol KOH (B) 2 mol Ca(OH)2 (C) 2 mol NaOH (D) 2 mol KOH

16. If 200mL of 0.1M KHC2O4, 300mL of 0.2 M H2C2O4 and 500mL of 0.3M NaCl is
neutralized by 140mL of Ca(OH)2 . What is its molarity ?
(A) 1 (B) 0.5 (C) 1.5 (D) 2

17. What volume of 0.955 M HCl, in milliliters, is needed to titrate 2.152 g of Na2CO3 to the
equivalence point? Na2CO3 (aq)  2HCl(aq)  2NaCl(aq)  CO2(g)  H2O(l)
(A) 4.25ml (B) 21.5ml (C) 84.0ml (D) 42.5ml

18. The normalities of 1 M solution of HCl, 1 M H2SO4 and 1 M H3PO4 in complete neutralization
are respectively:
(A) 1N, 2N and 3N (B) 2N, 3N and 1N
(C) 0.1N, 0.2N and 0.3 N (D) 3N, 2N and 1N

19. The equivalent weight of phosphoric acid (H3PO4 ) in the reaction

NaOH  H3PO4  NaH2PO4  H2O is:
(A) 89 (B) 98 (C) 59 (D) 29
20. KMnO4 (mol.wt. = 158) oxidizes oxalic acid in acidic medium to CO 2 and water as follows:
5C2O24  2MnO4  16H  10CO2  2Mn2  8H2O
. What is the equivalent weight of KMnO4
(A) 158 (B) 31.6 (C) 39.5 (D) 79

21. 0.7 g of a sample of Na2CO3.xH2O were dissolved in water and the volume was made to 100
ml. 20 ml of this solution required 19.8 ml of N/10 HCl for complete neutralization. The value
of ‘x’ is:
(A) 3 (B) 2 (C) 4 (D) 6
22. 3.92 of ferrous ammonium sulphate (Eq. mass = 392) are dissolved in 100 ml of water. 20 ml
of this solution requires 200 ml of potassium permanganate during titration for complete
oxidation. The weight of KMnO4 (Eq. mass = 31.6) present in one litre of the solution is:
(A) 13.6g (B) 0.316g (C) 14.76g (D) 34.78g
23. 3 g of an oxide of a metal is converted to chloride completely and it yielded 5g of chloride. The
equivalent weight of the metal is:
(A) 3.325 (B) 13.25 (C) 23.52 (D) 33.25

2
24. The ratio of equivalent weights of C2H5OH in the following reactions is:
(i) C2H5OH  CH3CHO (ii) C2H5OH  C2H5ONa
(A) 1 : 4 (B) 1 : 1 (C) 1 : 2 (D) 1 : 3

25. An element A in a compound ABD has oxidation number A n  . It is oxidized by Cr2O27 in acid
medium. In the experiment 1.68  10—3 moles of K2Cr2O7 were used for 3.26  10—3 moles of
ABD. The new oxidation number of A after oxidation is:
(A) 3 (B) 3 – n (C) n – 3 (D) +n

26. When the ion Cr7O27 acts as an oxidant in acidic aqueous solution the ion Cr3  is formed.
How many mole of Sn2 would be oxidized to Sn4  by one mole Cr2O27 ion:
(A) 2/3 (B) 3/2 (C) 2 (D) 3

27. If 10gm of V2O5 is dissolved in acid and is reduced to V2+ by zinc metal, how many mole of 2
could be reduced by the resulting solution if it is further oxidised to VO 2+ ions? [Assume no
change in state of Zn2+ions] (V = 51, O = 16,  = 127):
(A) 0.11 mole of 2 (B) 0.22 mole of 2
(C) 0.055 mole of 2 (D) 0.44 mole of 2

28. One gram of Na3 AsO4 is boiled with excess of solid KI in presence of strong HCl. The iodine
evolved is absorbed in KI solution and titrated against 0.2N hyposolution. Assuming the
reaction to be AsO43–  2H  2I–  AsO33–  H2O  I2 , calculate the volume of
thiosulphate hypo consumed. [Atomic weight of As = 75]
(A) 48.1 ml (B) 38.4 ml (C) 24.7 ml (D) 30.3 ml

29. 4.9 gm of K2Cr2O7 is taken to prepare 0.1 Ltr. of the solution. 10 ml of this solution is further
taken to oxidise Sn2+ ion into Sn4+ ion. Sn4+ so produced is used in 2nd reaction to prepare
Fe3+ ion then the millimoles of Fe3+ ion formed will be (assume all other components are in
sufficient amount) [Molar mass of K2Cr2O7 = 294gm]
(A) 5 (B) 20 (C) 10 (D) none of these

30. A 0.518 g sample of limestone is dissolved in HCl and then the calcium is precipitated as
CaC2O4. After filtering and washing the precipitate, it requires 40.0 mL of 0.250 N KMnO 4,
solution acidified with H2SO4to titrate it as. The percentage of CaO in the sample is:
MnO4– + H+ + C2O42–  Mn2+ + CO2 + 2H2O
(A) 54.0% (B) 27.1% (C) 42% (D) 84%

31. KMnO4 reacts with oxalic acid according to the reaction:

2KMnO4 + 5C2O24 + 16H+ 2Mn2+ + 10CO2 + 8H2O
Then, 20mL of 0.1 M KMnO4 is equivalent to:
(A) 30mL of 0.5 M C2H2O4 (oxalic acid) (B) 50mL of 0.1 M C2H2O4 (oxalic acid)
(C) 20mL of 0.5 M C2H2O4 (oxalic acid) (D) 10mL of 0.1 M C2H2O4 (oxalic acid)

3
32. Hg5 (IO6)2 oxidizes KI to I2 in acid medium and the other product containing iodine is K 2HgI4.
If the I2 liberated in the reaction requires 0.004 mole of Na2S2O3, the number of moles of Hg5
(IO6)2 that has reacted is
(A) 10–3 (B) 10–4 (C) 2.5 × 10–4 (D) 2.5 × 10–2

33. 1 litre solution of unknown molarity is titrated by taking its 50mL solution against KI solution
is strong acid medium of excess HCl. The equivalence point was detected when 10mL of
0.1M KI was consumed. The molarity of KIO3 solution is:
(A) 4  10—4 M (B) 2  10—2 M (C) 4  10—3 M (D) 2  10—3 M

34. BrO3  5Br  6H  3Br2  3H2O . If 25.0mL of 0.200 molar BrO3 is mixed with 30.0mL of
0.450 molar Br  solution that contains a large excess of H , the amount of Br2 formed,
according to the equation above is:
(A) 5.00  10—3 mole (B) 8.10  10—3 mole
(C) 1.35  10 mole
—2 (D) 1.50  10—2 mole

35. Manganese ions (Mn2 ) can be oxidized by persulphate ions (S2O82 ) according to the
following equations: Mn2  S2O82  SO24  MnO4 (Acidic medium). How many moles of
S2O28 are required to oxidize 1 mole of Mn2 :
(A) 2.5 (B) 2.0 (C) 1.0 (D) 0.4

36. When white phosphorous (P4) is boiled in alkaline medium, it disproportionate as

P4  NaOH  PH3  NaH2PO2
In the above redox reaction, NaH2PO2 and PH3 are produced in the molar ratio of:
(A) 1 : 1 (B) 1 : 3 (C) 3 : 1 (D) 2 : 1

37. Consider the temporary hardness of water is due to the presence of Ca(HCO 3)2 and specific
gravity of hard water is 1. Then the weight of CaO required for 10 6 litre of water remove the
temporary hardness of 1000ppm is:
(A) 3.6  104gm (B) 6.5  104gm (C) 5.6  105gm (D) 8.5  105gm

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. If 1 mole of H3PO4 is reacted with 1 mole of X(OH)2 as
H3PO4  X(OH)2  XHPO4  2H2O then:
mol.wt.
(A) The equivalent weight of base is
2
98
(B) The eq. wt of H3PO4 is
3
(C) The resulting solution is required 1 mole NaOH for complete neutralization
(D) 1 mole of X(OH)2 more required for complete neutralization of XHPO4

4
2. Dichromate ion in acidic medium oxidizes stannous ion as:
xSn2  yCr2O2  
7  zH  aSn
4
 bCr3  cH2O
(A) the value of x : y is 1 : 3 (B) the value of x + y + z is 18
(C) a:b is 3 : 2 (D) the value of z – c is 7

3. When a equimolar mixture of Cu2S and CuS is titrated with Ba(MnO4 )2 in acidic medium,
the final product’s contains Cu2 , SO2 and Mn2 . If the mole wt. of Cu2S,CuS and
Ba(MnO4 )2 are M1, M2 and M3 respectively then:
M1
(A) eq. wt. of Cu2S is
8
M
(B) eq. wt. of CuS is 2
6
M3
(C) eq. wt. of Ba(MnO4 )2 is
5
(D) Cu2S and CuS both have same equivalents in mixture

4. For the reaction:

PbS  4H2O2  PbSO4  4H2O
Which are correct about the equivalent mass of respective species? M represents molar mass.
M M M M
(A) EPbS  (B) EH2O2  (C) EPbSO4  (D) EPbSO4 
8 2 2 8

5. One mole of KMnO4 is used for complete oxidation of FeSO4 , FeC2O4 and H2C2O4
respectively and separately. Pick up the correct statement:
(A) 5 mole of FeSO4 can be oxidized (B) 3/5 mole of FeC2O4 can be oxidized
5
(C) mole of FeC2O4 can be oxidized (D) 2.5 mole of H2C2O4 can be oxidized
3

6. 1 mole of Fe2 is oxidized to Fe3  using K2Cr2O7 and KMnO4 solutions separately. Which of
the following are correct for titration of Fe2 to Fe3 ?
(A) VK2Cr2O7 : VKMnO4 : : 5 : 6 if both have molarity 1M
(B) VK2Cr2O7 : VKMnO4 :: 6 : 5 if both have molarity 1 M
(C) Moles of K2Cr2O7  moles of KMnO4
(D) Equivalent of K2Cr2O7  Eq. of KMnO4

7. Which of the following are correct for the change Fe2O3  Fe3O4 ?
2
(A) n-factor for Fe2O3  (B) n-factor for Fe3O4  1
3
(C) Fe3  is reduced to Fe8/3 (D) n-factor for Fe in Fe2O3  1

5
8. 100 g P4O6 is treated with 100g KMnO4 in presence of HCl to form H3PO4 and MnCl2 ,
then:
(A) KMnO4 will act as limiting reagent (B) n-factor of P4O6 is 4
(C) n-factor of KMnO4 is 5 (D) P4O6 will act as limiting reagent

9. Select the correct statements:

 
(A) n-factor for CrI3 when it oxidizes to Cr2O2
7 and IO4 is 27
 
(B) n-factor for As2S3 when it oxidizes to AsO3 and SO2
4 is 28
(C) n-factor for FeS2 when it is oxidized to Fe2O3 and SO2 is 11
(D) n-factor for Bi2S3 when it is oxidized to Bi5  and S is 10

10. Which are correct about?

(i) Pb3O4  8HCl  3PbCl2  Cl2  4H2O

(ii) Pb3O4  4HNO3  Pb(NO3 )2  PbO2  2HCl

(A) Pb3O4 is a mixed oxide having bases PbO and PbO2 in 2:1 ratio
(B) Reaction (i) is acid-base reaction of PbO and HCl along with redox change between
PbO2 and HNO3
(C) Reaction (ii) is simply acid-base reaction between PbO and HNO3
(D) PbO2 does not show redox change with HNO3

COMPREHENSION TYPE
PARAGRAPH FOR NEXT THREE QUESTIONS:
A 0.141 g sample of a phosphorus containing compound was digested in a mixture of HNO 3 and
H2SO4 which resulted in formation of CO2, H2O and H3PO4. Addition of ammonium molybdate
yielded a solid having the composition (NH4)3PO4.12MoO3. The precipitate was filtered, washed
and dissolved in 50.0 mL of 0.20 M NaOH:
NH4 3 PO4.12MoO3 s   26OH  HPO24  12MoO24  14H2O  3NH3 g 
After boiling the solution to remove the NH3, the excess NaOH was titrated with 14.1mL of 0.174
M HCl.
1. The reacted milli mole of NaOH with solid having composition (NH4)3PO4.12MoO3 is:
(A) 7.55 (B) 5.75 (C) 6.65 (D) 8.25

2. Produced mole of NH3 is:

(A) 7.62  10–3 (B) 8.71  10–4 (C) 6.85  10–3 (D) none of these

3. The percent of phosphorous in the given sample is:

(A) 3.36 (B) 5.56 (C) 6.38 (D) 7.25

PARAGRAPH FOR NEXT THREE QUESTIONS:

A 1.65 gm sample of FeS2 was oxidized by excess oxygen & the products were SO 2 and Fe2+. The
SO2 gas produced was passed through an acidified solution of 40 ml Ba(MnO 4)2 produced
SO4 & Mn2 . The excess permaganate was diluted to 100 ml & 10 ml of it was treated with

6
excess KI & iodine produced req. 0.05 M 5 ml hypo solution producing S4O26 . In a separate
titration the 25 ml of same solution of permagnate under alkaline condition when treated with KI
produced I2 that required 20 ml of 0.05 M hypo solution producing S4O62 & Mn6 .
4. The molarity of Ba(MnO4)2 is:
(A) 0.010 (B) 0.02 (C) 0.03 (D) 0.04

5. Produced milli mole of SO2 is:

(A) 2.75 (B) 3.63 (C) 4.5 (D) 5.15

6. The percentage of FeS2 in the sample is:

(A) 40 (B) 30 (C) 20 (D) 10

MATCH THE FOLLOWING COLUMN

1. Match the following:
COLUMN-I COLUMN-II
(A) Change of NO to NO3 (P) Oxidation number changes from +7 to +2
(B) Change of P4 to H2PO2 (Q) Oxidation number changes + 6 to + 3
(C) KMnO4 in acidic medium (R) Oxidation number of changes from 0 to + 1
(D) K2Cr2O7 in acidic medium (S) Oxidation number changes from + 2 to + 5

2. Consider the redox-reactions of Column I and match them with entries of with Column II:
COLUMN-I COLUMN-II
(A) KMnO4  H2O2  Mn2  O2 (P) One mole of reducing agent reduces more than
two moles of oxidizing agent
(B) K2Cr2O4  H2S  Cr3  SO2 (Q) One mole of oxidizing agent oxidizes more than
one mole of reducing agent
(C) H2O2  H2C2O4  H2O  CO2 (R) One mole of oxidizing agent oxidizes less than
one mole of reducing agent
(D) K2CrO4  FeS  Cr3  Fe3  SO2 (S) One mole of oxidizing agent oxidizes one mole
of reducing agent

INTEGER ANSWER TYPE

1. A sample of 28mL of H2O2(aq) solution required 10mL of 0.1 M KMnO4 (aq) solution for
complete reaction in acidic medium. What is the volume of strength of H2O2 ?

2. 0.98 g of a polybasic acid (molar mass 98) requires 30mL of 0.5 M Ba(OH)2 for complete
neutralization. The basicity of acid is
N
3. A solution of H2O2 has normality . Its % strength is
1.7
4. 100mL solution of an acid (molar mass 82) containing 39g acid per litre was completely
neutralized by 95.0mL of aqueous NaOH solution containing 40g NaOH per litre. The basicity
of acid is

7
5. The acidity of acid salt BaHPO4 is ………

6. The basicity of acid salt BaHPO4 is ………

7. Two acid solutions A and B are titrated separately each with 25mL of IN Na2CO3 solution. The
volume of each acid used for titration is 10mL & 40mL respectively for the complete
neutralization. The volume ratio of VB & VA which is mixed to prepare 1mL 1N solution is
8. 100g HCl solution having density 1.20 g/mL 1.20 g/mL contains 36.5 g HCl. How much
volume in litre of this HCl is required to neutralize exactly 36 litre of N NaOH solution.

9. The volume strength of H2O2 solution is 11.2. What is its normality?

10. A mixture of HCOOH and H2C2O4 is heated with conc. H2SO4. The gaseous mixture on
1
passing through KOH shows a reduction of in volume at same P & T. The mole ratio of
6
HCOOH & H2C2O4 in mixture is

SECTION-III
PREVIOUS YEAR JEE-ADVANCE QUESTIONS
1. To measure the quantity of MnCl2 dissolved in an aqueous solution, it was completely
converted to KMnO4 using the reaction,
MnCl2  K2S2O8  H2O  KMnO4  H2SO4  HCl (equation not balanced).
Few drops of concentrated HCl were added to this solution and gently warmed. Further,
oxalic acid (225 mg) was added in portions till the colour of the permanganate ion
disappeared. The quantity of MnCl2 (in mg) present in the initial solution is ____.
(Atomic weights in g mol1 : Mn = 55, Cl = 35.5) [2018]

2. In neutral or faintly alkaline solution, 8 moles of permanganate anion quantitatively oxidize

thiosulphate anions to produce X moles of a sulphur containing product. The magnitude of X
is [2016]

PARAGRAPH FOR NEXT TWO QUESTIONS:

Bleaching powder and bleach solution are produced on a large scale and used in several
household products. The effectiveness of bleach solution is often measured by iodometry. [2012]
3. Bleaching powder contains a salt of an oxoacid as one of its components. The anhydride of
that oxoacid is
(A) Cl2O (B) Cl2O7 (C) ClO2 (D) Cl2O6

4. 25 mL of household solution was mixed with 30 mL of 0.50 M KI and 10 mL of 4 N acetic acid.

In the titration of the liberated iodine, 48 mL of 0.25 N Na2S2O3 was used to reach the end
point. The molarity of the household bleach solution is
(A) 0.48 M (B) 0.96 M (C) 0.24 M (D) 0.024 M

8
 ANSWERS TO VOLUMETRIC ANALYSIS
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. B 9. A 17. D 25. B 33. C
2. B 10. B 18. A 26. D 34. B
3. A 11. D 19. B 27. A 35. A
4. A 12. C 20. B 28. A 36. C
5. B 13. A 21. B 29. C 37. C
6. B 14. B 22. B 30. A
7. C 15. B 23. D 31. B
8. D 16. B 24. C 32. C

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. A,C 3. A,B 5. A,B,C 7. A,B,C 9. A,B,C,D
2. B,C,D 4. A,B,D 6. A,D 8. A,C 10. A,B,C,D

COMPREHENSION TYPE
1. A 3. C 5. A
2. B 4. B 6. D

MATCH THE FOLLOWING COLUMN

1. A  S; B  R; C  P; D  Q 2. A  Q; B  R; C  S; D  PR

INTEGER ANSWER TYPE

1. 1 4. 2 7. 4 10. 4
2. 3 5. 2 8. 3
3. 1 6. 1 9. 2

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. 126 2. 6 3. A 4. C

9
 SOLUTION & COLLIGATIVE PROPERTIES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. For an ideal binary liquid solution with PAº  PBº
, which relation between X A (mole fraction of A in
liquid phase) and YA (mole fraction of A in vapour phase) is correct?
YA X A YA X A
(A) YA  YB (B) XA  XB (C)  (D) 
YB XB YB XB

2. The vapour pressure of a solvent decreased by 10 mm of Hg when a non-volatile solute was added to
the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of the solvent if
decrease in vapour pressure is 20 mm of Hg
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.8

3. The solubility of common salt is 36.0gm in 100gm of water at 20ºC. If systems I, II and III contain 20.0,
18.0 and 15.0g of the salt added to 50.0gm of water in each case, the vapour pressure would be in the
order:
(A) I < II < III (B) I > II > III (C) I = II > III (D) I = II < III

4. Which of the following plots, represents an ideal binary mixture:

(A) plot of Ptotal v/s 1/XB is linear (XB = mole fraction of ‘B’ in liquid phase)
(B) plot of Ptotal v/s YA is linear (YB = mole fraction of ‘A’ in vapour pressure)
1
(C) plot of v/s YA is linear
Ptotal
1
(D) plot of v/s YB is non-linear
Ptotal

5. The vapour pressure of a solution of a non-volatile electrolyte B in a solvent A is 95% of the vapour
pressure of the solvent at the same temperature. If the molecular weight of the solvent is 0.3 times the
molecular weight of solute then the ratio of mass of solvent and solute are:
(A) 0.15 (B) 5.7 (C) 0.2 (D) 4.0

6. At a given temperature total vapour pressure in torr of a mixture of volatile components A and B is
given by 1.   Ptotal  120 – 75 XB Hence, vapour pressure of pure A and B respectively (in torr) are:
(A) 120, 75 (B) 120, 195 (C) 120, 45 (D) 75, 45

7. The correct relationship between the boiling points of very dilute solution of AlCl3 (T1K) and CaCl2(T2K)
having the same molar concentration is:
(A) T1  T2 (B) T1  T2 (C) T2  T1 (D) T2  T1

8. A 0.001 molal solution of a complex [MA8] in water has freezing point of – 0.0054º C . Assuming 100%
ionization of the complex salt and K f for H2O  1.86 km–1 , write the correct representation for the
complex
(A) [MA8 ] (B) [MA7 ]A (C) [MA6 ]A2 (D) [MA5 ]A3

9. Assuming each salt to be 90% dissociated, which of the following will have highest boiling point?
(A) decimolar Al2(SO4 )3
(B) decimolar BaCl2
(C) decimolar Na2SO4
(D) a solution obtained by mixing equal volumes of (B) & (C)

10
10. What will be the molecular weight of CaCl2 determined in its aq. solution experimentally from
depression of freezing point?
(A) 111 (B) < 111 (C) > 111 (D) data insufficient

11. 1 molal aqueous solution of an electrolyte A2B3 is 60% ionized. The boiling point of the solution at


1atm is Kb H O  0.52 K kg mol1
2 
(A) 274.76 K (B) 377 K (C) 376.4 K (D) 374.76 K

12. The freezing point depression of a 0.1 M aq. solution of weak acid (HX) is – 0.20º C . What is the value
of equilibrium constant for the reaction? [Given : K f for water = 1.8 kg mol1 K & Molality = Molarity]
 
HX  aq   H  aq   X  aq 

(A) 1.46  104 (B) 1.35  103 (C) 1.21  102 (D) 1.35  104

13. The van’t Hoff factor for 0.1 M Ba(NO3 )2 solution is 2.74. The degree of dissociation is:
(A) 91.3% (B) 87% (C) 100% (D) 74%

14. Maximum freezing point will be for 1 molal solution of, assuming equal ionization in each case
(A) [Fe(H2O)6 ]Cl3 (B) [Fe(H2O)5 Cl]Cl2. H2O
(C) [Fe(H2O)4 Cl2 ]Cl . 2H2O (D) [Fe(H2O)3 Cl3 ] . 3H2O

15. The van't Hoff factor of a 0.005 M aqueous solution of KCl is 1.95. The degree of ionization of KCl is
(A) 0.95 (B) 0.97 (C) 0.94 (D) 0.96

16. To 10ml of 1M BaCl2 solution 5ml of 0.5M K2SO4 is added, BaSO4 is precipitated out. What will
happen for the remaining liquid
(A) Freezing point is increased (B) No change in Boiling Point
(C) Freezing point is lowered (D) Boiling Point is lowered

17. Two solutions of KNO3 and CH3COOH are prepared separately. Molarity of both is 0.1M and osmotic
pressures are P1 & P2 respectively. The correct relationship between the osmotic pressures is
P1 P2
(A) P2> P1 (B) P1 = P2 (C) P1> P2 (D) =
P1  P2 P1  P2

18. The substance A when dissolved in solvent B shows the molecular mass corresponding to A3. The vant
Hoff's factor will be
(A) 1 (B) 2 (C) 3 (D) 1/3

19. In certain solvent, phenol dimerizes to the extent of 60%. Its observed molecular mass in that solvent
should be
(A) > 94 (B) = 94 (C) < 94 (D) Unpredictable

20. Select correct statements:

(A) the fundamental cause of all colligative properties is the higher entropy of the solution relative to
that of the pure solvent
(B) the freezing point of hydrofluoride solution is larger than that of equimolal hydrogen chloride
solution
(C) 1 M glucose solution and 0.5 M NaCl solution are isotonic at a given temperature
(D) all are correct statements

11
21. The vapour pressure of an aqueous solution is found to be 750 torr at certain temperature ‘T’. If ‘T’ is
the temperature at which pure water boils under atmospheric pressure and same solution show
elevation in boiling point Tb = 1.04 K, find the atmospheric pressure (Kb  0.52 K kg mol –1 )
(A) 777 (B) 779 (C) 782 (D) 746

22. A 0.2 molal aqueous solution of a weak acid (HX) is 20 percent ionized. The freezing point of this
solution is (Given Kf  1.86º C kg mol –1 for water)
(A) – 0.45ºC (B) – 0.90ºC (C) – 0.31ºC (D) – 0.53ºC

23. In a 0.2 aqueous solution of a weak acid HX, the degree of ionization is 0.3. Taking K f for as 1.85, the
freezing point of the solution will be nearest to:
(A) – 0.480ºC (B) – 0.360ºC (C) – 0.260ºC (D) – 0.53ºC

24. Freezing point of an aqueous solution is –0.186ºC. Elevation of boiling point of the same solution is
Kb  0.512º C m–1, Kf  1.86º C m–1 . The increase in boiling point is:
(A) 0.186ºC (B) 0.0512ºC (C) 0.0092ºC (D) 0.2372ºC

25. The molecular weight of benzoic acid in benzene as determined by depression in freezing point of the
solution is:
(A) ionization of benzoic acid (B) dimerization of benzoic acid
(C) trimerization of benzoic acid (D) salvation of benzoic acid

26. Which salt may show the same value of Vant Hoff factor (i) as that of K4[Fe  CN6 ] in very dilute
solution state-
(A) Al2  SO4 3 (B) NaCl (C) Al  NO3 3 (D) Na2SO4

27. Which compound corresponds Vant Hoff factor (i) to be equal to 2 in dilute solution-
(A) K2SO4 (B) NaHSO4 (C) Sugar (D) MgSO4

28. In which of the following , the Vant Hoff factor (i) is equal to one
(A) NaCl (B) KNO3 (C) Urea (D) All

29. Assuming each salt to be completely dissociated which of the following will have highest osmotic
pressure-
(A) Decimolar Al2  SO4 3
(B) Decimolar BaCl2
(C) Decimolar Na2SO4
(D) A solution obtained by mixing equal volumes of (B) & (C) and filtering

30. Which one of the following pairs of solution can we expect to be isotonic at the same temperature-
(A) 0.1 M urea and 0.1 M NaCl (B) 0.1 M urea and 0.2 M MgCl2
(C) 0.1 M NaCl and 0.1M Na2SO4 (D) 0.1 M Ca  NO3 2 and 0.1 M Na2SO4

31. A complex containing K  , Pt(IV) and Cl – is 100% ionized giving i = 3. Thus, complex is
(A) K2 PtCl4  (B) K2 PtCl6  (C) K3 PtCl5  (D) K PtCl3 

12
32. A liquid mixture having composition corresponding to point z in the figure shown
is subjected to distillation at constant pressure. Which of the following statement
is correct about process:
(A) the composition of distillate differs from the mixture
(B) the boiling point goes on changing
(C) the mixture has highest vapour pressure than for any other composition
(D) composition of an azeotrope alters on changing the external pressure

33. Boiling point – composition diagram of the liquid vapour equilibrium for propanol-
2 (A) and 2-methyl-propanol-1(B) is shown a side. If a binary liquid mixture of A
and B is distilled fractionally, which of the following would be correct observation
(A) Composition of the still (residue) will approach pure liquid A
(B) Composition of the distillate will approach pure B
(C) Composition of distillate and residue will approach pure A and B respectively
(D) Neither of the components can be obtained in pure state

34. Select incorrect statements:

(A) NH3 is soluble in water due to hydrogen bonding as well as due to formation of ions
(B) gases which can be liquefied easily are more solution in water than the gases which cannot be
liquefied
(C) the solute follows Henry law at all pressure of gas
(D) the solute follows Henry law at low pressure of gas

35. 2 litre solution of 0.1 M NaCl and 4 litre of 0.1 M AgNO3 are mixed. The depression of freezing point of
the resultant solution will be [Kf (H2O)  1.86 K kg mol –1 ]
(A) 0.372 K (B) 1.488 K (C) 0.124 K (D) 0.248 K

36. How many grams of glucose should be dissolved in 100 gm water in order to produce a solution with
101.19ºC difference between the freezing point & boiling point temperatures?
(Given: Kf  1.86 K kg mol –1; Kb  0.52 K kg mol –1 )
(A) 9 gm (B) 18 gm (C) 180 gm (D) none of these

37. From separate solutions of four sodium salts NaW, NaX, NaY and NaZ had pH 7.0, 9.0, 10.0 and 11.0
respectively. When each solution was 0.1 M. Van’t Hoff factor (i) is maximum for acid:
(A) HW (B) HX (C) HY (D) HZ

38. Which of the following represents correctly the changes in thermodynamic properties during the
formation of 1 mole of an ideal binary solution:

(A) (B)

(C) (D)

13
39. Pressure cooker reduces cooking time because
(A) the heat is more evenly distributed inside the cooker
(B) a large flame is used
(C) boiling point of water is elevated
(D) whole matter is converted into steam

40. Solubility curves of four ionic salts X, Y, Z, W are given below :

In which case the value of H sol.< 0

(A) X (B) Y (C) Z (D) W

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. Which of the following are correct about the binary homogeneous liquid mixture?
(A) H2O and C2H5OH Hsol.  0, Vsol.  0 (B) C6H6 and C6H5CH3 Hsol.  0, Vsol.  0
(C) CH3 COCH3 and CHCl3 Hsol.  0, Vsol.  0 (D) H2O and HCl Hsol .  0, Vsol.  0

2. Which of the following cannot form ideal solution?

(A) Ethyl alcohol + water (B) Ethyl bromide+Ethyl iodide
(C) Benzene + Toluene (D) Chloroform + Benzene

3. A compound P undergoes association in a given solvent Q as follows:

4P  P4
Which of the following statements is/are correct?
(A)Observed molar  4  Normal molar mass of solute
(B) Experimental boiling point  4  Calculated boiling point
(C) van’t Hoff factor=0.25
(D) Observed osmotic pressure  4  Theoretical or calculated osmotic pressure

4. In a mixture A and B components show negative deviation as:

(A) Vmix  0
(B) Vmix  0
(C) A – B interaction is stronger than A – A and B – B interaction
(D) none of the above reasons is correct

5. Acetone and carbon disulphide form binary liquid solution showing deviation from Roults law. The
normal boiling point (Tb ) for pure acetone is less than that of pure CS2 . Pick out the incorrect
statements among the following:
(A) boiling temperature of mixture is always less than boiling temperature of acetone
(B) boiling temperature of Azeotorphic mixture is always less than boiling temperature of pure CS2
(C) when a small amount of CS2 (less volatile component) is added to excess of acetone boiling point of
resulting mixture increases
(D) a mixture of CS2 and CH3COCH3 can be completely separated by simple fractional distillation

6. Which one of the following statement are true?

(A) Raoult’s law states that the vapour pressure of a component over a solution is proportional to its
molal fraction

14
 (B) the osmotic pressure (  ) of a solution is given by the equation  = MRT, where M is the molality of
the solution
(C) the correct order of osmotic pressure for 0.01 M aqueous solution of each compound is
BaCl2  KCl  CH3COOH  sucrose
(D) two sucrose solution of same molality prepared in different solvents will have the same freezing
point depression

7. The vapour pressure of a dilute solution of a solute is influence by:

(A) temperature of solution (B) mole fraction of solute
(C) mole fraction of solvent (D) degree of dissociation of solute

8. According to Henry’s law, the partial pressure of gas (Pg ) is directly proportional to mole fraction of gas
in dissolved state. i.e, Pgas = KH  Xgas where KH is Henry’s constant. Which are correct:
(A) KH is characteristic constant for a given gas-solvent system
(B) higher is the value of KH lower is solubility of gas for a given partial pressure of gas
(C) KH has temperature dependence
(D) KH increases with temperature

9. Which of the following statement is (are) incorrect?

(A) 0.1 M KCl solution will have the same osmotic pressure as 0.1 M glucose solution
(B) 0.1 M KCl solution will have the same boiling point as 0.1 M urea solution
(C) 0.1 m glucose and 0.1 m urea are isotonic
(D) 0.1 m MgCl2 solution will have less relative lowering of vapour pressure than 0.1 m NaCl

10. Consider following solutions:

 
0.1m C6H5NH3 Cl ; 0.1m KCl; 0.1m Glucose; 0.1 m Na2C2O4 10H2O
(A) The solution with highest boiling point is 0.1 m Na2C2O4 10H2O
(B) The solution with highest freezing point is 0.1 m glucose
(C) 0.1 m C6H5NH3Cl and 0.1 m NaCl will have the same osmotic pressure
(D) 0.1 m glucose solution will have the lowest osmotic pressure

COMPREHENSION TYPE
PARAGRAPH FOR NEXT FOUR QUESTIONS
The vapour pressure of a mixture for liquid-liquid system is given by PM  PAo  X A  PB o
 XB
whereas for solid-liquid system vapour pressure of solution Ps is given by PS  Po  mole fraction
of solvent. The vapour pressure of ethanol + water system is given by
PM(mm)  32.80  11.20 Xethanol .
1. The vapour pressure of pure ethanol is:
(A) 32.80 mm (B) 40 mm (C) 44 mm (D) none of these

2. The vapour pressure of pure H2O is:

(A) 32.80 mm (B) 40 mm (C) 11.20 mm (D) none of these

3. The vapour pressure of a solution having 0.9 mole fraction of ethanol in ethanol water is:
(A) 42.88 (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg

15
4. The vapour pressure of a solution having 0.9 mole fraction of water in ethanol water is:
(A) 39.3 (B) 11.20 (C) 34 (D) 33.92

PARAGRAPH FOR NEXT THREE QUESTIONS

Solubility of an ionic solid substance depends upon temperature, nature of solute and solvent,
complex formation, and H-bonding. It may show exothermic or endothermic nature. The
solubility variation of some ionic compounds with temperature are shown as:
KNO3

solubility in wa ter
KBr
KCl
NaCl

Ca(OH)2
T
5. Which compound is not easily purified by recrystallisation?
(A) KNO3 (B) KBr (C) KCl (D) Ca(OH)2

6. Which shows exothermic dissolution?

(A) KNO3 (B) KBr (C) NaCl (D) Ca(OH)2

7. Which graph correctly represents for solubility of NaOH (Exothermic dissolution)?

S S S S

o o
(A) 0 C T (B) 0 C T (C) 0o C T
(D) 0o C T

MATCH THE FOLLOWING COLUMN

1. Match the column-I with column-II
COLUMN-I COLUMN-II
(Solution) (van’t Hoff factor assuming complete
dissociation/ association)
(A) Ca3 (PO4 )2(aq) (P) i>1
(B) Al2(SO4 )3 (aq) (Q) i=5
(C) Urea (R) i=1
(D) CH3COOH in benzene (S) i<1

2. Match the column-I with column-II

COLUMN-I COLUMN-II
(A) Benzene + Toluene (P) Does not form azeotrope
(B) n-Hexane + n-Heptane (Q) Form minimum boiling azeotrope
(C) Chloroform + acetone (R) Form maximum boiling azeotrope
(D) Ethanol + water (S) Can be separated by fractional
distillation

16
INTEGER ANSWER TYPE
1. A solution containing 25.6 g sulphur dissolved in 1000 g of naphthalene whose melting point is 80.1o C
gave the freezing point lowering by 0.68o C. How many atoms are therein sulphur molecule? (K f for
naphthalene=6.8 K m1 )

2. 1 litre hard water contains 2  103 g of CaCO3. Its degree of hardness in ppm will be equal to

3. An aqueous solution containing ionic salt having molality equal to 0.1892 freezes at 0.704o C. The
1
van’t Hoff factor of the ionic salt is given by ……… (Kf  1.86Km )

4. The ratio of the value of any colligative property for K4[Fe(CN)6 ] (assuming complete dissociation) to
that of the corresponding property of sucrose solution is

5. For [CrCl3  xNH3 ], elevation in boiling point of one molal solution is double of one molal urea solution.
Hence, the value of x (assuming complete dissociation) is

SECTION-III
PREVIOUS YEAR JEE-ADVANCED QUESTIONS
1. Liquids A and B form ideal solution over the entire range of composition. At temperature T,
equimolar binary solution of liquids A and B has vapour pressure 45 torr. At the same
temperature, a new solution of A and B having mole fractions x A and x B , respectively, has
vapour pressure of 22.5 torr. The value of x A / xB in the new solution is ____.
(given that the vapour pressure of pure liquid A is 20 torr at temperature T) [2018]

2. The plot given below shows P  T curves (where P is the pressure and T is the temperature)
for two solvents X and Y and isomolal solutions of NaCl in these solvents. NaCl completely
dissociates in both the solvents.

On addition of equal number of moles of a non-volatile solute S in equal amount (in kg) of
these solvents, the elevation of boiling point of solvent X is three times that of solvent Y.
Solute S is known to undergo dimerization in these solvents. If the degree of dimerization is
0.7 in solvent Y, the degree of dimerization in solvent X is ____. [2018]

17
3. If the freezing point of a 0.01 molal aqueous solution of a cobalt(III) chloride-ammonia
complex (Which behaves as a strong electrolyte) is – 0.0558 o C , the number of chloride(s) in
the coordination sphere of the complex is [Kf of water  1.86K kg mol1] [2015]

4. MX2 dissociates in M2+ and X- ions in an aqueous solution, with a degree of dissociation (α) of
0.5. The ratio of the observed depression of freezing point of the aqueous solution to the value
of the depression of freezing point in the absence of ionic dissociation is [2014]

5. Benzene and naphthalene form an ideal solution at room temperature. For this process, the
true statement(s) is(are) [2013]
(A) ΔG is positive (B) ΔSsystem is positive (C) ΔSsurrounding =0 (D) ΔH=0

18
 ANSWERS TO SOLUTION & COLLIGATIVE PROPERTIES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. C 10. B 19. A 28. C 37. A
2. C 11. D 20. D 29. A 38. C
3. D 12. B 21. A 30. D 39. C
4. C 13. B 22. A 31. B 40. A
5. B 14. D 23. A 32. D
6. C 15. A 24. B 33. C
7. B 16. C 25. B 34. C
8. C 17. C 26. A 35. D
9. A 18. D 27. D 36. A

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. A,B,C 3. A,B,C 5. A,C,D 7. A,B,C,D 9. A,B,D
2. A,D 4. A,C 6. A,B,C 8. A,B,C,D 10. A,B,C,D

COMPREHENSION TYPE
1. C 3. A 5. A 7. C
2. A 4. D 6. D

MATCH THE FOLLOWING COLUMN

1. A  P, Q; B  P, Q; C  R; D  S 2. A  P, S; B  P, S; C  R; D  Q

INTEGER ANSWER TYPE

1. 8 2. 2 3. 2 4. 5 5. 4

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. 19 2. 0.05 3. 1 4. 2 5. B,C,D

19
 CHEMICAL KINETICS
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. The rate constant is numerically the same for three reactions of first, second and third orders
respectively. Which of the following is correct (A is the reactant) :
(A) if [A] = 1 then r1  r2  r3 (B) if [A] < 1 then r1  r2  r3
(C) if [A] > 1 then r3  r2  r1 (D) All
d[A]
2. For the reaction 3A  Products the value of k  1103l mol1 min1 the value of  in
dt
mol/ (-sec) when [A] = 2M is:
(A) 6.67 103 (B) 1.2 102 (C) 2 104 (D) 4 103

3. The rate constant for the reaction A  B is 2 104lt mol1 min1 . The conc. of A at which rate
1
of the reaction is  105 M sec 1 is :
12
1 5
(A) 0.25 M (B) M (C) 0.5 M (D)None of these
20 3

4. What will be the order of reaction and rate constant for a chemical change having log t50% vs
log conc. (A) curves as:
(A) 0, 1/2
(B) 1, 1
(C) 2, 2
(D) 3, 1

5. Which of the following is wrong regarding half life : (take log2 = 0.3)
(A) Half life is proportional to initial conc. for zero order reaction
(B) Half life for 1st order reaction depends only upon temperature and catalyst
(C) 0.5 = 0.1 t99.9 for 1st order reactions
(D) None of these

6. If for a reaction in which A(g) converts to B(q) the reaction carried out at const. V & T results
into the following graph
(A) then the reaction must be A(g)  3B(g) & is a first order reaction

(B) then the reaction must be A(g)  3B(g) & is a second order reaction

(C) then the reaction must be A(g)  3B(g) & is a zero order reaction

(D) then the reaction must be A(g)  3B(g) & is a first order reaction

k k
7. The reaction A   , Products, is zero order while the reaction B   Products, is 1st
order. For what initial conc. of A the half lives of the two reactions are equal ?
(A) 2 M (B)ln 2 M (C) 2 log 2 M (D) 2 ln 2 M

20
8. The time required for 15% decomposition at an initial conc. of 0.1 M in a first order reaction
A  Products, at 80ºC is 25 min, then the time required for decomposition by 0.06 M at an
initial conc. of 0.4 M at 353 K is:
(A) 5 min (B) 0.25 min (C) 25 × n 2 min (D) 25 min
K
9. A reaction 2A + B   C + D is first order with respect to A and 2nd order with respect to
C
B. Initial conc. (t = 0) of A is Co while B is 2Co . If at t = 30 minutes the conc. of C is o then
4
rate expression at t = 30 minutes is:
7C3ok 27C3oK 247C3ok 49kC3o
(A) R  (B) R  (C) R  (D) R 
16 32 64 32

10. For the reaction A + 2B products (started with concentrations taken in stoichiometric
d [A]
proportion), the experimentally determined rate law is– = k [A] [B] . The half time of
dt
the reaction would be
0.693 0.693 0.693
(A) (B) (C) (D)not defined
k 1/ k 2k

11. Identify the statement which is true

(A) the order of reaction is determined by inspection of the stoichiometry of the process
(B) the catalyst changes the G of the reaction
(C) the value of the activation energy for an endothermic reaction is H
(D) diffusion controlled reactions are very rapid and consequently it is difficult to measure
their rates
12. For the reaction A + 2B  Products:
(A) if on changing the conc. of A the rate does not change, then rate may be R  k[A][B]2
(B) if the unit of rate constant is L mol –1sec –1 then rate law may be R  k  A B
3
(C) if the unit of rate constant is L2mol2 min1 min then rate law may be R  k B
(D) if it is known that reaction does not proceed in one step only then molecularity of the
reaction must be 3.

13. The hydrolysis of an ester (Rate law of reaction is, rate = k1 H  ester  = k ester  was carried
 
out separately with 0.05 N HCl and 0.05N H2SO4 . Which of the following will be true?
(A) kHCl  kH2SO4 (B) kH2SO4  kHCl
(C) kH2SO4  2kHCl (D) kH2SO4  kHCl

14. At 27º C it was observed during a reaction of hydrogenation that the pressure of hydrogen gas
decreases from 2 atmospheres to 1.1 atmosphere in 7.5 minutes. Calculate the rate of
reaction (in M sec –1 ) and rate of reaction in terms of pressure.
(A) 8.12 10–5 Ms –1 , 0.12 atm min–1 (B) 6.7 10–3 Ms –1 , 0.12 atm min–1
(C) 8.12 10–3 Ms –1 , 0.24 atm min–1 (D) 6.7 10–3 Ms –1 , 0.24 atm min–1

21
15. The rate of a reaction is expressed in different ways as follows:
1 d[C] 1 d[D] 1 d[A] d[B]
   
2 dt 3 dt 4 dt dt
The reaction is:
(A) 4A  B  2C  3D (B) B  3D 
 4A  2C
(C) A  B  C  D (D) B  D 
A  C

16. Consider the reaction: A  B  C ; Initial concentration of A is 1 M. 20 minutes time is

d[B]
required for completion of 20% reaction. If  k[A ]º , then half life ( t1/2 ) is:
dt
(A) 55.44 min (B) 50 min (C) 62.13 min (D) none of these

17. Consider the reaction A  B, graph between half life (t1/2) and initial concentration (a) of the
reactant is:

t1/2

a
d[A ]
Hence graph between  and time will be:
dt
d[A] d[A] d[A] d[A]
– – – –
d d d d
(A) t (B) t (C) t (D) t
t t t t

18. If decomposition reaction A(g)  B(g) follows first order kinetics then the graph of rate of
formation (R) of B against time t will be:
R R R R

(A) (B) (C) (D)

t t t t

19. The rate constant for the forward reaction A  g   2B  g  is 1.510 s at 100 K . If 10 moles
–3 –1 5

of A and 100 moles of B are present in a 10 litre vessel at equilibrium then rate constant for
the backward reaction at this temperature is:
(A) 1.50104 L mol –1s –1 (B) 1.51011L mol –1s –1
(C) 1.51010 L mol –1s –1 (D) 1.5 10–11L mol –1s –1
1 1
20. Reaction A  B C  D follows following rate law: rate  k[A] [B]2 . Starting with initial
2
conc. of 1 M of A and B each, what is the time taken for concentration of A of become 0.25M
Given: k  2.30310–3 sec –1
(A) 300 sec (B) 600 sec (C) 900 sec (D) none of these
k1 k2
21. Consider the following first order competing reactions: X  A  B and Y  CD
If 50% of the reaction of X was complete when 96% of the reaction of Y was completed, the
ratio of their rate constants (k 2 /k 1 ) is:
(A) 4.06 (B) 0.215 (C) 1.1 (D) 4.65

22
22. For the reaction A + B  C; starting with different initial concentration of A and B, initial rate
of reaction were determined graphically in four experiments:

S.NO. [A]0/M(Initial conc.) [B]0/M(Initial conc.) Rete/(M sec–1)

1. 1.6  10–3 5  10–2 10–3
2. 3.2  10–3 5  10–2 4  10–3
3. 1.6  10–3 10–1 2  10–3
4. 3.2  10–3 10–1 8  10–3

Rate law for reaction from above data is:

(A) r  k[A]2 [B]2 (B) r  k[A]2 [B] (C) r  k[A][B]2 (D) r  k[A][B]

23. At certain temperature, the half life period in the thermal decomposition of a gaseous
substances as follows:
P(mm Hg) 500 250
T1/2(in min) 235 950
Find the order of reaction [Given log (23.5) = 1.37; log (95) = 1.97]
(A) 1 (B) 2 (C) 2.5 (D) 3

24. Consider a reaction A  g   3B  g   2C  g  with rate constant 1.38610–2 min–1 . Starting

with 2 moles of A in 12.5 litre vessel initially, if reactions is allowed to takes place at constant
pressure & at 298 K then find the concentration of B after 100 min:
(A) 0.04 M (B) 0.36 M (C) 0.09 M (D) none of these
25. A first order reaction is 50% completed in 20 minutes at 27ºC and in 5 min at 47ºC. The
energy of activation of the reaction is:
(A) 43.85 kJ/mol (B) 55.14 kJ/mol (C) 11.97 kJ/mol (D) 6.65 kJ/mol
26. For the first order reaction A  B  C , carried out at 27ºC if 3.810–16 % of the reactant
molecules exists in the activated state, the Ea (activation energy) of the reaction is:
(A) 12 kJ/mole (B) 831.4 kJ/mole (C) 100 kJ/mole (D)88.57kJ/mole

27. M M 8
Z A(s) Z 4 B(s)   -particles
The radioactive disintegration follows first order kinetics. starting with 1 mole of A in a 1 litre
closed flask at 27ºC, pressure set up after two half-lives is approximately
(A) 25atm (B) 12atm (C) 37atm (D) 40atm
28. The number of neutrons accompanying the formation of 54 X
139
and 38 Sr
94
from the absorption
of slow neutron by 92 U 235 followed by nuclear fission is:
(A) 0 (B) 2 (C) 1 (D) 3
29. Two radioactive nuclides A and B have half lives of 50 min and 10 min respectively. A fresh
sample contains the nuclides of B to be eight time that A. How much time should elapse so
that the number of nuclides of A becomes double of B:
(A) 30 (B) 40 (C) 50 (D) none

30. The half-life of radioisotope is four hours. If the initial mass of the isotope was 200g, the mass
remaining after 24 hours undecayed is:
(A) 1.042g (B) 2.084g (C) 3.125g (D) 4.167g

23
31. A radioactive element gets spilled over the floor of a room. Its half-life period is 30 days. If the
initial activity is ten times the permissible value, after how many days will it be safe to enter
the room?
(A) 1000 days (B) 300 days (C) 10 days (D) 100 days

32. The radioactive sources A and B of half lives of t hr and 2t hrs respectively, initially contain
the same number of radioactive atoms. At the end of t hours, their rates of disintegration are
in the ratio:
(A) 2 2 : 1 (B) 1 : 8 (C) 2 : 1 (D) n 2 : 1

33. The analysis of a mineral of uranium revels that ratio of mole of 206 Pb & 238 U in sample is
0.2. If effective decay constant of process 238 U 206 Pb is  then age of rock is:
1 1 5 1 4 1 6
(A) (B) ln   (C) ln (D) ln  
  1  1  5

34. The half-life of Tc99 is 6.0hr. The delivery of a sample of Tc99 from the reactor to the nuclear
medicine lab of a certain hospital takes 3.0hr. What is the minimum amount of Tc99 that
must be shipped in order for the lab to receive 10.0 mg?
(A) 20.0 mg (B) 15.0 mg (C) 14.1 mg (D) 12.5 mg

A
35. A sample contains 0.1 gram atom of radioactive isotope Z X (t1/2  5 days) . How many
number of atoms will decay during eleventh day? [NA = Avogadro’s number]
  0.69311 
0.69310    0.69311 
0.69310 
(A) 0.1 e 5 e 5  (B) 0.1 e 5 e 5 
   
   
  0.693 11 0.693 10    0.693 11 0.693 10 
 
(C) 0.1 e 5 e 5  (D) 0.1 e 5 e 5 
   
   

36. The average (mean) life at a ratio nuclide which decays by parallel path is:

1 B ;
A  1  1.8 102 sec–1
2A 

1 C ; 2  103 sec–1
(A) 52.63 sec (B) 500 sec (C) 50 sec (D) none

37. The radioactive nuclides A and B have half-lives of 50 min and 10 min respectively. A fresh
sample contains the nuclides of B to be eight time that of A. How much time should elapse so
that the number of nuclides of A becomes double of B:
(A) 30 (B) 40 (C) 50 (D) none
14
38. A sample of CO2 was to be mixed with ordinary CO2 for a biological tracer experiment. In
order that 10cm3 of diluted gas should have 104 dis/min, what activity (in  Ci) of radioactive
carbon is needed to prepare 60 L of diluted gas at STP. [1 Ci  3.71010 dps]
(A) 270  Ci (B) 27  Ci (C) 2.7  Ci (D) 2700  Ci

24
39. Hydrogen peroxide solution was stored in a mild steel vessel. It was found, however, that the
hydrogen peroxide decomposed on the walls of the vessel (a first order reaction). An experiment
with 100 ml of a solution gave 10.31 ml oxygen (corrected to 1atm & 273 K) after 5.1 days
under similar storage conditions. Find how long the peroxide can be stored before the loss of
20.00 ml oxygen occurs (per 100 ml solution) if complete decomposition of the sample to H2O2
gave 46.34 ml oxygen.
(A) 8.5 days (B) 11.5 days (C) 13.5 days (D) 16.5 days

40. The following data were obtained in experiment on inversion of cane sugar
Time (minutes) 0 60 120 180 360 
Angle of rotation +13.1 +11.6 +10.2 +9.0 +5.87 – 3.8
After what time would you expect a zero reading in polarimeter?
(A) 533 min (B) 766 min (C) 966 min (D) 1333 min

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. Rate law expression of a reaction is:
Rate  k[A]2/3[B]
Which of one following are correct about the corresponding reaction?
2 5
(A) Order of reaction   1  (B) Unit of rate constant= L2/3mol2/3 sec1
3 3
(C) Unit of rate constant  atm2/3 sec1 (D) Unit of rate constant  mol L1 sec1

2. Which of the following are correct expression for Arrhenius equation?

E
(A) A  keEa /RT (B) ln k  ln A  a
RT
Ea E
(C) log10 k  log10 A  (D) ln A  ln k  a
2.303RT RT

3. Which of the following values of the molecularity are not possible?

(A) 0 (B) 2 (C) 3 (D) 4

4. Which of the following are true for the first order reaction?
(A) t3/4  2t1/2 (B) t15/16  4t1/2 (C) t15/16 (D) t7/8  2t3/4

5. Activation energy of forward and backward process of a reaction are 60kJ and 40kJ mol1
respectively. Which of the following are true for the reaction?
(A) it is endothermic reaction
(B) it is exothermic reaction
(C) Heat of reaction is +20 kJ mol1
(D) Threshold energy of reaction is 100 kJ mol1

6. If ‘a’ is initial concentration of reactant and (a-x) is the remaining concentration after time ‘t’
in a first order reaction of rate constant k1 . Then which of the following relations is/are
correct?

25
 2.303  a 
(A) x  a(1  ek1t ) (B) k1  log10  
t a x
n
1 t 1
(C) (a  x)  a   ,where n  (D) Average life  
2 t1/2 k

7. The observed rate of a chemical reaction is substantially lower than the collision frequency.
One or more of the following statement is/are true to account for this fact
(A) the reactants do not have the required energy
(B) the partners do not collide in the proper orientation
(C) collision complex exists for a very short time
(D) collision frequency overestimates the number of effective collision

8. Select the correct statement(s) among following:

(A) Increase in concentrations of reactant increases the rate of a zero order reaction
(B) Rate constant k is equal to collision frequency A, if Ea  0
(C) Rate constant k is equal to collision frequency A if Ea  
(D) log10 k vs 1/ T is a straight line

9. Select the correct statement(s):

(A) On bombarding 7 N14 nuclei with  -particle, the nuclei of the product formed after release
of proton would be 8 O17
(B) Decay constant does not depend upon temperature
(C) Nuclide and it’s decay product after  -emission are called isodiaphers
(D) Half-life of radium is 1580 years. It’s average life will be 1097.22 years

10. In electron capture (radioactive process):

(A) a neutron is formed (B) A proton is consumed
(C)  -ray emission takes place (D) X-ray emission takes place

COMPREHENSION TYPE
PARAGRAPH FOR NEXT THREE QUESTIONS:
Nuclei of a radioactive element ‘A’ are being produced at a constant rate  . The element has a
decay constant  . At time t = 0, there are N0 nuclei of the element.
1. The number of nuclei of A at time ‘t’ is:
(A)



1  et  (B) N0 .et

1 N .    
(C) [  (  N0 )et ] (D) 0 1  1   et 
     
2. If   2N0 , the number of nuclei of A after one half life of A becomes:
(A) zero (B) 2N0 (C) 1.5 N0 (D) 0.5 N0
3. If  = 4N 0  , the number of nuclei of A when A has reached steady state:
(A) zero (B) 4N0 (C) 2N0 (D) N0

26
PARAGRAPH FOR NEXT TWO QUESTIONS:
Mass defect in the nuclear reactions may be expressed in terms of the atomic masses of the
parent and daughter neuclides in place of their nuclear masses.
4. The mass defect of nuclear reaction: 4 Be10 5 B10  e is:
(A) m  At. mass of 4 Be10  At. mass of 5 B10
(B) m  At. mass of 10 At. mass of 10
4 Be  5 B – mass of one electron
(C) m  At. mass of 4 Be10  At. mass of 5 B10 + mass of one electron
(D) m  At. mass of 4 Be10  At. mass of 5 B10 – mass of two electron

5. The mass defect of the nuclear reaction: 5 B8 4 Be8  e is:

(A) m  At. mass of 5 B8  At. mass of 4 Be8
8
(B) m  At. mass of 5B  At. mass of 4 Be8 – mass of one electron
8
(C) m  At. mass of 5B  At. mass of 4 Be8 + mass of one electron
8
(D) m  At. mass of 5B  At. mass of 4 Be8 – mass of two electron

MATCH THE FOLLOWING COLUMN

1. Match the following column I & column II.
Column I (Linear plots (with non zero slope) Column II (Order)
 d[A] 
(A) ln    vs. ln[A] (P) 2
 dt 
1 1
(B) log e k vs (Q)
T 2
(C) log t1/2vs. log[A]0 (R) 0
d[A]
(D) vs. [A]2 (S) 1
dt
2. Match the following column I & column II.
Column I Column II

(A) log[B] vs t (P)

(B) [A] vs t (Q)

1
(C) vs t (R)
[A]

27
 1
(D) ln k vs (S)
T

INTEGER ANSWER TYPE

1
1. A reaction X2 (g)  Z(g)  Y(g) exhibits an increase in pressure from 150min. to 170mm in
2
10min. The rate of disappearance of X2 in mm per min is

2. For the reaction A2  B2  2AB

[ A2 ] [B2 ] Rate of reaction (mol L1 sec 1 )
0.2 M 0.2 M 0.04
0.1 M 0.4 M 0.04
0.2 M 0.4 M 0.08
Order of the reaction will be
1
3. A plot of vs time is linear for the reaction: 3BrO (aq)  BrO3 
(aq)  2Br  (aq)

[BrO ]
What is the order of the reaction with respect to the hypobromite ion BrO ?

4. In the reaction: 2NO(g)  Cl2(g)  2NOCl(g)

If the reaction rate doubles when the concentration of Cl2 is doubled and the rate quadruples
when the concentration of NO is doubled. By what factor will the rate increase if both
concentrations NO and Cl2 are doubled?

5. Half of a substance is 40 min. When the quantity of substance is decreased to half, the half-
life of the substance changes to 20min. The order of reaction is

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. Consider the following reversible reaction,
A(g)  B(g)  AB(g)
The activation energy of the backward reaction exceeds that of the forward reaction by
2RT (in J mol1) . If the pre-exponential factor of the forward reaction is 4 times that of the
reverse reaction, the absolute value of G0 (in J mol1) for the reaction at 300 K is ____.
(Given; ln(2) = 0.7, RT = 2500 J mol1 at 300 K and G is the Gibbs energy) [2018]

28
2. For a first order reaction A(g) → 2B(g) + C(g) at constant volume and 300 K, the total
pressure at the beginning (t = 0) and at time t are P0 and Pt , respectively. Initially, only A
is present with concentration [A]0 , and t1/3 is the time required for the partial pressure of
A to reach 1/3rd of its initial value. The correct option(s) is (are) [2018]
(Assume that all these gases behave as ideal gases)

(A) (B)

(C) (D)

3. In a bimolecular reaction, the steric factor P was experimentally determined to be 4.5. The
correct option(s) among the following is(are) [2017]
(A) The activation energy of the reaction is unaffected by the value of the steric factor
(B) Experimentally determined value of frequency factor is higher than that predicted by
Arrhenius equation.
(C) The value of frequency factor predicted by Arrhenius equation is higher than that
determined experimentally
(D) Since P  4.5, the reaction will not proceed unless an affective catalyst is used

4. A plot of the number neutrons (N) against the number of protons (P) of stable nuclei exhibits
upward deviation from linearity for atomic number, Z  20 . For a unstable nucleus having
N/P ratio less than 1, the possible mode(s) of decay is(are) [2016]
(A)   decay (emission) (B) orbital or K-electron capture
(C) neutron emission (D)   decay (positron emission)

5. According to the Arrhenius equation, [2016]

(A) a high activation energy usually implies a fast reaction.
(B) rate constant increases with increase in temperature. This is due to a greater number of
collisions whose energy exceeds the activation energy.
(C) higher the magnitude of activation energy, stronger is the temperature dependence of the
rate constant.
(D) the pre-exponential factor is a measure of the rate at which collisions occur, irrespective of
their energy.

29
6. A closed vessel with rigid walls contains 1 mole of 238
92 U
and 1 mol of air at 298 K. Considering
complete decay of 92 U to 82 Pb , the ratio of the final pressure to the initial pressure of the
238 206

system at 298 K is [2015]

7. In dilute aqueous H2SO4 , the complex diaquodioxalatoferrate (II) is oxidized by MnO4 . For
this reaction, the ratio of the rate of change of [H ] to the rate of change of [MnO4 ] is.
[2015]
8. The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100 th of that
of a strong acid (HX, 1M), at 25o C . The K a of HA is [2013]
(A) 1104 (B) 1105 (C) 1106 (D) 1103

9. In the nuclear transmutation

8
9
4Be+X  4 Be+Y
(X, Y) is (are) [2013]
(A) (γ,n) (B) (p,D) (C) (n, D) (D) (γ, p)

10. An organic compound undergoes first-order decomposition. The time taken for its
decomposition to 1/8 and 1/10 of its initial concentration are t1/8 and t1/10 respectively.
[t1/8 ]
What is the value of  10 ? (Take : log10 2  0.3 ) [2012]
[t1/10 ]

11. The periodic table consists of 18 groups. An isotope of copper, on bombardment with protons,
undergoes a nuclear reaction yielding element X as shown below. To which group, element X
belongs table? 63 1 1 1
29 Cu  1H  60 n    21H  X [2012]

12. The activity of a freshly prepared radioactive sample is 1010 disintegrations per second, whose
mean life is 109 s. The mass of an atom of this radioisotope is 1025 kg. The mass (in mg) of the of
the radioactive sample is [2011]
13. For the first order reaction 2N2O5(g)  4NO2(g)  O2(g) [2011]
(A)The concentration of the reactant decreases exponentially with time
(B)The half-life of the reaction deceases with increasing temperature
(C) The half-life of the reaction depends on the initial concentration of the reactant
(D) The reaction proceeds to 99.6% completion in eight half-life duration

14. The concentration of R in the reaction R  P was decreased as a function of time and the
following data is obtained: [2010]
[R] (molar) 1.0 0.75 0.40 0.10
T (min.) 0.0 0.05 0.12 0.18
The order of reaction is
15. The number of neutrons emitted when 235
92 U undergoes controlled nuclear fission to 142
54 Xeand
38 Sr is [2010]
90

16. The total number of  and  particles emitted in the nuclear reaction 238 214
92 U  82 Pb is
[2009]

30
 ANSWERS TO CHEMICAL KINETICS
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. D 10. C 19. D 28. D 37. C
2. C 11. D 20. B 29. C 38. B
3. C 12. B 21. D 30. C 39. B
4. A 13. D 22. B 31. D 40. C
5. D 14. A 23. D 32. C
6. C 15. B 24. C 33. D
7. D 16. B 25. B 34. C
8. D 17. B 26. C 35. C
9. D 18. C 27. C 36. C

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. A,B,C 3. A,D 5. A,C 7. A,B,D 9. A,B,C
2. C,D 4. A,B 6. A,B,C,D 8. B,D 10. A,B,D

COMPREHENSION TYPE
1. C 2. C 3. B 4. A 5. D

MATCH THE FOLLOWING COLUMN

1. A  PQS; B  PQRS; C  PQR; D  P 2. A  P; B  R; C  Q; D  S

INTEGER ANSWER TYPE

1. 4 2. 2 3. 2 4. 8 5. 0

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. 8500 5. B,C,D 9. A,B 13. A,B,D
2. A,D 6. 9 10. 9 14. 0
3. A,B 7. 8 11. 8 15. 4
4. B,D 8. A 12. 1 16. 8

31
 ELECTROCHEMISTRY
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. How many Faradays are required to reduce 1 mol of BrO 3 to Br  ?
(A) 3 (B) 5 (C) 6 (D) 4

2. Aluminium oxide may be electrolysed at 1000ºC to furnish aluminium metal. The cathode
reaction is Al 3  3e   Al . To prepare 5.12 kg of aluminium metal by this method would
require
(A) 5.49107 C of electricity (B) 1.83107 C of electricity
(C) 5.49104 C of electricity (D) 5.491010 C of electricity

3. One mole of electron passed through each of the solution of AgNO3 , CuSO4 and AlCl3 when
Ag, Cu and Al are deposited at cathode. The molar ratio of Ag, Cu and Al deposited are:
(A) 1 : 1 : 1 (B) 6 : 3 : 2 (C) 6 : 3 : 1 (D) 1 : 3 : 6

4. Salts of A (atomic weight = 7), B (atomic weight = 27) and C (atomic weight = 48) were
electrolyzed under identical conditions using the same quantity of electricity. It was found
that when 2.1 g of A was deposited, the weight of B & C deposited were 2.7 and 7.2g. The
valencies of A, B and C respectively are:
(A) 3, 1 & 2 (B) 1, 3 & 2 (C) 3, 1 & 3 (D) 2, 3 & 2

5. The density of Cu is 8.94 g cm–3 . The quantity of electricity needed to plate an area
10cm  10cm to a thickness of 10 –2 cm using CuSO4 solution, would be:
(A) 13586 c (B) 27172 C (C) 40758 C (D) 20348 C

6. During electrolysis of an aqueous solution of sodium sulphate, 2.4 L of oxygen at STP was
liberated at anode. The volume of hydrogen at STP, liberated at cathode would be:
(A) 1.2 L (B) 2.4 L (C) 2.6 L (D) 4.8 L
7. During electrolysis of an aqueous solution of CuSO4 using copper electrodes, if 2.5 g of Cu is
deposited at cathode, then at anode
(A) 890 ml of Cl2 at STP is liberated (B) 445 ml of O2 at STP is liberated
(C) 2.5 g of copper is deposited (D) a decrease of 2.5 g of mass takes place

8. An aqueous solution containing one mole per litre each of Cu  NO3 2 , AgNO3, Hg2  NO3 2 is
being electrolyzed by using inert electrodes. The value of standard potentials are:
º º º º
EAg 
|Ag
 0.80V, EHg 2
|Hg
 0.79V, ECu 2
|Cu
 0.34V and E Mg 2
|Mg
 2.3V
2

With increasing voltage, the sequence of deposition of metals on the cathode will be:
(A) Ag, Hg, Cu, Mg (B) Mg, Cu, Hg, Ag
(C) Ag, Hg, Cu (D) Cu, Hg, Ag

2
9. The charge required for the oxidation of one mole Mn 3O4 into MnO 4 in presence of alkaline
medium is
(A) 5  96500 C (B) 96500C (C) 10  96500 C (D) 2  96500 C

32
10. The cost at 5paise/KWH of operating an electric motor for 8 hours which takes 15amp at
110V is
(A) Rs.66 (B) 66paise (C) 37paise (D) Rs.6.60

11. A solution of sodium sulphate in water is electrolyzed using inert electrodes. The products at
the cathode and anode are respectively:
(A) H2, O2 (B) O2, H2 (C) O2, Na (D) none

12. When an aqueous solution of lithium chloride is electrolyzed using graphite electrodes:
(A) Cl2 is liberated at the anode
(B) Li is deposited at the cathode
(C) as the current flows, pH of the solution around the cathode remains constant
(D) as the current flows, pH of the solution around the cathode decreases

13. The equilibrium constant for the reaction Sr(s)  Mg 2 (aq)  Sr 2 (aq)  Mg (s) is
2 2
2.691012 at 25ºC .The Eº for a cell made up of the Sr /Sr and Mg /Mg half cells
(A) 0.3667 V (B) 0.7346 V (C) 0.1836 V (D) 0.1349 V

14. When G  100 kJ mol –1and n  1 , the potential of the cell is:
(A) 2V (B) 1 V (C) 10 V (D) 5 V
15. For a cell reaction involving a two electron change, the standard emf of the cell is found to be
0.295 V at 25ºC. The equilibrium constant of the reaction at 25ºC will be:
(A)110–10 (B) 29.510–2 (C) 10 (D) 11010
16. Standard electrode potential of three metals, A, B and C are + 0.5 V, – 3.0 V and – 1.2 V
respectively. The reducing power of these metals are:
(A) B > C > A (B) A > B > C (C) C > B > A (D) A > C > B

17. Consider the following Eº values: Eº  0.77V ; Eº 2  0.14V

Fe3 |Fe2 Sn |Sn
Under standard conditions the potential for the reaction is:
Sn(s)  2Fe3 (aq)  2Fe2 (aq)  Sn2 (aq)
(A) 1.68 V (B) 1.40 V (C) 0.91 V (D) 0/63 V
 2
18. In a cell that utilizes the reaction Zn s   2H  aq   Zn aq   H2  g  addition of
H2SO4 to cathode compartment, will
(A) lower the E and shift equilibrium to the left
(B) lower the E and shift the equilibrium to the right
(C) increases the E and shift the equilibrium to the right
(D) increase the E and shift the equilibrium to the left
19. When the electric current is passed through a cell having an electrolyte, the positive ions
move towards cathode and negative ions towards the anode. If the cathode is pulled out of the
solution
(A) the positive and negative ions will move towards anode
(B) the positive ions will start moving towards the anode while negative ions will stop moving
(C) the negative ions will continue to move towards anode while positive ions will stop moving
(D) the positive and negative ions will start moving randomly

33
20. Pure water is saturated with pure solid AgCl, a silver electrode is placed in the solution and
the potential is measured against normal calomel electrode at 25°C. This experiment is then
repeated with a saturated solution of AgI. If the difference in potential in the two cases is
0.177V. What is the ratio of solubilities of AgCl and AgI at the temperature of the experiment?
(A)103 (B)106 (C)102 (D) 102

21. For Zn2  / Zn, E  –0.76 V, for Ag  / Ag E  0.799 V . The correct statement is
(A) the reaction Zn getting reduced Ag getting oxidized is spontaneous
(B) Zn undergoes reduction and Ag is oxidized
(C) Zn undergoes oxidation Ag  gets reduced
(D) No suitable answer

22. A solution of cadmium sulphate is electrolysed using inert electrodes. What volume of moist
oxygen will be liberated per gram of cadmium produced? [Atomic weight of Cd = 112.41,
temperature = 25°C, aqueous tension at 25°C is 23.55 mm, pressure of moist oxygen = 760 m]
(A) 0.1012 l (B) 0.1123 l (C) 0.1312 l (D) 0.0998 l

AgBr(s), Br¯ Fe3  , Fe2

23. What is the emf at 25° C for the cell, Ag , Pt
a  0.34a  0.1 a  0.02
The standard reduction potentials for the half-reactions
AgBr  e¯  Ag  Br¯and Fe3  e¯ Fe2 are + 0.0713 V and + 0.770 V respectively.
(A) 0.474 volt (B) 0.529 volt (C) 0.356 volt (D) 0.713 volt
º
24. The E M3|M2  values for Cr, Mn, Fe and Co are – 0.41, + 1.57, 0.77 and + 1.97 V respectively.
For which one of these metals the change in oxidation state from + 2 and + 3 is easiest?
(A) Cr (B) Mn (C) Fe (D) Co

25. Consider the following Galvanic cell: By what value the cell voltage change when
concentration of ions in anodic and cathodic compartment both increased by factor of 10 at
298K
(A) + 0.0591
(B) – 0.0591
(C) – 0.1182
(D) 0

 
26. For the cell Pt|H2 (0.4atm)|H (pH  1)||H (pH  2)|H2 (0.1atm)|Pt
The measured potential at 25ºC is:
(A) – 0.1 V (B) – 0.5 (C) – 0.041 (D) none
º
27. For the fuel cell reaction 2H2(g)  O2(g)  2H2O(); f H298 (H2O, ) = – 285.5 kJ/mol. What is
Sº298 for the given fuel cell reaction? Given : O2(g)  4H (aq)  4e  2H2O() Eº = 1.23 V
(A) – 0.322 J/K (B) – 0.635 kJ/K (C) 3.51 kJ/K (D) – 0.322 kJ/K
2 2 
28. The standard reduction potentials of Cu /Cu and Cu /Cu are 0.337 and 0.153V

respectively. the standard electrode potential of Cu /Cu half cell is:
(A) 0.184 V (B) 0.827 V (C) 0.521 V (D) 0.490 V

34
29. A hydrogen electrode X was placed in a buffer solution of sodium acetate and acetic acid in
the ratio a : b and another hydrogen electrode Y was placed in a buffer solution of sodium
acetate and acetic acid in the ratio b : a. If reduction potential values for two cells are found
to be E1 and E2 respectively w.r.t. standard hydrogen electrode, the pKa value of the acid can
be given as:
E1  E 2 E2  E1 E1  E2 E1  E 2
(A) (B) (C)  (D)
0.118 0.118 0.118 0.118

30. Given the date at 25ºC

Ag  I   AgI  e  ; Eº = 0.152 V
 RT 
Ag  Ag   e  ; Eº = – 0.800 V  2.309  0.059V 
 F 
What is the value of log Ksp for AgI?
(A) – 8.12 (B) + 8.9612 (C) – 37.83 (D) – 16.13

31. The highest electrical conductivity of the following aqueous solutions is of:
(A) 0.1 M acetic acid (B) 0.1 M chloroacetic acid
(C) 0.1 M fluoroacetic acid (D) 0.1 M difluroacetic acid

32. The limiting molar conductivities º m for NaCl, KBr and KCl are 126, 152 and
150 S cm2mol –1 respectively. The  m for NaBr is:
º

(A)128 S cm2mol –1 (B)176 S cm2mol –1

(C) 278 S cm2mol –1 (D) 302 S cm2mol–1

33. The resistance of 0.5M solution of an electrolyte in a cell was found to be 50  . If the
electrodes in the cell are 2.2cm apart and have an area of 4.4cm2 then the molar conductivity
(in S m2mol –1 ) of the solution is
(A) 0.2 (B) 0.02 (C) 0.002 (D) none of these

34. Equivalent conductance’s of 0.1 M HA (weak acid) solution is 10Scm2 equivalent –1 and that at
infinite dilution is 200Scm2equivalent –1 . Hence pH of HA solution is:
(A) 1.3 (B) 1.7 (C) 2.3 (D) 3.7

35. If x is specific resistance of the electrolyte solution and y is the molarity of the solution, then
 m is given by
1000x x 1000 xy
(A) (B) 1000 (C) (D)
y y xy 1000

36. The dissociation constant of n-butyric acid is 1.610–5 and the molar conductivity at infinite
dilution is 38010–4 Sm2mol –1 . The specific conductance of the 0.01 M acid solution is:
(A) 1.5210–5 Sm–1 (B)1.5210–2 Sm–1 (C)1.5210–3 Sm–1 (D) none
º º
37. The molar conductivities  NaOAC and  HCl at infinite dilution is water at 25ºC are 91.0 and
º
426.2 S cm2/mol respectively. To calculate  HOAc the additional value required is:
º º º
(A) ºH O2
(B)  KCl (C)  NaOH (D)  NaCl

35
38. The conductivity of a saturated solution of Ag3PO4is 91-6Sm–1 and its equivalent
conductivity is 1.5010–4 S m2 equivalent –1 . The Kspof Ag3PO4 is:
(A) 4.3210–18 (B)1.810–9 (C) 8.6410–13 (D) none of these

39. A saturated solution in AgA (Ksp  310–14 ) and AgB(Ksp  110–14 ) has conductivity of

37510–10 Scm–1 and limiting molar conductivity of Ag and A

are 60 & 120 Scm2mol –1
respectivley then what will be the limiting molar conductivity of B  (in Scm2mol –1 )?
(A) 150 (B) 180 (C) 190 (D) 270

40. Equal volumes of 0.015 M CH3COOH & 0.015 M NaOH are mixed together. What would be
molar conductivity of mixture if conductivity of CH3COONa is 6.310–4 S cm–1 ?
(A) 8.4 S cm2mol –1 (B) 84 S cm2mol –1 (C) 4.2 S cm2mol –1 (D) 42 Scm2mol–1

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. In an electrochemical cell, a salt bridge is used
(A) to avoid mechanical contact of electrolyte solution in cathodic and anodic half-cell
(B) to maintain electrical neutrality in the cell
(C) to avoid liquid junction potential
(D) to mix the solution of anodic and cathodic half cell

2. If 9 gm H2O is electrolysed completely with the current of 50% efficiency then:

(A) 96500 charge is required (B) 2  96500C charge is required
(C) 5.6L of O2 at S.T.P. will be formed (D) 11.2L of O2 at S.T.P. will be formed

3. A galvanic cell involves the following reaction,

Zn(s)  2Ag  (aq)  Zn2 (aq)  2Ag(s)
Select the correct statement among the following:
(A) Zinc is negative charged
(B) The given redox process is spontaneous
(C) Ag   e  Ag, takes place at anode
(D) Zn(s)  Zn2  2e , takes place at cathode

4. Given that,
Eo 2  0.25V, Eo 2  0.34V
Ni /Ni Cu /Cu

Eo   0.80V, Eo 2  0.76V
Ag /Ag Zn /Zn
Which of the following redox processes will not take place in specified direction?
(A) Ni2 (aq)  Cu(s)  Ni(s)  Cu2 (aq) (B) Cu(s)  2Ag  (aq)  Cu2 (aq)  2Ag(s)
(C) Cu(s)  2H (aq)  Cu2 (aq)  H2(g) (D) Zn(s)  2H (aq)  Zn2 (aq)  H2(g)

36
5. The main factors which affect corrosion are:
(A) position of metal in electrochemical series (B) presence of CO2 in water
(C) presence of impurities in metal (D) presence of protective coating
6. Rusting on the surface of iron involves
(A) Fe(s)  Fe2 (aq)  2e (at anodic site)
(B) O2(g)  4H (aq)  4e  2H2O(l) (at cathodic site)
(C) 4Fe2 (aq)  O2(g)  4H2O(l)  2Fe2O3(s)  8H
(D) Fe2O3 (s)  xH2O(l)  Fe2O3.xH2O

7. Pb(s)| PbSO4 || PbI2 ||Pb(s)

Saturated Saturated
solution solution
o
Which of the following expression represents the cell potential of above cell at 25 C?
0.059 [Pb2 ]cathode 0.059 [Pb2 ]anode
(A) E  log10 (B) E  log10
2 [Pb2 ]anode 2 [Pb2 ]cathode
0.059 Ksp (PbI2 ) 0.059 (KspPbI2 /4)1/3
(C) E  log10 (D) E  log10
2 Ksp (PbSO4 ) 2 (KspPbSO4 )1/2

E
8. The temperature coefficient of cell is  
 . Then
 T P
E
(A) When    0, then H  nFE

 T P
E
(B) When  
  0, then nFE  H and it is endothermic reaction
 T P
E
(C) When  
  0, then nFE  H and it is endothermic reaction
 T P
E
(D) When  
  0, then H  nFE and it is endothermic reaction
 T P

9. During the discharge of lead storage battery

(A) PbO2 is reduced
(B) Pb is oxidized
(C) specific gravity of H2SO4 gives extent of discharging
(D) equivalent mass of H2SO4 is 98

10. In the following concentration cell,

10
Ag(s)|AgCl (saturated)|AgNO3 (aq)(1M)|Ag(s); Ksp AgCl  1 10 ; The cell potential will be
(A) Ecell  2.96V (B) Ecell  0.2955V
1 o 0.059
(C) Ecell  0.059 log (D) Ecell  Ecell  log Ksp AgCl
Ksp AgCl 1

37
COMPREHENSION TYPE
PARAGRAPH FOR NEXT TWO QUESTIONS:
Chromium metal can be plated out from an acidic solution containing CrO 3 according to
 
following equation: CrO 3 (aq)  6H (aq)  6e  Cr(s)  3H 2 O
1. How many grams of chromium will be plated out by 24000 coulombs
(A) 1.5 gm (B) 2.1554gm (C)2.75 gm (D)3.255 gm

2. How long will it take to plate out 1.5 gm of chromium by using 12.5 ampere current
(A) 1336.15 sec (B) 1124.25 sec (C) 1000.00 sec (D)1645.75 sec

PARAGRAPH FOR NEXT THREE QUESTIONS:

A sample of water from a large swimming pool has a resistance of 10000  at 25ºC when placed
in a certain conductance cell. When filled with 0.02 M KCl solution, the cell has a resistance of
100  at 25ºC. 585 gm of NaCl were dissolved in the pool, which was thoroughly stirred. A
sample of this solution gave a resistance of 8000  .
[Given: Molar conductance of NaCl at that concentration is 1251cm2mol –1 and molar
conductivity of KCl at 0.02 M is 200  1 cm2mol –1 ]
3. Cell constant (in cm–1 ) of conductance cell is:
(A) 4 (B) 0.4 (C) 410–2 (D) 410–5

4. Conductivity ( Scm–1 ) of H2O is:

(A) 4 10–2 (B) 410–3 (C) 410–5 (D) none of these

5. Volume (in litres) of water in the pool is:

(A) 1.25  105 (B) 1250 (C) 12500 (D) none of these

MATCH THE FOLLOWING COLUMN

1. Match the following column I & column II.
Column I Column II
(A) Dilute solution of HCl (P) O2 evolved at anode
(B) Dilute solution of NaCl (Q) H2 evolved at cathode
(C) Concentration solution of NaCl (R) Cl2 evolved at anode
(D) Rairly concentrate solution of AgNO3 (S) Ag deposition at cathode

2. Match the following column I & column II.

Column I Column II
(A) Galvanic cell (P) Used in space craft
(B) Electrolytic cell (Q) No transformation of electrical energy
into chemical energy
(C) Dead battery (R) Cell reaction is spontaneous
(D) Fuel cell (S) Cell reaction is non-spontaneous

38
INTEGER ANSWER TYPE
1. At what pH the potential of hydrogen electrode will be 0.059 V?

Amount of silver deposited in electroplating by a current of 4amp. for 2 minute

2. x
Amount of silver deposited by a current of 6 amp. for 40 second
The value of x will be
2.303RT
3. In the Nernst equal, E  Eo  log10 Q , Q will be equal to the equilibrium constant K c ,
nF
when the cell potential E is equal to

4. I2(s)/I (1.0M) half-cell is connected to H (aq)|H2 1 atm|Pt half-cell and its cell potential is
found to be 0.7714 V. If Eo  0.535V, the pH of H /H2 half-cell will be
I2/I

5. A solution containing 1M XSO4(aq) and 1M YSO4(aq) is electrolysed. If conc. of X2 is 10z M

when deposition of Y2 and X2 starts simultaneously. Calculate the value of Z.
2.303RT
Given:  0.06
F
Eo 2  0.12V; Eo 2  0.24V
X |X Y |Y

SECTION-III
PREVIOUS YEAR JEE-ADVANCE QUESTIONS
1. Consider an electrochemical cell: A(s)|An (aq, 2M)||B2n (aq,1M)|B(s) . The value of H0
for the cell reaction is twice that of G0 at 300 K. If the emf of the cell is zero, the S0
(in J K 1 mol1 ) of the cell reaction per mole of B formed at 300 K is ____.
(Given: ln(2) = 0.7, �(universal gas constant) = 8.3 J K 1 mol1 . H, S and G are enthalpy,
entropy and Gibbs energy, respectively.) [2018]
2. The surface of copper gets tarnished by the formation of copper oxide. N2 gas was passed
to prevent the oxide formation during heating of copper at 1250 K. However, the N2 gas
contains 1 mole % of water vapour as impurity. The water vapour oxidises copper as per
the reaction given below:
2Cu(s)  H2O(g)  Cu2O(s)  H2(g)
PH2 is the minimum partial pressure of H2 (in bar) needed to prevent the oxidation at
1250 K. The value of ln(pH2 ) is ____.
(Given: total pressure = 1 bar, R (universal gas constant) = 8 J K 1mol1 , ln(10) = 2.3. Cu(s)
and Cu2O(s) are mutually immiscible. [2018]
1
At 1250 K: 2Cu(s) + O2(g)  Cu2O(s); G0  78000, J mol1
2
1
H2(g)  O2(g)  H2O(g); G0  1,78000 J mol1; G is the Gibbs energy)
2

39
3. For the electrochemical cell, Mg(s)|Mg2 (aq,1M)||Cu2 (aq,1M)|Cu(s) the standard emf of the
cell is 2.70 V at 300 K. When the concentration of Mg 2 is changed to 𝒙 M, the cell potential
changes to 2.67 V at 300 K. The value of 𝒙 is ____.
R
(given,  11500K V 1, where 𝐹 is the Faraday constant and 𝑅 is the gas constant,
R
ln(10) = 2.30) [2018]

4. The conductance of a 0.0015M aqueous solution of a weak monobasic acid was determined
by using a conductivity cell consisting of platinised Pt electrodes. The distance between the
electrodes is 120 cm with an area of cross section of 1 cm2 w. The conductance of this
solution was found to be 5 107 S. The pH of the solution is 4. The value of limiting molar
conductivity (om ) of this weak monobasic acid in aqueous solution is Z 102 S cm1 mol1.
The value of Z is: [2017]

5. All the energy released from the reaction X  Y, rGo  193kJ mol1 is used for oxidizing

M and M  M3  2e ,E0  0.25V. Under standard conditions, the number of moles of M
oxidized when one mole of X is converted to Y is [F=96500 C mol1 ] [2015]

6. The molar conductivity of a solution of a weak acid HX (0.01M) is 10 times smaller than the
molar conductivity of a solution of a weak acid HY (0.10 M). If 0x  0Y , the difference in their
pK a values, pKa (HX)  pKa (HY), is (consider degree of ionization of both acids to be <<1)
[2015]

40
 ANSWERS TO ELECTROCHEMISTRY
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. C 10. B 19. D 28. C 37. B
2. A 11. A 20. A 29. C 38. D
3. B 12. A 21. C 30. D 39. A
4. B 13. A 22. B 31. B 40. D
5. B 14. B 23. D 32. D
6. D 15. D 24. A 33. A
7. D 16. A 25. C 34. C
8. C 17. C 26. C 35. C
9. C 18. C 27. D 36. C

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. A,B,C 3. A,B 5. A,B,C,D 7. A,D 9. A,B,C,D
2. B,C 4. A,C 6. A,B,C,D 8. A,B,C 10. B,C

COMPREHENSION TYPE
1. B 2. A 3. B 4. C 5. A

MATCH THE FOLLOWING COLUMN

1. A  PQ; B  PQ; C  QR; D  PS 2. A  QR; B  S; C  Q; D  PQR

INTEGER ANSWER TYPE

1. 1 2. 2 3. 0 4. 4 5. 4

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. 11.62 2. 14.6 3. 10 4. 6 5. 4 6. 3

41
 ALCOHOL, ETHER & PHENOL
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. Reaction of tertiarty butyl alcohol with hot Cu at 350°C produces
(A)Butanol (B)Butanal (C)2-Butene (D)2-methylpropene

2. The product (B)in the following sequence of reaction is:


C6 H5CO3H
 A 
HCl
B
CH2
OH Cl O
O
(A) (B) (C) (D)
Cl OH OH

Br
2Aq. KOH Aq.KOH con.
3.  
ethene
AlCl3 
A 

Br2 A 
  B  B
con.  C 
C  D D
 H 2SO4 H2SO4
Ethene O
O
H CHO
(A) (B) O (C) (D)

Jone's
4. CH3 – CH = CH – CH(OH) – CH3 
reagent
X, Product X is
(A) CH3CH2CH2CH(OH)CH3 (B) CH3CH = CHCOCH3
(C) Both (A) and (B) are correct (D) CH3CH2CH2COCH3
5. One mole of t-butyl methyl ether on being heated with 1 mole of concentrated hydriodic acid
gives -
(A) CH3OH (1 mole) and (CH3)3CI (1 mole) (B) CH3I (1 mole) and (CH3)3COH (1 mole)
(C) CH3I (1 mole) and (CH3)3CI (1 mole) (D)CH3OH (1 mole) and (CH3)3COH (1 mole)

6. The reaction
conc.H2SO4
2C2H5OH   (C2H5)2 O + H2O
140ºC
is an example of
(A) an elimination reaction (E2) (B) an electrophilic substitution (SE2) reaction
(C) anucleophilic substitution (SN1) reaction (D) a nucleophilic substitution (SN2) reaction

7. Pinacolvapour is passed over alumina heated at about 350ºC.

CH3 CH3
| |
CH3  C — C  CH3
| |
OH OH
The major product formed in the reaction is: CH3 CH3
| |
(A) CH3COC(CH3)3 (B) CH2  C — C  CH2
(C) (CH3 )2 C — C (CH3 )2 (D) (CH3)2CHOCH(CH3)2

42
 Al2O3
8. In the reaction; 2C2H5OH  (C2H5)2 O + H2Oalumina acts mainly as
240ºC
(A) an absorbent of water
(B) a provider of hot solid surface
(C) a Lewis acid to coordinate (C2H5)2O formed
(D)a Lewis acid catalyst to increase the leaving group ability of the —OH group by coordination
at oxygen.

9. Reaction of t-butyl bromide with sodium methoxide produces

(A) isobutane (B) isobutylene
(C) sodium t-butoxide (D) t-butyl methyl ether

10. In the reaction;

heat
(CH3)3 C — O — CH2CH3 + HI 

(1mole)
the product(s) formed is (are)
(A) (CH3)3 C—OH and CH3CH2I (B) (CH3)3 C— I and CH3CH2OH

(C) (CH3)3 C— I and CH3CH2I (D) (CH3 )3 C — O— CH2CH3 I
|
H
CH2CH3
H O
11. CH3  CHCH  CHCH3 
3

Major product of this reaction :
(A) will show optical isomerism (B) gives white turbidity with HBr immediately
(C) is dehydrated easily (D) all correct

2 MnO
12. H2C  CH  CH  CH2CH2OH  A. A is
|
OH
(A) H2C  CH  CCH2  CH2OH (B) H2C  CH  CH  CH2CHO
|| |
O OH O
||
(C) H2C  CH  CCH2  CHO (D) H2C  CH  CCH2  CHO
|| ||
O O

CH3 CH3
HBr
13. H3C   A (predominant) A is:

CH3 OH
CH3 Br Br CH3

(A) H3C (B) H3C (C) Both (D) None is correct

CH3 CH3 CH3 CH3

43
14. Dehydration of alcohols by conc. H2SO4 takes place according to following steps:
CH3 CH3 CH3 CH3
 + +
 H2O
H3C H
step 1
 H3C 
step  2
 H3C CH2 1,2  H  shift
step  3
 H C C CH
+ 3 3
H OH H OH2 H
CH3

H

step  4
 H2C CH 3
The slowest in the above reaction is
(A) step 1 is slowest (B) step 2 is slowest
(C) step 2 is slowest (D) all steps proceed at equal rate
15. Which of the carbonium ion is formed in the following reaction?
CH2 

H

OH O CH3

+
CH2 CH3 CH2
(A) (B) (C) (D) All the three
+
OH2 OH OH

16. The order of reactivity of the following alcohols towards conc. HCl is
CH3 H3C CH3
F CH3 Ph OH
F OH HO OH
(I) (II) (III) (IV)

(A) I > II > III > IV (B) I > III > II > IV (C) IV > III > II > I (D)IV> III > I > II
17. Consider the following sequence of reactions.
2
3 4  A  H PO 1. O .heat
C6H6 + CH3CH=CH2   B+C
heat 2. H3O ,heat
The product (B) and (C) are -
(A) benzaldehyde and acetaldehyde (B) benzoic acid and acetic acid
(C) phenol and propionaldehyde (D) phenol and acetone

18. The reaction :

O CH2 + HI

produces -

(A) CH2I and I (B) OH and CH2I

(C) OH and CH2OH (D) CH2OH and I

44
19. An organic compound having the molecular formula C 8H10O on being heated with I2 and dilute
NaOH gives a yellow precipitate. The compound is expected to be -

(A) C6H5CH2CH2OH (B) CH3 CH2OH (C) H3C OH (D) CHOHCH3

CH3
20. Denaturation of ethyl alcohol refers to:
(A) Mixing of methyl alcohol with it. (B)Mixing some copper sulphate and pyridine.
(C) Heating of ethyl alcohol (D)Sudden cooling of ethyl alcohol.

21. Which of the following statement is incorrect:

(A) PCC oxidises 1° alcohol to aldehyde and 2° alcohol to ketone.
(B) H2CrO4 (chromic acid) oxidises 1° alcohol to aldehyde.
(C) CrO3·H2SO4/acetone oxidises 2° alcohol to ketone.
(D) Jones reagent oxidises 1° alcohol to carboxylic acid and 2° alcohol to ketone without affecting
double bond
22. Sequence of reagents used in Vector–Meyer method of detection of primary, secondary and
tertiary alcohol:
(A) P/I2, AgNO2, NaNO2/H+, NaOH (B)AgNO2, P/I2, NaOH, NaNO2/H+
(C) NaNO2/H+, NaOH, P/I2, AgNO2 (D)P/I2, NaNO2/H+, AgNO2, NaOH

OH
X 2+OH 
23. R—CH—CH 3
(Haloform test)
Which of the following is not an intermediate of the above test.

OH O O O
(A) R—CH—CHX2 (B) R—C—CHX2 (C) R—C—CX3 (D) R—C—CH 2X

OH

CH–CH3 X2/OH Kolbe's
24.  A  B ; Product B is:
electrolysis
COO 

(A) (B) —CH 2— (C) (D)

25. Which of the following reactions is not correct:

ZnO—CrO
3  (CH OH) H SO
(A) CO + 2H2  3
2 4  CH =CH
(B) CH3CH2OH  2 2
200 300 atm 443 K
573 673 K
Zymase 2 4  C H OC H H SO
(C) C12H22O11  H2O 
 C6H12O6 +C6H12O6 (D) CH3CH2OH  2 5 2 5 413 K
Glucose Fructose

26. Hydrogen bonding is maximum in:

(A) ethanol (B) diethyl ether (C) ethyl chloride (D) triethyl amine

27. HBr reacts fastest with:

(A) 2-methyl propan-2-ol (B) propan-1-ol
(C) propan-2-ol (D) 2-methyl propan-1-ol

45
28. Diethyl ether on heating with conc. HI gives two moles of:
(A) ethanol (B) iodform (C) ethyl iodide (D) methyl iodide

29. The compound which reacts fastest with Lucas reagent at room temperature is:
(A) butan-2-ol (B) butan-1-ol
(C) 2-methyl propan-1-ol (D) 2-methyl propan-2-ol

30. Phenol reacts with bromine in carbon disulphide at low temperature to give:
(A) m-bromophenol (B) o- and p-bromophenol
(C) p-bromophenol (D) 2,4,6-tribromophenol

31. When phenol is reacted with CHCl3 and NaOH followed by acidification, salicylaldehyde is
formed. Which of the following species are involved in the above mention reaction as
intermediates?

(A) (B) (C) (D) None of these

32. When pinacol is heated with concentrated H2SO4, the major product formed is
CH3CH3
conc.H SO
CH 3  C  C  CH3 
2 4 

OH OH
pinacol CH3CH3
(A) CH3COC(CH3 )3 (B) CH2  C  C  CH2
(C) CH3 2 C  C CH3 2 (D)  CH3 2 CHOCH  CH3 2
O

33. Statement-1: p-Hydroxybenzoic acid has a lower boiling point than o-hydroxybenzoicacid .
Because
Statement-2 : o-Hydroxybenzoic acid has intramolecular hydrogen bonding.
(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.

34. Order of boiling point for the following compounds is -

OH
OH OH OH
OH

OH OH
(I)
(II) II)
((III) III)
((IV) IV)
((I)
(A) (I) < (II) < (III) < (IV) (B) (I) < (II) < (IV) < (III)
(C) (IV) < (I) < (II) < (III) (D) (II) < (I) < (III) < (IV)

46
35. On acid catalysed hydration, 2-phenyl propene gives:
(A) 3-phenyl-2-propanol (B) 2-phenyl-1-propanol
(C) 1-phenyl-3-propanol (D) 2-phenyl-2-propanol

2 5 C H ONa  (excess)
36. OH + C2H5I 

C2H5OH(anhydrous)

(A) OC2H5 (B) I (C) C6H5OC6H5 (D) C2H5OC2H5

2  A  P I 2 Mg HCHO H O

37. In the following sequence of reactions,CH3CH2OH   B  C 
ether
D, then compound ‗D‘ is –
(A) butanal (B) n-butyl alcohol (C) n-propyl alcohol (D) propanal
38. HBr reacts with CH2 = CH – OCH3 under anhydrous conditions at room temperature to give -

(A) BrCH2CHO and CH3OH (B) BrCH2 – CH2 – OCH3

(C) H3C – CHBr – OCH3 (D) CH3CHO and CH3Br

OH O Na 
39.  CHCl3  NaOH 
CHO
The electrophile involved in the above reaction is :
Θ
(A) dichlorocarbene ( :CCl2) (B) trichloromethyl anion ( CCl3 )
 
(C) formylcation ( CHO ) (D) dichloromethylcation ( CHCl2 )

40. The structure of the compound that gives a tribromo derivative on treatment with bromine water
is - CH OH CH CH
2 3 3 CH3
OH
(A) (B) (C) (D)
OH
OH

47
 SECTION-II
MULTIPLE CORRECT ANSWER TYPE
O

NH CH3
Me
1. (i) O 
Br2 / Fe
P (ii) 
Mononitration
Q
NO 2

H5C6
(iii)  Cl 
Anh. AlCl3
 R 
mononitration
S
O

Where P, Q, R and S are all major products of the respective reactions:

Now choose the correct choice (s) from the following:
Me O

(A) O Br and

(P) (R)
O O

HN CH3 HN CH3
O2 N O
or
(B) and
NO 2 NO 2
NO 2
NO 2
(Q) (S)
Br
Me O
(C) O and

(P) (R)
Br
Me O
(D) O and
NO 2
(P) (S)

2. Which of the following is / are the correct order of acidic strength?

(A)R — OH > H2O > HF (B)PhOH> H2O > R — OH
(C)RCOOH >PhOH> R — OH (D) m-Nitrophenol> Phenol > m-chlorophenol
O O
(i) CH3MgBr 3 (i) CH MgBr
3. H3C CH3  (A); H CH3 (B);
  (ii) H
(ii) H
Which of the following reagent can be used to differentiated between A and B?
(A) FeCl3 (B) Active metal Na (C) Lucas reagent (D) K2Cr2O7

48
4. Which of the following compounds do/does not react with NaHCO3 ?
OH OH OH

(A) (B) (C) (D) CH3  C  C  H

CH3
5. Which of the following reaction(s) are correctly matched with major product?
(A) H3C  O  CH2  CH3  PCl5  H3C  Cl  Et  Cl

(B) CH3COOH  PCl5  CH3COCl

(C) MeCOMe  PCl5  MeCH(Cl)Me

(D) Cyclohexanol  PCl5  Cyclohexylchloride

6. Which of the following will produces methylcyclohexene on heating with conc. H2SO4 ?
(A) 2-cyclopentylethanol (B) methylcyclohexanol
(C) ethylcyclopentanol (D) Cyclohexylmethanol

7. Which of the following reaction(s) follow the same pattern of energy graph for the formation of
major product only?

(A) (B)

(C) (D)

8. Which of the following reaction proceeds via formation of cabrocation?

(A) Dehydration of alcohols (B) Pinacol-Pinacolone rearrangement
(C) Diazotisation of aliphatic amines (D) Photo halogenations of alkanes

9. In which of the following reactions 3o alcohol will obtained as a product?

O
(A) MgBr (excess) + H  C  Cl  


H

49
 O
(B) PhMgBr (excess) + CH3  C  Cl  


H
O O
(C) CH3MgBr(excess) + CH3  C  O  C  CH3  


H
O
(D) CH3MgBr (excess) + Cl  C  O  Et  


H

10. Product of the following reaction are:

(A) (B) (C) (D)

11. Compounds which can give periodic cleavage are:

(A) (B) (C) (D)

12. Product of following reaction can be:

(A) (B) (C) (D)

SOCl
2
13.  Product is/are:

(A) (B) (C) (D)

14. Select reaction with correct major products:

(A)

Mg
(B) HOCH2CH2CH2CH2  Br 

Et2O
O

(C)

(D)

50
15. Which of the following compound(s) will give red colour with FeSO4  KCNS after keeping open
in sunlight for sometime?

(A) (B) (C) (D) Ph  O  Ph

COMPREHENSION BASED QUESTION

PARAGRAPH FOR NEXT TWO QUESTIONS

(P)
H /Pd/CaCO /Quinoline
1. P 
2 3
 Product(s)
The number of isomeric product(s) obtained in this reaction is :
(A) 1 (B) 2 (C) 4 (D) 8
Na/NH3 ( )
2. (P)   Product(s)
The product(s) has/have degree of unsaturation and number of isomeric product(s) formed are
respectively :
(A) 1, 4 (B) 4, 2 (C) 4, 1 (D) 2, 4
PARAGRAPH FOR NEXT THREE QUESTIONS
CH3 CH3
H OH CH3 CH3 CH3 H OH
CH2 H OH H OH H OH CH2
H OH H OH HO H HO H HO H
CH3 CH3 CH3 CH2–CH3 CH3
(I) (II) (III) (IV) (V)
Mrs. Aishwarya had worked for several days to prepare the above diols in her laboratory. She
carefully labeled them and went to abroad for her PhD interview. When she returned she found that
the labels had fallen off from the bottles. She get puzzled but her guide in the office told her that the
diols could be easily distinguished by these experiments.
Mrs. Aishwaryafollow her guide instruction and obtained the following results.
1. Compound P, Q,T are optically inactive while R and S are optically active.
2. Only one product is obtained from Q & R with HIO4 oxidation.
3. Two products are obtained from S with HIO4 oxidation.
4. P and T did not react with HIO4 oxidation.
3. Compound Q and R are :
(A) I & II (B) II & III (C) I & V (D) III & IV

4. When S is subjected to react with HIO4 then the product are :

(A) Both CH3CHO (B) CH3–CH=O and CH3CH2CHO
(C) Both CH3CH2CHO (D) HCHO and CH3CH2CHO

51
5. Which of the following is/are best reagent to obtain compound (Q) from the 2-butene ?
(A) Dil cold KMnO4 (B) Peroxy benzoic acid followed by hydrolysis
(C) Hot KMnO4 solution (D) Concentrate hot KMnO4

MATCH THE FOLLOWING COLUMN

1. Match the Column– I with Column – II and select the correct.
Column – I (Reagents) Column – II (Reactions involved)
(A) OsO4, NaHSO3.H2O (P) Reduction of carbonyl groups
(B) BH3THF; CH3CO2H (Q) Oxidation of –OH group from
allylic/benzylic position
(C) MnO2 (R) Reduction of alkene
(D) LiAlH4 ether; H2O (S)Hydroxylation of alkene

2. Match the reagent of Column – II with the reactions of Column–I

Column – I Column – II
O O
HO OH
(A) H Cl  (P) LiAlH4

O OH

(B)  (Q) NaBH4

O OH
O O
(C)  (R) Na/EtOH
O O

O O

(D)  (S) H2/Ni

52
INTEGER ANSWER TYPE
1. Following conversion can be done in four steps using four reagents one after the other. These
four reagents are listed below with some other reagents.
Write the number of most suited reagent in order you want to use them and present the four digit
number in OMR sheet. For example if you want to use (1) than (2) than (3) than (4) fill 1234 in OMR
sheet.
OH

OH 

(1) O3 /Zn/H2O (2) O3 /H2O (3) conc. H2SO4 / 

(4) aq. KOH/  (5) H2 / Zn (6) Zn  Hg /HCl
(7) NH2  NH2 /EtOK (8) H3O (9) NaOH/CaO/

2. Sum of molecular mass of iodides produced in following reactions is:

conc. HI
O 
(a)
anyhydrous


(b) O HI
(c) Ph  O  Me
If answer of part (a) is x, part (b) is y and part (c) is z then present sum of x+y+z in the OMR sheet.
For example if answer of (a) is 12, (b) is 13 and (c) is 3 you will fill 0028 in OMR sheet.

HI(excess)
3. 
 Pr oduct


(a) Number of organic products obtained in more than 5% yield.

(b) Number of moles of HI consumed
(c) Number of moles of I2 generated
(d) Number of fractions which can be obtained on fractional distillation of organic product from
mixture of products.
Write answer of part (a), (b), (c) and (d) in the same order and present the four digit number as
answer in OMR sheet. For example: If all these answers are 9 then fill 9999 in OMR sheet.

4. Find out the number of 1-2-shifts during the conversion of

5. How many out of the following reagents will change 1-propanol into propanaldehyde?
(a) H /KMnO4 /  (b) TsCl /DMSO  NaHCO3
(c) P.C.C. (Pyridinium chloro chromate) (d) Bendict solution

53
 (e) Red hot Cu tube (f) H /K2Cr2O7 / 
(g) NBS/  (h) SeO2 / 

6. How many moles of Grignard‘s reagent will be consumed per mole of following compound?

7.

Number of moles of Grinard reagent consumed per mol.

8. Number of mole of Grignard consumed per mole in given molecule. (When Grignard reagent is in
excess)

9. How many number of mole of R  MgX consumed per mole for one mole of following compound?

10. If ‗X‘ litres of ethene would be produced when 2.62 gm of vinyl magnesium bromide is treated
with 224 ml of ethyne at STP. Then what is the value of ―1000 X‖?

54
 SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE:
1. Aniline reacts with mixed acid (conc. HNO3 and conc. H2SO4 ) at 288 K to give P (51 %), Q (47%)
and R (2%). The major product(s) of the following reaction sequence is (are) [2018]
(1) Ac2O, pyridine (1) Sn/HCl
(2) Br2 ,CH3CO2H (2) Br2 /H2O (excess)
R 

S   major product(s)
(3) H3O (3) NaNO2, HCl/273  278K
(4)NaNO2,HCl/273  278K (4) H3PO2
(5) EtOH, 

(A) (B) (C) (D)

ANSWER TO ALCOHOL, ETHER & PHENOL

SECTION-I
STRAIGHT OBJECTIVE TYPE
1. D 8. D 15. B 22. A 29. D 36. D
2. B 9. B 16. C 23. A 30. C 37. C
3. D 10. B 17. D 24. A 31. A 38. D
4. B 11. B 18. B 25. C 32. A 39. A
5. A 12. A 19. D 26. A 33. D 40. D
6. D 13. B 20. B 27. A 34. C
7. B 14. C 21. B 28. C 35. D

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. AB 4. ABCD 7. ABCD 10. AD 13. AB
2. BC 5. ABD 8. ABD 11. ABCD 14. CD
3. CD 6. ABD 9. BCD 12. BC 15. AB

COMPREHENSION TYPE
1. A 2. C 3. B 4. B 5. A

MATCH THE FOLLOWING COLUMN

1. A  S; B  R; C  Q; D  P 2. A  PQRS; B  P; C  Q; D  S

INTEGER ANSWER TYPE

1. 3145 3. 3522 5. 4 7. 7 9. 8
2. 454 4. 3 6. 9 8. 7 10. 448
SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE:
1. D

55
 ALKYL HALIDE AND ARYL HALIDE
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. The organic compound (P) of the reaction:
Ph
Me H

alc. KOH

 P is
Br H
Ph
Ph Ph
Ph Me Ph Me
(A) (B) (C) M e H
(D) M e H

H Ph Ph H H H H OH
Ph Ph

2. Identify the set of reagent and reaction conditions „X‟ and „Y‟ in the following set of
transformations,
CH3 CH2 CH2Br
X Y
Product CH3 CH CH3
Br
(A) X = Dilute aqueous NaOH, 200C, Y = HBr/acetic acid, 200C
(B) X = Concentrated alcoholic NaOH, 800C, Y = HBr/acetic acid, 200C
(C) X = concentrated alchololicNaOH, 800 C, Y = HBr / in presence of H2O2
(D) X = Dilute agueousNaOH, 200 C, Y = HBr / in presence of H2O2
Br H
C 2 H5 O 
3. H C—C CH3 

C2 H5OH 
H3C C2H5
H CH3
Br H H C2H5 H H
(A) (B) C C CH3 (C) C==C (D) C2H5O C C CH3
H2C C2H5 H3C CH3 H3C C2H5
H3C C2H5
4. When (1R, 2R)–1,2-dibromo-1,2-diphenyl ethane is treated with alcoholic solution of KOH, the
most probable product would be
(A) trans-1,2-diphenylethene (B)a mixture of cis, trans alkenyl bromide
(C) cis-alkenylbromide (D)trans-alkenylbromide
H
Br 
Ag
5.   Rearranged carbocation + AgBr
Rearranged carbocation is
+
CH3 +

(A) + (B) (C) (D) +

6. Which of the following statement is not true

(A) nucleophiles possess unshared pair of electrons which are utilized in forming bonds with
electrophilic substrate.
(B) the cyanide ion is an ambident nucleophile and causes nucleophilic substitution of alkyl
halide either of its carbon atom or nitrogen atom.

56
 (C) the nitrite ion is an ambident nucleophile and causes nucleophilic substitution of alkylhalide
by either of its oxygen atom or nitrogen atom.
(D) strength of nucleophile generally decreases down the group in periodic table.
NaOH(aq)
7. ClCH2CH2CH2CH2OH  A. Product A is
(A) HO–CH2CH2CH2CH2OH (B) O

(C) ClCH2–CH–CH2CH2OH (D)ClCH2CH2CH2CH2ONa

HO
8. Which of the following reactions is the best choice for preparing methyl cyclohexyl ether
ONa I OH I
(A) +CH3I (B) +CH3ONa (C) +CH3I (D) +CH3OH

9. Which of the following chlorides will exclusively give 2-methylbut-2-ene on dehydrochlorination

by strong base
(A) 2-Chloro-3-methylbutane (B) 2-Chloro-2-methylbutane
(C) 1-Chloro-2-methylbutane (D)None of these
10. Select correct statement
(A) Solvolysis of (CH3)2C=CH–CH2Cl in ethanol is faster than primary alkyl chloride
(B) CH3–CH=CH–CH2–OH when reacts with HBr give a mixture of 1-bromo-2-butene and 3-
bromo-1-butene
(C) when solution of 3-buten-2-ol in aqueous sulphuric acid is allowed to stand for a weak, it is
found to contain both 3-buten-2-ol and 2-buten-1-ol.
(D) All of these

11. An optically active, pure four carbon containing saturated alcohol X when reacted with NaH
followed by CH3–I gives a compound M. Same alcohol (X) when treated with TsCl followed by
sodium methoxide gives M’, M and M’ are
(A) Homomers (B)Enantiomers (C) Geometrical isomers (D)Diastereomers

E-1
X
12.(CH3)3C–CH–CH3 X and Y are respectively
E-2 Y
Br
(A) (CH3)2C=C(CH3)2& (CH3)3CCH=CH2 (B) (CH3)3CCH=CH2& (CH3)2C=(CH3)2
(C) (CH3)2CH–C(CH3)=CH2& (CH3)2C=C(CH3)2 (D)(CH3)2C=C(CH3)2& (CH3)2CH–C(CH3)=CH2.
.. ..
13. For reaction 131
I + CH3I CH3I
131
+ I . The lowest rate will be observed in
(A) Water (B) Acetone (C)Dimethylsulphoxide (D)Ethanol

14. The best leaving group is :

(A) (B) (C) (D)

57
15. SN1 reaction undergoes through a carbocation intermediate as follows : -
 Slow
 2  ROH(aq)  H (aq) H O

R  X(aq)  R (aq)  X (aq)  fast
[R = t-Bu, iso-Pr, Et, Me] (X = Cl, Br, I)
The correct statements are
I. The decreasing order of rate of SN1 reaction is t-BuX>iso-PrX>EtX>MeX
II. The decreasing order of ionisation energy is MeX>EtX>iso-PrX> t-BuX
III. The decreasing order of energy of activation is t-BuX>iso-PrX>EtX>MeX
(A) I & II are correct (B) I & III are correct
(C) II and III are correct (D) I, II & III are correct

16. Decreasing order of reactivity for SN2

Cl Cl Cl Cl

(I) (II) (IV) (III)

OCH3 CH3 NO2

(A) I>II>III>IV (B) IV>III>II>I (C) IV>III>I>II (D)II>I>III>IV

17. Which of the following is strongest nucleophiliccentre in the given species (decreasing order)
O O
.. 4
..
1O 3

O S
O .. O
O2
(A) 4>1>3>2 (B)4>3>1>2 (C) 2>1>3>4 (D) 3>4>1>2

18. Which is correct reaction coordinate diagram for the following solvolysis reaction?
CH3 CH3 OCH3
CH OH

Br 3
+ OCH3 CH3

H
H H H
(A) (B) (C) (D)
Reaction Reaction Reaction Reaction
coordinate coordinate coordinate coordinate

19. Consider the

.. following reactions carried out at same temperature
..
CH3–Br + OH 
EtOH
 CH3OH + Br ............ (i)
.. ..
CH3–Br + OH 
DMSO
 CH3OH + Br ............ (ii)
Which of the following statements are correct
(A) Both the reactions take place at same rate
(B) The first reaction takes place at faster rate than (ii)
(C) Rate (i) < (ii)
(D) Both the reactions take place by SN1 mechanism

58
20. Decreasing order of relative nucleophilicity of the following nucleophiles in protic solvent is -
, , , , H2O

(A) > > H2O > > (B) > > > > H2O

(C) > > > H2O > (D) > > > > H2O

21. Which one of the following group has maximum leaving ability for SN reaction :
(A) OH (B) F3CCOO (C) Cl (D) F3CSO3

22. Which of the following is not expected to be intermediate of the following reaction ?

2  H O


(A) (B) (C) (D)

23. Which one of the following will be most reactive for SN1 reaction ?

(A) (B) (C) (D)

24. Product,

Identify the major product :

(A) (B) (C) (D)

25. In which of the following reactions an optically active single product is formed.

(A) CH3ONa + (B) NaI +

(C) (D) None

59
 2 4 NaBr, H SO
26. CH3 (CH2 )2  CH2OH   X,
1 butanol
Identify X and the mechanism of the reaction
(A) CH3 – CH2 – CH2 – CH2 – Br & SN1 (B) CH3 – CH2 – CH2 – CH2 – Br & SN2

(C) CH 3  CH  CH 2  CH 3& SN1 (D) CH 3  CH  CH 2  CH

& 3SN2
| |
Br Br
CH3
PCl5
27. H OH
  X ; (X) is
C2H5
(D-2-Butanol)
(A) S-2-Chlorobutane (B) R - 2-Chlorobutane
(C) Mixture of R and S 2-Chlorobutane (D) 1-Chlorobutane

3 PBr
28.  (X) , X is : (X)

(A) (B) (C) (D)

29. In the following compound, the order of decreasing reactivity of different chlorine atoms towards
NaSH in non aqueous solvent is :

(A) I > IV > II > III (B) IV > I > II > III (C) I > IV > III> II (D) III > II > IV > I

30. Which of the following will be most reactive for E1 reaction ?

(A) (B) (C) (D)

CH3OH
31. In the given reaction,  [X]


[X] as the major product among the elimination products is :

CH3
|
(A) C = CH2 (B) (C) (D)

60
32. Arrange the following in decreasing order of stability of their transition state during elimination
by strong base

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

33. The most probable product in the following reaction is :

Trans

(A) (B) (C) (D)

34. Which one of the following hexachlorocyclohexane is least reactive and which one is most
reactive for E2 reactions with a strong base for dehydrohalogenation.

(A) I least & II most (B) II least & I most (C) III least &I most (D) III least &II most
35. E1cB reaction is given by which of the following :

(A) CF3 – CHCl2 (B) (C) (D) All of these

36. The insecticide chlordane is warmed with dilute NaOH solution for some time. The expected
product would be :

(A) (B)

(C) (D)

61
37. Match the following:
Column I Column II
(P) CH3 – CHBr – CD3 on treatment with alc. KOH gives (1) E1 reaction
CH2  CH  CD3 as a major product.
(Q) Ph – CHBr  CH3 reacts faster than Ph  CHBr  CD3 . (2) E2 reaction
–
(R) Ph  CD2  CH2Br on treatment with C2H5OD/C2H5O (3) E1cb reaction
gives Ph  CD  CH2 as the major product.
(S) PhCH2CH2Br and PhCD2CH2Br react with same rate. (4) First order reaction
CODES: P Q R S
(A) 2 2 3,4 1,4
(B) 2 1 1,3 1,4
(C) 1 2 3 4
(D) 1 3 2 4

38. The structure of the major product formed in the following reaction
CH2Cl
NaCN
DMF
is

I
CH2Cl CH2CN CH2CN CH2Cl
(A) (B) (C) (D)
CN
CN I I

39. Compound (X) is reacted with aqueous acetone it gives following

products.

(A) K, L (B) K, M (C) L only (D) M only

62
 SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. The correct nucleophilicity order is/are
.. .. ..
(A) (CH3)3CO > ..CH3 ..
(B) CH3S > CH3SH
(C) CH3CH2CH2O >(CH3)3CO (D)(CH3CH2)3N > (CH3CH2)3P

2. The correct
.. order
.. of leaving group
.. ability.. is/are .. .. .. ..
(A) PhSO3>PhCOO (B) CF3SO3>CCl3SO3 (C) CN > I (D) NH2 > OH

3. Which of the following order is/are correct for solvolysis in 50% aqueous ethanol at 44.6°C.

(A) Cl< Cl < Cl

(B) <
Cl <
Cl Ph Cl

Cl
(C) <
Cl < Cl

Br Cl Br

(D) < <

4. Possible products are

CH OH

3


Br

(A) (B) (C) (D)

OCH3 OCH3
5. Which of the following order is/are correct for the rate of E2 reaction.
(A)5-Bromocycloheptene > 4-Bromocycloheptene
(B)2-Bromo-1-phenylbutane>3-Bromo-1-phenylbutane
(C)3-Bromocyclohexene>Bromocyclohexane
(D)3-Bromo-2-methylpentane>2-Bromo-4-methylpentane
6. Which of the following compound(s) will yield exclusive (only one) product on
dehydrogalogenation by strong base
Br

CH3 CH3
(A) (B) Br (C) H C 3 CH3 (D) H3C CH3
CH3 CH3
Br Br
7. Observe the following reaction and tick correct option(s)
I CH3
1r
CH3–CH–CH3 + CH3ONa  CH3–CH–OCH3 ......(i)
r2
CH3–I + CH3–CH–ONa
  CH3–CH–OCH3......(ii)
CH3 CH3

63
 (A) r1< r2
(B) transition state in reaction (i) is less stable than transition state in reaction (ii)
(C) substrate of both reaction are equally reactive towards a particular nucleophile
(D) r1 and r2 both are directly proportional to concentration of nucleophile CH3O¯Na+.

8. Which is/are correct about alkylbromide having molecular formula C 5H11Br.

(A) only isomeric alkyl bromide undergoes E-1 elimination at fastest rate
(B) only one is incapable of reacting by E-2
(C) only one isomer gives a single alkene on E-2
(D) 2-Bromopentane gives the most complex mixture of alkenes on E-2 elimination.

9. Which of the following are correct regarding the products of the given reaction

(A) only X and Z are formed (B) Y > Z (amount) (C) X > Y (amount) (D) Y > X (amount)

10. The relative rates of nucleophilic substitution for the given substrates are as follows
Compound Approx. Relative rate
CH3CH2Br 1.0
CH3CH2CH2Br 0.28
(CH3)2CHCH2Br 0.030
(CH3)3 CCH2Br 0.00000042
The correct statement (s) is/are :
(A) Each of the above reactions is likely to be SN2
(B) Each of the above reactions is likely to be SN1
(C) First two reactions follow SN2 and next two reactions follow SN1 pathway
(D) The important factor behind this order of reactivity is “steric effect”

11. Which of the following reaction is correct ?

Acetone
(A) 1, 4-Dichlorohexane + NaI  CH3  CH2  CH  CH2  CH2  CH2 + NaCl
1eq. | |
Cl I

64
 (B) 1, 2-Dibromoethane + NaS – CH2 – CH2 – SNa  + 2NaBr

2 Et O 
(C) 4-Chloro-1-butanol + NaH  C4H8ClONa 

NH3 CH I
3 C H
(D) Propyne + NaNH2   C3H3Na  4 6

TsCl NaBr
12. 
 X 
 Y. X and Y are :
Pyridine

(A) X = (B) Y = (C) X = (D) Y =

13. Which of the following reaction is / are possible :

(A)

(B)

(C)

(D)

80% EtOH
14. 


What is / are true about above reaction ?

(A) Major product is given by SN1 reaction.
(B) Through E1 mechanism 3 alkenes are formed.
(C) 3-Methylpentan -3-ol is also formed as one of the product.
(D) Fractional distilation of elimination product will give two fractions.

65
15. Which of the following is/are possible product formed by E1 mechanism for given reaction ?
3CH OH

 ?


(A) (B) (C) (D)

COMPREHENSION TYPE
PARAGRAPH FOR NEXT THREE QUESTION
Removal of two atoms or two groups from the substrate is known as elimination reaction.
Elimination reaction is always endothermic reaction. The most common elimination reactions are 
and  eliminations. The presence of at least one hydrogen on the -carbon is necessary for -
elimination and on --carbon is necessary for -elimination. The driving forces for elimination are
(a) stability of the olefin formed and (b) the relief from steric strain due to crowding in the substrate.
1. Which one of the following compounds can give -elimination with alc KOH/ ?
(A) CCl4 (B) CBr4 (C) CH2Cl2 (D) CBr2Cl2

2. Which of the following alkyl halide is likely to undergo -elimination most readily
(A) Ethyl bromide (B) n-Propyl bromide
(C) iso-Propyl bromide (D)tert-Butyl bromide
3. Which of the following is a -elimination reaction ?
CH 3 CH3
| |
EtOH

(A) CH 3  C  Br  KOH CH3  C  CH 2  KBr  H2O
|
CH 3
(B) HOCH2CH2Br + NaOH  + NaBr + H2O
(C) CHBr3 + (CH3)3C – OK  :CBr2 + (CH3)3COH + KBr

(D) BrCH2CH2CH2CH2OH + NaOH  + NaBr + H2O

PARAGRAPH FOR NEXT THREE QUESTION

One of the most interesting and useful aspects of stereochemistry is the study of what happens to
optically acitive molecules when they react. The product isolated from the reaction of a chiral
starting material can tell us a great deal about the reaction mechanism . We observe
SN2 --------- Inversion of configuration
SN1 --------- Racemisation
SNi --------- Retention of configuration

4. In the given reaction, mention reaction mechanism respectively

()  ()  +

()  (V) 

66
 (A) SN2 , SN1, SN2 , SNi (B) SN2 ,SN1 , SNi , SN2
(C) SN1 ,SN2,SNi , SN1 (D) SN2 ,SNi ,SN1 , SN2

5. The given reaction is an example of which type of Mechanism ?

C3H7
Ether
  D Cl + SO2 + HCl
C6H5

(A) SN2 (B) SN1 (C) SNi (D) None

6. In which of the following reaction retention of configuration is observed ?

H
Nal/acetone
(A) CH3 Br  (B) 
D
C2H5 CH3
Na
(C) CH3 Br + HOH  (D) H OTs
C3H7 C2H5

MATCH THE FOLLOWING COLUMN

1. Match the column I and II.
Column I Column II
Reaction Type of reaction

(A) (P) SN1

Alc.KOH
(B)  (Q) SN2


H SO
2 4
(C)  (R) E1


H O
2 
(D)  (S) E2

67
2. Match the List I (reaction) with List II (reaction intermediate) and select the correct answer using
the codes given below the Lists.
List I List II
alc.KOH/
(A) CF3–CHCl2 
 CF2 = CCl2 (P) Transition state only
CH 3
|
H
(B) CH 3  C  OH  CH 3  C  CH 2 (Q) Carbocation
| |
CH 3 CH 3
alc.KOH
(C) CH3–CH2–Br   CH2=CH2 (R) Carbanion


Br
| aq.KOH/
(D) CH 3  C  CH 3   CH 3  C  CH 2 (S) Free radical
| |
CH 3 CH 3

INTEGER ANSWER TYPE

1. The number of alkyl halides among the following that undergo hydrolysis through the same intermediate
is
Cl
Cl CH3 CH3
Cl

Cl
H3 C Cl H3 C Cl H2 C Cl

2. How many of the following substrates will react faster when compared with 1-bromopropane towards SN1
reaction in similar conditions ?
(i) CH3 – CH = CH - Br (ii) CH2 = CH – CH2Br (iii) CH3 – Br
Br
(iv) C6H5CH2Br (v) C6H5Br
CH3
| (vi)
(vii) CH3  C  Br (viii) CH3  CH  Br
| |
CH3 CH3
3. How many of the following solvents are better than water for the following S N2 reaction :
CH3Br + KOH 
 CH3OH
(i) Cyclohexane (ii) n-hexane (iii) CCl4 (iv) CH3  S  CH3
||
CH3 O
|
(ix)
(v) H  C N (vi) Benzene (vii) toluene
|| |
O CH3
Br
4. How many of the following orders are correct regarding leaving group ability.
(i) PhSO3> CCl3COO (ii) CH3COO>PhO (iii) F3CSO3> MeSO3 (iv) I> Br
(v) Cl> F (vi) H2O > OH (vii)OH> RO-

68
5. How many of the following substrates will react faster when compared with 1-bromopropane
towards SN2 reaction in similar conditions ?
(i) CH3 – CH = CH - Br (ii) CH2 = CH – CH2Br (iii) CH3 – Br (iv) C6H5CH2Br
O CH3
|| |
(v) C6H5Br (vi) CH3  C  CH 2Br (vii) CH3  C  Br (viii) CH3  CH  Br
| |
CH3 CH3
CH3
Cl
6. S 2 / E2

N x substitution product(s) + y elimination product(s), x + y is equal to
CH3

7. How many moles of AgNO3 will react with the given compound?

Br Br

Br Br

8. In the given reaction how many products are expected

CH2  Br
CH OH
3




9. Observe the following flow chart and write the sum of the number of x, y,z

Cl2 /hv KOH/DMSO Total number of 1o alcohols  (Z)

Isopentane   Monochlorides 
(S 2)

N including stereoisomers

Positional Total
isomers=(X) isomers=(X)

10. The number of substitution products formed when metabromo anisole is treated with KNH2 /
NH3

69
 SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IITJEE:
16. Match the chemical conversions in List – I with appropriate reagents in List – II and select the
correct answer using the code given below the lists [2013]
List-I List-II

(P) (1) (i) Hg(OAc)2; (ii) NaBH4

(Q) (2) NaOEt

(R) (3) Et-Br

(S) (4)(i) BH3; (ii) H2O2/NaOH

OH
Codes:P Q R S
(A) 2 3 1 4
(B) 3 2 1 4
(C) 2 3 4 1
(D) 3 2 4 1

70
 ANSWER TO ALKYL HALIDE AND ARYL HALIDE
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. B 9. D 17. B 25. C 33. C
2. B 10. D 18. B 26. B 34. D
3. C 11. B 19. C 27. B 35. D
4. D 12. A 20. B 28. A 36. D
5. B 13. A 21. D 29. A 37. A
6. D 14. A 22. A 30. A 38. B
7. B 15. A 23. D 31. C 39. A
8. A 16. B 24. A 32. A 40.

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. BC 4. ABCD 7. AB 10. AD 13. ACD
2. AB 5. BCD 8. ABD 11. ABCD 14. ABC
3. BC 6. ABD 9. BD 12. AB 15. BC

COMPREHENSIONBASEDANSWER
1. B 2. A 3. A 4. D 5. A 6. B

MATRIX-MATCH ANSWER
1. A  Q; B  S; C  R; D  P 2. A  R; B  Q; C  P; D  P

INTEGER ANSWER
1. 3 3. 2 5. 4 7. 3 9. 13
2. 5 4. 7 6. 1 8. 5 10. 3

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IITJEE:
1. A

71
 ALDEHYDES AND KETONES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. A compound has a vapour density of 29. On warming an aqueous solution of alkali, it gives a
yellow precipitate. The compound is
(A)CH3CH2CHO (B)CH3CHOHCH3 (C)CH3COCH3 (D)CH3CH2COOH
2. A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives
(A) Benzyl alcohol and sodium formate (B) Sodium benzoate and methyl alcohol
(C) Sodium benzoate and sodium formate (D) Benzyl alcohol and methyl alcohol
3. The reagent(s) which can be used to distinguish acetophenone from benzophenone is (are)
(A) 2, 4-dinitrophenylhydrazine (B) aqueous solution of NaHSO3
(C) Benedict reagent (D) I2 and Na2CO3
O
OH
||
4. C6H5CO  COC6H5    C6H5 2 C  COOH
The reaction is known as

(A) Benzilic acid rearrangement (B) Aldol condensation

(C) Birch reduction (D) Beckmann rearrangement

5. The reagent that can be used to distinguish acetophenone and benzophenone is -

(A) 2, 4-dinitrophenylhydrazine (B) aqueous NaHSO3
(C) Benedict’s reagent (D) I2 and Na2CO3
6. A cyanohydrin of a compound (X) on hydrolysis gives an-hydroxy acid which shows optical
activity after resolution. The compound (X) is
(A) Acetone (B) Formaldehyde (C) Diethyl ketone (D) Acetaldehyde
7. Acetaldehyde on treatment with a few drops of concentrated H2SO4 gives

(A) CH3CHOHCH2CHO (B) CH3CH = CHCHO (C) (D)

8. Phenylglyoxal, C6H5COCHO, on heating with concentrated NaOH gives

(A) C6H5COONa and CH3OH (B) C6H5CH2OH and HCOONa
(C) C6H5CHOHCOONa (D) C6H5COONa and HCOONa

9. Which of the following geminaldiols is the most unstable ?

(A) (B) (C) (D)

10. Consider the following reaction sequence.

750º
CH3COCH3 
A + B
B + CH3COOH  C
The products (A), (B) and (C) are, respectively,
(A) CH4, CH2 = C = O and (CH3CO)2O (B) C2H6, CO and CH3COOCH3

(C) H2, and (D) C2H4, HCHO and HCOOCOCH3

72
11. 2-Methylcyclohexanone is allowed to react with metachloroperoxobenzoic acid. The major
product formed in the reaction is

(A) (B) (C) (D)

12. The possible number of stereoisomers that may be produced by the reaction of racemic s-butyl
methyl ketone with ethylmagnesium bromide and subsequent hydrolysis is
(A) Two (B) Three (C) Four (D) Six
13. Consider the following sequence of reactions.
2 5 1.C H MgBr 1.O3 H2SO4, heat
 B 
Ketone A   C  
2.H2O  H2O 2.Zn,H2O
The ketone (A) is

(A) (B) (C) (D)

14. An organic compound (A), C5H10O, reacts with hydrazine to form a hydrazone derivative (B). The
hydrazone (B) on being heated with KOH at about 180ºC, gives n-pentane. The compound (A)
does not respond positively to Tollens reagent and to the iodoform test. The compound (A) is

(A) (B) (C) (D)

Raney Pt.1  equi. H

2
15. B  
Ni, H2

A, B and C are:

(A) in all cases (B) in all cases

(C) in all cases (D)A: , B: ,C:

,CN
16. 
 Benzoin. The reactant is obtained by dry distillation of the calcium salts of the
EtOH,H2O
following pairs –
(A) C6H5CH2COOH, HCOOH (B)C6H5COOH, HCOOH
(C) C6H4 (OH)COOH, HCOOH (D)C6H4 (NH2)COOH, HCOOH
17. HCHO and C6H5CHO can be distinguished by –
(A) Fehling solution (B) Tollen’s reagent (C) KMnO4 (D) All of these

NH OH
2 2  A. H O
18. C6H5CHO   An oxime 
The V. D. of A should be –
(A) 53 (B) 52 (C) 51 (D) 50

73
19. Replacement of carbonylic oxygen is observed in the reaction –
(A) C6H5CHO/2H (B) C6H5CHO/H2N – NH2
(C) C6H5COOH/PCl5 (D) C6H5CHO/HCN
20. Benzyl phenyl ketone is –
(A) C6H5COC6H5 (B) C6H5 – CO – CO – C6H5
(C) C6H5CH2 – CO – C6H5 (D) C6H5CH2 – CO – CH2 – C6H5
21. The following compound is obtained on refluxing benzaldehyde with aqueosethanolic potassium
cyanide –
(A) Benzoic acid (B) Benzyl acetate (C) Cinnamic acid (D) Benzoin
22. Which of the following is not a correct statement –
(A) Acetophenone does not give a red colour precipitate with fehling’s solution
(B) Benzaldehyde gives a red coloured precipitate with Fehling’s solution
(C) Benzaldehyde gives silver mirror with Tollen’s reagent
(D) Benzaldehyde gives a black grey precipitate with mercuric chloride solution
CH3COONa
23. Benzaldehyde   cinnamic acid, ‘I’ in the above reaction is obtained by –

I
(A) CH3COOH + PCl5 (B) CH3CH2OH + K2Cr2O7/H2SO4
(C) CH3COCl+ CH3COONa (D) CH3CONH2 + P2O5
24. An example of Perkin's reaction is -
KOH
(A) C6H5CHO + CH3NO2 
 C6H5CH = CHNO2
3  C H CH=CHCOOHAlc.NH
(B) C6H5CHO + CH2(COOH)2  6 5
NaOH
(C) C6H5CHO + CH3CHO  C6H5CH = CHCHO
3 CH COONa
(D) C6H5CHO + (CH3CO)2O 
 C6H5CH=CHCOOH

25. When calcium benzoate is heated with calcium formate, the major product formed is–
(A) benzaldehyde (B) acetophenone (C) benzophenone (D) acetaldehyde
OH –
26. In the Cannizzaro reaction;2PhOH  PhCH2OH + PhCOO–, the slowest step is–
(A) the attack of the OH– at the carbonyl group
(B) the transfer of the hydride ion to the carbonyl group
(C) the abstraction of proton from the carboxylic acid
(D) thedeprotonation of PhCH2OH
27. Consider the following two reactions.
CHO

NaBH4 SnCl2-HCl
A B
<100ºC
NO2
The two major products (A) and (B) are respectively–
CH2OH CHO CH2OH CHO

(A) and (B) and

NO2 NH2 NH2 NH2
CHO CH2OH CH2OH
CHO

(C) and (D) and

NH2 NH2 NH2 NH2

74
28. Product (A) is:

(A) (B) (C) (D)

29. Which of the following pair is differentiated by iodoform test?

(A) (B)

(C) (D)

30. product (A) is:

(A) (B) (C) (D)

31. Which of the following reagents is best used for the conversion shown below?

 
(A) 1. NaBH4 /2. D3O (B) 1. NaBD4 /2. H3O

(C) 1. LiAlH4 /2. D3O (D) 1. H2 /Pt /2. D2O

32.

Reaction between K1 and K 2 is:

(A) K1  K2 (B) K1  K2 (C) K2  K1 (D) K1  K2  1

33. is final product when which of following is reacted with base

(A) (B)

(C) (D)

75
34. When acetaldehyde is treated with Fehling’s solution, it gives a precipitate of:
(A) Cu (B) CuO
(C) Cu2O (D) Cu  Cu2O  CuO

35. In Cannizzaro’s reaction, the intermediate which is the best hydride donor is:
H H
| |
(A) C6 H 5  C  O  (B) C6 H 5  C  O  (C) (D)
| |
OH O

CHO  X   MeO

CH COONa
36. MeO 3
Ether CH CH COOH

The compound (X) is

(A) CH3COOH (B) BrCH2COOH (C)(CH3CO)2O (D) OHC—COOH

37. Compound A (Molecular formula C3H8O) is treated with acidified potassium dichromate to form
a product B (molecular formula C3H6O). B forms a shining silver mirror on warming with
ammoniacal silver nitrate. B when treated with an aqueous solution of H 2NCONHNH2 and
sodium acetate gives a product C. Identify the structure of C
(A)CH3CH2CH = N  NHCONH2 (B) H3C C N . NHCONH2
CH3
(C) H3C C N . CONHNH2 (D) CH3CH2CH  N  CONHNH2
CH3

38. A mixture of benzaldehyde& formaldehyde on heating with aqueous NaOH solution gives
(A)benzyl alcohol and sodium formate (B)sodium benzoate and methyl alcohol
(C)sodium benzoate and sodium formate (D)benzyl alcohol and methyl alcohol

39. Which of the following has the most acidic hydrogen?

(A)3-hexanone (B)2, 4-hexanedione
(C)2, 5-hexanedione (D)2,3-hexanedione

40. The appropirate reagent for the following transformation :

O

CH3 CH2CH3

HO
HO
is

(A)Zn(Hg), HCl (B)NH2NH2, OH– (C)H2 / Ni (D) NaBH4

76
 SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. A new carbon-carbon bond formation is possible in
(A)Cannizzaro reaction (B) Friedel-Craftsalkylation
(C)Clemmensen reduction (D) Reimer-Tiemann reaction

2. Which of the possible compound will be formed in the following sequence of reaction.
HBr Hydrolysis Na CO
CH2=CH2   X   Y 
2 3
Z
I2excess
(A)C2H5I (B) C2H5OH (C)CHI3 (D) CH3COO

3. Which of the following are the examples of aldolreaction?

OH CH3

(A) 2CH 3CHO 

dil. NaOH
 CHO (B) 2CH 3COCH 3 
dil. NaOH
 H3C CH2COCH3
H3C
OH
dil. NaOH dil. NaOH
(C)2HCHO  CH3OH (D)C6H5CHO+HCHO  C6H5CH2OH

4. Which of the following compound undergo cannizzaro reaction?

(A) (B) (C) (D)

5. In which of the following intramolecularaldol condensation reaction more than two product are
possible?

(A) (B)

(C) (D)

6. Which of the following gives positive test with 2, 4-DNP?

(A) (B) (C) (D)

7. Which of the following the following compounds reacts with NaHSO3 ?

(A) (B) (C) (D)

8. Which of the following compounds has active methylene group?

(A) (B)

(C) (D)

77
9. Which of the following products is/are correctly mentioned in the following reactions.
(A) HCOH  NaOD
 HCOONa + CH3OD (B) HCDO  NaOH
 DCOONa + CH2DOH
(C) HCDO NaOEt
DCOOEt + DCH2ONa (D) D2CO  NaOD
 DCOONa + CD3OD

10. Observe the following reaction Products.

The correct statement is
(A) The product is a mixture of two compounds
(B) The product is optically inactive
(C) The product is a mixture of two chiral and one achiral stereoisomer
(D) The product is a mixture of three stereoisomers.

11. In the given reaction

CHCH (X) (Y) (Z)

(A) X is CH3CHO (B) Y is (C) Z is (D) Z is CH3COOH

12. Point out the correct synthesis :

OH
O
MgBr
(1) CH3 C CH3
(A)
+
(2) H
OH
MgBr
(1) Mg, ether CH Ph
(B)
(2) Ph - CHO
N N
(3) H3O+
H
H
+
(2) H
(C) PhMgBr + CH 2 CH 2 Ph CH 2 CH 2 OH
O
(D) PhMgBr+ HCHO Ph CH2 OH
(2) H+

13.  - caprolactum is a starting material for the synthesis of nylon-6. The lactum can be prepared
by the reaction:
H SO MCBPA
(A) N  OH 
2 4  (B) O 

 

NaN CH NH
(C) O 
3  (D) 3 2 
O 
H2SO4 H2,Ni/

78
14. Which of the following correctly indicate(s) the rate.

CN CH CHO OH
3
(A) CH3CH   KCN + HCl

– –
Me – – CH
– –
OH(very fast) CN

CH3CH  O
(B) (hydrate)  H2O/H+ hydrate
(fast)

HCN /OH CH3MgBr

(C) Cyanohydrin  C2H5CHO  Adduct formation
slow fast
(D) All of these

15. Which of the following is an example of aldol condensation?

dil.NaOH
(A) 2CH3CHO  CH3CH(OH)CH2CHO
OH
dil. NaOH |
(B) 2CH3COCH3   H3C  C  CH2COCH3
|
CH3
dil. NaOH
(C) 2HCHO 
 CH3OH  HCOONa
dil. NaOH
(D) C6H5CHO 
 C6H5CH2OH  HCOONa

COMPREHENSION TYPE
PARAGRAPH FOR NEXT FOUR QUESTIONS
Aldehydes and ketones show nucleophilic addition reactions. The -hydrogens in aldehydes and
ketones are acidic. Therefore, aldehydes and ketones having at least one -H undergo aldol
condensation in the presence of a base such as NaOH. Aldehydes having no -hydrogen undergo
Cannizzaro reaction in the presence of concentrated alkali. The carbonyl group of aldehydes and
ketones can be reduced to methylene group by Clemmensen or Wolf Kishner reduction. Aldehydes
are easily oxidised to carboxylic acids by Tollen’s reagent and Fehling solution. Functional
derivatives of carboxylic acids undergo nucleophilic acyl substitution with nucleophiles.
1. R O
dil.H 
O  H2N   H2O
 A  B
H NH
H2N
In the reaction correct statement(s) about A and B are:
I. A is optically active and dextrorotatory
II. A is racemic mixture and optically inactive
R R
B is N B is N O
H NH H NH
O NH2 NH2
III. IV.
(A) I and III (B) II and IV (C) II and III (D) I and IV

79
2. To convert CH2 = CH – CH2CHO to CH2 = CH – CH2COOH best reagent will be
(A) KMnO4 (B) P.C.C. (C) [Ag(NH3)2]OH (D) HIO4
3. The reactivity order of following toward nucleophilic substitution will be
O O O O O
|| || || || ||
R  C  OR R  C  Cl R  C O C R R  C  NH2
(I) (II) (III) (IV)
(A) I  III  IV  II (B) II  III  I  IV (C) III  IV  I  II (D) III  I  IV  II

OH
A 
 Et  C  Et . The structure of A is :
1. EtMgCl
4.
2. NH4Cl (aq.)
O
Et ||
(A) COCl2 (B) CH3  CH2  C  OEt

O
||
(C) CH3  CH2  C  CH2  CH3 (D)All

PARAGRAPH FOR NEXT THREE QUESTIONS

In presence of excess base and excess halogen a methyl ketone is converted first into a trihalo
substituted ketone and then into a carboxylic acid. After the trihgalo substituted ketone is formed
hydroxide ion attacks the carboxyl carbon because the trihalo methyl ion is the group more easily
expelled from ktheteranhedral intermediate. The conversion of a methyl ketone to a carboxylic acid
is called a haloformreactioonbeacause one of the product is haloform (CCHLI3) or CHI3 or CcHBr3.
O O
R – C – CI3 OH
OH (excess)
R – C – CH3 R – C – CI3 R – C – OH + CI3 R – C – O + CHI3
I2 (excess)
O OH O O
5. Which of the following compound show haloform reaction and recemisation in OD - / D2O.
O Me Me
O O Me
O Me
O O O CO C C C
Me Me Me
Me Me Me Me Me
(A) CH
(A)3CH23OH
CH
(A)2OH
CH3CH
(A)2(B)
CH
OH3(B)
CH OH (B) Ph (B) (C) (C) (C) (C)(D) CH
(D)3 CH (D)
– C3 – CH
C CH
– –CH(D)
3Ph
––CPh
CH
– CH
3 ––
CPh
– CH – Ph
Et 2Et Et Ph Et Ph Ph
O Et
O Et O Et O Et
Et
(1) I2 /OH +
6. Ph – C – C – C – CH3 product is
(2) H+
O Me O (3)

Me
(A) Ph  C  C  COOH (B) Ph  C  CH  Me (C) Ph  C  O  CH  Et (D)Ph  C  CH  OEt
O Me
O Et O Et O Et

O
Ph
O (1) NaIO
7. product is
(2) H ,

80
 COOH COOH
HOOC Ph
O O O OH
(A) (B) (C) (D) Ph

PARAGRAPH FOR NEXT TWO QUESTIONS:

The conversion of aldehyde having no alpha hydrogen to a mixture of carboxylic acid and primary
alcohol is known as cannizzaro reaction. The most important feature of this reaction is the
conjugate base of hydrate of aldehyde.

8. Which step is rate determining step

(A) step I (B) step II (C) step III (D) step I & II both

9. In the given reaction final product is

(A) CH3OH + (B) HCOONa +

(C) HCOONa + (D) HCOONa +

MATCH THE FOLLOWING COLUMN

1. Aldoldondensation proceeds by carbon-carbon bond formation between an enolate donor and a
carbonyl acceptor. For each of the following aldol products (1 through 4)
O O
CO 2C2H5
OH
OH CH
CO 2C2H5
CHO
(1) (2) (3) (4)

81
 Match the donor and acceptor compound.
Donor Acceptor

(A) CH 2 CHO (P) CH2 = O

(B) O (Q) CHO

(C) O (R) O

CO 2C2H 5
(D) CH 2 (S) CH 2 CHO
CO 2C2H 5

2. Match the following column

COLUMN-I COLUMN-II
(A) Ph–C–H alkaline KCN Product (P) Final product formed give positive tollen test
O

O 
(1) OH
(B) 

Product (Q) Final product give test with 2, 4 DNP
(2) H
O

(1) C2H5ONa
(C) CH3–C–OEt Product (R) Final product react with NaHCO3 and liberated
O CO2 gas
(1) KOH
(D) Ph–CH=O Product (S) Final product react with Na and liberated H2 gas
(2) H

INTEGER ANSWER TYPE

1. Compound X is a carbonyl compound with lowest molecular mass that can show positive
iodoform test. Molar mass of X compound is completely divisable by eleven.The number comes
after division is

2. Sum of the number of primary alcoholic group present in open chain structure of glucose and
fructose are.

3. A compound has two isomers (A) and (B) of formula C 5H10O. Isomer (A) on treating with NaOH
(aq.) gives 2, 2-dimethylpropan-1-ol and 2, 2-dimethylpropanoic acid salt. The isomer (B) on
treating with NaOH (aq.) gives 3-hydroxy, 2-propylheptanal. If product of A are X, Y and sum of
carbon in X, Y are A + B and product of B having C number of carbon then what is the value of
C – A + B.
4. An organic compound ‘A’ on treatment with ethyl alcohol gives a carboxylic acid ‘B’ and
compound ‘C’. Hydrolysis of ‘C’ under acidic conditions gives ‘B’ and ‘D’. Oxidation of ‘D’ with
KMnO4 also gives ‘B’. ‘B´ on heating with Ca(OH)2 gives ‘E’ (C3H6O). E does not give Tollen’s test
and does not reduce Fehling’s solution but form a 2,4-dinitrophenyl hydrazone. How many
carbon are present in product (E).

82
5. How many aldol products are possible (structural only) when mixture of HCHO,CH3CHO and
O
||
CH3  C  CH3are reacted in dilute NaOH?
HO , 
6. CH3  CH  O  CH3CH2  CH  O   mixture ofaldols (Z) total number of aldols including
stereoisomers. Find the mole of Z?
7. Observe the following reaction sequence
(1) NaOH(1eq) (3) HCN,HCl/AlCl (5) NH  NHPh
2
3 (Y) 
Phenol    
(Z)
Me (4) H3O
(2) D I
H
Answer the following questions in the given format :
P Q R S

P = Number of organic products formed in step-1

Q = Number of organic products formed in step-2 (singnificant products)
R = Number of organic products formed in step-3 (singnificant products)
S = In which step aromatic electrophilic substitution has taken place
SECTION-III
PREVIOUS YEARS QUESTIONS ASKED IN IIT JEE
1. In the following reaction sequence, the amount of D (in g) formed from 10 moles of
acetophenone is ____.
(Atomic weights in g mol1 : H = 1, C = 12, N = 14, O = 16, Br = 80. The yield (%)
corresponding to the product in each step is given in the parenthesis) [2018]

PARAGRAPH FOR NEXT TWO QUESTIONS

In the following reaction
Pd  BaSO 2 6
4  C H  i. B H
C8H6  8 8 X
H2 ii. H2O2 , NaOH, H2X

H2O
HgSO4 ,H2SO4

i. EtMgBr, H O
2 Y
C8H8O 
 ii. H ,heat
[2015]
2. Compound X is

(A) (B) (C) (D)

3. The major compound Y is

(A) (B) (C) (D)

83
 ANSWERS TO ALDEHYDES AND KETONES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. C 9. D 17. A 25. B 33. A
2. A 10. A 18. A 26. B 34. C
3. D 11. C 19. B 27. A 35. D
4. A 12. C 20. C 28. B 36. C
5. D 13. B 21. D 29. B 37. A
6. D 14. C 22. B 30. A 38. A
7. D 15. D 23. C 31. B 39. B
8. C 16. B 24. D 32. B 40. B

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. BD 4. ABC 7. ABC 10. AC 13. AC
2. BCD 5. AB 8. BD 11. ABC 14. AC
3. AB 6. ABCD 9. ABCD 12. ACD 15. AB

COMPREHENSION TYPE
1. C 3. B 5. D 7. A 9. C
2. C 4. D 6. B 8. B

MATCH THE FOLLOWING COLUMN

1. A  S; B  P; C  Q; D  R 2. A  PQS; B  RS; C  Q; D  RS

INTEGER ANSWER TYPE

1. 4 2. 3 3. 0 4. 3 5. 6 6. 12 7. 1123

SECTION-III
PREVIOUS YEARS QUESTIONS ASKED IN IIT JEE
1. 495 2. C 3. D

84
 CARBOXYLIC ACID AND ITS DERIVATIVES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. In the following reaction identify compounds A, B, C and D :
PCl5  SO2  A  B ;
A + CH3COOH  C + SO2 + HCl
2C + (CH3)2Cd  D + CdCl2
(A) SOCl2, POCl3, CH3COCl, CH3COCH3 (B) SO2Cl2, HCl, CH3Cl, CH3CHO
(C) SO2, Cl2, C2H5Cl, CH3COCH3 (D) None of these.

2. What are A and B in the following sequence of reactions ?

P (i) Alc. KOH excess
(i) CH3CH2COOH 
Br
A (ii) A 

B
2 (ii) H

(A) CH 3 — CH.COOH, CH 2  CHCOOH (B) CH3CH2COBr, CH2  CH.COOH

Br
Br

(C) CH2 .CH2COOH, CH2  CH.COOH (D) H3C COOH , H2C C COOH

Br Br
Br

3. Ammonium acetate on heating gives -

(A) N2 gas (B) acetic acid (C) Acetamide (D) NH3 gas

4. Acetic anhydride is used -

(A) as an acetylating agent
(B) for the detection and estimation of –OH and –NH2 groups
(C) in the manufacture of aspirin
(D) all of the above

5. By treating acetic acid with an etheral solution of diazomethane, it forms -

(A) Methyl acetate (B) ethyl acetate
(C) acetamide (D) acetic anhydride

6. Which of the following esters cannot udergo Claisen self condensation -

(A) CH3CH2CH2CH2COOC2H5 (B) C6H5COOC2H5
(C) C6H11CH2COOC2H5 (D) C6H5CH2COOC2H5

7. Let us consider an esterification of isotopically labelled carboxylic acid –

O
18 H
CH3–C–OH + CH3CH2OH 
 (X) and (Y), (X) and (Y) respectively are -
O O
18 18
(A) CH3–C–OC2H5 ; H2O (B) CH3–C–OC2H5 ; H2O
O
(C) CH3–C–OC2H5 ; H2O (D) both (A) and (B)

85
 3 (i) CH MgBr
8. C4H8O2 
 C4H10O2 Alcohol (Y) gives Lucas test within 5 minutes. Thus, (X) and (Y)
(ii) HOH/HCl
Ester(X) Alcohol(Y)
respectively are-
(A) CH3COOC2H5; (CH3)3(COH) (B) HCOOC3H7; (CH3)2CHOH
(C) C2H5COOCH3; (C2H5)3COH (D) HCOOC3H7; (CH3)3COH

9. Methyl acetate on treating with excess of C2H5MgBr produces -

CH3 C2H5 C2H5 CH3
(A) CH3–C–OH (B) CH3–C–OH (C) C2H5–C–OH (D) CH3–C–OH
CH3 C2H5 C2H5 C2H5

10. H2N–CH2–CH2–NH2 when reacts with diethyl oxalate gives

H
COOC2H5 COOC2H5
N OC2H5 N O N=C N=C
COOC2H5 COOC2H5
(A) (B) (C) (D) COOC2H5
N OC2H5 N O NH2 N=C
COOC2H5
H
11. Which one of the following esters is the most reactive for saponification ?

(A) (B) (C) (D)

12. A compound with molecular formula C4H10O4 on acylation with acetic anhydride gives a
compound with molecular formula C12H18O8. How many hydroxyl groups are present in the
compound ?
(A) one (B) Two (C) Three (D) Four

CH NH
3 2
13.   X, X is
heat

O
(A) (B)
(A) CH3 – CH – CH2 – C – OH and CH3 – CH – CH2 – O – H
O O O–H CO2H
O
(C) (D)
(A) CH3(A)
– CH
CH–
3 –
CHCH
2 ––C
CH– 2OH
– Cand
– OHCHand
3 – CH
CH–3–
CHCH
2 ––O
CH– 2H– O – H
(B) CH
(A) – CH – CH – C – OH and CH – CH – CH – O – H
CH33 – CH2 –CH2 – CO2H and (CH3)2 3C(OH)CO2H2
O–H O–H CO2H CO2H
14. Which pair of compounds on heating give isomeric products O – HO – H CO2H
O
(B) CH3(B)
– CH
CH23–CH
– CH–2 CO
–CHH–and
CO2(CH
H and
3)2 C(OH)CO
(CH3)2 C(OH)CO
2H 2H
(A) CH3 – CH – CH2 – C –2 OH and CH 3 – CH – CH2 – O – H (B)
(C) CHCH
3 –2CH2 –CH
– CH – CO H and (CH )2 C(OH)CO
2 –CH2 – 2CO2H and 3CH 2H3 – CH2– OH
3 –CH – CH
O–H O–H
O–H CO2H HO O–H CO2H
(C) CH (C)2 – CH
CH22–CH
– CH CH222H–and
2 2––CH
CO CO2CH
H and
3 –CH
CH–3 CH
–CH3 ––CH
CH2–
3 –OH
CH2– OH (D) All the above
(B) CH3 – CH2 –CH – CO2H and (CH3)2 C(OH)CO2H (C) CH2 – CH2 –CH2 – CO2H and CH3 –CH – CH3 – CH2– OH
HO HO CO2H CO2H
O–H HO CO2H
(D) All the
(D)above
All the above
15. The correct sequence of reagents for the following conversion
(D) All theisabove
(C) O 2 – CH2 –CH2 – CO2H and CH3 –CHO– CH3 – CH2– OH
CH

HOC – O – H CH2CO
– C2H
– OH

(D) All the

NOabove NO2
2

SOCl2 Ag CH2N2 SOCl2 CH2N2 Ag

(A) H2O
(B) H2O

CH2N2 SOCl2 Ag Ag SOCl2 CH2N2

(C) 86 H2O
(D) H2O
 O O O O
O O O O
C C – O – HCH – C – OH CH – C – OH
C––O
O––H
H C – O – HCH22 – C – OH CH22 – C – OH

NO NO NO NO
NO22 NO22 NO22 NO22
SOCl Ag SOCl Ag CH2NSOCl SOCl CH N Ag
(A) SOCl22 Ag (A) CH
CH2N
SOCl 2
2N2 2
2 Ag 2
CH NSOCl2
(B)
CH
CH22N
N(B)
2 Ag
Ag 22
SOCl CH22N22 Ag
(A) H
H2O
O
(A) H2O
H2O
(B) 2 2 2 2
(B) H
H22O
O
H2O
H2O
2

CH CH
Ag N SOCl AgAg AgN SOCl CH N
CH22N
N22 SOCl
SOCl(C)
2 Ag22N22
CH SOCl22 AgAg SOCl
SOCl22 (D) CH
CHAg
2N2 SOCl22 CH22N22
(C)
(C)
2
(C) (D) HH
(D) H 2O H 2 2
(D) H 2OO
H
H22O
O HO2O
O
22 2

OO O O O
C—Cl C—Cl
C—Cl C—Cl C—Cl
NaOEt NaOEt
NaOEt NaOEt NaOEt
16. CH
CH2(COOEt)
2(COOEt)
CH2(COOEt)
2 2+
+ CH
2 + 2(COOEt)2CH Finalproduct
+ 2(COOEt)2 + Final

product
Final isis
productFinal
is productFinal
is product is
(1(1eq.)
eq.) (1 eq.) (1 eq.) (1 2.H3O 
eq.)
C
C C C C
OO OEt
OEtO OEt O OEt O OEt
OO O O O
COOEt COOEtOO CH
COOEt O COOH
CH
2 2 COOH
COOEt O OOCH CH
CH2 COOH
COOEt CHOCOOH
OCOOH
2 COOH CH O OO
CHCOOH
2 COOHCHCH
CHO O CHCH COOH
COOH
33 3
O CH3 O CH3
CC CH
CH C CH CC
C CH CC CH C CC COOH CC C CC CC C C
COOEt
COOEt COOEt COOEt COOEt COOH COOH COOH COOH
(A)
(A) (A) (B)
(A) (B) (B)
(A) (C)
(B)(C) (C)
(B) (D)
(C)(D) (D)
(C) (D) (D)

CC C COOH COOH
C COOH C COOH COOH
COOH
COOH COOH COOH COOH
COOH
COOH COOH COOH COOH
OEtO OEt
OO OEt O OEt O OEt

17. Which statement is correct about the following reaction?

COCl

NaOH (1 eq.)
H Br

CH3
(A) There is inversion of configuration at asymmetric C* atom
(B) There is No change of configuration at asymmetric C* atom
(C) There is 100% racemisation at C* atom
(D) % inversion > % retention at C* atom
CH3

COOH   X , X will be

NaOH
18. H2C CH C CaO / 

CH3
CH3 CH3

(A) H3C CH C CH3 (B) H2C CH C CH3

H
CH3 CH3

(C) H3C CH C CH 2OH (D) H2C CH C COONa

CH3

2 3  (A) K CO
19. R  CH2  NH2 
THF
(71%)

In above reaction identify major product (A) of the reaction :

87
 (A) (B) (C) (D)

(i) Na
20. CH2(CO2Me)2  ?  CH(CO2Me)3
(ii) AcOH
Which of the following reactants will complete the above reaction?
(A) CH2(CO2Me)2 (B) (CO2Me)2 (C) Cl  CO2Me (D) COCl2

21. Products obtained in the given reactions are shown below.

The number of possible products for x and y are:

(A) 1, 1 (B) 1, 2 (C) 2, 1 (D) 2, 2

22. Which is the major product of the following reaction?

(A) (B)

(C) (D)

23. Which reaction is not possible for acetic anhydride?

O O
|| || 
(A) (CH3C)2 O  2HN(CH3 )2  CH3C N(CH3 )2  CH3CO2  H2 N(CH3 )2

O O
|| ||
(B) (CH3C)2 O  CH3CH2OH  CH3COCH2CH3  CH3CO2H

O O
|| AlCl3 ||
(C) (CH3C)2 O  C6H6  CH3CC6H5  CH3CO2H

O O
|| ||
(D) (CH3C)2 O  NaCl  CH3CCl  CH3CO2Na 

88
24. Consider the following sequence of reaction:

The compound A is:

(A) (B) (C) (D)

25. Which of the following reaction will give racemic mixture?

(A) (B) (C) (D)

N H
3
26. 
 Major product:
H2SO4

(A) (B) (C) (D)

27. When propanoic acid is treated with aqueous sodium bicarbonate, CO 2 is liberated. The C from
CO2 comes from
(A) methyl group (B) carboxylic acid group
(C) methylene group (D) Bicarbonate

28. Which does not react with Fehling’s solution ?

(A) CH3CHO (B) C6H5CHO (C) C6H12O6 (D) HCOOH.

29. Which does not form a phenyl hydrazone? O

O
(A) H C C.COOH (B) H3C C CH2 CH3
3
O O
(C) H3C C OH (D) H3C C H

30. The sodium salt of the acid which does not form an alkane when subjected to electrolysis
(A) sodium formate (B) sodium acetate
(C) sodium propionate (D) sodium butanoate

89
 O
31. CO2H

The above conversion can be done by which of the following process?

CH3
|
(A) HBr peroxide; CH  C  O at high temperature, O3 – H2O
3
|
CH3
(B) HBr; CH3CH2O– at high temperature; O3 – H2O
(C) HI, CH3O– at high temperature, O3 – H2O in presence of Zn
(D) HCl peroxide

32. Which of the following dicarboxylic acids gives a linear polymeric anhydride?
(A) HOOC(CH2)3COOH (B) HOOC(CH2)4COOH
(C) HOOC(CH2)5COOH (D) HOOC(CH2)6COOH

33. Acetic acid in the vapour state has a molecular weight of 120 because :
(A) its molecule gets solidified
(B) its molecule gets stabilized by resonance
(C) it undergoes intermolecular H-bonding and exists as the dimer
(D) it forms anhydride in this condition.
34. Which of the following will not yield a cyclic compound on heating :

(A) (B) (C) (D)

35. What is the product of the following reaction?

(A) (B) (C) (D)

36. Which is the major product of the following reaction?

(A) (B)

(C) (D)

90
37. Which reaction is not possible for acetic anhydride?
O O
|| || 
(A) (CH3C)2 O  2HN(CH3 )2  CH3C N(CH3 )2  CH3CO2  H2 N(CH3 )2

O O
|| ||
(B) (CH3C)2 O  CH3CH2OH  CH3COCH2CH3  CH3CO2H

O O
|| AlCl3 ||
(C) (CH3C)2 O  C6H6  CH3CC6H5  CH3CO2H

O O
|| ||
(D) (CH3C)2 O  NaCl  CH3CCl  CH3CO2Na 

38. Identify Z in sequence.

(i) heat
2 H O(H )
CH3COONH4  Y Z
(ii) P2O5
(A) CH3CH2CONH2 (B) CH3CN (C) CH3COOH (D) (CH3CO)2 O


KCN H3 O
39. In the reaction A 
 B  Identify A:
reflux

(A) (B) (C) (D) All are correct

40. Consider the following sequence of reactions:

Identify A, B, C and D.
(A) F, COOH, COCH3 , OCH2CH2CH3 (B) CHO, COOH, COCl, COCH2CH3
(C) Br,COOH, COCl, COCH2CH3 (D) Br, COOH, COCl  CHO

MeOH PCl MeNH

2  C; Product (C) of the reaction is:
3  B 
41.  A 

(A) (B) (C) (D)

91
 SECTION-II
MULTIPLE CORRECT ANSWER TYPE
NaOEt H /H O
1. CH2(COOEt)2 + BrCH2CH2CH2Br 
excess
 ‘A” 
Δ
2  B

COOEt COOH
(b)
(a) A =
(A) COOEt (B) B =

COOEt CH = CHCOOH
(c) A =
(C) (d) B =
(D)
O
||
Ozonolysis [O] Hydrolysis P/Br
2. (A) 
 CH3  C CH3 + Aldehyde   (B) 
2  (C)  (D)
(i) HCN/CN-
Hydroxy acid
(ii) Hydrolysis
which of the following compounds can be identified as from A to D.
CH3 CH3
(a)
(A) C CH CH (b)
(B) CH3 CH COOH
CH3 CH3
CH3
Br OH
(c)
(C) CH3 C COOH (d)
(D) CH3 C COOH
CH3 CH3

3. Of the following orders regarding basicity which are incorrect

(A) CH3CH2NH2 > PhCONH2 > CH3CONH2 (B) CH3CH2NH2 < PhCONH2 > CH3CONH2
(C) CH3CH2NH2 > PhCONH2 < CH3CONH2 (D) CH3CH2NH2 < PhCONH2 > CH3CONH2
4. Which of the following reactions are not possible?
O

(A) H2C CH 2COOH 

Mg / Ether
 H2 C CH 2 C OH

Br MgBr
Br MgBr
H2C H2 C

(B)  Mg 
Ether

MgBr
O O O O
(C) C C
ONa   CH MgBr
H3C 3 H3C ONa
Ether
CH3

MgBr
O O O O
C
H H
(D) CH3 
CH3MgBr
 CH3
CH3

92
 CH
| 3
5. Ph  CH  CH TsCl KSH
2  OH   X  Y :
( )
CH CH3
| 3 |
(A) X is Ph  CH2  CH  OTs (B) X is Ph  CH  CH OTs
2
( ) ( )
CH CH
| 3 | 3
(C) Y is Ph  CH2  CH  SH (D) Y is Ph  CH2  CH  OTs
() ( )

O
|| 18
6. Ph  CH2  O  C  CH3  OH  X  Y
18
(A) X is Ph  CH2  OH (B) X is Ph  CH2  OH
O
||
(C) Y is CH  C  O (D) Y is CH3  C  O18
3 ||
O

7. H2CN2  X  Y :

(A) (B) (C) (D)

2 SOCl AlCl Zn Hg

3  Y 
8.  X  Z:
HCl

(A) (B)

(C) (D)


LiAlH4 HBr NaCN H3 O,CaO CaO,
9. C4H8O4        Y  Hexanedioic acid:

(X)

(A) (B) (C) (D)

93
 10.

(A) (B) (C) (D)

11. The intermediates formed during the reaction:

4  C H CH Br CCl
C6H5CH2COOAg  Br2  6 5 2 


(A) (B) C6H5 C H2 (C) Br (D)

12. An ester A of the formula C5H8O2 on acidic, hydrolysis gives an acid B, which reduces Tollen’s
reagent and an alcohol C, which gives iodoform test. Ester A can also be converted into alcohol B
by reaction with excess of Grignard reagent D.

(A) (B)

(C) (D) D is C2H5MgBr

COOH
CH3 CHOH
3 OH
1.PCI5 NH2OH.HCI H2SO4 COCH3 COCH3 C=N C=N
13. H Ar 2.CH3MgBr
X Y Z
(1eq.)
(A) H (A) H Ar Ar (B) H (B) H Ar Ar
Et
X, Y, Z are –
CH3 CH3 Et
OH Et Et Et
OH
COCH3 COCH3 C=N C=N
NHCOCH3 NHCOCH3 NHCOCH3 NHCOCH3

A) H (A) Ar
H Ar (B) H (B) H
Ar Ar
(C) H (C) H Ar Ar (D) H (D) H Et Et

Et Et Et Et
Et Et Ar Ar
X Y Z Z
NHCOCH3 NHCOCH3 NHCOCH3 NHCOCH3
(1)2/OH
EtO (2)H 
C) H 14. (C) Ar
H Ar (D) 
H (D)(P)
HEt  Et  (Q) 
 (R)

Et Et Ar Ar

94
 The products of the above reaction is / are :

(A) (B) (C) (D)

15. Which of the following gives benzoic acid as major product?

O
H O/H

H 2
(A) C6H5CONH2  HNO2  (B) C6H5MgBr  C  O 
O O
 
K2Cr2O7 2 (i)Cl NaOH
(C) C6H5  C CH3   (D) C6H5  C CH3 


H2SO4(conc.) (ii) H2O/H

COMPREHENSION TYPE
PARAGRAPH FOR NEXT THREE QUESTIONS
Observe the esterfication mechanisms for primary and tertiary alcohols.
Type.1
O
CH3–COOH + CH3–CH2–CH2–OH Conc. H2SO4 CH3–C–O–CH2–CH2–CH3
Propyl = Pr
Mechanism
O OH OH O
H
OH O
Pr H Step 3
CH3–C CH3–C CH3–C CH3–C–OH CH3–C–O–CH2–CH2–CH3
Step 1. Step 2 –H 
OH OH OH –H2O
O
Pr H
Type. 2


Mechanism




Conc.H SO
1. CH3 – COOH + C2H518OH 
2 4
 (P)
Conc.H SO
CH3 – COOH + (CH3)3C – 18OH  2 4
 (Q)
In the above reaction (P) and (Q) are respectively :
O O O OCH O
O CH3 O
CH O O O CH O
O CH3
CH
3 18 3 18 3 3
18 18 18 18
CH –C–O–C H , (A)
CH CH
CH
–C –C
–C –O–C
–O–C
–O–C–CH H
H ,, CH
CH –C
–C –O–C–CH
–O–C–CH
CH –C–O–C H , (B)
CH CH
CH
–C –C
–C –O–C
–O–C
–O–C–C HH
H ,, CH
CH –C
–C –O–C–C
–O–C–C H H
(A) 3 2 5 (A)3 33 2 5
23 5 3
3 (B) 3 3
3 2 5 (B) 3 33 2 5
22 35 3
3 22H333

CH CH3
CH CH CH3
CH
3 3 3 3

O O O OCH O
O CH3 O
CH O O O CH O
O CH3
CH
18 183
18
3
18 18 3
18 18 18
18
3
(C) C
(C)3C
(C) C2H5–C–O–CH3, CH –C H –C –O–CH , CH –C –O–C–CH (D) CH
CH3CH
CH3–C33–O–C2H5, (D) –C –O–C
3–C–O–C223
–C3–O–C–CH H , CH –C –O–C–CH
H55, CH33–C–O–C–CH33
22H55–C–O–CH
–O–C–CH 3 33, CH33–C(D)
–O–C–CH
CH CH
CH 3 CH CH3
CH
3 3 3 3

95
 H
Conc.H2SO4
2. CH3COOH + D OH (X)

CH3
CH3
Conc.H2SO4
CH3–COOH + Ph–C–OH (X)
C2H5
(A) (X) is optically active while (Y) is optically inactive
(B) Both (X) and (Y) are optically active
(C) Both X and (Y) are optically inactive
(D) (X) is optically inactive while (Y) is optically active

3. (+) Octan-2-ol esterifies with Acetic acid to give optically inactive racemised product. It must
have gone by
(A) Type I mechanism (B) Type II mechanism
(C) Mix type I and type II mechanism (D) More by type I less by type II mechanism

PARAGRAPH FOR NEXT THREE QUESTIONS

Observe the following sequence of reaction and answer the questions based on it
CH3MgBr i) CO2 H2O/H2SO4 O
Phenylacetylene x y z wO COOH COOH
– CH4 HgSO4 (B) Ph – CH
(B) Ph – CH
(A)
(A) Ph – CH2 –Ph
C –– COOH
CH2 – C – COOH
4. Compound z is COOH COOH
O O O O
COOH COOH
A) Ph – CH2 – (A)
C –Ph – CH2 – C – COOH
COOH (B) Ph – CH (B) Ph – CH
(C) Ph – C (C)
– CPh – C – CH2–COOH
H2–COOH (D) Ph – CH2–Ph
(D) – CH2– COOH
COOH
COOH COOH
O O
C) Ph – C5. Which
(C)
– CH of– the
Ph – C
2–COOH
following
CH2–COOH statement
(D) Ph – CH2is not
(D)
– COOH Phcorrect
– CH2– COOH
(A) y decolourises Br2/H2O solution
(B) on heating z CO2 is liberated
(C) w on reaction with NaOI gives yellow ppt
(D) x liberates H2 gas with Na metal

6. Which of the following compound give benzoic acid on KMnO4 oxidation

(A) w (B) y (C) z (D) all.

MATCH THE FOLLOWING COLUMN

1. Match the following column I & column II:
Column I Column II

(A) (P) Cyclic

(B) (Q) Exhibit geometrical isomerism

(C) (R) Can be optically active


(D) HO  CH2  COOH 
 (S) Lactone

96
2. Match the column
Column I Column II

(i) OH
(A) MeCO(CH2)4COMe 
 (P)
(ii) H /


OEt
(B) (CH2)4 
 (Q)

3CH COO–
(C) PhCHO + 
 (R) (Ph)2 C — COO –
|
OH

OH
(D) PhCOCOPh 
 (S)

INTEGER ANSWER TYPE

1. A compound (A) of molecular formula C14H10O2 is formed from C14H14O2 by oxidation Cr2O7–2.
(A) upon treatment with OH gives (B). (B) on treatment with conc. H2SO4 and heat gives
compound (C) of molecular formula C28H20O4(B) responds to NaHCO3 test and effervescence
comes out. What should be the molecular wt. of B ?

2. Two stereoisomers (cis and trans) of 3, 4-dibromocyclopentane-1, 1-Dicarboxylic acid undergo

decarboxylation, find out the total number of product formed.

3. In the following sequence of reaction how many nucleophilic substitution taking place.
OH O
SOCI2 alc.KOH CI –C – CI CH3MgBr (2eq) HBr
AICI3
H
4. Write the number of CO2 molecule released only on heating following molecule.
For example if all are releasing one CO2 molecule per molecule fill 1111 in OMR sheet.

(a) (b)

(c) (d) CH2  CH  COOH

97
5. Convert

In exactly four steps. Select the reagent from the given set and write the four digit
number in correct sequence.
(1) Aqueous KOH (2) CH2N2 / Ag,  /H2O (3) CHCl3 /KOH
(4) CO2 /H (5) KCN (6) SOCl2
(7) Br2 /KOH (8) Mg/dry ether

6.

Number of products formed .

7. Number of compounds, which can evolve CO2 on heating are:

8. Number of reaction which gives ester as major product.

ROH m CPBA
(1) R  CH  C  O 

 (2) H  C  CH3 
H
O 
P2O5 / OEt
(3) H3C  C  OH 
 (4) H3C  C  O  C  CH3  
O O O
CO/BF3 MeMgX(1 eq)
(5) H3C  CH2  O  CH2  CH3   (6) Diethyl-carbonate  
O
CO MeOH
CH2N2
(7) HC   high P
CH  (8) Me  C  OH  
Ca(CO)8
9. Formic acid can be detected with how many of following test(s)?
(a) Iodoform test (b) Tollen’s test
(c) Litmus test (d) Fehling test
(e) NaHCO3 test (f) Benedicts test
(g) Brady’s test (h) HKMnO4 test
(i) H /K2Cr2O7 test (j) Hinsberg test

98
10. A compound with molecular formula C6H14O4 does not give litmus test and does not give
colour with 2,4-DNP, It reacts with excess MeCOCl to give a compound whose vapour
density is 117. Compound A contains how many hydroxyl groups?

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IIT-JEE
PARAGRAPH FOR NEXT TWO QUESTIONS
Treatment of benzene with CO/HCl in the presence of anhydrous AlCl3 /CuCl followed by reaction
with Ac2O/NaOAc gives compound X as the major product. Compound X upon reaction
with Br2 /Na2CO3 , followed by heating at 473 K with moist KOH furnishes Y as the major product.
Reaction of X with H2 /Pd  C , followed by H3PO4 treatment gives Z as the major product. [2018]
1. The compound Y is

(A) (B) (C) (D)

2. The compound Z is

(A) (B) (C) (D)

PARAGRAPH FOR NEXT TWO QUESTIONS

An organic acid P (C11H12O2 ) can easily be oxidized to a dibasic acid which reacts with
ethyleneglycol to produce a polymer dacron. Upon ozonolysis, P gives an aliphatic ketone as one of
the products. P undergoes the following reaction sequences to furnish R via Q. The compound P
also undergoes another set of reactions to produce S. [2018]
(1) H2 /Pd  C
(2) NH3 / (1) H2 /Pd  C (1) HCl
(3) Br2 /NaOH (2) SOCl2 (2) Mg/Et2O
S  P  Q  R
(4) CHCl3 ,KOH (3) MeMgBr, CdCl2 (3) CO2(dry ice)
(5) H2 /Pd  C (4) NaBH4 (4) H3O 

3. The compound R is

(A) (B)

(C) (D)

99
4. The compound S is

(A) (B) (C) (D)

5. Different possible thermal decomposition pathways for peroxyesters are shown below. Match
each pathway from List I with an appropriate structure from List II and select the correct
answer using the code given below the lists. [2014]

Code:
P Q R S
(A) 1 3 4 2
(B) 2 4 3 1
(C) 4 1 2 3
(D) 3 2 1 4

100
 ANSWER TO CARBOXYLIC ACID AND ITS DERIVATIVES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. A 10. B 19. B 28. B 37. D
2. A 11. A 20. C 29. C 38. C
3. C 12. D 21. C 30. A 39. B
4. D 13. C 22. C 31. B 40. C
5. A 14. D 23. D 32. D 41. B
6. B 15. B 24. B 33. C
7. B 16. B 25. A 34. A
8. A 17. B 26. D 35. C
9. B 18. A 27. D 36. C

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. AB 4. AB 7. AD 10. ACD 13. ABC
2. ABCD 5. AC 8. ABD 11. ABC 14. ACD
3. BCD 6. BD 9. BC 12. ABC 15. ABCD

COMPREHENSION TYPE
1. B 3. B 5. D
2. A 4. ? 6. D

MATCH THE FOLLOWING COLUMN

1. A  P,Q,R; B  Q; C  P,R,S, D  Q,S 2. A  Q; B  P; C  S; D  R

INTEGER ANSWER TYPE

1. 204 3. 3 5. 4862 7. 5 9. 7
2. 4 4. 4330 6. 6 8. 0006 10. 2

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IIT-JEE
1. C 2. A 3. A 4. B 5. A

101
 AMINES
SECTION-I
STRAIGHT OBJECTIVE TYPE
R1
1. The compound R2
 N  R3 forms nitroso amines when the substitutents are
(A) R1 = CH3, R2 = R3 = H (B) R1 = R2 = H, R3 = C2H5
(C) R1 = H, R2 = R3 = CH3 (D) R1 = CH3, R2 = C2H5, R3 = C3H7

2. Aniline when diazotized in cold and then treated with dimethyl aniline gives an coloured
product. Its structure would be

(A) (CH 3)2N N N (B)(CH 3)2N NH

(C) CH 3NH N N NHCH 3 (D)CH 3 N N NH 2

3. Aniline reacts with acetaldehyde to form

(A) Schiff’s base (B) Carbylamine (C) Immine (D) None of these

4. –NH2 group shows acidic nature while reacts with reagent.

(A) Na (B) CS2 (C) Br2 + NaOH (D) Water

5. Product of Hofmann mustard’s oil reaction’s

(A) Mustard gas (B) Alkyl isocyanate
(C) Alkyl thiocyanate (D) Alkyl isothiocyanate

CH3
| HNO2
6. CH3 – C – CH2NH2 A (major product) A is
|
CH3
CH3 CH3 CH3 CH3
| | | |
(A) CH3 – C – CH2OH (B) CH3 – C – CH2CH3 (C) CH3 – C – CH2N2 (D) CH3 – C – CH = CH2
| | |
CH3 OH CH3

7. Secondary amine can be produced by —

(A) Reduction of isocyanides (B) Reduction of amides
(C) Reduction of aldehydes (D) Reduction of nitrobenzene
8. Which process is most suitable for getting primary amine from alkyl isocyanide —
(A) Reduction with H2/Pt (B) Reduction with Zn/HCl
(C) Acidic hydrolysis (D) None of these

NH
3  X 
2 5  Y  PO Ni
9. C6H5COCl  Z
H2
The end product in the above sequence of reaction is :
(A) Benzoic acid (B) Aniline (C) Benzyl amine (D) Benzonitrile

102
10. Which one of the following reaction does not produce amine —
Na/C H OH H2O/H 
(A) RCH = NOH 
2 5
 (B) RCN  

2 Br /KOH
 (C) RCO NH2 
 (D) All of these

11. Identify S in the following sequence of reactions

CuCN LiAlH
4  Y 
2 S. HNO
C6H5N2Cl   X 
KCN
(A) Benzoic acid (B) Phenyl acetic acid (C) Benzyl alcohol (D) Benzamide

12. Identify the end product in the following sequence

2 NaNO /HCl 2 5 S. NaOH(aq.) C H I
C6H5NH2 
 X  Y 
 320K
N2Cl OC2H5 OC2H5 OC2H5
C2H5 C2H5 HO OH
(A) (B) (C) (D)

C2H5 C2H5 OH

13. Which of the following will not give coloured dye with benzene diazonium chloride
OH CH2OH OH OH
(A) (B) (C) (D)
CH3
Br2 /KOH
14. m-bromobenzamide   X. The compound X can be
(A) m-bromoaniline (B) 3, 5-Dibromobenzamide
(C) m-bromobenzyl amine (D) m-bromophenol

15. Which of the following structure can exist as Zwitter ion

(A) p-amino benzoic acid (B) Benzene diazonium chloride
(C) o-amino benzene sulphonate ion (D) Benzene diazonium hydrogen sulphate

16. Which of the following amine will not react with benzoyl chloride
(A) isopropyl amine (B) p-toludine
(C) N, N-Diethyl aniline (D) N-methyl aniline

17. Which of the following substance does not give dinitrogen gas with nitrous acid
(A) Acetamide (B) Methyl amine (C) Diethyl amine (D) Isopropyl amine

18. Which sequence of steps will be able to produce 3, 3'-Dinitrobiphenyl from benzene
(A) HNO3/H2SO4, Cl2/FeCl3, Na/Ether (B) Cl2/FeCl3, HNO3/H2SO4, Na/Ether
(C) Cl2/FeCl3, H2SO4, Na/Ether (D) I2/HIO3, Cl2/FeCl3, C6H5NO2

Cl2 778K NH3 (alc.)

19. Propene   X   Y (Major product)
The product Y in the above sequence is
(A) Allylamine (B) n-Propylamine
(C) 1, 2-Diaminopropane (D) 1, 1-Diaminopropane

103
 SOCl NH
3  B 
2  A  PO
2 5  C 
2 H /Pd
20. C6H5COOH  
Py
In the above sequence D is
(A) Aniline (B) Benzylamine
(C) Phenol (D) Cyclohexylamine

21. Which of the following product is formed when benzyl amine is oxidised with KMnO4
(A) p-benzoquinone (B) toluene (C) phenol (D) benzoic acid

22. Production of amines by ammonia and alkylhalides is called

(A) Frankland reaction (B) Hoffmann ammonolysis
(C) Hoffmann’s mustard oil reaction (D) Hoffmann’s bromamide reaction

23. Which of the following cannot show tautomerism

(A) 2-Methyl-2-nitropropane (B) 2-Nitropropane
(C) 1-Nitropropane (D) Vinyl alcohol

24. Which one of the following is least soluble in water

(A) C2H5OH (B) C2H5NH2

(C) C2H5 – NH – C2H5 (D) C2H5  – N – C2H5

|
C2H5
25. Which one of the following is incapable of forming hydrogen bonding
(A) NH [CH3]2 (B) CH3CH2NHCH3 (C) CH3CH2CH2NH2 (D) (CH3)3N

26. Grignard reagent will react with..................amines to form hydrocarbons

(A) 1o (B) 2o (C) 3o (D) Both 1o & 2o

27. Schiff’s base on reduction gives

(A) Aniline (B) Sec. amine (C) Primary amine (D) Tertiary amine

28. Which of the following compounds can undergo coupling reaction with benzene diazonium
chloride —
(A) Chlorobenzene (B) Benzoic acid (C) Nitrobenzene (D) Phenol

29. Which of the following compounds will react in the presence of ethanolic KCN
(A) Ethane (B) Acetyl chloride (C) Chlorobenzene (D) Benzoic acid

CuCN dil. NaOH/CaO

30. C6H5N2Cl– X
HCl
Y Y
The compound Z is
(A) Benzoic acid (B) Sodium benzoate (C) Benzene (D) Phenol

31. Which of the following reagents will convert p-methyl benzene diazonium chloride into p-cresol
(A) Cu powder (B) H2O (C) H3PO2 (D) C6H5OH

32. In the reaction p-chlorotoluene with KNH2 in liq. NH3, the major product is :
(A) o-toludine (B) m-toluidine (C) p-toluidine (D) p-chloroaniline

104
33. The formation of cyanohydrin from a ketone is an example of :
(A) Electrophilic addition (B) Nucleophilic addition
(C) nucleophilic substitution (D) Electrophilic substitution

34. Find (X):

(A) (B) (C) (D)

35. Predict the product of following reaction:

(A) (B) (C) (D)

36. What is the product of following reaction sequence:

(A) (B) (C) (D)

37. Compound (X) C9H10O gives yellow coloured ppt. with 2,4 DNP but does not give red coloured
ppt. with Fehling’s solution. (X) on treatment with NH2OH/H+ gives compound (Y) C9H11NO. (Y)
when treated with PCl5 gives isomeric compound (Z). (Z) on hydrolysis gives propanoic acid and
aniline. What will be the correct structure of (X), (Y) and (Z) ?
(X) (Y) (Z)
(A) ; ;

(B) ; ;

(C) ; ;

(D) ; ;

105
 Br2
38. (X) X is :
.. NaOH
N
Me
OH Br Br Me
N

(A) (B) (C)

.. .. .. (D)
Br N OH N N
HO O
Me Me Me

39. The set of reagents required for the change.

NO 2 OH

are
NO 2 NO 2
(A) (1) NaNO2 + H2SO4 (2) Sn/HCl (3) H3PO4/ (B) (1) Sn/HCl (2) NaNO2 + HCl (3) H2O
(C) NH4HS (2) H2PO4/ (3) NaNO2 + HCl (D) NH4HS (2) NaNO2 + H2SO4 (3) H2O

40. The major product (B) formed in the reaction sequence is:

(A) (B) (C) (D)

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. Identify compound (A) in the following oxidation reaction.

(A)  
K 2 Cr2 O7 , H 2SO4
O O

NH2 OH OH

(A) (B) (C) (D)None of these.

NH2 NH2
OH
2. C4H11N (X) + HNO2  C4H10O (30 alcohol) hence, X will give :
(A) Carbylamine reaction (B) Hofmann mustard oil reaction
(C) Diazonium salt (as the intermediate) (D) Hofmann’s bromamide reaction
3. Sanger’s reagent is:
(A) 2-fluoro 1, 4 dinitrobenzene (B) Phenylisothiocyanate
(C) 1-fluoro 2, 4 dinitrobenzene (D) FDNB

106
4. Phenyl cyanide can be obtained by
P O ,
2 5  2 Ac O, /HCl
(A) C6H5CONH2  (B) C6H5  CH  NOH 

alc. KOH (i) NaNO /HCl
2
(C) C6H5Cl  (D) C6H5NH2 

(ii) CuCN

5. Which of the following can give 1o amine?

(A) (B)

(C) (D)

6. Which of the following sequence of reagent is the good means to furnish the conversion?
R  CH2OH  R  CH2NH2
(A) KMnO4,SOCl2,NH3, ,NaOBr (B) SOCl2,NaCN,H2,/Ni
(C) CrO3 in dilute acetone, NH3 ,H2,Ni  (D) Cu,300o C,NH2,LiAlH4

7. Which of the following reactions represent major products?

(A)

(B)

(C)

(D)

8. Which of the following products will not form by following reaction?

(A) (B)

(C) (D)

107
9. The correct statement/s about the following reaction sequence is / are

CI2 / FeCI3 HNO3 + H2SO4 HNO3 + H2SO4 NH2NH2,

(P)
(1) (2) (3) (4)
O2N
(R)
CH = N – NH NO2 (Q)
(5)
(A) 'R' gives an aldol condensation reaction on heating with NaOH solution
(B) The compound ‘Q’ gives yellow ppt in acetone.
(C) Step ‘4’ is an aromatic nucleophilic substitution reaction.
(D) The end product is a mixture of three compounds.

10. Which of the following will give isocyanide on reaction with CHCl3  KOH
O
NH2 N
(A) (B) (C) NH2 (D) NH2
H
11. With reference to the scheme given below, which of the following statement(s) is/are incorrect
about compounds (A), (B), (C) and (D)?
O

NH

(A) CH3

LiAlH4

(i) MeI(excess) NaNO2/Con.HCl

(D) (B) (C)
(ii) AgOH, 

(A) Compound (A) releases ammonia when boiled with concentrated NaOH solution.
(B) Compound (C) is a yellow oily liquid and is chiral.
(C) Compound (D) shows geometrical isomerism.
(D) Compound (D) on reaction with NaNO 2/Con.HCl gives a compound which has two chiral
centres.
12. Which of the following reactions is/are correctly indicating the formation of major product?
O H
H
Br2/NaOH
(A) H3C NH2
NH2
H3C
Et
Et
O
Br 2/NaOH
(B) H3C (CH 2) 8 C NH2 H3C-(CH2)9-NH2
O

NH2 NH2
(C) Br2/NaOH

CH3
CH3

108
 O
Ag 2O /  OH
H5C 6
(D) H 5C 6 CHN 2 H 2O
O
13. A positive carbylamines test is given by:
(A) N, N-dimethyl aniline (B) 2,4- dimethyl aniline
(C) N-methyl-o-methyl aniline (D) p-methyl benzyl amine

COMPREHENSION TYPE
PARAGRAPH FOR NEXT THREE QUESTIONS
Compound (A) C3H5O4N, gives effervescence with NaHCO3 and a blue colour with HNO2 & KOH
solution. (A) on treatment with Sn and HCl gives (B) C3H7O2N. (B) gives offensive smelling compound
on heating with chloroform and KOH and effervescence with NaHCO 3. (B) reacts with HNO2 to form
a hydroxy acid (C), C3H6O3. Which on heating with I2 and NaOH gives CHI3 and sodium oxalate.
1. The probable structure of ‘A’ is
OH O
H3C
(A) H (B)O2N CH 2 C CH 2OH
O2 N
O NO2
(C) HO2C–CH2—CH2—NO2 (D) H3C CH CO 2H
i) PBr
3 D H3O
2. C   E
ii) KCN 
Which of the following test will the compound E respond to ?
(A) Effervescence with NaHCO3 (B) Yellow ppt with 2, 4 DNP
(C) Blue colouration with freshly prepared FeCl3 (D) Ag mirror test

3. B can be prepared by which of the following reaction

O

(A) NK 

O (B) H3C CH 2CH 2C NH2 
KOBr

i) H3C CH2 CH OH
O
O Br

ii) H3 O O
O

(i) Br2/Red P i) Cl CH2 OC 2 H5

(C) CH3CH2COOH (D) NK  
(ii) excess NH3 ii) H3 O
(iii) H +
O
PARAGRAPH FOR NEXT THREE QUESTIONS
A compound ‘P’ (C13H11NO) is soluble in aq.NaOH. When heated in the presence of acid it converted
into another compound ‘Q’. Q is soluble in aq.NaOH and aq.HCl. Q on prolonged heating in NaOH
gives a liquid ‘R’ (which can be steam distilled) and another compound ‘S’. Liquid ‘R’ upon treatment
with NaNO2 & dil.HCl at 50C gives ‘T’. T reacts with β-naphthol in presence of base to give red
coloured compound ‘U’. P can be obtained by benzoylation of benzenefollowed by treatment with
hydroxylamine hydrochloride.
4. The compounds P and Q are
(A) Geometrical isomers (B) Tautomers (C) Functional isomers (D) Not isomers

109
5. Which of the following reaction is shown by the compound ‘S’
(A) HVZ reaction (B) diazotization reaction
(C) Hofmann bromamide reaction (D) None of the above

6. The compound ‘T’ reacts with N,N-dimethyl aniline to form a coloured compound in
(A) Slightly basic medium (B) Slightly acidic medium
(C) Strongly acidic medium (D) Neutral medium

MATCH THE FOLLOWING COLUMN

1. Match the following column I & column II.
Column I Column II
(A) Hofmann degradation (P) Aldehyde + 1o amine
(B) Curtius rearrangement (Q) Isocyanate
(C) Lossen rearrangement (R) Br2  KOH
O
||  
(D) Substituted imine (S) R  C  N  N  N

2. Match the following column I & column II.

Column I (Amines) Column II (Distinguished by)
(A) C2H5NH2 and C6H5NH2 (P) Carbylamine test

(B) (C2H5 )3 N and (C2H5 )2 NH (Q) Azo dye test

(C) C2H5NH2 and (C2H5 )3 N (R) Hinsberg reagent

(D) (C2H5 )3 N and C6H5NH2 (S) Liebermann nitroso reaction

INTEGER ANSWER TYPE

NO2

1.
(C2H 5)2SO 4 Zn/HCI/ NaNO2, HCI Phenol Br2/H2O
(I) (II) (III) (IV) (V)
(2) 5°C (3) NaOH (4) (5)
OH (1)
OH
The steps involved in the above reaction can be arranged as.
Electrophilic substitution = step (w)
Nucleophilic substitution=step (x)
Reduction reaction = step (y)
Diazocoupling reaction = step (z)
w x y z
Assign the correct numbers to the type of reactions as follows

2. How many 1o amine of the formula C5H13N can be used to resolve racemic 2-methylbutanoic
acid?

3. How many amines are possible by C4H11N which form product having unpleasant smell on

reaction with CHCl3 and OH ?

110
4. x= moles of KOH consumed is:

14
NH3  Number of amines produced.
5. Cl  CH2  C H2  S  CH2  CH3 

6. Number of moles of N2 liberated by reaction of

With NaNO2 /HCl /0o in excess are:

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT-JEE
1. Match the four starting material given in column I with the corresponding reactions schemes
provides in column II and select the correct answer using the code give below. [2014]

Codes: A B C D
(A) 1 4 2 3
(B) 3 1 4 2
(C) 3 4 2 1
(D) 4 1 3 2

111
 ANSWER TO AMINES
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. C 9. C 17. C 25. D 33. B
2. A 10. B 18. A 26. D 34. B
3. A 11. C 19. A 27. B 35. D
4. A 12. B 20. B 28. D 36. B
5. D 13. B 21. D 29. B 37. B
6. B 14. A 22. B 30. C 38. D
7. A 15. A 23. A 31. B 39. D
8. C 16. C 24. D 32. B 40. A

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. ABC 4. ABD 7. AC 10. AC 13. BD
2. ABC 5. BCD 8. ABD 11. ACD
3. CD 6. AC 9. BC 12. AC

COMPREHENSION TYPE
1. D 3. C 5. D
2. B 4. C 6. B

MATCH THE FOLLOWING COLUMN

1. A  S; B  R; C  Q; D  P 2. A  S; B  R; C  Q; D  P

INTEGER ANSWER TYPE

1. 5 3. 5 5. 2
2. 6 4. 3 6. 0

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT-JEE
1. C

112
 BIOMOLECULES, POLYMER & EVERYDAY LIFE
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. Which of the following is a protein?
(A) Nylon (B) Natural silk (C) Rayon (D) Terrylene

2. A certain compound gives negative test with ninhydrin and positive test with Benedict’s solution.
The compound is
(A) A protein (B) A monosaccharide
(C) A lipid (D) An amino acid.

3. Glucose when heated with CH3OH in the presence of dry HCl gas, - and  - methyl glycosides
are formed. This is because it contains
(A) an aldehydic group (B) –CH2OH group
(C) a ring structure (D) five hydroxyl groups

4. Cellulose on hydrolysis yields

(A) -D-Fructose (B) -D-Glucose (C) -D-Glucose (D) -D-Fructose

5. The reagent used in Ruff’s degradation is

(A) Baeyer’s reagent (B) Tollen’s reagent
(C) Fenton’s reagent (D) Benedict’s reagent
6. Glucose when treated with CH3OH in presence of dry HCl gas gives - and -methylglucosides
because it contains
(A) an aldheydic group (B) a-CH2OH group
(C) a ring structure (D) five –OH group
7. The letter D in D-glucose signifies
(A) dextro rotatory (B) mode of synthesis
(C) its configuration (D) its diamagnetic nature.

8. Sucrose on hydrolysis yields a mixture which is

(A) Optically inactive (B) Dextrorotatory (C) Laevorotatory (D) Racemic

9. Which of the following is radical initiator

O O
|| ||
(A) CH3  C  O  O  C  CH3 (B) (C) (D) All

HOH2C CH2OH
10. N–C–N
HOH2C || CH2OH
O
The polymer obtained by the above compound is
(A) Bakelite (B) Urea formaldehyde resine
(C) Melamine formaldehyde resin (D) Tefflon
11. Which of the following contains isoprene unit?
(A) Natural rubber (B) Polyethylene (C) Nylon – 66 (D) Dacron

113
12. Which of the following is condensation polymer?
(A) Polystyrene (B) PVC (C) Polyester (D) Teflon

13. Carbohydrates contain ?

(A) –OH group (B) –CHO group (C) >C=O group (D) All

14. Which of the following monosaccharide is pentose ?

(A) Glucose (B) Fructose (C) Arabinose (D) Galactose

15. On heating glucose with Fehling solution. We get a precipitate whose colour is ?
(A) Yellow (B) Red (C) Black (D) White

16. Which of the following compounds is found abundantly in nature ?

(A) Fructose (B) Starch (C) Glucose (D) Cellulose

17. Glucose on reduction with Na/Hg and water gives ?

(A) Sorbitol (B) Fructose (C) Saccharic acid (D)Gluconic acid

18. Glucose or fructose is converted into C2H5OH in the presence of ?

(A) Diastage (B) Maltase (C) Invertase (D) Zymase

19. Glucose cannot be calassified as ?

(A) Hexose (B) Carbohydrate (C) Aldose (D) Oligo saccharide

20. Milk sugar is commonly known as

(A) Maltose (B) Lactose (C) Fructose (D) Glucose

21. It is best to carry out reaction with sugers in neutral or acidic medium and not is alkaline
medium because in alkaline medium sugars undergo ?
(A) Racimisation (B) Decomposition (C) Inversion (D) Rearrangement

22. The reagent which forms crystalline osazone derivatives when heated with glucose is ?
(A) Fehling solution (B) Phenyl hydrazine
(C) Benedict solution (D) Hydroxyamine

23. Consider following reagent :

I. Br2 water II. Tollen’s reagent III. Fehling’s solution
which can be used to make distinction between an aldose and a ketose ?
(A) I, II and III (B) II and III (C) I only (D) II only

24. The organic compound that will response Fehling’s solution test is
(A) Ethanol (B) Acetone (C) Maltose (D) Benzaldehyde

25. In osazone formation of three molecules of phenylhydrazine which is the correct statement
(A) All the three molecules react in similar manner
(B) Two molecules reacts in similar manner whereas the third reacts in different way
(C) All the three molecules react in different way
(D) Only two react in same manner but the third molecules remains unreacted
26. Two hexoses form the same osazone find the correct statement about these hexoses.
(A) Both of them must be aldoses
(B) They are epimers at C-3

114
 (C) The carbon atoms 1 and 2 in both have the same configuration
(D) The carbon atoms 3, 4 and 5 in both have the same configuration

27. An organic compound ‘A’ with molecular formula C6H12O6 forms a yellow crystalline solid with
C6H5—NH—NH2 and on reduction with sodium gives a mixture of sorbitol and mannitol. The
compound ‘A’ is
(A) Glucose (B) Fructose (C) Mannose (D) Sucrose

28. Which of the following is a non-reducing sugar ?

H H
H CH2OH CH OH
OH OH CH22OH
OHCH OH O O CH2OH O O
HO OH HO 2 OH O
CH2OH O O
HO OH HO OHO O H
CH2OH O O CH2OH O O H
HO
(A) (A) O
CH2OH O O (B) HOOO (B) HO H
(A) CH OH CH HO
OH
OH (B) HO
H HO
OH H
OH OH OH
HO OH H HO 2 OH H CH22OH HO H OH
HO HO
H HO OH H H OH OH
HO H OH

CH2OH O H CH OH O H CH2OH O O CH OH O O
CH22OH O H CH 2OH O O
CH2 2 CH
CH22
HO HO
(C) HOHO HO
OH O (C) HO OH O (D) HOCH OH OH (D) HOHO
H HO O OH H HO O
O OH
(C) OHOHO CH
OH2OH
O
O
O CH22OH (D) HO OH
OH H HO
HO OH HO OH HO HO OH
HO OH HO
OH OH
OH OH OH
OH H H
H

29. The two forms of D-glucopyranose obtained from the solution of D-glucose are called:
(A) Isomer (B) Anomer (C) Epimer (D) Enantiomer

30. Which of the following pairs gives positive Tollen’s test?

(A) Glucose, sucrose (B) Glucose, fructose
(C) Hexanal, acetophenone (D) Fructose, sucrose
+
H3N
31. In the compound (Y) + the order of acidity of positions X, Y and Z is
H3N
(Z)
COOH
(X)
(A) X > Y > Z (B) X > Z > Y (C) Z > X > Y (D) Y > X > Z
Assertion and Reason
32. STATEMENT-1: (Assertion) and STATEMENT-2 (Reason). Each question has 4 choices (A), (B) (C)
and (D) out of which ONLY ONE is correct.
STATEMENT-1: Glucose gives a reddish-brown precipitate with Fehling’s solution
because ]
STATEMENT-2: Reaction of glucose with Fehling’s solution gives CUO and gluconic acid.
(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

33. Which of the following is a polyamide ?

(A) Bakelite (B) Terylene (C) Nylon-66 (D) Teflon

115
34. Which of the following is fully fluorinated polymer
(A) PVC (B) Thiokol (C) Teflon (D) Neoprene

35. Complete hydrolysis of cellulose gives

(A) D-fructose (B) D-ribose (C) D-glucose (D) L-glucose

36. Nylon threads are made up of

(A) polyvinyl polymer (B) Polyester polymer
(C) Polyamide polymer (D) Polyethylene polymer

37. A substance forms zwitter ion. It can have functional group.

(A) – NH2 , – COOH (B) – NH2 , – SO5H (C) Both (A) and (B) (D)None of these

38. Monomers are converted to polymers by

(A) Hydrolysis of monomer (B) Condensation between monomers
(C) Protonation of monomers (D) none

39. Compound A given below is :

OCOCH3

COOH

(A) antiseptic (B) antibiotic (C) analgesic (D) pesticide

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. Salicin (structure given below) is a glycoside, found in the bark of willow tree, used in relieving
pain. Observe the following reaction of salicin.
CH2OH CH2OH
O O
H
H
dil. HCl P +Q
OH H
HO Carbohydrate
H OH
Salicin
The correct statement (s) is (are)
(A) P is D- glucose
(B) Q is 2-hydroxybenzylalcohol
(C) Q can be converted to a modern anlgesic (pain killer), aspirin
(D) The above reaction occurs through a carbocation

2. Glucosazone is osazone derivative very similar to that formed from

(A) Fructose (B) Galactose (C) mannose (D) glucose

3. The correct statements about peptides are

(A) A dipeptide has one peptide link between two amino acids.
(B) By convention N-Terminus is kept at left and C-terminus at right in the structure of a
peptide
(C) If only one amino group and one carboxylic acid, group are available for reaction, then only
one dipeptide can forms.
(D) A polypeptide with more than hunderd amino acid recidues (mol. mass > 10,000) is called a
protein

116
4. The correct statements about anomers are
(A) Anomers have different stereochemistry at anomeric carbon atom
(B)  -D-glucopyranose and  -D-glucopyranose are anomers
(C)  -D-glucopyranose and  -D-glucopyranose are diastereomer
(D) When pure  -D-glucopyranose is dissolved in water its optical rotation slowly changes

5. Observe the following reaction and mark the correct statements (s) given below-
H MeO H
CHO OMe
C C
H OH H OH
H OH
HO H MeOH HO H O
HO H O
H OH +
dry HCl H OH H OH
H OH
H H
CH2OH CH2OH CH2OH
D-glucose
(A) Methyl glucosides do not react with Fehling's or Tollen's reagent.
(B) The reaction passes through a carbocation
(C) The two forms of glucosides are enantiomers
(D) The non-reducing charcter of glucoside indicates the absence of free-CHO group in it.

6. Regarding structure of proteins which of the following statement(s) is (are) incorrect.

(A) Primary structure represents the particular sequence of aminoacids in a polypeptide chain.
(B) As long as the number and kind of amino acid units in a polypeptide chain are the same, any
change in the sequence of amino acids results in the same protein.
(C) When a protein is heated gently its primary structure gets destroyed.
(D) Alkaline hydrolysis of polypeptide gives amino acids in their cationic form

7. (I) (II) (III)

The correct statement about the sugars given above are

(A) I and II are L-Sugars (B) II and III above D-Sugar
(C) I and III are D-sugars (D) I is L-sugar

8. Glucose

The correct statements about above structure of glucose are :

(A) It is a Pyranose form (B) It is a furanose form
(C) It is a -anomer (D) It is a D -sugar
9. D-Mannose differs from D-glucose in its stereochemistry at C-2. The pyranose form of D-Mannose is

(A) (B) (C) (D)

117
10. The correct statements about anomers are
(A) Anomers have different stereochemistry at C-1(anomeric carbon)
(B) -D-glucopyranose and -D-glucopyranose are anomers
(C) Both anomers of D-glucopyranose can be crystallised and purified.
(D) When pure -D-glucopyranose is dissolved in water its optical rotation slowly changes
11. The correct statements about peptides are
(A) A dipeptide has one peptide link between two amino acids.
(B) By convention N-Terminus is kept at left and C- terminus at right in the structure of a peptide
(C) If only one amino group and one carboxylic acid, group are available for reaction, then only one
dipeptide can forms.
(D) A polypeptide with more than hunderd amino acid recidues (mol. mass > 10,000) is called a protein

12. Which of the following is not associated with rubber?

(A) conducting nature (B) oriented nature
(C) elastic nature (D) commercially available strong fibre
13. Which of the following is soluble in water?
(A) -Keratin (B) Albumin (C) Haemoglobin (D) Casein

14. Teflon, Polystyrene and Neoprene are all

(A) Addition polymers (B) Chain growth polymer
(C) Condensation polymer (D) Step growth polymer
15. Which of the following are natural polymers?
(A) Proteins (B) Cellulose (C) Teflon (D)Natural rubber

COMPREHENSION TYPE
PARAGRAPH FOR NEXT FOUR QUESTIONS
On the basis of the structures given below answer the following questions:
6
CH 2OH
5 O
H H H
4 1 Glucose unit
OH H
HO link
3 2
H HO
O
6
HOH 2C O link

5 2 Fructose unit
H HO
H CH 2OH
1
4 3
HO H

118
 CH 2OH H OH CH 2OH CH 2OH
3 2 O
O O
HO H H H H H
H O OH H H H
1 1 4
 4 1 O
OH H H 6 OH H OH H
H H H OH OH OH
O
5
H OH CH 2OH H OH H OH
Galactose unit Glucose unit
Lactose Maltose
CH 2OH CH 2OH CH 2OH
O O O
H H H H H
H H H
O— O O —O
OH H OH H OH H

H OH H OH H OH
Amylose
1. In which disaccharide, glycoside linkage is formed between anomeric —OH of glucose and
anomeric —OH of glucose and anomeric —OH of fructose?
(A) Sucrose (B) Lactose (C) Cellobiose (D) Maltose

2. Glycosidic linkage is present between the two glucose units at positions ........ in maltose.
(A) 1, 2 (B) 1, 3 (C) 1, 4 (D) 1, 1
3. Sucrose molecule consists of
(A) a glucopyranose and a fructopyranose (B) a glucopyranose and a fructofuranose
(C) a glucofuranose and a fructopyranose (D) a glucofuranose and a fructofuranose

4. Which is/are correct?

(A) In sucrose, glucose and fructose are joined by 1, 2 linkage.
(B) In lactose, galactose and glucose are joined by 1, 4 linkage.
(C) In amylose, –D glucose units are joined by 1,4 linkage.
(D) All of these

PARAGRAPH FOR NEXT THREE QUESTIONS

Monosaccharides have —CHO (or C=O) and —OH groups, so they undergo usual oxidation and
reduction. Further, monosaccharides form osazone when treated with excess of phenylhydrazine (3
equivalents). In osazone formation only the first two carbon atoms are involved. Thus
monosaccharides having identical configuration on rest of C atoms except first two will form same
osazone. As is the case with glucose and fructose.
A, B and C are three hexoses and form same osazone D. Compounds A to D behave as below:
HCl Zn
(i) D   
CH COOH

 D  Fructose
3
Ni, H2 HNO3 Na Hg
(ii) A 
    
BC
H3O
HNO3
(iii) B   Optically active glycaric acid
HNO
(iv) C 
3  Optically inactive glycaric acid

5. Compound D is a osazone which can be obtained from:

(A) Only one compound (B) Two compounds
(C) Three compounds (D) Four compounds

119
6. Compound A should be:
(A) D-glucose (B) D-fructose (C) L-glucose (D) L-fructose

7. Compound B and C, respectively, are:

(A) D-glusoe and D-mannose (B) D-mannose and D-glucose
(C) D-glucose and L-glucose (D) D-glucose and L-mannose

MATCH THE FOLLOWING COLUMN

1. Match the column I with column II
Column – I (Carbohydrate) Column – II (Hydrolysis Product)
(A) Sucrose (P) many glucose units
(B) Maltose (Q) Glucose + Fructose
(C) Lactose (R) Glucose + Galactose
(D) Starch (S) Glucose + Glucose

2. Which of the following is correct match of vitamin and its deficiency disease
Column I Column II
(A) Vitamin A (P) Beri beri
(B) Thiamine (Q) Cheilosis
(C) Riboflavin (R) Xerophthalmia
(D) Pyridoxine (S) Convulsions
(E) Vitamin B12 (T) Pernicious anaemia

INTEGER ANSWER TYPE

1. A pentapeptide has given four types of amino acids Glycine, Alanine, Phenyl alanine and Leucine
on hydrolysis. If neither NH2 nor COOH present at chiral center then how many primary
structure(s) of such pentapeptides are possible:

2. A tetrapeptide has group on alanine. This produces glycine (Gly), valine (Val), phenyl alanine
(Phe) and alamine (Ala), on complete hydrolysis. For this tetrapeptide, the number of possible
sequences (primary structures) with group attached to chiral centre is

3. Give the amino acid sequence of the following polypeptides using the data given by partial
hydrolysis.
2 4 3 1 + A B C D
H3O
(a) (Ser, Hyp, Pro, Thr) Ser, Thr + Thr, Hyp + Pro, Ser

4. The number of dipeptides that can be made from alanine and glycine are.

5. Observe the following reaction and find out that how many number of reactant stereoisomers
can be reduced to optically inactive meso products.
CHO CH2OH
CHOH CHOH
CHOH NaBH4 CHOH
CHOH CHOH
CHOH CHOH
CH2OH CH2OH

120
 SECTION-III
PREVIOUS YEARS QUESTION ASKED IN IIT JEE
1. The total number of distinct naturally occurring amino acids obtained by complete acidic
hydrolysis of the peptide shown below is [2014]

2. The substituents R1 and R2 for nine peptides are listed in the table given below. How many of
these peptides are positively charged at pH = 7.0? [2012]

Peptide R1 R2
I H H
II H CH3
III CH3COOH H
IV CH2CONH2 (CH2 )4 NH2
V CH2CONH2 CH2CONH2
VI (CH2 )4 NH2 (CH2 )4 NH2
VII CH2COOH CH2CONH2
VIII CH2OH (CH2 )4 NH2
IX (CH2 )4 NH2 CH3

3. When the following aldohexose exists in its D-configuration, the total number of stereoisomers in
its pyranose form is [2012]
CHO
CH2
CHOH
CHOH
CHOH
CH2OH

4. A decapeptide (Mol. Wt. 796) on complete hydrolysis gives glycine (Mol. Wt. 75), alanine and
phenylalanine. Glycine contributes 47.0 % to the total weight of the hydrolysed products. The
number of glycine units present in the decapeptide is [2011]

121
 ANSWER TO BIOMOLECULES & POLYMER & EVERYDAY LIFE
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. A 10. B 19. D 28. C 37. C
2. B 11. A 20. B 29. B 38. B
3. A 12. C 21. D 30. B 39. C
4. C 13. D 22. B 31. A 40.
5. C 14. C 23. C 32. C
6. C 15. B 24. C 33. C
7. C 16. D 25. B 34. C
8. C 17. A 26. D 35. C
9. D 18. D 27. B 36. C

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. ABCD 4. ABCD 7. BD 10. ABCD 13. BCD
2. ACD 5. ABD 8. ACD 11. ABCD 14. AB
3. ABCD 6. BCD 9. AC 12. ABD 15. ABD

COMPREHENSION TYPE
1. A 3. B 5. C 7. A
2. C 4. D 6. B

MATCH THE FOLLOWING COLUMN

1. A  Q; B  S; C  R; D  P 2. A  R; B  P; C  Q; D  S; E  T

INTEGER ANSWER TYPE

1. 6 2. 4 3. 3214 4. 4 5. 4

SECTION-III
PREVIOUS YEARS QUESTION ASKED IN IIT JEE
1. 1 2. 4 3. 8 4. 6

122
 P-BLOCK ELEMENT (OXYGEN FAMILY, HALOGEN & INERT GAS)
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. Which is incorrectly matched?
(A) CsBr3 = Cs+ + Br3 (B) I4O9 = I3+ + (IO3 )
(C) AgBrO3 = Ag+ + BrO3 (D) I2O4 = + IO2
2. Which of the following species is not a pseudohalide?
(A) CNO– (B) RCOO– (C) OCN– (D) N3

3. An explosive compound (A) reacts with water to produce NH4OH and HOCl. Then, the compound
(A), is
(A) TNG (B) NCl3 (C) PCl3 (D) HNO3
4. An inorganic compound (A) made of two most occuring elements into the earth crust, having a
polymeric tetra-headral network structure. With carbon, compound (A) produces a poisonous
gas (B) which is the most stable diatomic molecule. Compounds (A) and (B) will be
(A) SiO2’ CO2 (B) SiO2’ CO (C) SiC,CO (D) SiO2’ N2
5. The correct order of acidic strength of oxy-acids of chlorine is
(A) HCIO < HCIO2 < HCIO3 < HCIO4 (B) HCIO4 < HCIO3 < HCIO2 < HCIO
(C) HCIO > HCIO4 > HCIO3 > HCIO2 (D) HCIO4 < HCIO2 > HCIO3 > HCIO

6. The structures of O3 and N3– are

(A) linear and bent, respectively (B) both linear
(C) both bent (D) bent and linear, respectively
7. When conc. H2SO4 was treated with K4[Fe(CN )6], CO gas was evolved. By mistake, somebody
used dilute H2SO4 instead of conc. H2SO4 then the gas evolved was
(A) CO (B) HCN (C) N2 (D) CO2

8. Concentrated HNO3 reacts with iodine to give

(A) HI (B) HOI (C) HOIO2 (D) HOIO3

9. Conc. H2SO4 cannot be used to prepare HBr from NaBr because it

(A) reacts slowly with NaBr (B) oxidises HBr
(C) reduces HBr (D) disproportionates HBr

10. Molecular shapes of SF4, CF4 and XeF4 are

(A) the same, with 2, 0 and 1 lone pairs of electrons respectively
(B) the same, with 2, 0 and 1 lone pairs of electrons respectively
(C) the different, with 0, 1 and 2 lone pairs of electrons respectively
(D) the different, with 1, 0 and 2 lone pairs of electrons respectively

11. When chlorine reacts with a gas X, an explosive inorganic compound Y is formed. Then X and Y
will be
(A) X = O2 and Y = NCl3 (B) X = NH3 and Y=NCl3
(C) X = O2 and Y = NH4Cl (D) X = NH3 and Y = NH4Cl

123
12. When AgNO3 is heated strongly, the products formed are
(A) NO and NO2 (B) NO2 and O2 (C) NO2 and N2O (D) NO and O2

13. A gas which exists in three allotropic forms ,  and  is

(A) SO2 (B) SO3 (C) CO2 (D) NH3

14. There is no S–S bond in

(A) S2O42– (B) S2O52– (C) S2O32– (D) S2O72–

15. When chlorine gas is passed through an aqueous solution of a potassium halide in the presence
of chloroform, a voilet colouration is obtained. On passing more of chlorine water, the voilet
colour is disappeared and solution becomes colourless. This test confirms the presence of
........... in aqueous solution.
(A) chlorine (B) fluorine (C) bromine (D) iodine

16. A sulphate of a metal (A) on heating evolves two gases (B) and (C) and an oxide (D). Gas (B) turns
K2Cr2O7 paper green while gas (C) forms a trimer in which there is no S–S bond. Compound (D)
with HCI, forms a Lewis base (E) which exists as a dimer. Compounds (A), (B), (C), (D) and (E)
are respectively
(A) FeSO4, SO2, SO3, Fe2O3, FeCl3 (B) Al2(SO4)3, SO2, SO3, Al2O3, FeCl3
(C) FeS, SO2, SO3, FeSO4, FeCl3 (D) FeS, SO2, SO3 , Fe2(PO4)3, FeCl2

17. A  O2  X  Y  Z
(organic Compound)
Compound (A) in pure form does not give ppt. with AgNO 3 solution. A mixture cootaining 70% of
(A) and 30% of ether is used as an anaesthetic. Compound (X) and (Y) are oxides while (Z) is a
pungent smelling gas. (X) is a neutral oxide which turns cobalt chloride paper pink. Compound
(Y) turns lime water milky and produces an acidic solution with water. Compounds (A), (X), (y)
and (Z) respectively will be
(A) CH4, H2O, CO2’ Cl2 (B) CHCl3 , H2O, CO2, Cl2
(C) CH3OH, H2O, CO2, N2 (D) NH2CONH2, H2O, N2O, CO2

18. When an inorganic compound reacts with SO2 in aqueous medium, produces (A). (A) on reaction
with Na2CO3, gives compound (B) which with sulphur, gives a substance (C) used in
photography. Compound (C) is
(A) Na2S (B) Na2S2O7 (C) Na2SO4 (D) Na2S2O3
19. When excess of water is added to BiCl3 solution
(A) Ionization of BiCl3 is increased (B) A white ppt. of Bi(OH)3 is obtained
(C)BiCl3 is hydrolysed to give white ppt. of BiOCl (D) BiCl3 is precipitated

20. Cyclic trimer sturcture of SO3 contains -

(A) 6 S=O bonds and three S–O–S bonds (B) 3 S=O bonds and six S–O–S bonds
(C) 6 S=O bonds and six S–O–S bonds (D) None of these

21. Mark the wrong statement. When Na2S is added to sodium nitroprusside solution -
(A) Beautiful violet colour is produced (B) A complex [Fe(CN)5NOS]4– is formed
2–
(C) A complex [Fe(CN)5NOS] is formed (D)A complex Na4[Fe(CN)5NOS] is formed

124
22. A certain compound when burnt gives three oxides. The first turne lime water milky. The second
turned anhydrous CuSO4 dark blue and the third formed an aqueous solution of
pH = 3. The elements present in the compound are -
(A) C, O and S (B) C, H and Ca (C) C, H and Na (D) C, H and S

23. When SO2 gas is passed into an acidified K2Cr2O7 solution, the oxidation no. of chromium
change from -
(A) + 3 to + 6 (B) + 6 to + 3 (C) + 12 to + 3 (D) + 6 to – 3
24. When chlorine water is added to an aqueous solution of sodium halide in the presence of
chloroform, a violet colouration is obtained. When more of chlorine water is added, the violet
colour disappears and solution becomes colourless. This confirms that sodium halide
is -
(A) Chloride (B) Fluoride (C) Bromide (D) Iodide

25. Anion of Prussic (HCN) acid is:

(A) Iso electronic with carbon monoxide (B) Isoelectronic with N2
(C) Called pseudohalide (D) All of these
26. ClO3 is the mixed anhydride of:
(A) HClO2 and HClO3 (B) HClO2 and HClO4
(C) HOCl and HClO3 (D) HClO3 and HClO4

27. XeO3 in strong alkaline medium (above pH 10.5) forms:

(A) HXeO4 (perxenate ion) (B) XeO64  (xenate ion)
(C) HXeO4 (xenate ion) (D) XeO64  (perxenate ion)

28. What is the maximum coordination number of iodine in the mixture of IF7 and CSF :
(A) 2 (B) 4 (C) 6 (D) 8

29. A greenish yellow gas reacts with KOH to give potassium halide which can be used in
fire works and safety matches. The gas and half Fe respectively are:
(A) Br2; KBrO3 (B) Cl2; KClO3 (C) I2; NaIO3 (D) None

N gas
30. Metal (M) 
2 
 Solid(S)
S  H2O  G(gas)
G  CuSO4 solution  Blue colour solution(X) Blue colour solution is:
(A) [Cu(NH3 )6 ]SO4 (B) [Cu(NH3 )4 ]SO4 (C) [Cu(NH3 )2 ]SO4 (D) [Cu(NO3 )4 ]SO4


31. KOCN  (NH4 )2 SO4 
In the following reaction one of the product is:
(A) NH4NO2 (B) NH4NO3 (C) NH2CONH2 (D) Both N2 & O2

125
32. A black solid X reacts with NH3 to form a mild explosive which decomposes to give violet
coloured gas. X also reacts with H2 to give an acid Y. Y can also be prepared by heating
its salt with H2PO4. X and Y are:
(A) Cl2, HCl (B) F2 , HF (C) Br2 , HBr (D) I2 , KI

33. Which of the following product is formed when one mole periodate ion (IO4 ) reacts with
excess of iodide ions followed by the acidification of solution?
(A) IO (B) IO3 (C) I2 (D) I2O5

34. 2MX  H2SO4  2HX  M2SO4 MX can be:

(A) MI (B) MCl (C) MBr (D) MI

35. Aqueous solution of bleaching powder is source of:

(A) O2  Cl (B) OH  Cl2 (C) OH  Cl (D) O3  Cl

36. A pale yellow solid (A) having crown shape is heated with concentrated H2SO4 , it gives
suffocating smell of gas B, which is passed through moistened with starch iodide paper
and turn it into blue. The gas B and solid A are respectively.
(A) SO3 & S8 (B) SO2 & S8 (C) SO2 & S2N2 (D) SO3 & SO2

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. HI can be prepared by which of the following methods?
(A) PI3  H2O  (B) KI  H2SO4 (conc.) 
(C) H2  I2  (D) I2  H2S 

2. Mixture of gold and platinum when reacts with aqua regia it produces:
(A) AuCl4 (B) PtCl26 (C) N2O (D) NO

3. Which of the following chloride(s) is/are partially hydrolysed in water?

(A) BiCl3 (B) PCl3 (C) AsCl3 (D) SbCl3

4. Which of the given method produce Cl2 ?

(A) Elelctrolysis of brine (B) Deacon’s process
(C) Heating MnO2 with conc. HCl (D) Heating KCl with conc. H2SO4

5. If Y2 in given reaction is Cl2 then " X" is/are:

 
Y2  2X(aq.)  2Y(aq.)  X2
(A) F (B) Cl (C) Br (D) I

126
6. The correct statement(s) about O3 is(are):
(A) O  O bond lengths are equal
(B) thermal decomposition of O3 is endothermic
(C) O3 is diamagnetic in nature
(D) O3 has a bent structure `

7. Identify the correct statement(s):

(A) Ozone is a powerful oxidizing agent as compared to O2
(B) Ozone reacts with KOH and gives an orange coloured solid KO3
(C) There is a decrease in volume when ozone decomposed to form O2
(D) The decomposition of O3 to O2 is exothermic

8. Oxygen is evolved when:

(A) Zinc oxide is treated with NaOH (B) Ammonium nitrate is heated
(C) Sodium peroxide reacts with conc. Acid (D) Potassium superoxide reacts with H2O

9. A green coloured solution of a salt changes its colour to light pink on passing ozone through it.
Which of the following species represent pink and green colour respectively:
(A) Mn2 and MnO2 (B) MnO4 and MnO24
(C) Co2 and Co3 (D) MnO24 and MnO4

10. Sulphur on reaction with concentration HNO3 . Gives (A) which reacts with NaOH gives (B). (A)
and (B) are:
(A) H2SO3 , Na 2S2O3 (B) NO2 , Na 2S
(C) H2SO4 , Na 2SO4 (D) H2S2O3 , Na 2S2O3

11. What are the products in the following reaction?


S  OH  ?

(A) S2  (B) SO23 (C) S52  (D) S2O32

12. Identify the correct statements:

(A) SCN is a pseudohalide (B) Iodine show Lewis basic nature
(C) AgF is insoluble in water (D) Fluorine is a super halogen

13. Which of the following product(s) is/are obtained when Cl2O6 reacts with NaOH?
(A) KClO4 (B) KClO3 (C) KClO2 (D) KCl

14. The possible product(s) formed in the following reaction is/are:

IF5  H2O  ?
(A) HF (B) HIO2 (C) HIO (D) HIO3

127
15. Cl2O6  NaOH  ?
(A) NaClO3 (B) NaClO2 (C) NaOCl (D) NaClO4

16. When deep red PtF6 vapour was mixed with Xe at room temperature to produce a yellow ionic
solid. The product is:
(A) Xe [PtF6 ] (B) [XeF  ][Pt2F11] (C) Both (A) and (B) (D) None

17. Which of the following reactions of xenon compounds is incorrect?

(A) XeF2  HF  H[XeF3 ]
(B) XeF6  RbF [XeF5 ][RbF2 ]
(C) XeF4  PF5 [XeF3 ][PF6 ]
1
(D) 3XeF4  6H2O  2Xe  XeO3  12HF  O2
2

COMPREHENSION TYPE
PARAGRAPH FOR NEXT FIVE QUESTIONS
Sulphur and rest of the elements of group 16 are less electronegative than oxygen. Therefore, their
atoms cannot take electrons easily. They can acquire ns2np6 configuration by sharing two electrons
with the atoms of the elements and thus, exhibit +2 oxidation state in their compounds In addition
to this, their atoms have vacant d-orbitals in their valence shell to which electrons can be promoted
from the p and s-orbitals of the same shell. As a result, they can show +4 and +6 oxidation states.
1. The oxidation state of sulphur in S8 , SO3 and H2S respectively are:
(A) 0,  6,  2 (B) 2,  6,  2 (C) 0,  4,  2 (D) 2,  6,  2

2. The oxidation state of sulphur in Na 2S4O6 is:

(A) 2/3 (B) 3/2 (C) 3/5 (D) 5/2

3. The nature of the compounds of sulphur having +4 oxidation state is:

(A) Act as oxidizing agent (B) Act as reducing agent
(C) Act as oxidizing as well as reducing agents (D) Cannot be predicted

4. Like sulphur, oxygen does not show +4 and +6 oxidation stats. The reason is:
(A) That oxygen is a gas while sulphur is a solid
(B) That oxygen has high ionization enthalpies is comparison to sulphur
(C) That oxygen has high electron affinity in comparison to sulphur
(D) That oxygen has no d-orbitals in its valence shell

5. Oxygen exhibits +2 oxidation state in:

(A) H2O (B) OF2 (C) Cl2O (D) H2O2

PARAGRAPH FOR NEXT FIVE QUESTIONS

Halogens react with each other to form a number of compounds called interhalogen compounds.
Their general formula is AXn , where A is less electronegative halogen while X is a more
electronegative halogen and n is its number. The interhalogen compounds are essentially covalent

128
and more reactive than the halogens since the bond A  X is weaker than A  A or X  X bond. The
reactions of interhalogens are similar to those of halogens.
6. Which of the following interhalogen compound is not possible?
(A) IF7 (B) IF5 (C) ClF3 (D) FBr3

7. Which halogen shows maximum oxidation state in forming interhalogen compound?

(A) I (B) Br (C) Cl (D) F

8. How many lone pairs of electrons are present on chlorine in ClF3 molecule?
(A) 0 (B) 1 (C) 2 (D) 3

9. Which of the following statements is wrong for inter-halogen?

(A) The value of n in AXn (interhalogen) can be 1, 3, 5 or 7
(B) The value of n in AXn (interhalogen) can be 2,4, or 6
(C) A can never be fluorine as it is most electronegative halogen
(D) X can never be iodine as it is least electronegative halogen

MATCH THE FOLLOWING COLUMN

1. Match the following:
Column I (Complete hydrolysis) Column II (Characteristics of any
hydrolysed product/hydrolysis)
H O
2 
(A) NCl3  (P) Dibasic
H O
2 
(B) NO2  (Q) Can act as flexidentate ligand
2  H O
(C) H2S2O8  (R) Can act as both oxidizing and reducing
agent
H O
2 
(D) SF4  (S) Can act as monodentate ligand
(T) Non-redox hydrolysis

2. Match the items given in Column I with that in Column II and III.
Column I Column II Column III
Interhalogen compound Characteristics (I) Characteristics (II)
(a) IF (i) Undergo hydrolysis to give (p) sp3d, arrow shape, 2 lp
periodic acid
(b) IF3 (ii) Undergo hydrolysis to give (q) sp3 , linear, 3 lp
hypoiodous acid
(c) IF5 (iii) Undergo hydrolysis to give (r) sp3d3 , pentagonal
iodous acid
bipyramidal, zero lp
(d) IF7 (iv) Undergo hydrolysis to give (s) sp3d2 , square pyramid 1 lp
iodic acid

129
INTEGER ANSWER TYPE
1. If P, Q, and R are total number of (p  d) bonds in
(i) H2S2O5 (ii) H2S2O6 (iii) H2SO3 then calculate the value of (P  Q  R) .

2. Sodium iodate is treated with calculated amount of sodium bisulphate to prepare iodine. How
many moles of sodium bisulphate are required to prepare one mole of iodine from sodium
iodate?

3. Chlorine water on cooling deposits greenish yellow crystals of formula Cl2  XH2O . What is the
value of X?

4. For oxyacid HClOx, If x  y  z (x, y and z are natural numbers), then calculate the value of
(x  y  z) where
x  Total number of lone pair on central atom
y  Total number of ‘O’ atoms
z  Total number of ‘O’ atoms

5. How many d  p bonds are there in XeO4 ?

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. The colour of the X2 molecules of group 17 elements changes gradually from yellow to violet
down the group. This is due to: [2017]
(A) The physical state of X2 at room temperature changes form gas to solid down the group
(B) Decrease in  *  * gap down the group
(C) Decrease in ionization energy down the group
(D) Decrease in HOMO-LUMO gap down the group

PARAGRAPH FOR NEXT TWO QUESTION

Upon heating KClO3 in the presence of catalytic amount of MnO2 , a gas W is formed. Excess
amount of W reacts with white phosphorus to give X. The reaction of X with pure HNO3 gives Y &
Z. [2017]
2. Y and Z are respectively
(A) N2O4 and HPO3 (B) N2O4 and H3PO3
(C) N2O3 and H3PO4 (D) N2O5 and HPO3

3. W and X are, respectively

(A) O2 and P4O10 (B) O2 and P4O6
(C) O3 and P4O6 (D) O3 and P4O10

130
4. Under ambient conditions, the total number of gases released as products in the final step of the
reaction scheme shown below is Complete [2014]
hydrolysis
XeF6   P  Other product
HO /H2O
Q
Slow disproportionation
in HO /H2O
Pr oducts
(A) 0 (B) 1 (C) 2 (D) 3

PARAGRAPH FOR NEXT TWO QUESTION

The reactions of Cl2 gas with cold-dilute and hot-concentrated NaOH in water give sodium salts of
two (different) oxoacids of chlorine, P and Q, respectively. The Cl2 gas reacts with SO2 gas, in
presence of charcoal, to give a product R. R reacts with white phosphorus to give a compound S.
On hydrolysis, S gives an oxoacid of phosphorus, T. [2013]
5. P and Q, respectively, are the sodium salts of
(A) hypochlorus and chloric acids (B) hypochlorus and chlorus acids
(C) chloric and perchloric acids (D) chloric and hypochlorus acids
6. R, S and T, respectively, are
(A) SO2Cl2, PCl5 and H3PO4 (B) SO2Cl2, PCl3 and H3PO3
(C) SOCl2, PCl3 and H3PO2 (D) SOCl2, PCl5 and H3PO4

131
 P-BLOCK ELEMENT (OXYGEN FAMILY, HALOGEN & INERT GAS)
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. D 9. B 17. B 25. D 33. C
2. B 10. D 18. D 26. D 34. B
3. B 11. B 19. C 27. C 35. B
4. B 12. B 20. A 28. D 36. B
5. A 13. B 21. C 29. B
6. D 14. D 22. D 30. B
7. B 15. D 23. B 31. C
8. C 16. A 24. D 32. D

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. ACD 5. CD 9. D 13. AB 17. AB
2. ABD 6. ACD 10. C 14. AD
3. AD 7. ABD 11. ACD 15. AD
4. ABC 8. CD 12. AD 16. C

COMPREHENSION TYPE
1. A 3. C 5. B 7. A 9. B
2. D 4. D 6. D 8. C

MATCH THE FOLLOWING COLUMN

1. A  R,S,T; B  Q,R,S; C  P,Q,R,S,T; D  2. ii-q; iii-p; iv-s; i-r
P,Q,R,S,T

INTEGER ANSWER TYPE

1. 8 2. 5 3. 8 4. 2 5. 4

SECTION-III
PREVIOUS YEAR QUESTIONS ASKED IN IIT JEE
1. BD 2. D 3. A 4. C 5. A 6. A

132
 COORDINATION COMPOUND
SECTION-I
STRAIGHT OBJECTIVE TYPE
2
1. Amongst Ni(CO)4, [Ni(CN)4]2- and NiCl4 
2
(A) Ni(CO)4 and NiCl4  are diamagnetic and [Ni(CN)4]2- is paramagnetic
2
(B) NiCl4  and [Ni(CN)4]2- are diamagnetic and Ni(CO)4 is paramagnetic
2
(C) Ni(CO)4 and [Ni(CN)4]2- are diamagnetic and NiCl4  is paramagnetic
2
(D) Ni(CO)4 is diamagnetic and NiCl4  and [Ni(CN)4]2- are paramagnetic

2. Among the following, the compound that is both paramagnetic and coloured is
(A) K2Cr2O7 (B) (NH4)2 [TiCl6] (C) CoSO4 (D) K3[Cu(CN)4]

3. The structures of Ni(CO)4 and Ni(PPh3 )2 Cl2 are

(A) square planar
(B) tetrahedral and square planar respectively
(C) tetrahedral
(D) square planar and tetrahedral respectively.
4. The hybrid state of Ni in Ni(CO)4 is
(A) sp3 (B) sp2 (C) sp3d (D) dsp3
5. Which of the following is an outer orbital complex –
(A) [Fe(CN)6]3– (B) [Fe(CN)6]4– (C) [FeF6]3– (D) [Cr(CN)6]3–

6. The geometry of some complex ions are given against them –

(1) [Ag(NH3)2]+ – Linear (2) [MnCl4]2– – Tetrahedral
(3) [Cu(NH3)4]2+ – Square planar (4) [Ni(CN)4]2– – square planar
The correct match is –
(A) 1 and 4 (B) 1, 2 and 3 (C) 1, 3 and 4 (D) 1, 2, 3 and 4
7. The complex that violates the EAN rule –
(A) Potassium ferrocyanide (B) Potassium ferricyanide
(C) Tetra carbonyl Nickel (D) Cobalt (III) hexamine chloride

8. Match List I with List II and Select the correct answer using the codes given below the lists –
List-1 List-2
Complex ions Magnetic Moment in Bohr Magnetons
a. [Fe(CN)6]–4 1. 1.73
b. [Fe(CN)6]3+ 2. 5.93
c. [Cr(H2O)6] 3+ 3. 0.00
d. [Ni(H2O)6] 2+ 4. 2.83
e. [FeF6]–3 5. 3.88
Code:
a b c d e
(A) 1 2 3 4 5
(B) 3 1 5 4 2

133
 (C) 2 3 4 5 1
(D) 4 5 1 2 3
A
A B

9. The isomer M Can be marked as –

B A
A
(A) Dextro isomer (B) Laevo isomer (C) Cis isomer (D) Trans isomer

10. The formula of potassiumdicyano bis (oxalato) nickelate (II) is –

(A) K4[Ni(CN)2 (Ox)2] (B) K3[Ni2(CN)2 (Ox)2] (C) K [Ni(CN) (Ox)2] (D) K2[Ni(CN)2(Ox)2]

11. How many H-bonds are present in the complex entity formed by Ni2+ and dmg ligands –
(A) 2 (B) 3 (C) 4 (D) None

12. The correct order for the wavelength of absorption in the visible region is –
(A) [Ni(NO2)6]4– < [Ni(NH3)6]2+ < [Ni(H2O)6]2+ (B) [Ni(NO2)6]4– < [Ni(H2O)6]2+ < [Ni(NH3)6]2+
(C) [Ni(H2O)6]4– < [Ni(NH3)6]2+ < [Ni(NO2)6]4– (D) [Ni(NH3)6]2+ < [Ni(H2O)6]2+ < [Ni(NO2)6]4–

13. Three arrangements are shown for the complex, [Co(en)(NH3)2Br2]+. Which one is the wrong
statement –
Br Br Br
Br H3N Br
Co en Co en en Co
H3N H3N NH3
NH3 Br NH3

(I) (II) (III)

(A) I and II are geometrical isomers (B) II and III are optical isomers
(C) I and III are optical isomers (D) II and III are geometrical isomers

14. Which statement is wrong –

(A) All the octahedral complexes of Ni2+ are outer orbitals complexes.
(B) (SCN)– shows linkage isomerism in coordination compounds.
(C) All ligands are Lewis bases.
(D) NH4+ ion can act as a ligand

15. [PdCl2(PMe3 )2 ] [is a diamagnetic complex of Pd (II). How many unpaired electrons are present in
analogous complex of Ni (II)?
(A) Zero (B) 1 (C) 2 (D) 3

16. If EAN of central metal cation M2 in a non-chelating complex is 36 and atomic no. of metal M
is 26, then the number of monodentate ligand in this complex are
(A) 5 (B) 4 (C) 6 (D) None of these

17. Magnetic moment (spin only) of octahedron complex having CFSE=-0.8 0 and surrounded by
weak field ligands can be
(A) 15BM (B) 8BM (C) (A) and (B) both (D) none of these

134
18. Which of the following pairs of complexes are isomeric with each other but their aqueous
solutions exhibit different molar conductivities?
(A) [PtCl2(NH3 )4 ]Br2 and [PtBr2(NH3 )4 ]Cl2 (B) [CoCl2(NH3 )4 ]NO2 & [CoCl(NO2 )NH3 )4 ]Cl
(C) [Co(NO2 )(NH3 )5 Cl2 and [Co(ONO)(NH3 )5 ]Cl2 (D) [CoBr(NH3 )5 SO4 and [Co(SO4 )(NH3 )5 Br

19. A six coordinate complex of formula CrCl3.6H2O has green colour. A 0.1 M solution of the
complex when treated with excess of AgNO3 gave 28.7g of white precipitate. The formula of the
complex would be
(A) [Cr(H2O)6 )]Cl3 (B) [CrCl(H2O)5 ]Cl2  H2O (C) [CrCl2(H2O)4 Cl  2H2O (D) [Cr(H2O)3 Cl3 ]

20. Which is not true about metal carbonyls?

(A) Here CO acts as a Lewis base as well as Lewis acid
(B) Here metal acts as Lewis base as well as Lewis acid
(C) Here d  p back bonding takes place
(D) Here p  p back bonding takes place

21. The magnetic moment of a complex ion is 2.83 BM. The complex ion is
(A) [V(H2O)6 ]3 (B) [Cr(H2O)6 ]3 (C) [Cu(CN)4 ]2 (D) [MnCl4 ]2

22. For the complexes showing the square pyramidal structure, the d-orbital involved in the
hybridization is
(A) d 2 2 (B) d 2 (C) d xy (D) d xz
x y z

23. The hybridization states of the central atom in the complexes [Fe(CN)6 ]3 , [Fe(CN)6 ]4 and
[Co(NO2 )6 ]3 are
(A) d2sp3 ,sp3d2 and dsp2 respectively (B) d2sp3 ,sp3d2 and sp3d2 respectively
(C) d2sp3 ,sp3d2 and d2sp3 respectively (D) all d2sp3

24. For which of the following types of ions is the number of unpaired electrons in octahedral
complexes fixed at the same number as in the free ion no. matter, how weak or strong the
crystal field is
(A) d3 (B) d4 (C) d5 (D) d6

25. What is the magnetic moment (spin only) and hybridization of the brown ring complex
[Fe(H2O)5 NO]SO4 ?
(A) 3BM,sp3d2 (B) 3BM,d2sp3 (C) 15BM,sp3d2 (D) 15BM,d2sp3

26. The crystal field stabilization energy [Co(NH3 )6 Cl3 is

(A) 7.20 (B) 0.40 (C) 2.40 (D) 3.60

27. A metal complex of coordination number six having three different types of ligands a, b, ad c of
composition Ma 2b2c2 can exist in several geometrical isomeric form; the total number of such
isomers is
(A) 3 (B) 5 (C) 7 (D) 9

135
28. Which one of the following pairs of isomers and types of isomerism are correctly matched?
(i) [Co(NH3 )5 (NO2 )]Cl2 and [Co(NH3 )5 (ONO)]Cl2...(Linkage)
(ii) [Cu(NH3 )4 ][PtCl4 ] and [Pt(NH3 )4 ][CuCl4 ]...(Coordination)
(iii) [PtCl2(NH3 )4 Br2 and [PtBr2(NH3 )4 ]Cl2...(Ionization)
Select the correct answer using the codes given below:
(A) (ii) and (iii) (B) (i), (ii) and (iii) (C) (i) and (iii) (D) (i) and (ii)

29. Complexes given below show:

(A) Optical isomerism (B) Coordinate isomerism

(C) Geometrical isomerism (D) Bridge isomerism

30. Three arrangements are shown for the complex [CoBr2(NH3 )2(en)] . Which one is wrong
statement?

(A) I and II are geometrical isomers (B) II and III are optically active isomers
(C) I and III are optically active isomers (D) II and III are geometrical isomers
31. Where among the following metal complexes the one which exhibits optically activity is
(AA = bidentate ligand; A, X=monodentate ligand)
(A) cis  [MA4X2 ] (B) trans [MA4 X2 ]
(C) cis  [M(AA)2 X2 ] (D) trans  [M(AA)2 X2 ]

32. Which of the following will show optical isomers?

(I) cis  [Co(NH3 )2(en)2 ]3 (II) trans  [IrCl2(C2O4 )2 ]3

(III) [Rh(en)3 ]3 (IV) cis  [IrH2O)3 Cl3 ]
(A) I, III only correct (B) II, IV only correct (C) I, III, IV only correct (D) III only correct

33. In the complex K2Fe(CN)6 ] :

(A) both Fe atoms are in the same oxidation state
(B)both Fe atoms are in different oxidation state
(C) the coordination number of ion is 4
(D) the complex is a high spin complex

34. Mixture X of 0.02 mole of [Co(NH3 )5 SO4 ]Br and 0.02 mole of [Co(NH3 )5 Br]SO4 was prepared in
2 litre of solution
1 litre of mixture X + excess of AgNO3  Y
1 litre of mixture X + excess of BaCl2  Z

136
 Number of moles of Y and Z respectively are
(A) 0.01, 0.02 (B) 0.02, 0.01 (C) 0.01, 0.01 (D) 0.02, 0.02

35. An aqueous solution of titanium chloride, when subjected to magnetic measurement, measured
zero magnetic moment, Assuming the octahedral complex in aqueous solution, the formulae of
the complex is
(A) [Ti(H2O)6 ]Cl2 (B) [Ti(H2O)6 ]Cl4 (C) [TiCl3 (H2O)3 ] (D) [TiCl2(H2O)4 ]

36. What is electronic arrangement of metal atom/ion in octahedral complex with d4 configuration,
if 0  paring energy?
4 0
(A) t2g eg (B) e4 0
g t2g (C) t3 1
2g eg (D) e2 2
g t2g

37. The value of ‘spin only’ magnetic moment for one of the following configuration is 2.84 BM. The
correct one is
(A) d4 (in strong field ligand) (B) d2 (in weak field ligand)
(C) d3 (in weak as well as in strong field ligand) (D) d5 (in strong field ligand)

38. Which one of the following complexes exhibit chirality?

(A) [Cr(ox)3 ]3 (B) cis  [PtCl2(en)]
(C) cis  [RhCl2(NH3 )4 ] (D) mer  [Co(NO2 )3(dien)]

39. An ion M2 , forms the complexes [M(H2O)6 ]2 , [M(en)3 ]2 and [MBr6 ]4 , match the complex
with the appropriate colour:
(A) Green, blue and red (B) Blue, red and green
(C) Green, red and blue (D) Red, Blue and green

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. Which combination of the coordination complex and possible isomerism is/are correct ?
(A) K[Ag(CN)2], linkage (B) [Ag(NH3)2] [CuCl2], ionization
(C) [CrCl(NH3)5]I2, ionization (D) [PtCl4I2], geometric
2. The compounds having metal in zero oxidation state are:
(A) Ni(CO)4 (B) Cr(CO)6 (C) Fe2(CO)9 (D) Co(CO)6

3. Which of the following statement(s) is (are) correct ?

(A) hexacyanidoferrate (II) ion has four unpaired electrons in 3d-orbital.
(B) tetracyanidonickelate (II) ion is square plannar.
(C) IUPAC name of [Zn(OH)4]–2 ion is tetrahydroxidozinc (II) ion
(D) the coordination number of Cr in [Cr(NH3)2(en)2]+3 is 6.

4. Which of the following exhibit geometrical isomerism (M stands for a metal, and a and b are
achiral ligands)?
(A) Ma2b2 (B) Ma4b2 (C) Ma5b (D) Ma6

5. Which of the following compound(s) show(s) optical isomerism.

(A) [Pt(bn)2]2+ (B) [CrCl2(en)2]+ (C) [Co(en)3] [CoF6] (D) [Zn(gly)2]2+

137
6. Choose incorrect statement(s) regarding following complex ion.
[Fe(ox)3]3– and [Fe(NO2)6]3–
(A) [Fe(ox)3]3– complex ion is more stable than [Fe(NO2)6]3–.
(B) Both complex ions are optically inactive.
(C) Both follow Sidwick’s rule of E.A.N.
(D) Both are paramagnetic.

7. Which of the following statements is not true about the complex ion [CrCl(NO2)(en)2]+ (en =
ethylene diamine)
(A) It has two geometrical isomers-cis and trans
(B) cis and trans forms are not diastereomers to each other
(C) Only the cis isomer displays optical activity
(D) It has three optically active isomers : d, l and meso forms

8. Which of the following statement(s) is/are incorrect?

(A) The state of hybridisation of central atom of anionic part of solid PBr5 is sp3d2.
(B) [Co(NH3)6]2+ ion is easily oxidisable while [Co(NO2)6]4– is not.
(C) Bis(glycinato) Zinc (II) is optically active.
(D) d 2 orbital of central metal atom / ion is used in dsp2 hybridisation.
z

9. Select the correct statement(s).

(A) Co(III) is stabilised in presence of weak field ligands, while Co(II) is stabilised in presence of
strong field ligand.
(B) Four coordinated complexes of Pd(II) and Pt(II) are diamagnetic and square planar.
(C) [Ni(CN)4]4– ion and [Ni(CO)4] are diamagnetic tetrahedral complexes.
(D) Ni2+ ion does not form inner orbital octahedral complexes
10. Which of the following statement(s) is/are incorrect
(A) In [CoBrCl(en)2 ] geometrical isomerism exists, while optical isomerism does not exist
(B) Potassium aquadicyanidosuperoxidoperoxidochromate(III) is IUPAC name for K2[Cr(CN)2
O2(O2)(H2O)]
(C) There are 3 geometrical isomers and 15 stereoisomers possible for [Pt(NO2)(NH3)(NH2OH)
(py)]+ and [PtBr Cl I (NO2)(NH3)(py)] respectively
(D) cis and trans forms are not diastereomers to each other

11. Which of the following statement is true about the complex [CrCl3(OH)2(NH3)]2– ion.
(A) It has three geometrical isomers.
(B) Only one space isomer is optically active and remaining are inactive.
(C) There are total four space isomers.
(D) The magnetic moment of complex ion is 3.89 B.M.

12. Which of the following is correct about

Tetraamminedithiocyanato-s cobalt(III) tris(oxalato)cobaltate(III)
(A) formula of the complex is [Co(SCN)2(NH3)4][Co(ox)3]
(B) It is a chelating complex and show linkage isomerism.
(C) It shows optical isomerism.
(D) It shows geometrical isomerism.

138
13. Which is correct statement(s)?
(A) [Ag(NH3)2]+ is linear with sp hybridised Ag+ ion
 3 
(B) NiCl2
4 , VO4 and MnO4 have tetrahedral geometry
(C) [Cu(NH3)4]2+ , [Pt(NH3)4]2+ & [Ni(CN)4]2– have dsp2 hybridisation of the metal ion
(D) Fe(CO)5 has trigonal bipyramidal structure with d 2sp3 hybridised iron.
z

14. In which of the following pairs of complexes the central metals/ions do have same effective
atomic number ?
(A) [ Cr (CO)6 ] and [ Fe (CO)5 ] (B) [ Co (NH3)6 ]2+ and [Ni (NH3)6]2+
(C) [Cu (CN)4]3– and [ Ni (CO)4 ] (D) [V(CO)6]– and [Co(NO2)6]3–

15. Which of the following ligands can show linkage isomerism ?

(A) CNS– (B) NO2– (C) CN– (D) NO3–

COMPREHENSION TYPE
PARAGRAPH FOR NEXT FOUR QUESTIONS
To explain the nature of bonding in transition metal complexes, valence bond theory (VBT) has great
importance, which is based on the theory of covalent bonding. It deals with electronic structures of
central metal ion in its ground state, kinds of geometry and magnetic properties of the complex.
According to VBT
(i) The central metal ion or atom makes available a number of s, p and d atomic orbitals equal to its
co-ordination number. First of all, these atomic orbital hybridise together to form hybrid orbital
which are same in number as the atomic orbital hybridizing together. These are vacant, equivalent
in energy and have definite geometry.
(ii) The complexes having unpaired electron is known as para-magnetic complex and having no
unpaired electron is known as diamagnetic complex.
Magnetic moment due to spin only = spin only = n(n  2) B.M.
where, n = number of unpaired electron.
(iii) Nature of ligands, also influences the nature of the complex compounds. Stronger ligands make
pairing of electron against Hund’s rule, and generally produces inner orbitals complex are
complexes in which ligands use the inner d-orbital of central metal ion.
Weaker ligands does not make pairing of electrons and obey’s Hund’s rule and generally produces
outer d-orbital complexes.
Keep in mind that the chelated complex is more stable than that of the non-chelated complex.
1. Which of the following is not the square planar complex ?
(A) [Ni(CN)4]-2 (B) [Cu(NH3)4]2+ (C) [Pt(NH3)4]2+ (D) [Ni(CO)4]

2. In square planar complex, which of the following d-orbitals are used up ?

(A) d 2 2 (B) d 2 (C) d xy (D) d yz
x y z

3. What is the magnetic moment (spin only) and hybridization of the brown ring complex
[Fe(H2O)5NO]SO4 ?
(A) 3 B.M., sp3d2 (B) 3 B.M., d2sp3 (C) 15 B.M., sp3d2 (D) 15 B.M., d2sp3
4. Which of the following complex is more stable ?
(A) [Cr(en)3]2+ (B) [Cr(CN)6]3- (C) [Cr(H2O)6]3+ (D) [Cr(EDTA)]-

139
PARAGRAPH FOR NEXT TWO QUESTIONS
On the basis of stability of complex ion in the solution, complexes may be of two types, perfect and
imperfect complexes. The stability depends upon the extent of dissociation which in turn depends
upon the strength of metal-ligand bond. The stability of complex also depends upon charge on
central metal atom, basic, nature of ligand, chelation, and nature of metal ion and ligand according
to HSAB principle.
5. Which one of the following does not follow EAN rule?
(A) Fe(CO)5 (B) V(CO)6 (C) K4[Fe(CN)6 ] (D) Mn2(CO)10

6. Which complex is most stable?

(A) [Cu(CN)2 ] Kd  1 1016 (B) [Fe(CN)6 ]4 Kd  1 1037
(C) [Fe(CN)6 ]3 Kd  1 1044 (D) [Ag(CN)2 ] Kd  1 1020

MATCH THE FOLLOWING COLUMN

1. Match the column I with column II
Column – I (Complexes) spin only formula Column – II (Magnetic Moment B.M.)
(A) K2[NiF6] (P) 5.8
(B) K3[CoF6] (Q) 2.8
(C) [Fe(SCN)6]3- (R) Zero
(D) [NiCl4]2- (S) 4.9

2. Match the column I with column II

Column – I (Complexes) Column – II (Colour) B.M.)
(A) Cu2[Fe(CN)6] (P) Brown
(B) Cu3[Fe(CN)6]2 (Q) Orange
(C) Ag4[Fe(CN)6] (R) Green
(D) Ag3[Fe(CN)6] (S) Blue
(T) White

3. Match the complexes in the column I with coordination number in the column II
Column I Column II
(A) [Co(en)3] 2+ (P) 6
(B) [Ca (EDTA)]2– (Q) 4
(C) [Ni(CO)4] (R) 2
(D) [Ag(NH3)2]Cl (S) 5

INTEGER ANSWER TYPE

1. Give the number of ligand(s) in which donor atom is only N.

NH2CH2COO , en, dien, Py, EDTA, ph

2. Give the number of ligands which are monodentate as well as ambidentate.

 
CN, C2O24 ,S22 , NO2 , OCN, SCN

3. The sum of primary and secondary valencies of chromium in the complex CrBr3  6NH3 is:

4. How many coordinate water molecule(s) is/are present in brown ring complex?

140
5. What are the values of m and n in the anionic species [V(CO)m ]n  , if it is following Sidwick EAN
rule and having octahedral shape?

6. Give the total number of possible isomers of [ZnBr3F2 ]2 .

7. Give the total number of isomer of [Be(gly)2 ] .


8. Write the sum of geometrical isomers in [Pt(H2N  CH(CH3 )  COO)2 ] complex and stereoisomers
of [Pt(gly)3 ] complex.

9. In hexacyanidomanganate(II) ion the Mn atom assumes d2sp3  hybrid state. Then the number of
unpaired electrons in the complex is:

10. Give the number of 3d electrons occupied in t2g orbitials of hydrated Cr3  ion (octahedral).

SECTION-III
PREVIOUS YEARS QUESTIONS ASKED IN IIT-JEE
1. In the complex acetylbromidodicarbonylbis(triethylphosphine) iron (II), the number of Fe – C
bond (s) is [2015]

2. Among the complex ions, [Co(NH2  CH2  CH2  NH2 )2 Cl2 ] ,[CrCl2 (C2O4 )2 ]3 , [Fe(H2O)4 (OH)2 ] ,
[Fe(NH3 )2 (CN)4 ] , [Co(NH2  CH2  CH2  NH2 )2 (NH3 )Cl]2 and [Co(NH3 )4 (H2O)Cl]2 , the number of
complex ion(s) that show cis-trans isomerism is [2015]

PARAGRAPH FOR NEXT TWO QUESTIONS [2014]

An aqueous solution of metal ion M1 reacts separately with reagents Q and R in excess to give
tetrahedral and square planar complexes, respectively. An aqueous solution of another metal ion
M2 always forms tetrahedral complexes with these reagents. Aqueous solution of M2 on reaction
with reagent S gives white precipitate which dissolves in excess of S. The reactions are summarized
in the scheme given below.
SCHEME :
Q R
Tetrahedral 
 M1 
 Squareplanar
excess excess
Q R
Tetrahedral   M2   Tetrahedral
excess excess

S,stoichiometric amount

S
White precipitate 
 precipitate dissolves
excess

141
3. M1, Q and R, respectively are
(A) Zn2 ,KCN and HCl (B) Ni2 ,HCl and KCN
(C) Cd2 ,KCN and HCl (D) Co2 ,HCl and KCN

4. Reagent S is
(A) K4[Fe(CN)6 ] (B) Na 2HPO4 (C) K2CrO4 (D) KOH

5. Match each coordination compound in list-I with an appropriate pair of characteristics from list-
II and select the correct answer using the code given below the lists: [2014]
(en  H2NCH2NH2; atomic numbers; Ti  22, Cr  24; Co  27; Pt  78)
List-I List-II
P. [Cr(NH3 )4 Cl2 ]Cl 1.Paramagnetic and exhibits ionization Q. isomerism
Q. [Ti(H2O)3 Cl](NO3 )2 2.Diamagnetic and exhibits cis-trans isomerism
R. [Pt(en)(NH3 )Cl]NO3 3. Paramagnetic and exhibits cis- trans isomerism
S. [Co(NH3 )4(NO3 )2 ]NO3 4. Diamagnetic and exhibits ionization isomerism
Code:
P Q R S
(A) 4 2 3 1
(B) 3 1 4 2
(C) 2 1 3 4
(D) 1 3 4 2

6. EDTA4 is ethylenediaminetetraacetate ion. the total number of N  Co  O bond angles in

[Co(EDTA)]1 complex ion is [2013]

7. Among the following complexes (K-P)

K3[Fe(CN)6 ] (K), [Co(NH3 )6 ]Cl3 (L),
Na3[Co(oxalate)3 ] (M), [Ni(H2O)6 ]Cl2 (N)
K2[Pt(CN)4 ] (O) and [Zn(H2O)6 ](NO3 )2 (P) [2011]
(A) K, I, M, N (B) K, M, O, P (C) L, M, O, P (D) L, M, N, O

142
 COORDINATION COMPOUND
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. C 9. D 17. C 25. C 33. A
2. C 10. A 18. D 26. C 34. C
3. C 11. A 19. B 27. B 35. B
4. A 12. A 20. D 28. B 36. C
5. C 13. B 21. A 29. C 37. B
6. D 14. D 22. A 30. B 38. A
7. B 15. C 23. D 31. C 39. B
8. B 16. C 24. A 32. A

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. ABC 4. AB 7. BD 10. ABCD 13. ABCD
2. ABCD 5. ABCD 8. ABD 11. AD 14. ACD
3. BD 6. ABC 9. BCD 12. BCD 15. ABC

COMPREHENSION TYPE
1. B 2. D 3. C 4. D 5. B 6. C

MATCH THE FOLLOWING COLUMN

1. A  S, B  P, C  R, D  Q 3. A  P, B  P C  Q, D  R
2. A  P, B  R, C  S, D  T

INTEGER ANSWER TYPE

1. 4 3. 9 5. 6,1 7. 2 9. 1
2. 4 4. 5 6. 2 8. 8 10. 3

SECTION-III
PREVIOUS YEARS QUESTIONS ASKED IN IIT-JEE
1. 3 2. 6 3. B 4. D 5. B 6. 8 7. C

143
 METALLURGY & d-f BLOCK ELEMENT
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. Select the correct statement :
(A) Magnetite is an ore of manganese (B) Pyrolusite is an ore of lead
(C) Siderite is carbonate ore of iron (D) FeS2 is rolled gold

2. Three most occuring elements in the earth crust are

(A) O, Si, Al (B) Si, O, Fe (C) Fe, Ca, Al (D) Si, O, N

3. An ore containing the impurity of FeCr2O4 is concentrated by

(A) magnetic-separation (B) gravity separation
(C) froth-floatation method (D) electrostatic method

4. Select the correct statement:

(A) Black jack is ZnS
(B) Sulphide ores are concentrated by floatation method
(C) Parke's process is based on distribution principle
(D) All are correct

5. The process, which does not use a catalyst is

(A) Contact process (B) Thermite process
(C) Ostwald's process (D) Haber's process
6. % of silver in 'german silver' is
(A) 0 (B) 80 (C) 90 (D) 10

7. Which of the following ores is concentrated by leaching –

(A) Pyrite (B) Galena (C) Millerite (D) Argentite
8. Which of the following mineral does not contain Al –
(A) Cryolite (B) Mica (C) Felspar (D) Fluorspar
9. Carnalite is a mineral of -
(A) Ca (B) Na (C) Mg (D) Zn
10. Leaching is a process of -
(A) Reduction (B) Concentration (C) Refining (D) Oxidation
11. In zone refining, pure metal is obtained at the –
(A) Right end, if zone is travelling from left to right
(B) Left end, if zone is travelling from left to right
(C) Left end, if zone is travelling from right to left
(D) Centre, if zone is travelling from any side
12. Galena is an ore of:
(A) Pb (B) Hg (C) Sn (D) Zn
13. Purest form of iron is –
(A) Iron flings (B) Cast iron (C) Wrought iron (D) Stainless steel
14. Choose the set of carbonate ore –
(a) Galena (b) Siderite (c) Copper pyrites (d) Malachite

144
 Answer is-
(A) a,c (B) b,d (C) b,c (D) a,d
15. Polling process is used for –
(A) Hg (B) Fe (C) Cu (D) All
16. By the cupellation of Pb+ Ag we obtain –
(A) Pure silver (B) Pure lead (C) Impure silver (D) Impure lead
17. Which reaction take place in Bessemer converter –
(A) 2Cu2O + Cu2S  6Cu + SO2 (B) 2Cu2S + 3O2  2Cu2O + 2SO2
(C) CuO + C Cu + CO (D) CuCO3 CuO + CO2

18. In the froath floatation process the particles of the ore come on the froth because –
(A) They become water repellent (B) They have light
(C) They are lower molecular weight (D) Both 1 & 2 are correct
19. Cupellation process is involved in the metallurgy of –
(A) Copper (B) Silver (C) Gold (D) Lead
20. Which of the following is not a refining process
(A) Bayer Process (B) Van-arkel process (C) Cementation (D) Poling
21. An ore after levigation is found to have acidic impurities. Which of the following can be used as
flux during smelting operation?
(A) H2SO4 (B) CaCO3 (C) SiO2 (D) Both (A) and (B)

22. Cinnabar is:

(A) CuS (B) Ag2S (C) ZnS (D) HgS

23. The following equation represents a method of purification of nickel by,

(A) Cupellation (B) Mond’s process
(C) van Arkel method (D) Zone refining
24. The actual reducing agent of haematite in blast furnace is:
(A) C (B) CO (C) Al (D) CO2
25. order of magnetic moments (spin only values in BM) among is -
(A) [MnCl4]2– > [CoCl4]2– > [Fe(CN)6]4– (B) [Fe(CN)6]4– > [CoCl4]2– > [MnCl4]2–
(C) [Fe(CN)6]4– > [MnCl4]2– > [CoCl4]2– (D) [MnCl4]2– > [Fe(CN)6]4– > [CoCl4]2–
26. Which pair of compound is expected to show similar colour in aqueous solution:
(A) FeCl2, CuCl2 (B) VOCl2, FeCl2 (C) VOCl2, FeCl2 (D) FeCl2, MnCl2
27. A solution when diluted with H2O and boiled gives a white ppt. On addition of excess of
NH4Cl/NH4OH, the volume of precipitate decreases leaving behind a white gelatinous precipitate.
The precipitate which dissolved in NH4OH/NH4Cl is:
(A) Zn(OH)2 (B) Al(OH)3 (C) Mg(OH)2 (D) Ca(OH)2

28. Wrought iron, pig iron and steel differ in properties due to
(A) carbon content (B) malleability (C) conductivity (D) softeness.

29. The false statement about iron (III) hydroxide is that

(A) it is a weaker base than Fe(OH)2
(B) with concentrated KOH, it forms a complex K3[Fe(OH)6 ]

145
 (C) it gradually loses water and transforms into Fe2O3
(D) it exhibits amphoteric properties with its predominating acidic nature
30. Which compound is formed when iron reacts with carbon
(A) FeC2 (B) Fe3C (C) FeC3 (D) Fe2C

31. A blood red colour is obtained when ferric chloride solution reacts with:
(A) KCN (B) KSCN (C) K4[Fe(CN)6 ] (D) K3[Fe(CN)6 ]

32. Metal-metal bonding is more frequent in 4d or 5d series than in 3d series due to

(A) their greater enthalpies of atomization
(B) the large size of the orbitals which participates in the metal-metal bond formation
(C) their ability to involve both ns and (n-1) d electron in the bond formation
(D) the comparable size of 4d and 5d series elements

33. The maximum and minimum m.p. of Ist transition and 2nd transition series respectively are
obtained with
(A) Cr and Zn (B) Cr and Cd (C) Cr and Hg (D) Mo and Cd
34. Identify the wrong statement regarding copper sulphate
(A) It reacts with KI to give I2
(B) It reacts with KCl to give Cl2
(C) It’s tartarate complex reacts with NaOH and glucose to give Cu2O
(D) It gives CuO on strong heating in air
35. The treatment of zinc with very dilute nitric acid produces:
(A) NO (B) N2O (C) NO2 (D) NH4

36. The pair in which both the elements generally shows only one oxidation state is -
(A) Sc and Zn (B) Zn and Cu (C) Cu and Ag (D) Zn and Au

37.  = 15 is true for the pair -

(A) Co+2, Cr+3 (B) Fe+2, Cr+3 (C) Fe+3, Cr+2 (D) Mn+2, Fe+2

38. The ion pair of the following in which both the ions have unpaired electron -
(A) Cr3+, Co2+ (B) Sc3+, Cr3+ (C) Cu+, Fe3+ (D) Mn2+, Cu+
39. The highest oxidation state achieved by a transition metal is given by -
(A) ns electrons (B) (n – 1) d electrons
(C) (n + 1) d electrons (D) ns + (n – 1) d electrons

40. Titanium shows magnetic moment of 1.73 B.M. in its compounds. What is the oxidation
number of Ti in the compound ?
(A) + 1 (B) + 4 (C) + 3 (D) + 2
41. Which of the following compounds is most likely to contain non-metal atoms in the interstices of
a metals lattice ?
(A) Fe3O4 (B) TiN (C) MnO2 (D) CoF2

42. The magnetic moment of a transition metal ion is found to be 3.87 B.M. The number of unpaired
electrons present in it is -
(A) 2 (B) 3 (C) 4 (D) 5

146
43. CuSO4 solution + lime is called -
(A) Luca's reagent (B) Barfoed's reagent
(C) Fehling solution A (D) Bordeaux mixture
44. Which of the following compounds is used as the starting material for the preparation of
potassium dichromate -
(A) K2SO4.Cr2(SO4)3.24H2O (Chrome alum) (B) PbCrO4 (Chrome yellow)
(C) FeCr2O4 (Chromite) (D) PbCrO4PbO (Chrome red)

45. Which of the following compounds is (are) coloured due to charge transfer spectra and not due
to d-d transition ?
(A) K2Cr2O7 (B) KMnO4 (C) Both (A) & (B) (D) None of these

46. The correct order of increasing acidic nature for the following is -
(A) MnO < Mn2O3 < MnO2 < MnO3 < Mn2O7 (B) MnO2 < MnO < Mn2O3 < MnO3 < Mn2O7
(C) Mn2O7 < MnO3 < MnO2 < Mn2O3 < MnO (D) None of these

47. The number of d-electrons in Fe2+ (atomic number of Fe = 26) is not equal to that of the -
(A) p-electron in Cl– (atomic number of Cl = 17)
(B) d-electron in Fe
(C) s-electron in Mg (atomic number of Mg = 12)
(D) p-electron in Ne (atomic number Ne = 10)

48. The complex CoCl3.5NH3 is aqueous solution ionizes to give a total number of ions equal to –
(A) 0 (B) 2 (C) 3 (D) 4

49. From the stability constant (hypothetical values) given below, predict which is the strongest
ligand –

(A) Cu2+ + 4NH3  [Cu(NH3)4]2+, (K = 4.5×1011)

(B) Cu2+ + 4CN–  [Cu(CN)4]2–, (K = 2.0×1027)

(C) Cu2+ + 2en  [Cu(en)2]2+, (K = 3.0×1015)

(D)Cu2+ + 4H2O  [Cu(H2O)4]2+, (K = 9.5×108)

50. Which of the following statement(s) is/are not correct ?

(A) The blue colour of aqueous CuCl2 is due to [Cu(H2O)4]2+
(B) The yellow colour of aqueous CuCl2 is due to [CuCl4]2–
(C) The green colour of aqueous CuCl2 is due to the presence of both [Cu(H2O)4]2+ and [CuCl4]2–
(D) The blue colour of aqueous CuCl2 is due to [CuCl4]2–

51. Select correct statement (s).

(A) MnO4– is intense pink colour due to d-d transition of electron.
(B) Cu(I) is diamagnetic while Cu(II) is paramagnetic.
(C) CrO3 is amphoteric oxide.
(D) [Ti(H2O)6]3+ and [Sc(H2O)6]3+ both are coloured in aqueous solution

147
 SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. In photography, quinol is used as developer according to following reaction.
HO – – OH + 2AgBr + 2OH–  O= = O + 2Ag + 2H2O + 2Br–
Which of the following describe(s) the role of quinol in this reaction ?
(A) It acts as an acid. (B) It acts as a weak base.
(C) It acts as an oxidising agent. (D) It acts as a reducing agent.
2. The colour of the transition metal ions is/are due to :
(A) d-d transition of electrons in presence of ligands
(B) charge transfer from ligand to metal ion.
(C) change in the geometry
(D) polarisation of anion by cation
3. Correct statements about transition metals are that they :
(A) form complex (B) show variable oxidation states
(C) show magnetic properties (D) do not form coloured compounds
4. Transition elements have greater tendency to form complexes because they have :
(A) vacant d–orbitals (B) small size
(C) higher nuclear charge (D) variable oxidation states
5. Which of the following reaction(s) is/are incorrect for silver nitrate ?
(A) 6 AgNO3 + 3I2 (excess) + 3 H2O  AgIO3 + 5 AgI + 6HNO3
(B) AgNO3 (excess) + 2 KCN  K[Ag(CN)2] + KNO3
(C) 2AgNO3 + 4Na2S2O3(excess)  2Na3[Ag(S2O3)2] + 2NaNO3
(D) PH3 + 6AgNO3 + 3H2O  6Ag + 6HNO3 + H3PO3

6. Which of the following chemical reaction(s) is/are involved in developing of photographic plate ?
(A) C6H4(OH)2 + 2AgBr  2Ag + C6H4O2 + 2HBr
(B) AgBr + 2Na2S2O3  Na3 [Ag(S2O3)2] + NaBr
(C) 2AgNO3 + Na2S2O3  Ag2S2O3 + 2NaNO3
(D) AgNO3 + KCN  AgCN + KNO3

7. The melting point of Zn is lower as compared to those of the other elements of 3d series because
(A) the d-orbitals are completely filled. (B) the d-orbitals are partially filled.
(C) d-electrons do not participate in metallic bonding. (D) size of Zn atom is smaller

8. The less stable oxidation states of Cr are :

(A) Cr2+ (B) Cr 3+ (C) Cr 4+ (D) Cr 6+

9. Which of the following statements are correct ?

(A) Transition elements exhibit higher enthalpies of atomization as they have stronger
interatomic interaction
(B) E2 of 23V < 24Cr > 25Mn and 28Ni < 29Cu > 30Zn
(C) Ni(II) compounds are more stable than Pt(II) where as Pt(IV) compounds are more stable than
nickel (IV).
(D) The elements which gives the greatest number of oxidation states does not occur in or near
the middle of the series.

148
10. Which of the following ions give(s) colourled aqueous solution?
(A) Ni2+ (B) Fe2+ (C) Cu2+ (D) Cu+

11. Which of the following statement is/are correct ?

(A) Transition metals and their many compounds act as good catalyst.
(B) The enthalpies of atomistation of the transition metals are high.
(C) The transition metals generally form interstitial compounds with small atoms like C, B, H
etc.
(D) All transition metal compounds are not paramagnetic.

12. Which is true statement about KMnO4 ?

(A) Its solution is unstable in acidic medium
(B) It has purple colour
(C) MnO4 changes to Mn2 in basic solution
(D) It is self-indicator in Fe2 or C2O24

13. Which reagents can convert Mn2 toMnO4 :

(A) S2O28 /H (B) PbO2 /H (C) BiO3 /H (D) H2O2 /H

14. Select the correct statements:

(A) When CO2 is passed into aqueous solution of CrO24 , CrO5 is formed
(B) When CO2 is passed into MnO24 (green) solution it turns purple and a brown precipitate of
MnO2 is formed
(C) The yellow colour of CrO24 is due to d-d transition
(D) The yellow colour of CrO24 is due to charge transfer

15. Select the correct statements:

(A) There is a very small difference in the melting point of Cr and Zn
(B) Chromium is a typical hard metal while mercury is a liquid
(C) Pt4  compounds are more stable than Ni4  compound
(D) Ni2 compounds are more stable than Pt2 compounds

16. Which of the following statements are correct regarding metallurgy of iron?
(A) Coke reduces FeO to Fe above 1073 K
(B) CO reduces Fe2O3 to FeO below 1073 K
(C) Coke reduces Fe2O3 to FeO above 1073 K
(D) Coke reduces Fe2O3 to FeO below 1073 K

17. Select the correct statement:

(A) In hydrometallurgy, Zn is used as oxidizing agent in the purification of Ag from [Ag(CN)2 ]
(B) When pine oil or eucalyptus oil is added into the water, it lower down the surface tension by
which froth is formed
(C) Sodium ethyl xanthate is used as collector

149
 (D) Basic copper carbonate or PbSO4 is concentrated by froth floatation method by using an
activator

18. The major role of fluorspar, CaF2 which is added in small amount in the electrolytic reduction of
Al2O3 dissolved in fused cryolite is:
(A) To increase the conductivity of the fused mixture
(B) To lower the fusion temperature of the melt
(C) To act as catalyst
(D) To decrease the rate of oxidation of carbon at the anode

COMPREHENSION TYPE
PARAGRAPH FOR NEXT SIX QUESTIONS
Metals are extracted from their ores by a wide variety of techniques. The most common ores are
oxides MnO2,Al2O3,SnO2), sulfides (PbS, ZnS), chlorides (NaCI, KC1, CaCI2, MgCl2), and phosphates
(Ca3 (PO4 )2). Most metals are obtained by direct treatment of their ores with chemical agents, but
the extraction of certain other requires electrolysis. An example of the former type of process is the
extraction of iron from its oxide, described by the following equation
Fe2O3 + 3C  2Fe + 3CO
The relative case of extraction of a metal from its oxide can be estimated using the Ellingham
diagram, which is shown in Figure -1. This diagram plots the free energies of formation of various
oxides per mole of consumed oxygen as a function of absolute temperature.
G°f
(kJ)
CO O3
Fe2 CO2

1000 2000 T(K)

Electrolytic extraction proceeds in three steps (see equations). In the first step, the crystalline lattice
of the ore is thermally disintegrated to form a liquid containing free metal cations. In the second
step, the metal cations are stabilized by solvating them with some thermally stable non-aqueous
solvent (NAS). In the final step, an applied electric potential reduces the cations to neutral atoms.
Step-1 Ore(s)  Mn+ (l)
Step-2 Mn+ (l)  Mn+ (solvated)
Step-3 Mn+ (solvated) + ne  M
Extraction of a metal is usually preceded by enrichment of the ore. Some ores can be concentrated
after pulverization by the use of specific collectors such as salts of organic acids and bases, which
make the ores hydrophobic and thus separable from hydrophilic admixtures. Other enrichment
techniques include density separation and magnetic separation.
1. All of the following agents could be used to extract lead from its oxide EXCEPT.
(A) molecular fluorine (B) molecular boron
(C) molecular nitrogen (D) elemental carbon

2. If for a certain ore the enthalpies of steps-1 and 2 were 248.50 and 250.25 kJ, respectively,
which of the following would determine the rate of extraction?
(A) The lattice energy of the ore
(B) The solvation energy of the metal cations
(C) The magnitude of the electric potential used
(D) The size of the metal cations

150
3. For the extraction : 2CaO (s) + C (s) —— 2Ca (s) + CO2 (g)
the standard free energy change of the forward reaction is 814.1 kJ. According to this data,
standard conditions are likely to favor :
(A) the forward reaction
(B) the reverse reaction
(C) both forward and reverse reactions
(D) neither the forward not the reverse reaction

4. Which of the following best explains why the free energy of formation of Fe2O3 become less
negative as the temperature increases?
(A) The free energy of formation is independent of the absolute temperature
(B) Entropy drops as a result of the consumption of oxygen
(C) At low temperature, the free energy of formation become less dependent on the enthalpy
of formation
(D) As entropy increases, the free energy of formation increases
5. Elemental carbon is most likely to reduce Fe 2O3 in which of the following temperature ranges?
(A) 500- 1000 K (B) 500-1500 K (C) Below 1000 K (D) Above 1000 K
6. When ferric oxide is reduced to obtain iron metal, CO 2 or CO can be produced. The production of
CO :
(A) is directly proportional to the temperature (B)is inversely proportional to the temperature
(C) is independent of the temperature (D) requires cooling of the CO

PARAGRAPH FOR NEXT FOUR QUESTIONS

The multiplicity of oxidation state shown by most transition metals is due to the ability of these
elements to lose a variable number of a electron, for example in aqueous solution vanadium exist in
the +2, +3, +4 and +5 oxidation state. Chemistry of vanadium consists, to the large extent, of the
oxidation reduction reactions of vanadium.
1.0V 0.36V 0.25V 1.2V
VO2   VO2+  V3+   V2+  V
Yellow Blue Green Violet
If the given oxidation state is a stronger oxidizing agent than the next higher state,
disproportionation can occur.
E0 /Zn  0.76V and E0 2+  0.77V
Zn2+ Fe3+/Fe
E0 /Sn  0.14V
Sn2+
7. Which of the following oxidation state of vanadium undergoes disproportionation
(A) +5 (B) +4 (C) +3 and +2 (D) none of these
8. If excess of Zn is added to a solution of (VO2)2SO4 in dilute sulphuric acid, the yellow solution
turns to
(A) Blue – green – violet (B) Blue (C) Green (D) Colourless

9. If ferrous sulphate is added to a solution of (VO2)2SO4 in dilute H2SO4, the yellow solution turns
to
(A) Green (B) Violet (C) Blue (D) Blue to green
10. If Sn2+ salt is added to the yellow solution of (VO2)2SO4, the solution turns to
(A) Blue (B) Blue to green (C) Blue - green - violet (D) Violet directly

151
PARAGRAPH FOR NEXT THREE QUESTIONS
(i) A powdered substance (A) on treatment with fusion mixture gives a green coloured compound (B).
(ii) The solution of (B) in boiling water on acidification with dilute H 2SO4 gives a pink coloured
compound (C) and brown colour compound (D).
(iii) The aqueous solution of (A) on treatment with NaOH and Br2–water gives the compound (D).
(iv) A solution of (D) in concentrated HNO3 on treatment with lead peroxide at boiling temperature
produced a compound (E) which was of the same colour at that of (C).
(v) A solution of (A) on treatment with a solution of barium chloride gave a white precipitate of
compound (F) which was insoluble in concentrated HNO 3 and concentrated HCl.

11. Which of the following is true for compound (C) ?

(A) It oxidises ammonia to nitrogen dioxide in neutral medium.
(B) It's pink colour is due to d-d transition.
(C) It can be oxidised by ozone.
(D) It is obtained by alkaline fusion of pyrolusite followed by electrolytic oxidation.
12. The oxidation state of central metal ions of (A), (B) and (C) compounds are respectively :
(A) +II , + VI and + VII (B) +II , + VI and + VI
(C) +II , + VII and + VII (D) +VI , + VII and + VII
13. Consider the following statements ;
(I) anions of both (B) and (C) are diamagnetic and have tetrahedral geometry.
(II) anions of both (B) and (C) are paramagnetic and have tetrahedral geometry.
(III) anion of (B) is paramagnetic and that of (C) is diamagnetic but both have tetrahedral
geometry.
(IV) green coloured compound (B) in a neutral or acidic medium disproportionates to give (C) and
(D).of these select the correct one from the codes given :
(A) I and III only (B) II and III only  (C) II and IV only  (D) III and IV only

MATCH THE FOLLOWING COLUMN

1. Match the reactions listed in column (I) with processes listed in column (II).
Column – I (reactions) Column – II (processes)
(A) 4 Au + 8 NaCN + 2 H2O + O2 (air)  4 Na [Au (CN)2] + 4 NaOH (P) Leaching
(B) CuFeS2 + 2 H2SO4  CuSO4 + FeSO4 + 2H2S (Q) Smelting

(C) CaO + SiO2 
 CaSiO3 (R) Hydrometallurgy

(D) MgCl2. 6 H2O 
 MgCl2 + 6 H2O (S) Calcination
Dry HCl(g)

2. Match the salts/mixtures listed in column() with their respective name listed in column(II).
Column - I Column - II
(A) ZnS + BaSO4 mixture (P) Lunar caustic
(B) FeSO4 (NH4)2SO4. 6H2O (Q ) Schwitzer`s regent.
(C) AgNO3 (R) Lithopone
(D) [Cu(NH3)4]SO4 (S) Mohr's salt

152
INTEGER ANSWER TYPE
1. What is the value of x in the following equation.
Cr2O72  8H  xS2O32  2Cr3  3SO24  3S  4H2O

2. Out of the following, how many oxides are acidic.

MnO,Mn2O3 ,MnO2,MnO3 , Mn2O7

3. Out of the following, how many of them have magnetic moment value 24BM.
2 3 2 2 3 2 2
Ti ,Ti ,V ,Cr ,Cr ,Mn ,Fe

4. How many of the transition elements are called coinage metals?

5. Out of the following how many of them are coloured compounds:
MnO 2 2 3 4 2 3 2 2
4 , CrO7 , CrO4 , Sc , Ti , Zn , Mn , Cu , Fe , Fe
3

6. How many cyanide ions are involved in the following chemical equation?

Au  CN  H2O  O2 [Au(CN)2 ]  OH

7. Find the number of reaction from the given reactions which can show calcinations process:
(i) CaCO  MgCO   
(ii) CuCO  Cu(OH) 
3 3 CaO  MgO  CO2 3 2 2CuO  H2O  CO2

(iii) Al O  2H O  
(iv) 2Cu S  3O 
2 3 2 Al2O3  2H2O 2 2 2Cu2O  2SO2

8. Find the number of following reaction which are involved in roasting process:

(i) S  8O  
(ii) P  5O 
8 2 8SO2  4 2 P4O10 

(iii) 4As  3O  
(iv) 2ZnS  3O 
2 2As2O3  2ZnO  2SO2 

(v) ZnCO 
3 4ZnO  CO2 

SECTION-III
PREVIOUS YEARS QUESTIONS ASKED IN IIT-JEE
1. Copper is purified by electrolytic refining of blister copper. The correct statement(s) about this
process is (are) [2015]
(A) Impure Cu strip is used as cathode
(B) Acidified aqueous CuSO4 is used as electrolyte
(C) Pure Cu deposits at cathode
(D) Impurities settle as anode-mud

2. Match the anionic species given in Column I that are present in the ore(s) given in Column II
Column I Column II [2015]
(A) Carbonate (P) Siderite
(B) Sulphide (Q) Malachite
(C) Hydroxde (R) Bauxite
(D) Oxide (S) Calamine
(T) Argentite

153
 ANSWER TO METALLURGY & d-f BLOCK ELEMENT
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. C 10. B 19. B 28. A 37. A 46. A
2. A 11. B 20. A 29. C 38. A 47. A
3. A 12. A 21. B 30. B 39. D 48. C
4. D 13. C 22. D 31. D 40. C 49. B
5. B 14. B 23. B 32. B 41. B 50. D
6. A 15. C 24. B 33. A 42. B 51. B
7. D 16. A 25. A 34. A 43. D
8. D 17. A 26. A 35. B 44. C
9. C 18. D 27. A 36. A 45. D

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. AD 5. AB 9. ABC 13. ABC 17. BCD
2. ABD 6. AB 10. ABC 14. BC 18. AB
3. ABC 7. AC 11. ABCD 15. BCD
4. ABC 8. ACD 12. ABD 16. AB

COMPREHENSION TYPE
1. A 4. B 7. D 10. C 13. D
2. C 5. A 8. A 11. D
3. B 6. C 9. C 12. A

MATCH THE FOLLOWING COLUMN

1. A P,R; B  P, R; CQ; DS 2. A  R; B  S; C  P; D  Q

INTEGER ANSWER TYPE

1. 3 2. 3 3. 2 4. 3 5. 7 6. 8 7. 3 8. 4

SECTION-III
PREVIOUS YEARS QUESTION ASKED IN IIT JEE ADVANCED
1. BCD 2. A-PQS ; B-T ; C-Q; D-RS

154
 QUALITATIVE ANALYSIS
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. Two test tubes containing a nitrate and a bromides are treated separately with H 2SO4 ; brown
fumes evolved are passed in water. The water will be coloured by vapours evolved from the test
tube containing.
(A) Nitrate (B) Bromide (C) both (A) and (B) (D) none of these
2. The solution of a chemical compound X reacts with AgNO 3 solution to form a white precipitate of
Y which dissolves in NH4OH to give a complex Z. When Z is treated with dilute HNO 3, Y
reappears. The chemical compound X can be :
(A) NaCl (B) CH3Cl (C) NaBr (D) NaI

3. To an inorganic mixture dil. H2SO4 is added in cold; colourless, odourless gas is evolved. The
mixture contains.
(A) Sulphite (B) Acetate (C) Nitrite (D) Carbonate
4. Nessler’s reagent is used to detect
   
(A) CrO2
4 (B) PO34 (C) Mn4 (D) NH4

5. The metal sulphate (A) on heating evolves two gases (B) and (C) and an oxide (D). Gas (B) turns
K2Cr2O7 paper green while gas (C) forms a trimer in which there is no S-S bond. Compound (D)
with conc. HCl forms a Lewis acid (E) which exists in a dimer. Compounds (A), (B), (C), (D) and
(E) respectively
(A) FeSO4,SO2,SO3,Fe2O3,FeCl3 (B) Al2(SO4 )3 ,SO4 ,SO3,Al2O3,FeCl3
(C) FeS,SO2,SO3,FeSO4,FeCl3 (D) FeS,SO2,SO3,Fe2(PO4 )3,FeCl2

6. Aqueous solution of a salt when treated with AgNO 3 solution gives a white precipitate, which
dissolves in NH4OH. Radical present in the salt is
(A) Cl (B) NO3  
(C) I (D) All of them

7. A solution of white crystals gives a precipitate with AgNO 3 but no precipitate with solution of
Na2CO3. The action of conc. H2SO4 on the crystal yields a brown gas. The crystals are of
(A) NaNO3 (B) KCl (C) Ca(NO3)2 (D) NaBr

8. A white salt is insoluble in cold water but soluble in boiling water. Its solution when treated
with potassium chromate solution gives yellow precipitate. The salt may be :
(A) BaCl2 (B) SrCl2 (C) PbCl2 (D) Hg(NO3)2

9. A white powder when strongly heated gives off brown fumes. A solution of this powder gives a
yellow precipitate with a solution of KI. When a solution of barium chloride is added to a
solution of powder, a white precipitate results. This white powder may be :
(A) A soluble sulphate (B) KBr and NaBr (C) Ba(NO3)2 (D) AgNO3

10. Ammonium dichromate is used in some fireworks. The green coloured powder blown in air is
due to
(A) CrO3 (B) Cr2O3 (C) Cr (D) CrO(O2)

155
11. A white precipitate obtained in the analysis of a mixture becomes black on treatment with
NH4OH. It may be
(A) PbCl2 (B) AgCl (C) HgCl2 (D) Hg2Cl2

12. When a KI solution is added to a metal nitrate, a black precipitate is produced which dissolves
in an excess of KI to give an orange solution. The metal ion is
(A) Hg2+ (B) Bi3  (C) Cu2 (D) Pb2

13. Which of the following compounds does not exist?

(A) CrO2Br2 (B) CrO2Cl2 (C) POCl3 (D) BiOCl

14. Salt (A) gives brick red fumes (B) with cone. H2SO4 and K2Cr2O7 which gives yellow solution (C)
with NaOH and it gives yellow ppt. (D) with acetic acid and lead acetate. What is (C)?
(A) Na2CrO4 (B) CrO2Cl2 (C) PbCrO4 (D) NaCl

15. There is mixture of Cu(II) chloride and Fe(II) sulphate. The best way to separate the metal ions
from this mixture in qualitative analysis is
(A) hydrogen sulphide in acidic medium, where only Cu(II) sulphide will be precipitated
(B) ammonium hydroxide buffer, where only Fe(II) hydroxide will be precipitated
(C) hydrogen sulphide in acidic medium, where only Fe(ll) sulphide will be precipitated
(D) ammonium hydroxide buffer, where only Cu(II) hydroxide will be precipitated
16. The ion that cannot be precipitated by H2S and HCl is
(A) Pb2+ (B) Cu2+ (C) Ag+ (D) Ni2+
17. A substance on treatment with dil. H2SO4 liberates a colourless gas which produces (i) turbidity
with baryta water and (ii) turns acidified dichromate solution green. The reaction indicates the
presence of
(A) CO2
3

(B) S2– (C) SO2
3

(D) NO2

18. When copper nitrate is strongly heated, it is converted into

(A) Cu metal (B) cupric oxide
(C) cuprous oxide (D) copper nitrate

19. A white solid is first heated with dil H2SO4 and then with conc. H2SO4. No action was observed
in either case. The solid salt contains
(A) sulphide (B) sulphite (C) thiosulphate (D) sulphate

20. A pale green crystalline metal salt of M dissolves freely in water. On standing it gives a brown
ppt on addition of aqueous NaOH. The metal salt solution also gives a black ppt on bubbling
H2S in basic medium. An aqueous solution of the metal salt decolourizes the pink colour of the
permanganate solution. The metal in the metal salt solution is
(A) copper (B) aluminium (C) lead (D) iron

21. Sodium borate on reaction with conc. H2SO4 and C2H5OH gives a compound A which burns with
a green edged flame. The compound A is
(A) H2B4O7 (B) (C2H5)2B4O7 (C) H3BO3 (D) (C2H5)3BO3

22. When K2Cr2O7 crystals are heated with conc. HCl, the gas evolved is
(A) O2 (B) Cl2 (C) CrO2Cl2 (D) HCl

156
23. Which is most soluble in water?
(A) AgCl (B) AgBr (C) AgI (D) AgF

24. On passing H2S gas in II group sometimes the solution turns milky. It indicates the presence of
(A) oxidising agent (B) acidic salt
(C) thiosulphate (D) reducing agent.

25. Dimethyl glyoxime in a suitable solvent was refluxed for 10 minutes with pure pieces of nickel
sheet, it will result in
(A) Red ppt (B) Blue ppt. (C) Yellow ppt. (D) No ppt.

26. Statement-1: On passing CO2 gas through lime water, the solution turns milky.
because
Statement-2: Acid-Base (neutralisation) reaction takes place.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for
statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

27. An aqueous solution of a substance gives a white ppt. on treatment with dil. HCl, which
dissolves on heating. When hydrogen sulphide is passed through the hot acidic solution, a black
ppt. is obtained. The substance is a
(A) Hg2+ salt (B) Cu2+ salt (C) Ag+ salt (D) Pb2+ salt

28. Which of the following does not react with AgCl?

(A) Na2CO3 (B) NaNO3 (C) NH4OH (D) Na2S2O3

29. A pale yellow crystalline solid insoluble in water but soluble in CS2 is allowed to react with nitric
oxide to give X and Y. X is a colourless gas with pungent odour. X is further allowed to react in
aqueous medium with nitric oxide to yield Z and T. Compounds X, Z and T are
(A) SO3, H2SO3, N2O (B) SO2, H2SO4, N2O
(C) SiO2, H2SO4, N2 (D) SO3, H2SO3, N2

30. Which metal salt gives a violet coloured bead in the borax bead test?
(A) Fe2+ (B) Ni2+ (C) Co2+ (D) Mn2+

31. Which of the following gives a precipitate with Pb(NO 3)2 but not with Ba(NO3)2?
(A) Sodium chloride (B) Sodium acetate
(C) Sodium nitrate (D) Sodium hydrogen phosphate

32. Which of the following is soluble in yellow ammonium sulphide?

(A) CuS (B) CdS (C) SnS (D) PbS

33. A chloride dissolves appreciably in cold water. When placed on a platinum wire in Bunsen flame
no distinctive colour is noticed, the cation would be:
(A) Mg2+ (B) Ba2+ (C) Pb2+ (D) Ca2+

157
34. A white salt is readily soluble in water and gives a colourless solution with a pH of about 9. The
salt could be:
(A) NH4NO3 (B) CH3COONa (C) CH3COONH4 (D) CaCO3

35. An element (X) forms compounds of the formula XCl3, X2O5 and Ca3X2, but does not form XCl5.
Which of the following is the element X?
(A) B (B) Al (C) N (D) P
36. A white sodium salt dissolves readily in water to give a solution which is neutral to litmus. When
silver nitrate solution is added to the solution, a white precipitate is obtained which does not
dissolve in dil. HNO3. The anion could be:
 
(A) CO23 (B) Cl– (C) SO2
4 (D) S2–
37. A mixture of two salts is not water soluble but dissolves completely in dil HCl to form a
colourless solution. The mixture could be:
(A) AgNO3 and KBr (B) BaCO3 and ZnS
(C) FeCl3 and CaCO3 (D) Mn(NO3)2 and MgSO4

38. Three separate samples of a solution of a single salt gave these results. One formed a white
precipitate with excess of ammonia solution, one formed a white precipitate with dil NaCl
solution and one formed a black precipitate with H2S. The salt could be:
(A) AgNO3 (B) Pb(NO3)2 (C) Hg(NO3)2 (D) MnSO4

39. Which one of the following ionic species will impart colour to an aqueous solution?
(A) Ti4+ (B)Cu+ (C) Zn2+ (D)Cr3+

40. When a substance A reacts with water it produces a combustible gas B and a solution of
substance C in water. When another substance D reacts with this solution of C, it also produces
the same gas B on warming but D can produce gas B on reaction with dilute sulphuric acid at
room temperature. A imparts a deep golden yellow colour a smokeless flame to Bunsen burner.
A, B, C and D respectively are:
(A) Na, H2, NaOH, Zn (B) K, H2, KOH, Al
(C) Ca, H2, Ca(OH)2, Sn (D) CaC2, C2H2, Ca(OH)2, Fe
41. Which is not dissolved by dil HCl?
(A) ZnS (B) MnS (C) BaSO3 (D) BaSO4

42. The brown ring test for NO2  and NO3 is due to the formation of complex ion with formula:
(A) [Fe(H2O)6]2+ (B) [Fe(NO)(CN)5]2–
(C) [Fe(H2O)5(NO)]2+ (D) [Fe(H2O)(NO)5]2+
43. In Nessler’s reagents, the ion present is:

(A) HgI2– (B) HgI2
4 (C) Hg+ (D) Hg2+

44. The cations present in slightly acidic solution are Fe 3+, Zn2+ and Cu2+. The reagent which when
added in excess to this solution would identify and separte Fe3+ in one step is:
(A) 2 M HCl (B) 6 M NH3 (C) 6 M NaOH (D) H2S gas

45. Which of the following leaves no residue on heating?

(A) Pb(NO3)2 (B) NH4NO3 (C) Cu(NO3)2 (D) NaNO3

158
46. When I2 is passed through KCl, KF, KBr :
(A) Cl2 and Br2 are evolved (B) Cl2 is evolved
(C) Cl2, F2 and Br2 are evolved (D) None of these

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. Highly pure dilute solution of sodium in liquid ammonia
(A) shows blue colour (B) exhibits electrical conductivity
(C) produces sodium amide (D) produces hydrogen gas

2. Identify the correct statements of the following

(A) Transition metals have high enthalpies of sublimation
(B) the atomic sizes of third series of transition metals are not very much different from those of
second series in respective groups.
(C) Most of the transition metals of first series have negative reduction potentials and hence
react readily with dilute acids to liberate H2.
(D) Cr, Mo and W are very hard metals because of greater number of the covalent bonds
involving unpaired electrons.
3. Which of the following statements is/are correct ?
(A) Anhydrous ferric chloride can be obtained by heating hydrated ferric chloride
(B) A solution of ferric oxalate in dilute H2SO4 will decolorise KMnO4.
(C) Ferric salts are more stable than ferrous salts
(D) The Mohr’s salt is resistant to oxidation by atmospheric oxygen.

4. Nitrogen dioxide can be obtained by heating :

(A) KNO3 (B) Pb(NO3)2 (C) LiNO3 (D) AgNO3

5. Which of the following anions is not easily removed by precipitation from its aqueous solution:
 
(A) NO3 (B) CH3COO (C) SO24

(D) I

6. When oxalic acid is heated with conc. H2SO4, it produces:

(A) CO (B) CO2 (C) SO2 (D) SO3

7. Iodine imparts brown colour to :

(A) Water (B) Ether (C) Alcohol (D) Chloroform

8. Hydrogen iodide cannot be made by the action of concentrated sulphuric acid on potassium
iodide because :
(A) H2SO4 in an oxidizing agent (B) HI is stronger acid than H2SO4
(C) HI is strong reducing agent (D) H2SO4 is stronger acid then HI
9. A solution giving yellow ppt. with ammonium molybdate contains:
(A) PO3
4

(B) As3  (C) Bi3+ (D) none of these
10. Which one of the following does not produce metallic sulphide with H2S?
(A) ZnCl2 (B) CdCl2 (C) CoCl2 (D) CuCl2

159
11. In  B group of basic radicals the yellow ppt.are given by :
(A) As3+ (B) Sb3+ (C) Sn4+ (D) Sn2+
12. Reddish brown gas is obtained when the following are treated with conc. H 2SO4 :
(A) Br– (B) NO3– (C) NO2– (D) –

13. Raddish brown gas is obtained when the following are treated with conc. H2SO4
(A) Br  (B) NO2 (C) NO3 (D) SO23

14. If (X) turns lime water milky then X may be:

(A) CO2 (B) SO2 (C) NO2 (D) O2

15. S2 and SO23 can be distinguished by using:

(A) (CH3COO)2 Pb (B) Na2[Fe(CN)5 NO] (C) Cr2O72 solution (D) CaCl2

KMnO4 Purple colour of KMnO4 decolourises

gas
16.
Br2 Brown colour of Br2 water become colourless
water

The gas will be:

(A) CO2 (B) SO2 (C) H2S (D) SO3

17. CaCO3  A  B(gas)

A  H2O  C

C  B  D  H2O
(white ppt.)
Boil
D  B(gas)  E 
BaCl
 F
(water so lub le) 2 (white ppt.)
Select the correct option (s) for white ppt. shown in the above reactions:
(A) CaCO3 (B) MgCO3 (C) BaCO3 (D) Na 2CO3

18. Which of the following is (are soluble in excess of NaOH?

(A) Cr(OH)3 (B) Fe(OH)3 (C) Al(OH)3 (D) Zn(OH)2

19. Concentrated aqueous sodium hydroxide cannot separate a mixture of:

(A) Al3 and Sn2 (B) Al3 and Fe3  (C) Al3 and Zn2 (D) Zn2 and Pb2

160
COMPREHENSION TYPE
PARAGRAPH FOR NEXT THREE QUESTIONS
A bluish green coloured compound ‘A’ on heating gives two products ‘B’ and ‘C’. A metal ‘D’ is
deposited on passing H2 through heated ‘B’. The compound ‘A’ and ‘B’ are insoluble in water. ‘B’ is
black in colour, dissolves in HCl and on treatment with K4[Fe(CN)6] gives a chocolate brown ppt of
compound ‘E’. ‘C’ is colourless, odoulress gas and turns lime water milkly.
1. Compound ‘A’ is
(A) CuSO4 (B) CuCO3 (C) FeSO4 (D) CrCl3

2. The compounds ‘B’ and ‘C’ are respectively

(A) CuS, SO2 (B) CuO, CO2 (C) FeO, H2S (D) Cr2O3, CO

3. The compounds ‘D’ and ‘E’ are respectively

(A) Cu, Cu2[Fe(CN)6] (B) Fe, Cu2[Fe(CN)6] (C) Cr, CuCO3 (D) Zn, CuO

PARAGRAPH FOR NEXT THREE QUESTIONS

(i) A white solid mixture of tow salts containing a common cation is insoluble in water. It dissolves
in dilute HCl producing some gases (with effervescence) that turn an acidified dichromate
solution green. After the gases are passed through the acidified dichromate solution, the
emerging gas turns baryta water milky.
(ii) On treatment with dilute HNO3 , the white solid gives a solution which does not directly give a
precipitate with a BaCl2 solution but give a white precipitate when warmed with H2O2 and then
treated with a BaCl2 solution
(iii) The solution of the mixture in dilute HCl, when treated with NH4Cl, NH4OH and an Na 2HPO4
solution, gives a white precipitate.

4. The gases evolved in (i) are

(A) CO2 and HCl (B) SO2 and CO2 (C) SO2 and H2S (D) NH3 and CO2

5. The white precipitate obtained in (ii) indicates the presence of a

(A) carbonate (B) sulphide (C) sulphite (D) chloride

6. The white precipitate obtained in (iii) consists of

(A) Ba 3 (PO4 )2 (B) Sr3 (PO4 )2 (C) Ca 3 (PO4 )2 (D) MgNH4PO4  6H2O

161
MATCH THE FOLLOWING COLUMN
1. Match the following colum-I with column-II
Column-I Column-II
(A) Soluble in a concentrated NH3 (P) Fe4[Fe(CN)6 ]3
(B) Prussian blue (Q) Cu(OH)2
(C) Dissolves in a concentrated NH3 solution (R) AgBr
and gets reprecipitated when the ammoniacal
solution is acidified with HNO3
(D) Dissolves in NH3 and the ammonical solution (S) AgCl
on acidification with acetic acid and treatment
with K4[Fe(CN)6 ] gives a chocolate coloured
precipitate

2. Match the following colum-I with column-II

Column-I Column-II
(A) Blue, soluble in amyl alcohol (P) (NH4 )2[Co(SCN)4 ]
(B) White (Q) ZnS
(C) Obtained in the analysis of group IIIB cations (R) PbSO4
(D) Soluble in a ammonium acetate solution (S) CrO3

INTEGER ANSWER TYPE

1. An aqueous solution contains Hg2 ,Hg 22 ,Pb2 and Cd2 . Out of these, how many ions will
produce white precipitate with dilute HCl?

2. How many water molecule(s) is/are present in compound which is used in borax bead test?

3. In how many of the following reactions one of the products is obtained as a black precipitate?
2
(i) Bi(OH)3  [Sn(OH)4 ](aq.)  Products
3 
(ii) Bi(aq.)  I(aq) (not in excess)  Products
 H
(iii) Ag(aq)  H2S(g)  Products
 Dilution
(iv) [BiI4 ](aq)  H2O(l) 
 Products

3 
4. Fe(aq)  I(aq)  H2SO4 (conc.)  Brown ring. The oxidation number of iron in brown ring
complex is:

5. Na2SO3 ,Na 2S2O3, Na 2CO3, Na 2CrO4 are separately treated with AgNO3 solution. In how many
cases is/are red ppt. obtained?

162
 SECTION-III
PREVIOUS YEARS QUESTION ASKED IN IIT-JEE
1. Addition of excess aqueous ammonia to a pink coloured aqueous solution of MCl2  6H2O (X)
and NH4Cl gives an octahedral complex Y in the presence of air. In aqueous solution, complex Y
behaves as 1:3 electrolyte. The reaction of X with excess HCl at room temperature results in the
formation of a blue coloured complex Z. The calculated spin only magnetic moment of X and Z is
3.87 B.M., whereas it is zero for complex Y.
Among the following options, which statement(s) is(are) correct? [2017]
(A) When X and Z are in equilibrium at 0o C, the colour of the solution is pink
(B) Z is a tetrahedral complex
(C) The hybridization of the central metal ion in Y is d2sp3
(D) Addition of silver nitrate to Y gives only two equivalents of silver chloride

2. In the following reaction sequence in aqueous solution, the species X, Y and Z respectively are
2 Ag  Ag  with time
S2O3 
 X 
 Y 
 Z [2016]
clear solution white precipitate black precipitate

(A) [Ag(S2O3 )2 ]3 , Ag2S2O3, Ag2S (B) [Ag(S2O3 )3 ]5  , Ag2SO3, Ag2S

(C) [Ag(SO3 )2 ]3 , Ag2S2O3 , Ag (D) [Ag(SO3 )3 ]3 , Ag2SO4 , Ag

3. The pair(s) of ions where BOTH the ions are precipitated upon passing H2S gas in presence of
dilute HCl, is(are) [2015]
2 2 3 3 2 2 2 3
(A) Ba ,Zn (B) Bi ,Fe (C) Cu ,Pb (D) Hg ,Bi

PARAGRAPH FOR NEXT TWO QUESTIONS: [2013]

An aqueous solution of a mixture of two inorganic salts, when treated with dilute HCl, gave a
precipitate (P) and a filtrate (Q). The precipitate P was found to dissolve in hot water. The filtrate (Q)
remained unchanged, when treated with H2S in a dilute mineral acid medium. However, it gave a
precipitate  with H2S in an ammonical medium. There precipitate R gave a coloured solution (S),
when treated with H2O2 in an aqueous NaOH medium.
4. The precipitate P contains

(A) Pb2 (B) Ag 2
2 (C) Ag  (D) Hg 2

5. The colour solution (S) contains

(A) Fe2(SO4 )3 (B) CuSO4 (C) ZnSO4 (D) Na 2CrO4

PARAGRAPH FOR NEXT THREE QUESTION

p-Amino-N, N-dimethylaniline is added to a strongly acidic solution of X. The resulting solution is
treated with a few drops of aqueous solution of Y to yield blue coloration due to the formation of
methylene blue. Treatment of the aqueous solution of Y with the reagent potassium
hexacyanoferrate(II) leads to the formation of an intense blue precipitate. The precipitate dissolves
on excess addition of the reagent. Similarly, treatment of the solution of Y with the solution of
potassium hexacyanoferrate(III) leads to a brown coloration due to the formation of Z. [2009]
6. The compound X is
(A) NaNO3 (B) NaCl (C) Na2SO4 (D) Na2S

163
7. The compound Y is
(A) MgCl2 (B) FeCl2 (C) FeCl3 (D) ZnCl2

8. The compound Z is
(A) Mg2[Fe(CN)6] (B) Fe[Fe(CN)6] (C) Fe4[Fe(CN)6]3 (D) K2Zn3[Fe(CN)6]2

9. Match each of the reactions given in Column I with the corresponding product(s) given in
Column II. [2009]
Column I Column II
(A) Cu + dil. HNO3 (P) NO
(B) Cu + conc. HNO3 (Q) NO2
(C) Zn + dil. HNO3 (R) N2O
(D) Zn + conc. HNO3 (S) Cu(NO3)2
(T) Zn(NO3)2

164
 ANSWER TO QUALITATIVE ANALYSIS
SECTION-I
STRAIGHT OBJECTIVE TYPE
1. B 11. D 21. D 31. A 41. D
2. A 12. B 22. B 32. C 42. C
3. D 13. A 23. D 33. A 43. B
4. D 14. A 24. A 34. B 44. B
5. A 15. A 25. D 35. C 45. B
6. A 16. D 26. B 36. B 46. D
7. D 17. C 27. D 37. B
8. C 18. B 28. B 38. B
9. D 19. D 29. B 39. D
10. B 20. D 30. D 40. A

SECTION-II
MULTIPLE CORRECT ANSWER TYPE
1. AB 5. AB 9. AB 13. ABC 17. AC
2. ABD 6. AB 10. AC 14. AB 18. CD
3. BCD 7. BC 11. AC 15. ABD 19. ACD
4. BCD 8. AC 12. ABC 16. BC

COMPREHENSION TYPE
1. B 2. B 3. A 4. B 5. C 6. D

MATCH THE FOLLOWING COLUMN

1. A  Q,R,S; B  P; C  R,S; D  Q 2. A  P,S; B  Q,R; C  P,Q; D  R

INTEGER ANSWER TYPE

1. 2 2. 10 3. 3 4. 1 5. 1

SECTION-III
PREVIOUS YEARS QUESTION ASKED IN IIT-JEE
1. ABC 4. A 7. C 9. A- P,S; B-
2. A 5. A 8. B Q,S;C- R,T;
3. CD 6. D D-Q,T

165