C Module 7A

CHEMISTRY
Solution to Module 7A
Topics Page No.
9. Coordination Compounds 1
10. Haloalkanes and Haloarenes 12
11. Alcohols, Phenols and Ethers 27
12. Aldehydes, Ketones and Carboxylic Acids 53

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9. Coordination Compounds
Exercise
Very short answer questions (VSA)
1. Classify the following as cationic, anionic or neutral complexes:
(i) [Co( NH 3 ) 6 ]Cl3 (ii) [Fe(CO) 5 ] (iii) [Ag( NH 3 ) 2 ]Cl (iv) Na 3 [Co( NO 2 ) 6 ]
Solution
(i) cationic complex (ii) neutral complex
(iii) cationic complex (iv) anionic complex
2. Write an example of a cationic complex.
Solution
Hexaamminecobalt(III) chloride
3. What is a neutral complex?
Solution
Complex which does not ionize in solution
4. Write the equation for the ionization of K 4 [Fe(CN ) 6 ] solution and how many ions are formed per mole
of the salt.
Solution
K4[Fe (CN)6] 4K+ + [Fe(CN)6]4 ; 5 ions are formed per mole of the salt
5. Write an example for unidentate ligand.
Solution
H2O
6. Write an example for an anionic ligand.
Solution
Cyanide ion, CN−
7. How many water molecules are present as ligand in Pentaaquachloridochromium(III) chloride?
Solution
Five water molecules are present as ligand in Cr ( H 2 O )5 Cl  Cl2
8. What is the coordination number of chromium in the complex, [Cr ( NH 3 ) 3 ( NO 2 ) 3 ] ?

Solution
Six
9. What is the oxidation number of the central metal in the following coordinates entities?
(i) [Co(H2O)(CN)(en)2]2+ (ii) [CoBr2(en)2]+
(iii) [Cr(NH3)3Cl3] (iv) K3[Fe(CN)6] [One mark each]
Solution
(i) x = +3 (ii) x = +3 (iii) x = +3 (iv) x = +3
10. What is the oxidation state of iron in haemoglobin?
Solution
+2
11. Name the following ligands:
(i) SO 24− (ii) NH 3 (iii) H2O (vi) NO
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Solution
(i) sulphato (ii) ammine (iii) aqua (iv) nitrosyl
12. Write the IUPAC name of
(i) [ Ni(CO) 4 ] (ix) [Pt(NH3)2Cl(NH2CH3)]Cl
(ii) [ Zn (OH) 4 ] 2−
(x) [Co(en)3]3+
(iii) K3[Co(NO2)6] (xi) [Co(NH3)4Cl(NO2)]Cl [July 2015]
(iv) [Co(NH3 )5 (NO 2 )]Cl2 (xii) [Cr(NH )
3 3 (H 2 O) 3]Cl 3 [March 2018, July 2018]
3−
(v) [Co(ox)3] (xiii) [Co(NH3)4 (H2O)Cl]Cl2
(vi) [Pt(NH 3 )4 Cl2 ]Br2 (xiv) K.2 [Zn(OH)4] [March 2018, July 2018]
(vii) [Pt(NH 3 ) 2 Cl4 ] (xv) K3 [Cr(C2O4)3] [March 2019]
2+
(viii) [Mn(H2O)6]
Solution
(i) Tetracarbonylnickel(0)
(ii) Tetrahydroxozincate(II) ion
(iii) Potassium hexanitrito-N-cobaltate(III)
(iv) Pentaamminenitrito-N-cobalt(III) chloride
(v) Trioxalatocobaltate(III) ion
(vi) Tetraamminedichloridoplatinum(IV) bromide
(vii) Diamminetetrachloridoplatinum(IV)
(viii) Hexaaquamanganese(II) ion
(ix) Diamminechloridomethanamineplatinum(II) chloride
(x) Tris(ethane-1,2-diamine)cobalt(III) ion
(xi) Tetraamminechloridonitrito-N-cobalt(III) chloride
(xii) Triamminetriaquachromium(III) chloride
(xiii) Tetraammineaquachloridocobalt(III) chloride
(xiv) Potassium tetrahydroxozincate(II)
(xv) Potassium trioxalatochromate(III)
13. Write the formula of
(i) Tris(ethane-1,2-diamine)cobalt(III) sulphate (ii) Pentaamminenitrito-O-cobalt(III) bromide
(iii) Potassium tetrachloridopalladate(II) (iv) Pentaamminenitrito-O-cobalt(III) ion
(v) Potassium trioxalatochromate(III) (vi) Pentaamminenitrito-N-cobalt(III) ion
Solution
(i) [Co(en)3]2 (SO4)3 (ii) [Co(NH3)5(ONO)]Br2 (iii) K2[Pd (Cl4]
2+
(iv) [Co(NH3)5(ONO)] (v) K3[Cr(ox)3] (vi) [Co(NH3)5(NO2)]2+
14. [Co(NH3)5SO4]Br does not give a precipitate with barium chloride solution. Why?
Solution
Since SO 24− acting as ligand present within in the coordination sphere
15. Indicate the type of isomerism in the following set of complex compound: [March 2020]
[Co(NH3)5(SCN)]Cl2 and [Co(NH3)5 (NCS)]Cl2
Solution
Linkage isomerism
16. Name the type of structural isomerism arises when ambidentate ligand present in the complex.
[July 2018]
Solution
Linkage isomerism
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17. Draw the facial and meridional isomeric structures of [Co(NH3)3(NO2)3]. [July 2015, March 2019]
Solution
NH3 NH3
O2N NH3 H3N NO2
Co Co
O2N NH3 O2N NO2
NO2 NH3
facial meridional
18. Write the structure of trans isomer of [Co(NH3)4Cl2]+. [July 2017]

Solution
+
Cl
H3N NH3
Co
H 3N NH3
Cl
trans-isomer
19. What is the primary valence of copper in [Cu ( NH 3 ) 4 ]SO 4 ?
Solution
2
20. What is the secondary valence of
(i) iron in Potassium hexacyanoferrate(II) (ii) cobalt in [Co(en ) 3 ]Cl 3 ?
Solution
(i) 6 (ii) 6
21. Write an example for the ligand that satisfies both primary and secondary valence.
Solution
In K3[Fe(CN)6], three CN− ions satisfy primary valence as well as secondary valence of Fe3+.
22. What is the type of hybridization of nickel in Tetracarbonylnickel(0)?
Solution
sp3
23. What is the geometry of K 4 [Fe(CN) 6 ] ?
Solution
Octahedral
24. Which set of d-orbitals of a metal atom/ion experience more repulsion in octahedral field created by the
ligands? [June 2019]
Solution
d x 2 − y2 , d z2 i.e., eg set experiences more repulsion in octahedral field created by the ligands.
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25. Which among the following has the highest magnetic moment value?
(i) [Cr(H2O)6]3+ (ii) [Fe(H2O)6]2+
Solution
[Fe(H2O)6]2+ ; four unpaired electrons
Short answer questions (SA)

26. Write two differences between a double salt and a complex salt?
Solution
A double salt in aqueous solution undergo complete ionization and loses its identity. A complex salt in
aqueous solution undergo partial ionization or no ionization and retain its identity.
27. What is a ligand? Give an example.
Solution
A ligand is an ion or a neutral molecule that donates lone pairs of electrons to a metal atom or ion to
form a complex.
Example: Ammonia
28. Identify the following as monodentate or polydentate ligand:
(i) NH 3 (ii) Oxalate ion (iii) CO (iv) Cl −
Solution
(i) NH3: monodentate ligand
(ii) Oxalate ion: bidentate (polydentate) ligand
(iii) CO: monodentate ligand
(iv) Cl−: monodentate ligand
29. Write the structure of EDTA, a hexadentate ligand. Write one use of it.
Solution
.. CH2COO
N
CH2COO
CH2
CH2
.. CH2COO
N
CH2COO
Used to estimate the hardness of water

30. What is a neutral ligand? Give an example.
Solution
Ligands which do not carry any charge.
Example: NH3
31. What is an ambidentate ligand? Explain with an example. [March 2018]

Solution
Ligand which can ligate through different atoms.
Example :
← CN− (cyano) ; ← NC− (isocyano)
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32. What is a chelating complex? Give an example.

Solution
A complex containing a polydentate ligand.
Example: [Co(en)3]Cl3
33. What is the coordination number of Fe in K4[Fe(CN)6]? [July 2018]
Solution
Coordination number of Fe in K4[Fe(CN)6] is 6
34. What is the coordination number of Fe in [FeCl2 (en)2]Cl? [March 2017]
Solution
Co-ordination number of Fe is six.
35. What are homoleptic complexes? [July 2016]
Solution
Complexes containing only one type of ligand are called homoleptic complexes.
36. Explain the following with an example
(i) coordination entity (ii) heteroleptic complex
Solution
(i) coordination entity is the part of the complex in which the metal atom or ion is surrounded by a
definite number of ligands.
Example: in cuprammonium sulphate, [Cu (NH3)4]2+ is coordination sphere
(ii) Complexes containing different types of ligands are called heteroleptic. Example: [Co(NH3)4Cl2]+
37. Define coordination number.
Solution
Number of ligand donor atoms to which the central metal atom / ion is directly bonded to the complex.
38. Identify the error and write the correct IUPAC name of the following compounds:
(i) K 4 [Fe(CN) 6 ] -Potassium hexacyanoiron(II)
(ii) [Co( NH 3 ) 6 ]Cl 3 -Hexaaminecobaltchloride
Solution
(i) K4[Fe(CN)6] - The name of the central metal in an anionic complex ends with suffix –ate.
Hence the correct IUPAC name is Potassium hexacyanoferrate(II)
(ii) [Co(NH3)6]Cl3 - As a ligand NH3 is named as ammine and IUPAC name is written without leaving
space in between. Oxidation state of cobalt has to be written as (III).
Hence, the correct name is Hexaamminecobalt(III) chloride.
39. Explain ionization isomerism with an example. [July 2016]
Solution
Complex compounds with the same molecular formula but produce different ions in solution. This is due
to exchange of ions inside and outside the coordination sphere.
Example:
(a) [Co(NH3)5Br]SO4 gives white precipitate with barium chloride solution
(b) [Co(NH3)5(SO4)] Br does not give white precipitate with barium chloride solution
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40. Explain hydrate isomerism with an example.

Solution
In hydrate isomerism, compounds have the same molecular formula but water molecules are
exchanged inside and outside the coordination sphere.
Example: (i) [Cr(H2O)6]Cl3 ; (ii) [Cr(H2O)5Cl]Cl2.H2O ; (iii) [Cr(H2O)4Cl2]Cl.2H2O
41. For the given complex [Co(NH3)5Br]SO4, write the IUPAC name and its ionization isomer.
[March 2015]
Solution
The IUPAC name of the complex [Co(NH3)5Br]SO4 is pentamminebromidocobalt(III) sulphate. Its
ionization isomer is [Co(NH3)5SO4]Br.
42. Write the cis and trans isomeric structures of [Fe(NH3)2(CN)4]−. [March 2017]
Solution
−
NH3
NH3
NC CN
NC NH3
Fe
Fe
NC CN
NC CN
NH3
CN
Cis- Trans-
43. Which of the following compounds gives a precipitate with silver nitrate solution? Give reason.
(i) [Co( NH 3 ) 6 ]Cl3 (ii) [Co( NH 3 ) 3 Cl3 ]
Solution
[Co(NH3)6]Cl3 gives white precipitate with silver nitrate solution because chloride ions are outside the
coordination sphere and they ionize in solution.
[Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3Cl
44. Explain linkage isomerism with an example.

Solution
Compounds have the same molecular formula but a ligand is bonded to central metal atom through
different atoms
Example: [Co (NH3)5 (NO2)] Cl2 and [Co (NH3)5 (ONO)]Cl2.
45. Name the type of isomerism exhibited by the following isomers:
(i) [Co(NH 3 )5 NO 2 ]Cl2 and [Co(NH 3 )5 (ONO)]Cl2 (ii) [Cr(H 2 O)Cl(en)2 ]Cl2 and [CrCl2 (en)2 ]Cl.H 2 O
Solution
(i) Linkage isomerism (ii) Hydrate isomerism
46. For a given complex [Co(NH3)5NO2]Cl2. Write its IUPAC name and linkage isomer. [June 2019]
Solution
IUPAC name : Pentaaminenitrito−N−cobalt(III) chloride
Linkage isomer of the complex is [Co(NH3)5 (ONO)]Cl2.
47. Draw the structure of optical isomers of
(i) [Cr(C2O4)3]3−
(ii) [PtCl2(en)2]2+
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Solution
3 3
Ox Ox
(i) Ox Cr Cr Ox
mirror
Ox
Ox
Cl 2+ Cl 2+
Cl Cl
(ii) en Pt Pt en
mirror
en en
48. What are the two types of valences exhibited by transition metal? Explain with an example.
Solution
Transition metals exhibit two types of valences
(i) Primary valence which is variable (ii) Secondary valence which is fixed.
Example: K3[Fe(CN)6]
Primary valence of Fe is 3 Secondary valence of Fe is 6.
49. Write two differences between primary and secondary valence.
Solution
Primary valence Secondary valence
Primary valence of metal is satisfied by Secondary valence of a metal is satisfied by
negative ions negative ions or neutral molecules
Primary valence is ionisable Secondary valence is non-ionisable
50. What is the primary and secondary valences of iron in K 4 [Fe(CN ) 6 ] ?
Solution
In Potassium ferrocyanide, K4[Fe(CN)6],
Primary valence of Fe is 2 and Secondary valence of Fe is 6.
51. Dilute solution of [Fe(H2O)6]2+ and [Fe(CN)6]4− have different colour. Explain the reason.
Solution
CN– is a strong field ligand having a higher CFSE value than H2O. This means that the absorption of
energy for the intra d-d transition also differs. Hence, the transmitted colour also differs.
Long answer questions (LA)

52. State the postulates of Werner’s theory. [July 2017, March 2020]
Solution
(1) The central metal in coordination compounds show two types of valences, primary and secondary.
(2) The primary valences are normally ionisable and are satisfied by negative ions.
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(3) The secondary valences are non-ionisable and are satisfied by molecules or negative ions.
(4) The secondary valence is equal to the coordination number of the central metal.
(5) The primary valence is variable and secondary valence is fixed for a metal.
(6) The secondary valence is directional. It is directed in space about the central metal atom or ion. This
results in definite geometrical shape for coordination compounds.
53. Write the salient features of valence bond theory of coordination compounds.
Solution
1. The central metal provides vacant orbitals for the formation of complex.
2. The number of vacant orbitals provided by the central metal is equal to its coordination number.
3. The vacant orbitals undergo hybridisation to give equal number of hybrid orbitals.
4. The hybrid orbitals of central metal atom or ion overlap with ligand orbitals containing lone pairs of
electrons to form coordinate bonds.
5. The geometry of the complex depends on the number of hybrid orbitals and type of hybridisation.
6. The complex containing unpaired electrons is paramagnetic and the one which does not contain
unpaired electrons is diamagnetic.
54. Discuss the nature of bonding and magnetic nature of the following on the basis of valence bond theory:
(a) [CoF6]3− [July 2015, March 2020]
2−
(b) [Ni(CN)4] [March 2014, July 2014, March 2015, 2017, March 2019]
3+
(c) [Co(NH3)6]
(d) [NiCl4]2− [July 2016, March 2018, June 2019]
Solution
(a) Electronic configuration of 27Co is [Ar]3d74s2 4p
In this complex, cobalt is in the +3 oxidation state.
3+ 6
27Co is [Ar]3d 4s4p
3d6 4s 4p 4d
3+
27Co [Ar]
While forming the complex, electrons in d-orbitals remains unpaired.

(ii) The vacant one 4s, three 4p and two 4d-orbitals hybridise to give six sp3d2 hybrid orbitals.
These orbitals are directed towards the corners of octahedron.
3d6 sp3d2 4d
3+ [Ar]
27Co
(iii) The orbitals containing a lone pair of electrons from each of the six F− ions overlap with sp3d2
orbitals to form the complex.
3d sp3d2
[CoF6]3− [Ar] xx xx xx xx xx xx
The complex is octahedral and is paramagnetic since it has four unpaired electrons.
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(b) [Ni(CN)4]2−:
(i) Electronic configuration of 28Ni is [Ar]3d84s2 4p
In this complex, nickel is in the +2 oxidation state.
2+
28Ni is [Ar]3d8 4s4p
3d 4s 4p
2+
28Ni [Ar]
While forming the complex, electrons in 3d-orbitals are paired.

(ii) The vacant one 3d orbital, one 4s orbital and two 4p orbitals hybridise to give four dsp2
hybrid orbitals. These orbitals are directed towards four corners of a square planar
geometry.
3d dsp2 hybridisation 4p
2+
28Ni [Ar]
(iii) The orbitals containing a lone pair of electrons from each of four CN− ions overlap with dsp2
orbitals to form the complex.
3d dsp2 4p
2−
[Ni (CN)4] [Ar]
The complex is square planar due to dsp2 hybridisation and is diamagnetic as there are no unpaired
electrons.
(c) [Co(NH3)6]3+:
(i) Electronic configuration of 27Co is [Ar]3d74s2 4p
In this complex, cobalt is in the +3 oxidation state

3+
27Co is [Ar]3d6 4s4p
3d6 4s 4p
3+ [Ar]
27Co
While forming the complex, electrons in d-orbitals are paired.

(ii) The vacant two 3d, one 4s and three 4p-orbitals hybridise to give six d2sp3 hybrid orbitals.
These orbitals are directed towards corners of octahedron.
3d d2sp3
3+ [Ar]
27Co
(iii) The ligand orbitals of NH3 molecules contain a lone pair of electrons each, overlap with
d2sp3 orbitals to form the complex.
3d d2sp3
3+
[Co(NH3)6] [Ar]
The complex is octahedral and is diamagnetic since all the electrons are paired.
(d) [NiCl4]2− :
(i) Electronic configuration of 28Ni is [Ar]3d84s2 4p
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In this complex, nickel is in the +2 oxidation state

2+
28Ni is [Ar]3d8 4s4p
3d 4s 4p
2+
28Ni [Ar]
While forming the complex, electrons in 3d-orbitals remains unpaired.

(ii) One s and three p orbitals (4s and three 4p) hybridise to give four sp3 hybrid orbitals. These
orbitals are directed towards four corners of a tetrahedron.
3d sp3 hybridisation
2+
28Ni [Ar]
(iii) The orbitals containing a lone pair of electrons from each of four Cl− ligands overlap with
sp3 orbitals to form four coordinate bonds.
3d
2−
[NiCl4] [Ar] xx xx xx xx
Four pairs of
electrons from Cl−
The complex has tetrahedral geometry. The complex contains two unpaired electrons and hence is
paramagnetic.
55. What is a spectrochemical series? Explain the difference between weak field ligand and strong field
ligand.
Solution
Spectrochemical series gives the arrangement of ligands in the increasing order of crystal field spilting.
Weak field ligands Strong field ligands
• Cause small crystal field splitting • Cause large crystal field splitting
• Form high spin complexes • Form low spin complexes
Example : Cl–, F–, etc. Example : CN–, CO, etc.
56. Discuss the possibility of a d4 electron system of central metal to have different electron configurations
as (a) t2g4 eg0 and (b) t2g3 eg1
Solution
(a) Under the influence of strong ligands, the energy difference between t2g and eg sets is relatively high.
Thus, the distribution of d-electrons in t2g and eg sets do not occur according to Hund’s rule.
Therefore, the electronic configuration will be t2g4 eg1
(b) Under the influence of weak ligands, the energy difference (∆0) between t2g and eg sets is relatively
small. The distribution of electrons in t2g and eg sets occur according to Hund’s rule. Therefore, the
electronic configuration will be t2g3 eg1
57. What are inner orbital and outer orbital complexes? Explain with one example each.
Solution
The inner orbital complexes involve the hybridisation of the atomic orbital of the central metal atom of
inner shell d orbitals whereas the outer orbital complexes involve the hybridisation of the atomic orbital
of the central metal atom of outermost shell d orbitals
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Example: In the formation of [Co(NH3)6]3+ complex, the inner d-orbital (3d) is used in hybridization
(d2sp3). Hence, this complex is called ‘inner orbital’ or ‘low spin’ or ‘spin paired’ complex.
The octahedral complex [CoF6]3 − uses outer d orbital (4d) for hybridisation (sp3d2). Hence, it is called
‘outer orbital’ or ‘high spin’ or ‘spin free’ complex
58. (a) Draw energy level diagram for the splitting of d-orbitals in an octahedral crystal field. [July 2020]
(b) How many Cl− ions can be precipitated as AgCl by adding excess of aqueous AgNO3 solution into
one mole of [Co(NH3)6]Cl3? [July 2020]
Solution d 2 2d 2
(a) x −y z
OOO
eg
3
∆0
5
Bary centre
OOOOO ∆0
Energy OOOOO
2
∆0
5
d 2 2 d 2 d xy d xz d yz OOO t2g
x −y z Average
energy of d d d
xy xz yz
d-orbitals
Degenerate in a
d-orbitals in a Splitting of
spherical
free metal atom d-orbitals
symmetrical
or ion degeneracy is lost
field
(b) 3
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10. Haloalkanes and Haloarenes

Exercise
Unit I
1. Name the following alkyl halides according to IUPAC system and classify them as primary, secondary
and tertiary alkyl halides:
(i) (CH3)2CHCHClCH3 (ii) CH3C(C2H5)2CH2Br
(iii) CH3C(Cl)(C2H5)CH2CH3 (iv) CH3CH2CH(CH3)CH(C2H5)Cl
(v) CH3CH(CH3)CBr(CH2CH3)2 (vi) (CH3)3CCH2CH(Br)C2H5
(vii) CH3CH2C(CH3)2CH2I
Solution
(i) 2-Chloro-3-methylbutane: secondary alkyl halide
(ii) 1-Bromo- 2-ethyl-2-methylbutane: primary alkyl halide
(iii) 3-Chloro-3-methylpentane: tertiary alkyl halide
(iv) 3-Chloro-4-methylhexane: secondary alkyl halide
(v) 3- Bromo-3-ethyl-2-methylpentane: tertiary alkyl halide
(vi) 4-Bromo-2,2-dimethyl hexane: secondary alkyl halide
(vii) 1-Iodo-2,2-dimethylbutane: primary alkyl halide
2. Write the structures for the following compounds:
(i) 2-Chloro-3-methylpentane (ii) 4-tert-butyl-3-iodoheptane
Solution
(i) CH3 CH CH CH2 CH3 (ii) CH3 CH2 CH CH CH2 CH2 CH3
Cl CH3 I CH3 C CH3
CH3
3. What happens when ethanol is heated with conc. HCl and anhydrous ZnCl2?
Solution
Chloroethane (C2H5Cl) is formed
4. Mention the product formed when 2-propanol is heated with PCl5.
Solution
2-chloropropane (or isopropyl chloride)
5. CH3Br + AgF → CH3F + AgBr. Name the reaction. [March 2014, July 2016, March 2018]
(or)
Solution
Swarts reaction
acetone
6. CH 3Cl + NaI  → CH 3 I + NaCl . Name the above reaction. [July 2015, July 2018]
Solution
Finkelstein reaction
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7. Write the structure of the major organic compound formed in each of the following reactions:
pyridine
(i) CH3CH2CH2CH2OH + SOCl2
(ii) CH3 CH C CH3 + HBr

CH3
(iii) CH3 CH2 CH CH2 + HBr peroxide
(iv) CH3 CH CH2 + HI
Cl
HNO3
(v)
Solution
(i) CH3CH2CH2CH2Cl
Br
(ii) CH3 CH2 C CH3

CH3
(iii) CH3 CH2 CH2 CH2 Br
(iv) CH3 CH CH3
Cl Cl
NO2
(v) +
NO2
8. Arrange the following in the order of increasing boiling points:

(i) CH3CH2Cl, CH3CH2Br, CH3CH2I, CH3CH2F
(ii) 1-chloropropane, 2-chloropropane, 1-chlorobutane
Solution
(i) CH3CH2F, CH3CH2Cl, CH3CH2Br, CH3CH2I
(ii) 2-chloropropane, 1-chloropropane, 1-chlorobutane
9. Complete the reaction:
∆
CH 3 − CH 2 − Br + AgCN  → [July 2015, March 2020]
(Alc)
Solution
CH3CH2NC
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10. Complete the following reactions:
(i) CH3CH2CH2Cl + NaI acetone (ii) CH3CH(Br)CH2CH3 + NaOH water

heat heat
ethanol ethanol
(iii) (CH3)3CBr + KOH (iv) CH3CH2CH2Cl + KCN
heat heat
Solution
(i) CH3CH2CH2I
(ii) CH3CH(OH)CH2CH3
CH3
(iii) CH3 C CH2
(iv) CH3CH2CH2CN
11. Give the reaction of ethyl bromide with magnesium in dry ether.
Solution
C2H5Br + Mg dry ether
C2H5 Mg Br
Ethyl magnesium bromide
12. Between CH3Br and CH3I, which reacts faster with OH ion by SN2 mechanism?
Solution
CH3−I
13. What is chirality? [March 2014]
Solution
The objects which are non-superimposable on their mirror image are said to be chiral and this property is
known as chirality
14. What is asymmetric carbon? [March 2017]
Solution
Carbon bonded to four different atoms or groups
15. What are enantiomers? [July 2015]
Solution
Stereoisomers which form a pair of non-superimposable mirror images.
16. What is racemisation? [March 2020]
Solution
Process of conversion of enantiomer into a racemic mixture
17. What is racemic mixture? [June 2019]
Solution
Equimolar mixture of a pair of enantiomers
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18. What happens when bromoethane is heated with sodium in the presence of dry ether?
Solution
Butane is formed
19. Name the reagent used in the dehydrohalgenation of haloalkanes.
(or)
What is the reagent used in the conversion of alkyl halide into alkene? [July 2015, March 2018]
Solution
Alcoholic KOH
20. Name the major organic product formed when 2-bromopentane is heated with alcoholic potassium
hydroxide solution. [June 2019]
Solution
Br
H3C CH2 CH CH2 CH3 + KOH(alc) H3 C CH2 CH CH CH3 + KBr + H2O
2-Bromopentane Pent-2-ene
(Major product)
21. Write the general formula of Grignard reagent. [March 2016]

Solution
RMgX
22. Mention the major product formed in the following reactions:
Dry ether
(i) C6 H5 Br + Mg  →
alc. KOH, ∆
(ii) 2-Bromopentane →
dry acetone
(iii) CH 3Cl + NaI  → [July 2014]
alc.KOH, ∆
(iv) t-butylbromide →
Solution
(i) C6H5MgBr
(ii) Pent-2-ene
(iii) CH3I
CH3
alc. KOH CH3
(iv) H3C C Br
∆
C CH2
H3C
CH3
2-Methylpropene
23. Write the general equation for Wurtz reaction. [March 2019]
Solution
dry ether
2R X + 2Na R R + 2NaX
Higher alkane
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2PBBBCCM7AS

24. Explain the order of reactivity of hydrogen halides towards alcohols.
Solution
The order of reactivity of hydrogen halides is HI > HBr > HCl as reactivity is inversely proportional to
bond dissociation enthalpy.
25. What is the order of reactivity of alcohols with a given halogen acid? Explain.
Solution
The order of reactivity of alcohols with a halogen acid is
tertiary alcohol > secondary alcohol > primary alcohol. This is because, more the number of electron
releasing groups on the α-carbon atom of the alcohol, higher the polarity of the C−OH bond and easier
the bond breakage.
26. Write the reaction of 1-propanol with red phosphorous and bromine.
Solution
Red P + Br2
3CH3CH2CH2OH + PBr3 3CH3CH2CH2Br + H3PO3
heat
27. Write the reaction of 2-propanol with KBr and conc. H2SO4.
Solution
KBr +
conc. H2SO4
CH3 CH CH3 + HBr CH3 CH CH3 + H2O
heat
OH Br
28. What is the action of KI and orthophosphoric acid on alcohols? Give an example.
Solution
Alcohols react with KI and H3PO4 on heating to form respective alkyl iodides.
Example: KI + H3PO4 HI + KH2PO4
acetone
RX + NaI R I + NaX
heat
(X = Cl or Br)
29. Explain Darzen’s reaction with an example.
Solution
An alcohol reacts with thionyl chloride in the presence of pyridine to give a chloroalkane. This reaction
is called Darzen’s reaction.
pyridine
Example: CH3CH2OH + Cl.SO.Cl CH3CH2Cl + SO2 + HCl
Ethanol (SOCl2) Chloroethane
30. Explain Finkelstein reaction with an example.

Solution
Iodoalkanes can be obtained by treating bromoalkanes or chloroalkanes with a solution of sodium iodide
in acetone. This reaction is known as Finkelstein reaction.
acetone
C2 H5 Cl + NaI  → C2 H5 I + NaCl
chloroethane Iodoethane
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31. Give a method of preparation of an alkyl fluoride from an alkyl halide with an example. Name the
reaction.
Solution
An alkyl chloride or bromide reacts with silver fluoride or mercurous fluoride on heating to form the
alkyl fluoride. This is Swarts reaction.
Example: CH3Br + AgF CH3F + AgBr
Methyl bromide Methyl fluoride
32. A hydrocarbon, C5H12 reacts with chlorine in the presence of sunlight to give a single monochloro
compound C5H11Cl. Identify the hydrocarbon and write the reaction.
Solution
CH3
The hydrocarbon is neopentane, CH3 C CH3
CH3
CH3 CH3
light
CH3 C CH3 + Cl2 CH3 C CH2 Cl + HCl
CH3 CH3
Neopentane Neopentyl chloride
Since all H–atoms are equivalent, only one monochloro compound is formed.
33. Explain Kharasch or peroxide effect with an example.
Solution
Addition of HBr to an unsymmetrical alkene in the presence of organic peroxide takes place in the
manner opposite to that of Markownikov’s rule to form a primary alkyl halide as a major product.
benzoyl peroxide
CH3 CH CH2 + HBr CH3 CH2 CH2 Br
Propene 1-Bromopropane
(major product)
34. What are ambident nucleophiles? Give an example.
Solution
Species which attack an electron deficient carbon atom through different nucleophilic centers are called
ambident nucleophiles. Examples: CN − , NO −2
35. What happens when bromoethane is heated with
(i) aqueous KOH (ii) ethanolic solution of sodium ethoxide
(iii) alcoholic KCN (iv) alcoholic AgCN
(v) alcoholic ammonia (vi) ethanolic AgNO2
(vii) alcoholic silver acetate (viii) LiAlH4 in dry ether
(ix) Methyl lithium
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2PBBBCCM7AS
Solution
heat
(i) C2H5Br + KOH C2H5OH + KBr
(aq)
Ethanol
(ii) C2H5Br + C2H5ONa+ ethanol C2H5 O C2H5 + NaBr

heat
Diethyl ether
heat
(iii) C2H5Br + KCN C2H5CN + KBr
(alcoholic) Ethyl cyanide
heat
(iv) C2H5Br + AgCN C2H5NC + AgBr
(alcoholic) Ethyl isocyanide
heat
(v) C2H5Br + NH3 C2H5NH2 + HBr
(alcoholic) Ethyl amine
heat
(vi) C2H5Br + AgNO2 C2H5 ONO + AgBr
(ethanolic) Ethyl nitrite
O O
heat
(vii) C2H5Br + CH3 C OAg CH3 C O C2H5 + AgBr
(ethanol) Ethyl acetate
ether
(viii) 4C2H5Br + LiAlH4 4C2H6 + LiBr + AlBr3
Ethane
(ix) C2H5Br + CH3Li CH3 CH2 CH3 + LiBr
Propane
36. Explain dehydrohalogenation with an example (or) Explain Zaitsev rule with an example.
Solution
When alkyl halides with β-hydrogen atom are heated with alcoholic KOH, the halogen atom and a
β-hydrogen atom are removed as hydrogen halide forming an alkene.
According to Zaitsev rule, the alkene with more number of alkyl groups attached to doubly bonded
carbon atoms (more substituted alkene) will be formed as the major product.
β α
heat
CH3 CH2 Br + KOH CH2 CH2 + KBr + H2O
Alcoholic Ethene
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37. Predict the alkenes that are formed by the dehydrohalogenation of 2-chloro-2-methylbutane.
Solution
CH3
CH3 C CH CH3
CH3
2-methylbut-2-ene (major product)
CH3 C CH2 CH3
HCl
Cl CH3
CH2 C CH2 CH3

2-methylbut-1-ene (minor product)
38. Explain the relative reactivity of primary, secondary and tertiary alkyl halides towards β -elimination.
Solution
β-elimination proceeds through the formation of carbocation Hence, the order of reactivity of
haloalkanes towards β -elimination is tertiary > secondary > primary.
39. What is Wurtz reaction? Give an example.
Solution
Haloalkanes react with sodium metal in dry ether to form higher alkanes. This reaction is called Wurtz
reaction. dry ether
2R X + 2Na R R + 2NaX
Higher alkane
40. Alkyl chlorides react with aqueous KOH to give alcohols, but react with alcoholic KOH to give alkenes
as major products. Explain.
Solution
There is a competition between nucleophilic substitution and elimination reactions. In the presence of
solvent of high polarity such as water, substitution is favoured resulting in the formation of an alcohol.
In the presence of solvent of low polarity such as ethanol, elimination is favoured forming an alkene as a
major product.
41. How are the following conversions carried out?
(i) Propene to 1-propanol
(ii) 1-Bromopropane to 2-Bromopropane
(iii) Ethanol to propanenitrile
(iv) 2-Chlorobutane to 3,4-Dimethylhexane
(v) Isopropyl chloride to Isopropyl magnesium chloride
Solution
peroxide aq. KOH
(i) CH3 CH CH2 + HBr CH3 CH2 CH2 Br CH3 CH2 CH2 OH
heat
KBr
alcoholic KOH
(ii) CH3 CH2 CH2 Br CH3 CH CH2 + HBr CH3 CH CH3
KBr, H2O
Br
KBr + Conc. H2SO4 alcoholic KCN

(iii) CH3CH2OH heat
CH3CH2Br CH3CH2CN
KBr
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dry ether
(iv) CH3 CH2 CH Cl + 2Na + Cl CH CH2 CH2 CH3 CH2 CH CH CH2 CH3
heat
CH3 CH3 2NaCl CH3 CH3
dry ether
(v) CH3 CH CH3 + Mg CH3 CH CH3
Cl MgCl
42. (i) Name the product formed for the reaction of isopropyl iodide on alcoholic KOH.
(ii) What is the condition to be satisfied for a compound to be chiral? [March 2019]
Solution
(i) Propene
(ii) Condition for chirality is that the carbon must be bonded to four different atoms or groups in a
molecule.
Solution to Long answer questions (LA)

43. Write the equations for the preparation of 1-Iodobutane from
(i) 1-Butanol (ii) 1-Chlorobutane (iii) 1-Butene
Solution
KI/H3PO4
(i) CH CH CH CH OH + HI CH3CH2CH2CH2I + H2O
3 2 2 2
heat
acetone
(ii) CH3 CH2 CH2 CH2 Cl + NaI CH3CH2CH2CH2I + NaCl
heat
peroxide
(iii) CH3 CH2 CH CH2 + HBr CH3 CH2 CH2 CH2 Br CH3 CH2 CH2 CH2 I
NaI
44. Write equations for the steps in SN1 mechanism for the conversion of tertiary butyl alcohol. (or) Explain
the mechanism of SN1 reaction taking 2-Bromo-2-methyl propane (t-butylbromide)
[March 2015, 2016, 2020, July 2014, 2018, June 2019]
Solution
Step 1: Heterolytic fission of C−Br bond to form carbocation.
CH3 H3 C CH3
slow
CH3 C Br C+ + Br −
∆
CH3 CH3
tert-butyl bromide tert-butyl carbocation
Step 2: Attack of nucleophile on the carbocation.
CH3 CH3
fast
CH3 C+ + OH− CH3 C OH
nucleophile
CH3 CH3
tert-butyl bromide tert-butyl alcohol
[2-Bromo-2-methylpropane] [2-Methylpropan-2-ol]
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45. Mention the factors that favour SN1 and SN2 mechanisms.
Solution
SN1 mechanism SN2 mechanism
• Favoured by low concentration of the • Favoured by high concentration
nucleophilic reagent of the nucleophilic reagent
• Favoured by polar solvents • Favoured by non-polar solvents
• Weak nucleophile favours SN1 • Strong nucleophile favours SN2
46. An alkyl halide C4H9Br(A) is treated with alcoholic KOH to give compound B, which is treated with
HBr to give (C), which is an isomer of A. (A) is reacted with Na in dry ether to give the compound
C8H18(D), which is different from the compound obtained from n-butyl bromide is reacted with Na in dry
ether. Identify the compound (A) and write all the reactions.
Solution
Compound A is CH3 CH CH2 Br (isobutyl bromide)
CH3
CH3
alcoholic KOH
CH3 CH CH2 Br HBr
CH3 C CH2 CH3 C CH3
KBr, H2O
CH3 CH3 Br
(A) (B) (C)
2Na/dry ether
2 CH3 CH CH2 Br CH3 CH CH2 CH2 CH CH3
heat
CH3 NaBr CH3 CH3
(A)
47. Identify the products A, B and C in the following equation: [March 2015]
red P NaI C6 H5 I
CH 3OH  Cl2
→ A 
dry acetone
→ B →
Na and dry ether
C
Solution
CH3
red P NaI CHI

6 5
CH3OH CH3Cl dry
CH3I
Cl2 Na and
A acetone B dry ether
C
A=CH3Cl B=CH3I C=C6H5CH3
Unit II Haloarenes
1. Name the product of the reaction between benzene and bromine in the presence of FeBr3 catalyst.
Solution
Bromobenzene
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2. Name the organic compound formed when chlorobenzene is treated with sodium in dry ether.
[March 2015, 2017]
Solution
Diphenyl or Biphenyl
Cl
3. Write the IUPAC name of . [July 2016]
CH3
Solution
1-Chloro-2-methylbenzene
4. In arylhalides, what is the hybridization of carbon atom to which halogen is attached? [July 2018]
Solution
The hybridization of carbon atom to which halogen is attached in aryl halides is sp2
5. Explain Sandmeyers reaction.
Solution
When benzene diazonium chloride is heated with cuprous chloride and conc. HCl or cuprous bromide
and conc.HBr forms halobenzene. This reaction is called Sandmeyers reaction.
N2Cl Cl
Cu2Cl2 / conc.HCl
+ N2
heat
Chlorobenzene
6. Write the preparation of iodobenzene from benzenediazonium chloride.

Solution
Iodobenzene is prepared by shaking benzenediazonium chloride with potassium iodide solution.
N2Cl I
+ KI + N2 + KCl
Benzenediazonium Iodobenzene
chloride
7. How do you convert chlorobenzene to phenol?
Solution
When chlorobenzene is heated with aqueous solution of NaOH under pressure −Cl atom is replaced by
−OH group only to form phenol.
Cl OH
+ NaOH 623 K, 300 atm + NaCl
aqueous
Phenol
8. The dipole moment of chlorobenzene is lower than that of chloroethane. Why?

Solution
The C−Cl bond in chlorobenzene is shorter and less polar than that in chloroethane due to resonance
effect.
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9. p-Dichlorobenzene has higher melting point than those of ortho and meta isomers. Give reason.
[July 2016]
Solution
p-Dichlorobenzene has higher melting point than ortho and meta isomers due to higher symmetry.
10. Aryl halides are less reactive than alkyl halides towards nucleophilic substitution reaction. Explain based
on resonance effect. (or)
Haloarenes are less reactive towards nucleophilic substitution reactions than haloalkanes. Give reasons.
[March 2014, March 2017]
Solution
Resonance effect
The lone pair of electrons on halogen atoms are in conjugation with π-electrons of the ring. Due to
resonance, the C−X bond acquires partial double bond character. As a result the C−X bond is relatively
strong and hence the bond cleavage is difficult.
.. + .. + .. + .. ..
:X : X: X: X: :X:
−
−
Hybridised state of carbon atom

In haloalkanes, the halogen atom is bonded to sp3 hybridised carbon atom, while in haloarenes it is
bonded to sp2 hybridised carbon atom.
sp2 hybridised carbon atom is more electronegative than sp3 hybridised carbon atom. Hence sp2
hybridised carbon pulls the bonding pair of electrons in C–X bond. Hence the C−X bond is shorter and
stronger in haloarenes than in haloalkanes.
Polarity of C−X bond
The C−X bond in haloarenes is less polar than that in haloalkanes. This is due to resonance effect in
haloarenes.
Repulsive interaction
The nucleophile being electron rich gets repelled by delocalised electron density in the benzene ring.
Instability of carbocation
Due to the strong C−X bond in haloarenes, the self ionisation to form phenyl carbocation is not possible.
Even if it is formed, it cannot be stabilised by resonance.
11. Explain the following electrophilic substitution reactions of chlorobenzene:
(i) Chlorination (ii) Nitration (iii) Sulphonation
(iv) Friedel - Crafts methylation (v) Friedel - Crafts acetylation [June 2019]
Solution
(i) Chlorobenzene reacts with Cl2 in the presence of Fe or FeCl3 to form a mixture of
1,2-dichlorobenzene and 1,4-dichlorobenzene.
23
2PBBBCCM7AS
Cl Cl Cl
1
1
anh. FeCl3 Cl 2
+ 2Cl2 2 + + 2HCl
2 3
4
Cl
1,2-Dichlorobenzene 1,4-Dichlorobenzene
or or
o-Dichlorobenzene p-Dichlorobenzene
(minor) (major)
(ii) Chlorobenzene reacts with nitrating mixture on heating to form a mixture of

ortho-nitrochlorobenzene and para-nitrochlorobenzene.
Cl Cl Cl
1 1
conc.H2SO4 NO2 2
2 + 2HO.NO2 2 + + 2H2O
heat 3
(conc.HNO3) 4
NO2
Chloro 2 nitrobenzene Chloro 4 nitrobenzene
(o-Chloronitrobenzene) (p-Chloronitrobenzene)
(minor) (major)
(iii) Chlorobenzene reacts with fuming sulphuric acid, on heating to form a mixture of 2-chlorobenzene
sulphonic acid and 4-chlorobenzene sulphonic acid.
Cl Cl Cl
4
2
heat SO3H 3
2 + HO.SO3H 1 + + 2H2O
(fuming H2SO4) 2
1
SO3H
2-Chlorobenzene 4-Chlorobenzene
sulphonic acid sulphonic acid
(minor) (major)
(iv) Chlorobenzene reacts with methyl chloride in the presence of anhydrous AlCl3 catalyst to form a
mixture of 2-chlorotoluene and 4-chlorotoluene.
Cl Cl Cl
2 4
anhydrous AlCl3 CH3 3
2 + CH3Cl 1 + + 2HCl
2
1
CH3
2-Chlorotoluene 4-Chlorotoluene
(v) Chlorobenzene reacts with acethyl chloride in the presence of anhydrous AlCl3 catalyst to form a
mixture of 2-methylacetophenone and 4-methyl acetophenone.
Cl Cl O Cl
O 2 4
anhydrous AlCl3 C CH3 3
2 + 2CH3 C Cl 1
+ + 2HCl
2
1
C
O CH3
2-Chloroacetophenone 4-Chloroacetophenone
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12. Explain Wurtz-Fittig reaction with an example. [March 2016]

Solution
A mixture of an alkyl halide and aryl halide reacts with sodium in dry ether to form an alkylbenzene.
This is called Wurtz-Fittig reaction.
Cl CH3
+ CH3 Cl + 2Na dry ether + 2NaCl
heat
Toluene
13. What is Fittig reaction? Give an example.

Solution
Chlorobenzene reacts with sodium in dry ether on heating to form biphenyl. This is called Fittig reaction.
dry ether
Cl + 2Na + Cl + 2NaCl
heat
Biphenyl

14. Explain the influence of halogen atom in aryl halides towards electrophilic substitution reactions.
Solution
Aryl halides undergo usual electrophilic substitution reactions, but less reactive than benzene. This is
because, the electron withdrawing inductive effect (−I effect) of the halogen atom decreases the electron
density on the benzene ring. In other words, the benzene ring is deactivated. As a result, the electrophilic
substitution reactions take place not only slowly but also under drastic conditions as compared to
benzene.
Unit III Polyhalogen compounds

1. What are polyhalogen compounds?
Solution
Organic compounds containing two or more halogen atoms are called polyhalogen compounds.
2. What are Freons? [July 2014]
Solution
Chloroflorocarbon compounds of methane and ethane are called Freons.
3. Name the poisonous gas formed when chloroform is oxidised? [August 2020]
Solution
Phosgene or COCl2
4. Mention any two applications of each of the following polyhalogen compounds:
(i) Dichloromethane (ii) Chloroform (iii) Carbon tetrachloride
(iv) Iodoform (v) Freons
Solution
(i) Dichloromethane:
(a) As a solvent in paint remover, in the manufacture of drugs, metal cleaning and finishing
(b) As a propellant in aerosols
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2PBBBCCM7AS
(ii) Chloroform:
(a) As a solvent for fats, alkaloids, iodine (b) In the production of freon refrigerant
(iii) Carbon tetrachloride:
(a) In the manufacture of refrigerants, propellants for aerosol cans and chloroform
(b) As an industrial solvent
(iv) Iodoform:
(a) As an antiseptic for dressing wounds (b) In the pharmaceuticals
(v) Freons:
Refrigeration, air conditioning units, propellants for aerosol
5. Mention the harmful effects of
(i) Dichloromethane (ii) Chloroform (iii) Carbon tetrachloride (iv) Freons (v) DDT
Solution
(i) Dichloromethane:
(a) Harms the central nervous system
Exposure to methylene chloride in lower levels in air causes slight impairment of hearing and
vision.
(b) Higher levels of methylene chloride in air cause dizziness, nausea, tingling and numbness in
fingers and toes.
(ii) Chloroform:
(a) Harms the central nervous system
(b) Exposure to methylene chloride in lower levels in air can lead to slightly impaired hearing and
vision. Higher levels of methylene chloride in air cause dizziness, nausea, tingling and numbness
in fingers and toes.
(iii) Carbon tetrachloride:
(a) Inhalation of chloroform vapours depresses the central nervous system, causes dizziness, fatigue
and headache.
(b) Damages liver and kidneys
(iv) Freons :
Depletes the ozone layer
(v) DDT:
Not metabolised in animals and gets deposited in fatty tissues and is highly toxic
6. What is the structure of DDT?
Solution
Cl
Cl C CH Cl
Cl
Cl
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11. Alcohols, Phenols and Ethers

Exercise
Unit I Alcohols
1. Write the IUPAC names of the following compounds:
CH2OH CH2OH
(i) CH3 CH2 CH CH CH CH3 (ii) CH3 CH CH2 CH CH CH3
CH2Cl CH3 CH3 OH
(iv) CH3 C C CH2OH
CH3 Br
(iii) H3C CH CH CH2 CH2 CH3
OH
OH
(v)
Br
Solution
1 1
CH2OH CH2OH
5 4 3 2 6 5 2 4 3
(i) CH3 CH2 CH CH CH CH3 (ii) CH3 CH CH2 CH CH CH3
CH2Cl CH3 CH3 OH
3-Cholromethyl-2-isopropylpentan-1-ol 2, 5-Dimethylhexane-1, 3-diol
1 2 3 4 5 6 4 3 2 1
(ii) H2C CH CH CH2 CH2 CH3 (iv) CH3 C C CH2 OH
OH CH3 Br
Hex-1-en-3-ol
2-Bromo-3-methylhex-2-en-1-ol
OH
1
2
(v) 3
Br
3-Bromocyclohexanol
2. Write the IUPAC names of the following compounds and classify them as secondary, dihydric and
trihydric alcohols:
CH3
(i) CH3 CH CH C CH3 (ii) CH3 CH CH2 CH CH CH2 CH3
CH3 OH CH3 OH OH C2H5
(iii) CH3 CH CH CH3 (iv) CH2 CH CH2

OH OH OH OH OH
Solution
(i) 2,2,4-Trimethylpentan-3-ol : secondary alcohol
(ii) 5-Ethylheptane-2,4-diol : dihydric alcohol
(iii) Butane-2,3-diol : dihydric alcohol
(iv) Propane-1,2,3-triol : trihydric alcohol
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3. Write structures of the following compounds:

(i) 2-Methylbutan-2-ol (ii) 1-Phenylpropan-2-ol
(iii) 3, 5-Dimethylhexane-1, 3, 5-triol (iv) Cyclohexylmethanol
(v) 3-Cyclohexylpentan-3-ol (vi) Cyclopent-3-en-1-ol
(vii) 3-Chloromethylpentan-1-ol
Solution
CH3
CH3 C CH2CH3 CH2 CH CH3
(i) (ii)
OH OH
OH OH
(iii) HOCH2 CH2 C CH2 C CH3 (iv) CH2OH

CH3 CH3
OH
CH3 CH2 C CH2CH3 OH
(v) (vi)
CH3 CH2 CH CH2 CH2OH

(vii)
CH2Cl
4. (a) Classify the following into primary, secondary and tertiary alcohols:
CH3
(i) CH3 C CH2OH (ii) H2C = CH − CH2OH (iii) CH3 − CH2 − CH2OH
CH3
HO CH CH3 CH3
CH2 CH CH3 CH CH C OH
(iv) (v) OH
(vi)
CH3
(b) Identify allylic alcohol in the above examples.

Solution
(a) (i) Primary alcohol (ii) Primary alcohol
(iii) Primary alcohol (iv) Secondary alcohol
(v) Secondary alcohol (vi) Tertiary alcohol
(b) Allylic alcohols : (ii) and (vi)
5. Mention the product formed when acetone is heated with LiAlH4.
Solution
Isopropyl alcohol or propan-2-ol
6. What happens when ethyl ethanoate is heated with LiAlH4 in ether?
Solution
Ethyl ethanoate gets reduced to ethanol.
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2PBBBCCM7AS
7. Name the product formed by the reaction of tert-butyl alcohol with aluminium.
Solution
Aluminium tertiary butoxide CH3
8. What is the order of acidic strength of CH3CH2OH, CH3 CH CH3 and CH3 C CH3 ?
OH OH
Solution
CH3
CH3CH2OH > CH3 CH CH3 > CH3 C CH3
OH OH
9. What happens if propan-2-ol is heated with HBr?
Solution
2-Bromopropane
10. What is the order of reactivity of hydrogen halides towards alcohols?
Solution
HI > HBr > HCl > HF
11. What is Lucas reagent? [July 2016]
Solution
Mixture of conc. HCl and anhydrous ZnCl2
12. Write the general equation for the reaction of primary alcohol with SOCl2. [July 2016]
Solution
pyridine
Example: ROH + Cl.SO.Cl RCl + SO2 + HCl
(SOCl2)
13. What is molasses?

Solution
Molasses is a dark brown syrupy liquid left over after crystallisation of sugar from sugarcane juice.
14. What is rectified spirit?
Solution
95.5% ethanol
15. What is denatured alcohol?
Solution
Ethanol mixed with methanol and little pyridine and some copper sulphate to make it unfit for drinking
is called denatured alcohol.
29
2PBBBCCM7AS

16. (a) Draw the structures of all isomeric alcohols of molecular formula C5H12O and write their IUPAC
names.
(b) Classify the isomers of alcohols as primary, secondary and tertiary alcohols.
Solution
Isomeric alcohols IUPAC name Classification
CH3CH2CH2CH2CH2OH Pentan-1-ol Primary
CH3CH2CHCH2OH
2-Methylbutan-1-ol Primary
CH3
CH3 CHCH2CH2OH
3-Methylbutan-1-ol Primary
CH3
CH3
CH3 C CH2OH 2, 2-Dimethylpropan-l-ol Primary
CH3
CH3CH2CH2 CHCH3
Pentan-2-ol Secondary
OH
CH3CH2 CHCH2CH3
Pentan-3-ol Secondary
OH
CH3 CH CHCH3
3-Methylbutan-2-ol Secondary
CH3 OH
CH3
CH3CH2 C OH 2-Methylbutan-2-ol Tertiary
CH3
17. Show how would you synthesize the following alcohols from appropriate alkenes?
CH3
(i) OH (iii) (iii) (iv) OH
Solution
The alkenes for synthesising the alcohols can be predicted by first dehydrating the alcohol to give single
alkene or a mixture of alkenes. If a mixture of alkenes is possible, then find out which alkene gives the
desired alcohol. It must be remembered that acid catalysed addition of H2O to alkenes occurs in
accordance with Markovnikov’s rule.
CH3 CH3 CH3
− H2 O
(i) OH +
Dehydration
1-Methylcyclohexan-1-ol 1-Methylcyclohexene 1-Methylcyclohexene
The desired alcohol can be obtained by addition of H2O to either of these,
30
2PBBBCCM7AS
CH3 H+ CH3 H+ CH3
1-Methyl .. Methylene
cyclohexene H2O : cyclohexane
CH3 CH3
+ H+
OH OH
1-Methylcyclohexan-1-ol
OH −H2O
(ii)
4-Methylheptan-4-ol 4-Methyl heptan-3-ene
Addition of water in the presence of an acid gives the desired alcohol.

H+, H2O OH
4-Methylheptan-3-ene 4-Methylheptan-3-ol
OH
−H2O
(iii) +
Pentan-2-ol Pent-1-ene Pent-2-ene
Addition of H2O to pent-1-ene gives two desired alcohol.

Addition of H2O to pent-1-ene gives two products.
OH
H + , H2 O
Pent-1-ene Pentan-2-ol
However, pent-2-ene will give two products.

OH
H+ , H2 O
+ OH
Pent-2-ene Pentan-2-ol Pentan-3-ol
Thus, the desired alkene is pent-1-ene and not pent-2-ene.
−H2O
(iv) OH + +
2-Cyclohexyl 2-Cyclohexyl 2-Cyclohexylidene 2-Cyclohexyl 2-Cyclohexyl

butan-2-ol but-2-ene butane but-1-ene but-1-ene
Addition of H2O to either of these alkenes gives the desired alcohol.

+
H+ H+
2-Cyclohexyl .. 2-Cyclohexylidene 2-Cyclohexyl

−H+ H2O:
but-2-ene butane but-1-ene
OH
2-Cyclohexylbutan-2-ol
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2PBBBCCM7AS
18. Show how will you synthesize

(i) 1-phenylethanol from a suitable alkene
(ii) cyclohexylmethanol using an alkyl halide by an SN2 reaction
(iii) pentan-1-ol using a suitable alkyl halide
Solution
CH CH2 CH CH3
(i) dil. H2SO4
+ HOH OH
Markovnikov's
addition
Ethenyl benzene 1-Phenylethanol
CH2Br CH2OH
∆
(ii) + NaOH + NaBr
SN2 hydrolysis
Cyclohexylmethyl Cyclohexylmethanol
bromide
∆
(iii) CH 3CH 2CH 2CH 2CH 2 Br + NaOH 
SN 2 hydrolysis
→ CH 3CH 2CH 2CH 2OH + NaBr
1− Bromopentane Pen tan −1− ol
19. What is meant by hydroboration-oxidation reaction? Illustrate it with an example.

Solution
Diborane adds on to propene to form tri n-propylborane which upon their oxidation with alkaline
hydrogen peroxide forms n-propyl alcohols is called hydroboration-oxidation reaction.
(BH3)2 OH− , H2O2
Example: 3CH3CH CH2 THF
(CH3CH2CH2)3 B 3CH3CH2CH2OH + B(OH)3
Propene Tri-n-propylborane Propan-1-ol Boric acid
20. How are the following conversions carried out?

(i) Propane to Propan-2-ol
(ii) Benzyl chloride to Benzyl alcohol
(iii) Ethyl magnesium chloride to Propan-1-ol
(iv) Methyl magnesium bromide to 2-Methylpropan-2-ol
Solution
Conc. H2SO4 H2O
(i) CH3 CH CH2 CH3 CH CH3 CH3 CH CH3
Propene Boil
OSO3H OH
Propan-2-ol
CH2OH
CH2Cl
Hydrolysis
(ii) + NaOH (aq) + NaCl
Benzyl alcohol
Benzyl chloride
H δ+ H O MgCl
δ− δ −δ + H+ , H2 O
(iii) C O + CH3CH2MgCl C CH3CH2CH2OH
−Mg(OH)Cl
H H CH2CH3
Propan-1-ol
Methanal
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2PBBBCCM7AS
CH3 CH3 O MgBr CH3 OH

H+, H2O
(iv) C O + CH3MgCl C C
−Mg(OH)Br
CH3 CH3 CH3 CH3 CH3
Propanone 2-Methylpropan-2-ol
21. Show how the following alcohols can be prepared by the action of suitable Grignard reagent on
methanol?
CH2OH
(i) CH3 CH CH2OH (ii)

CH3
Solution
(i) The structure of alcohol suggest that the Grignard reagent that reacts with methanal is isopropyl
magnesium halide.
O OMgBr
Dry ether H2O / H+
H C + (CH3)2 CHMgBr H C CH(CH3)2
Mg(Br)OH
H H
Methanal Isopropyl magnesium Addition compound

bromide
OH OH CH3
H C CH(CH3)2 or CH2 CH CH3
H
2-Methylpropan-1-ol
(Isobutyl alcohol)
(ii) The structure of alcohol suggest that the Grignard reagent that reacts with methanal is cyclohexyl
magnesium halide
O OMgBr OH
H2O / H+
H C + MgBr H C H2C
Mg(Br)OH
H H
Methanal Cyclohexyl magnesium Addition compound Cyclohexylmethanol
bromide
22. Write the structures of the products of the following reactions:

+
H 2 O/H
(i) CH 3 − CH = CH 2  →
O
CH2 C OCH3 NaBH4
(ii) O
(iii) CH3 CH2 CH CHO NaBH4

CH3
33
2PBBBCCM7AS
Solution
(i) CH3 CH CH3
OH
(ii) NaBH4 being a weak reducing agent reduces only the ketonic group to secondary alcoholic group.
However, it does not affect ester group.
O OH
2 1
CH2 C OCH3 NaBH4 CH2 C OCH3
O (Reduction) O
(iii) NaBH4 reduces aldehydic group to a primary alcoholic group.

4 3 2 1 NaBH4 4 3 2 1
CH3 CH2 CH CHO CH3 CH2 CH CH2 OH
(Reduction)
CH3 CH3
2-Methylbutanal 2-Methylbutan-1-ol
23. Alcohols have higher boiling points compared to hydrocarbons of comparable molar mass. Explain.
Solution
This is due to association of alcohol molecules through hydrogen bonding.
H O H O H O H O
R R R R
24. Explain why propanol has higher boiling point than butane?
Solution
The molecules of propanol are held together by intermolecular hydrogen bonding while butane
molecules have only weak van der Waal’s forces of attraction. Since hydrogen bonds are stronger than
van der Waals forces, propanol has higher boiling point than butane.
δ+ δ δ+ δ δ+ δ
H O .........................H O................... H O ..............
CH2CH2CH3 CH2CH2CH3 CH2CH2CH3
25. The lower members of alcohols are more soluble in water than higher alcohols. Why?
Solution
The lower alcohols are completely soluble in water due to the association of the −OH group in alcohol
and H2O molecules through hydrogen bonding. In higher alcohols, as the length of the carbon chain
increases, hydrophobic nature increases and solubility decreases.
26. Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses.
Explain this fact.
Solution
Alcohols can form hydrogen bonds with water and break the hydrogen bonds existing between water
molecules. Hence, they are soluble in water.
δ δ+ δ δ+ δ
R O H O H O
δ+
H H R
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2PBBBCCM7AS
27. What is the effect of

(i) electron donating group on acidity of alcohols.
(ii) boiling point of alcohols on increasing number of carbon atoms. [July 2014]
Solution
(i) Electron releasing alkyl group (+I effect) increases the electron density around the oxygen atom,
polarity of the O−H bond decreases and acidic nature decreases.
(ii) The boiling point increases with increase in the number of carbon atoms due to increase is the
magnitude of van der Waal’s forces.
28. When 3-methylbutan-2-ol is treated with HBr following reaction takes place:
Br
HBr
CH3 CH CH CH3 CH3 C CH2 CH3
CH3 OH CH3
Write the mechanism for the reaction.

Solution
(i) Alcohol gets protonated
H+
CH3 CH CH CH3 CH3 CH CH CH3
CH3 OH CH3 OH2
+
(ii) Protonaed alcohol loses H2O molecule to form 2° carbocation

H2O +
CH3 CH CH CH3 CH3 CH CH CH3
+
CH3 OH2 CH3
2° Carbocation
(iii) 2° carbocation undergoes 1,2-hydride shift to form a gives more stable 3° carbocation
H
+ 1,2-hydride shift +
CH3 C CH CH3 CH3 C CH2 CH3
H CH3
2° - Carbocation 3° - Carbocation
(iv) Nucleophilic attack by Br− ion gives alkyl halide

Br
+ Br −
CH3 C CH2 CH3 CH3 C CH2 CH3
CH3 CH3
2-Bromo-2-methylbutane
29. Complete the following equations:

Cu
(i) R − CH 2 − OH 
573 K
→
+
H
(ii) CH 3 − CH = CH 2 + H 2 O ↽ ⇀ [March 2014, July 2015]
35
2PBBBCCM7AS
Solution
H
Cu H+
(i) R CH2 OH R C O + H2 (ii) CH3 CH CH2 + H2O CH3 CH CH3
573 K
OH
30. Write the equation of the following reactions:
Oxidation of propan-1-ol with alkaline KMnO4 solution
Solution
alk KMnO4
CH 3CH 2CH 2OH  Oxidation
→ CH 3CH 2COOH
Pr opan −1− ol Pr opanoic acid
H 2O/H+ CrO3
31. Identify ‘A’ and ‘B’ in the following equation: CH 3 − CH = CH 2 → A → B . [July 2016]
Solution
(A) Propan-2-ol (B) Acetone (propanone)
32. Name the reagents used in the following reaction:
(i) Oxidation of a primary alcohol to carboxylic acid
(ii) Oxidation of a primary alcohol to aldehydes
(iii) Benzyl alcohol to benzoic acid
(iv) Dehydration of propan-2-ol to propene
(v) Butan-2-one to butan-2-ol
Solution
(i) Acidified K2Cr2O7 or KMnO4
(ii) Pyridinium chlorochromate (PCC) in CH2Cl2 or pyridinium dichromate (PDC) in CH2Cl2
(iii) Acidified or alkaline KMnO4 followed by hydrolysis with dil. H2SO4
(iv) Conc. H2SO4 at 443 K
(v) NaBH4 or Ni/H2
33. Name the product formed when phenol is treated with acidified solution of Na2Cr2O7. Give equation.
[March 2015]
Solution
OH O
Na2Cr2O7 + H2SO4
+ 2 [O] + H2O
O
Benzoquinone
34. How is ethanol manufactured from molasses?

Solution
Ethanol is manufactured by the fermentation of molasses. Molasses is a dark brown syrupy liquid left
over after crystallization of sugar from sugar cane juice. It contains 30% - 50% sugar. The dilute solution
of molasses is treated with yeast and allowed to ferment for about 3 days. The enzyme invertase present
in yeast cell hydrolyses sucrose to glucose and fructose.
invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose glucose fructose
36
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The enzyme zymase present in yeast converts glucose and fructose in to ethanol and carbon dioxide.
zymase
C6H12O6 2 C2H5OH + 2CO2
Ethanol

35. Distinguish primary, secondary and tertiary alcohols with Lucas reagent.
Solution
Mixture of concentrated hydrochloric acid and anhydrous ZnCl2 is called Lucas reagent
No turbidity at room temperature Primary alcohol

Given alcohol + Lucas reagent Turbidity appears after 5 minutes Secondary alcohol
Turbidity appears immediately Tertiary alcohol
36. Give the reaction of a primary alcohol with (i) PCl3, (ii) red phosphorus and bromine and (iii) PCl5
Solution
(i) Alcohols react with PCl3 to form respective alkyl chlorides and phosphorous acid.
heat
Example: 3CH 3CH 2 OH + PCl3  → 3CH 3CH 2 Cl + H 3 PO3
Ethanol chloroethane
(ii) Alcohols react with phosphorous tribromide and phosphorous triiodide to form alkyl bromides
and alkyl iodides respectively.
Red P + Br2
Examples: 3CH3CH2OH + PBr3 3CH3 CH2Br + H3PO3
heat
Ethanol Bromoethane
(iii) Alcohols react with PCl5 to give respective alkyl chlorides, phosphorous oxychloride and HCl.
Example: CH3CH2CH2OH + PCl5 CH3CH2CH2Cl + POCl3 + HCl
Propan-1-ol 1-Chloropropane
37. Write the mechanism of acid catalysed dehydration of ethanol to ethene.

[March 2015, 2017, July 2017, March 2018, July 2018, March 2019, June 2019]
Solution
Step 1: Alcohol gets protonated, in the presence of H+ ions
H H H H H
.. fast +
H C C ..O H + H+ H C C O H ..
H H H H
Protonated alcohol
Step 2: Loss of a molecule of water from protonated alcohol to form carbocation
H H H H H
+
slow +
H C C
H C C O H .. + H2O
H H H H
Carbocation
37
2PBBBCCM7AS
Step 3: Carbocation loses a proton to form the alkene

H H
H H
+ + H+
H C C C C
H H
H H
38. Explain the oxidation of primary and secondary alcohols with a suitable example.
Solution
A primary alcohol when heated with strong oxidizing agents such as acidified potassium dichromate,
acidified potassium permanganate etc. forms an aldehyde. The aldehyde undergoes further oxidation and
forms a carboxylic acid with same number of carbon atoms as that in parent alcohol.
H H OH
Example: K2Cr2O7 / H2SO4 [O]
CH3 C OH + [O] CH3 C O CH3 C O
heat
H − H2O
A secondary alcohol when heated with acidified K2Cr2O7 forms a ketone.

Example: CH 3 − CHOH − CH 3 + ( O )  → CH 3 − CO − CH 3 + H 2 O
39. Explain the oxidation of a tertiary alcohol with an example.

Solution
A tertiary alcohol when heated with strong oxidizing agent such as conc. HNO3 (or acidified KMnO4)
undergoes dehydration to form alkene. The alkene formed is oxidized to a ketone, which is finally
oxidized to carboxylic acid with less number of carbon atoms than the original alcohol.
CH3 CH3 CH3 OH
conc. HNO3 3[O] 4[O]
CH3 C OH CH3 C CH2 CH3 C O CH3 C O
heat − CO2 − CO2
CH3 −H2O −H2O
tert-Butyl alcohol Isobutylene Acetone Acetic acid
40. Explain the dehydrogenation of primary, secondary and tertiary alcohols with an example.
Solution
When the vapours of primary alcohol are passed over heated copper catalyst at 573 K, dehydrogenation
takes place forming respective aldehyde.
H H
Cu, 573K
Example: CH3 C OH CH3 C O + H2
H
Ethyl alcohol Acetaldehyde
When the vapours of a secondary alcohol are passed over heated copper catalyst at 573 K,
dehydrogenation takes place forming respective ketone.
Example: CH3 CH CH3 Cu, 573K CH3 C CH3 + H2

OH O
Isopropyl alcohol (2 o alcohol) Acetone
Under similar conditions, a tertiary alcohol undergoes dehydration to form an alkene.
38
2PBBBCCM7AS
Example: CH3 CH3

Cu, 573K
CH3 C OH CH3 C CH2 + H2O
CH3
tert-Butyl alcohol Isobutylene
Unit II Phenols
1. Write IUPAC names for the following:
CH3 CH3 CH3 CH3
OH OH
(i) (ii) (iii) (iv)
OH CH3
OH CH3
Solution
(i) 2-Methylphenol (ii) 4-Methylphenol
(iii) 2,5-Dimethylphenol (iv) 2,6-Dimethylphenol
2. Among alcohols and phenols, which one is more acidic? [March 2016, 2018, June 2019]
Solution
Phenols more acidic than alcohols.
3. Why o-nitrophenol is weaker acid than p-nitrophenol?
Solution
In o-nitrophenol, there is intramolecular H-bonding.
Therefore, the release of proton takes place less readily.
4. Arrange the following in the increasing order of their acidic strength:
OH OH OH
NO2 CH3
; ; ; CH3CH2 OH
Solution
OH OH OH
NO2 CH3
> > > CH3CH2 OH
5. Complete the reaction: [March 2014]

OH
∆
+ Zn
39
2PBBBCCM7AS
Solution
OH
∆
+ Zn
Phenol Benzene
6. Complete the following reaction: [July 2015]

OH
conc. HNO3
∆
Solution
OH
OH
O2N NO2
conc. HNO3
∆
NO2

7. Write the structure of the compound whose IUPAC name for 2, 3-Diethylphenol.
Solution
OH
CH2CH3
CH2CH3
8. Write the structures and IUPAC names of monohydric phenols of molecular formula, C7H8O.
Solution
Three isomers are possible
OH OH OH
CH3
CH3
CH3
2-Methylphenol 3-Methylphenol 4-Methylphenol
9. How is phenol obtained from chlorobenzene?

Solution
When chlorobenzene is fused with NaOH at 623 K under 320 atm pressure gives sodium phenate. This
on acidification with HCl gives phenol
Cl ONa OH
623K, 300 atm HCl
+ NaOH
HCl NaCl
Chlorobenzene Sodium phenate Phenol
40
2PBBBCCM7AS
10. Give the preparation of phenol from benzenesulphonic acid.

Solution
Benzenesulphonic acid is obtained by reaction between benzene and oleum. Benzenesulphonic acid is
fused with solid NaOH to get sodium phenate which on acidification with HCl gives phenol.
SO3H O Na OH
573 K, fuse HCl
+ 3NaOH
Na2SO3 NaCl
2H2O
Benzenesulphonic acid Sodium phenate Phenol
11. How is phenol prepared from benzenediazonium chloride?

Solution
Benzenediazonium chloride when warmed with dilute sulphuric acid forms phenol liberating nitrogen.
N2 Cl OH
dil. H2SO4
+ H2O + N2 + HCl
warm
Benzenediazonium chloride Phenol
12. (a) Write two reactions that show the acidic nature of phenol.
(b) Compare acidity of phenol with that of ethanol.
Solution
(a) Phenol reacts with sodium to give H2 gas
OH ONa
2 + 2Na 2 + H2
Sodium phenoxide
(b) Phenol dissolve in NaOH to give sodium phenoxide and water
OH ONa
+ NaOH + H2O
Sodium phenoxide
Phenol is more acidic than ethanol because of more resonance stabilized structures of phenoxide.
..
R OH R :O:
.. + H
+
The negative charge on alkoxide is intensified due to electron releasing +I effect.

13. What is the effect of electron withdrawing group on acidity of phenols? [July 2014]
Solution
The presence of electron withdrawing groups (−I effect) such as −NO2, −CN, −CHO, −COOH increases
the acidic strength of phenol. This is due to stabilisation of phenoxide ion due to delocalization of
negative charge.
14. Explain why is ortho nitrophenol more acidic than ortho methoxyphenol?
Solution
Due to strong −R and −I effect of −NO2 group, electron density in O − H bond decreases and hence the
loss of proton becomes easy.
41
2PBBBCCM7AS
.. +
O H :O H O H O−
+
O +
NO2 N
N
−
O− O Resonance
stabilized
−I effect decreases electron −R effect results in +ve charge on
density in the O−H bond and O atom and hence facilitates the
makes the release of proton easy release of a proton
Moreover, the o-nitrophenoxide formed after the loss of a proton is stabilized by resonance of alkyl
group.
So, phenols are more acidic than alcohols.
O O O
O− O− O
+ + +
N N −..
.. N
O− O− O−
−
O O O
O O O
N+ N+ −..
..
N+
O− O− O−
..−
..
Resonance stabilized
o-nitrophenoxide ions is stabilized by resonance and hence o-nitrophenol is a stronger acid. On the other
hand, due to +R effect of the − OCH3 group, the electron density on oxygen of the O − H bond increases
and this makes the loss of proton difficult.
O H O H
.. +
OCH
.. 3 .−. OCH
.. 3
Other structures
Futhermore, after the loss of proton o-methoxyphenoxide ion formed is destabilized by resonance.
.. ..
:O:− :O :−
.. +
OCH .−. OCH
.. 3 .. 3
\ Other structures
The two negative charges repel each other and therefore, destabilize the o-methoxyphenoxide ion. Thus,
o-nitrophenol is more acidic than o-methoxyphenol.
15. Explain acetylation of phenol.
Solution
Phenol reacts with acetyl chloride in the presence of pyridine in which the −H of the −OH group is
O
replaced by acetyl (CH3 C ) group to form the ester, phenyl acetate. This reaction is called
acetylation.
42
2PBBBCCM7AS
O
O H O O C CH3
pyridine
+ CH3 C Cl + HCl
Phenol Acetyl chloride Phenyl acetate
16. Write the reaction of phenol with bromine in CCl4.

Solution
Phenol reacts with bromine in CS2 at low temperature to form a mixture of o-bromophenol and
p-bromophenol.
OH OH OH
Br
CCl4
2 + 2Br2 + + 2HBr
Br
Phenol o-Bromophenol p-Bromophenol
17. Name the reagent used in the following reaction:

Bromination of phenol to 2, 4,6-tribromophenol
Solution
Br2 / H2O
18. How does phenol react with bromine water?
Solution
Phenol reacts with bromine water at room temperature to form a white precipitate of
2,4,6-tribromophenol. The reddish brown colour of bromine is discharged.
OH OH
Br Br
water
+ 3Br2 + 3HBr
Br
Phenol 2,4,6-Tribromophenol
19. While separating a mixture of ortho and para nitrophenols by steam distillation, name the isomer which
will be steam volatile. Give reasons.
Solution
p-Nitrophenol is steam volatile due to chelation because of intramolecular hydrogen bonding. On the
other hand, p-nitrophenol is not steam volatile because of intermolecular hydrogen bonding. Hence,
o-nitrophenol can be separated from p-nitrophenol by steam distillation.
O H +
+
+
.....H O N O H O N O
N O
O O
O
Intramolecular Intermolecular H-bonding
H-bonding
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20. Explain Reimer-Tiemann reaction. [July 2016, July 2019]

Solution
Phenol is heated with chloroform and NaOH solution. Sodium salt of salicylaldehyde is obtained, which
on acidification with HCl gives salicylaldehyde. This reaction is called Reimer-Tiemann reaction.
OH ONa ONa OH
CHCl3 + aq NaOH CHCl2 2 NaOH CHO HCl CHO
2 NaCl 2 NaCl NaCl

H2O H2O
Phenol Substituted Sodium salt of Salicylaldehyde

benzal Salicylaldehyde
chloride
21. Explain Kolbe reaction. [March 2014, 2015, 2017, July 2017, March 2019]
Solution
Sodium phenoxide reacts with CO2 under pressure on heating to form sodium salicylate. This on
acidification with HCl gives salicylic acid. This reaction is called Kolbe reaction.
ONa OH OH
COONa COOH
400 K / 6 - 7 atm HCl
+ CO2
NaCl
Sodium phenoxide Sodium salicylate Salicylic acid
22. Write equations of the following reactions:

(i) Bromine in CS2 with phenol
(ii) Treating phenol with chloroform in presence of aqueous NaOH
Solution
OH OH OH
Br2
+
(i) CS2
Phenol o-Bromophenol Br
(Minor) p-Bromophenol
(Major)
OH OH OH
CHO CHO
(ii) CHCl3, NaOH H+, H2O
343 K
(Reimer Tiemann
Phenol Salicylaldehyde
reaction)

(i) Kolbe’s reaction
(ii) Reimer-Tiemann reaction
Solution
(i) Kolbe’s reaction
When sodium phenoxide is heated with carbon dioxide at about 400 K and under to 7 atmospheric
pressure, sodium salicylate is formed as major product. This on acidification gives salicylic acid.
44
2PBBBCCM7AS
ONa OCOONa OH OH
400 K Rearrangement COONa dil HCl COOH
+ CO2
4−7 atm −NaCl
pressure
Sodium phenoxide Phenyl sodium Sodium salicylate 2-Hydroxy benzoic acid
carbonate (Salicylic acid)
(ii) Reimer-Tiemann reaction

When phenol is refluxed with chloroform in the presence of aqueous sodium hydroxide at 340 K
followed by hydrolysis, an aldehydic group (−CHO) gets introduced in the ring at a position ortho to
the phenolic group. Ortho hydroxyl benzaldehyde or salicyladehyde is formed as the product of the
reaction. This reaction is called Reimer-Tiemann reaction.
OH ONa
NaOH, 340 K CHCl2
+ CHCl3
−NaCl, −H2O
Chloroform −2NaCl 2NaOH
Phenol
ONa ONa ONa
CHO dil. HCl CHO −H2O CH(OH)2

−NaCl
(Unstable)
2-Hydroxy benzaldehyde
(Salicylaldehyde)

24. How is phenol manufactured from cumene? [March 2014, 2016]
Solution
Step 1: Cumene is heated with air. It gets oxidized to cumene hydroperoxide.
CH3 CH3
CH3 C H CH3 C O O H
+ O2
air
Cumene Cumene hydroperoxide
Step 2: Cumene hydroperoxide on acidification with dilute H2SO4 gives phenol and acetone.
CH3
CH3 C O O H OH
O
dil. H2SO4
+ CH3 C CH3
Cumene hydroperoxide Phenol Acetone
Acetone is a valuable byproduct of this process.
45
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25. Explain the nitration of phenol with (i) dilute nitric acid and (ii) conc. nitric acid and conc. H2SO4.
[July 2018, June 2019]
Solution
(i) With dilute nitric acid
Phenol undergoes nitration even with dilute nitric acid at low temperature (298 K) to form a mixture
of ortho-nitrophenol and para-nitrophenol.
OH OH OH
NO2
+ 2HNO3 + + 2H2O
NO2
Phenol O-Nitrophenol p-Nitrophenol
(ii) With concentrated nitric acid
Phenol on heating with conc. HNO3 acid gives 2,4,6-trinitrophenol (picric acid).
OH OH
O2 N NO2
+ 3HNO3 + 3H2O
heat
conc.
NO2
Phenol 2,4,6-Trinitrophenol
Unit III Ethers

1. Write the IUPAC names of the following ethers:
(i) CH3 CH CH2 O CH3 (ii) CH3 CH2 CH O CH2 CH3
CH3 CH3
O C 2 H5
(iii)
(iv) CH3OCH2CH2Cl (v) O2N − C6H4 − OCH3(p)

H3C CH3
(vi) CH3CH2CH2OCH3 (vii)
OC2H5
Solution
(i) 1-Methoxy-2-methylpropane
(ii) (ii) 2-Ethoxybutane
(iii) Ethoxybenzene
(iv) 2-Chloro-1-methoxyethane
(v) 4-Nitroanisole
(vi) 1-Methoxypropane
(vii) 4-Ethoxy-1, 1-dimethylcyclohexane
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2. Write the structures of

(i) 1-Ethoxypropane
(ii) 2-Ethoxy-3-methylpentane
Solution
(i) CH3−CH2−CH2−O−CH2−CH3
(ii) CH3 CH2 O CH2 CH CH2 CH3

CH3 CH3
3. Complete the reaction: [July 2015]
OCH3
+ HI
Solution
OCH3 OH
∆
+ HI + CH3I
Phenol and methyliodide are formed

4. Write the IUPAC name of major product formed in Friedel-Crafts acylation of anisole. [July 2015]
Solution
Methoxy acetophenone

5. Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method. Give
reason.
Solution
Acid catalysed dehydration of 1° alcohols to ethers takes place by SN2 reaction involving nucleophilic
attack by the alcohol molecule on the protonated alcohol molecule as
.. + SN2
CH3CH2CH2OH
. . + CH3CH2CH2 OH2 CH3CH2CH2 O CH2CH2CH3
−H+, −H2O
Protonated alcohol
However, under these conditions, 2° and 3° alcohols give alkenes rather than ethers. This is because of
the steric hindrance, nucleophilic attack by the alcohol on the protonated alcohol molecule does not take
place. Instead of this, the protonated 2° and 3° alcohols lose a molecule of water to form stable 2° and 3°
carbocations. These carbocations then lose a proton to form alkenes rather than undergoing nucleophilic
attack by alcohol molecule to form ethers.
47
2PBBBCCM7AS
H+ + +
CH3 CH OH CH3 CH OH2 CH3 CH
CH3 CH3 CH3
Propan-2-ol Protonated Isopropyl carbocation
(2° alcohol) (2° Carbocation)
CH3
CH3 CH3
CH3 CHOH + −H+
CH3 CH O CH CH3 CH3 CH CH3 CH CH2
2-Propoxy-2-propane −H+ CH3 Propene
Isopropyl
carbocation
Similarly, 3° alcohols give alkenes.

CH3 CH3 CH3 CH3
H+ + + −H+
CH3 C OH CH3 C OH2 CH3 C CH3 C CH2
−H+ −H2O
CH3 CH3 CH3 2-Methylprop-1-ene
tert-Bulyl
Carbocation
6. Explain Williamson’s synthesis with an example. Write the general equation.

[March 2014, July 2014, July 2015, July 2016, March 2019, June 2019]
Solution
An alkyl halide reacts with alcoholic solution of sodium alkoxide or phenoxide to form an ether. This
reaction is called Williamson’s ether synthesis. This reaction involves SN2 attack of an alkoxide ion on
primary alkyl halide.
heat
R X + R' O Na R O R' + NaX
Alkyl halide Sodium alkoxide Ether
(i) Williamson ether synthesis (ii) Unsymmetrical ether
Solution
(i) This is one of the best methods for preparing symmetrical and unsysmmetrical ethers in laboratory. In
this method an alkyl halide is treated with a suitable sodium alkoxide prepared by the action of
sodium on a suitable alcohol. The reaction involves nucleophilic substitution (SN2) attack of an
alkoxide ion on primary alkyl halide.
2R ′OH + 2Na  → 2R ′O − Na + + H 2
Sodium alkoxide
.. δ+ δ−
S N2
R′Ο − + R X R′ O R + X−
Alkoxide Alkyl halide Ether
(nucleophile)
∆
or R′ O− Na+ + X R R′ O R + NaX
Ether
(ii) If the alkyl or aryl groups attached to the O atom of the ethers are different, ethers are called
unsymmetrical ethers.
For example, CH 3OC2 H 5 CH 3OC6 H 5
Ethylmethyl ether Methylphenyl ether
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2PBBBCCM7AS
8. Write the reactions of Williamson’s synthesis of 2-ethoxy-3-methoxypentane starting from ethanol and
3-methylpentan-2-ol.
Solution
The product of Williamson’s synthesis is formed as a result of the following reaction:
5 4 3 2
CH3 CH2 CH CH ONa + BrCH2CH3 CH3 CH2 CH CH OCH2CH3 + NaBr
CH3 CH3 CH3 CH3

1
2-Ethoxy-3-methylpentane
9. How is anisole prepared?

Solution
Bromomethane reacts with alcoholic sodium phenoxide to form methoxybenzene (anisole).
O Na O CH3
+ CH3Br + NaBr
10. Which of the following is an appropriate set of reactants for the preparation of
1-methoxy-4-nitrobenzene and why?
Br ONa
(i) + CH3ONa (ii) + CH3Br
NO2 NO2
Solution
The second set of reactants is more appropriate to give the products. i.e., 1-methoxy-4-nitrobenzene. In
the first set, breakage of C–Br bond. It is difficult since the carbon atom is sp2 hybridised and the bond
has partial double bond character due to resonance. The product is formed as a result of Williamson’s
synthesis.
ONa OCH3
+ CH3Br + NaBr
NO2 NO2
4-Nitrosodiumphenoxide 1-Methoxy-4-nitrobenzene
11. Write the names of reagents and equations for the preparation of the following ethers by Williamson’s
synthesis:
(i) 1-Propoxypropane (ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane (iv) 1-methoxyethane
Solution
(i)
CH 3CH 2 CH 2 ONa + CH 3CH 2 CH 2 Br 
→ CH 3CH 2 CH 2 OCH 2 CH 2 CH 3 + NaBr
Sodium propoxide 1− Bromopropane 1− Propoxypropane
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2PBBBCCM7AS
(ii)
ONa OC2H5
+ C2H5Br + NaBr
Sodium phenoxide Ethoxybenzene

(iii)
CH3 CH3
CH3 C ONa + CH3Br CH3 C OCH3 + NaBr
CH3 CH3
Sodium 2-methyl- Bromomethane 2-Methyl-
2-propoxide 2-methoxypropane
(iv)
CH 3CH 2 ONa + CH Br
3 
→ CH 3OCH 2 CH 3 + NaBr
Sodium ethoxide Bromomethane 1− Methoxyethane
12. Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Solution
The boiling point of ethanol is higher than methoxymethane because of the presence of strong
intermolecular hydrogen bonding between ethanol molecules. Because of hydrogen bonding, energy has
to be supplied to overcome the forces of attraction between molecules and therefore, boiling point is
high.
δ− δ+ δ− δ+ δ−
H O H O H O
C2H5 C2H5 C2H5
However, no such hydrogen bonding exists in methoxymethane.

13. The boiling point of ethanol is higher than methoxymethane. Why?
Solution
Boiling point of ethanol is higher because of inter molecular hydrogen bonding in ethanol which is not
presenting in methoxymethane.
14. Give the reactions of HI with (i) ethoxyethane and (ii) methoxybenzene
Solution
(i) When ethoxyethane is heated with HI, ethanol and iodoethane are formed.
373 K
C2H5 O C2H5 + HI C2H5OH + C2H5I
(ii) When methoxybenzene is heated with HI phenol and alkyl halide are formed.
O CH3 373 K
OH
+ HI + CH3I
Methyl phenyl ether Phenol Methyl iodide
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2PBBBCCM7AS
15. Write the equation of the reaction of hydrogen iodide with

(i) 1-propoxypropane (ii) benzyl ethyl ether.
Solution
HI
(i) CH 3CH 2CH 2 − O − CH 2CH 2CH 3  373 K
→ CH 3CH 2CH 2OH + CH 3CH 2CH 2 I
1− Pr opoxypropane Phenol 1− Iodopropane
OCH3 OH
(ii) HI
+ CH3I
373 K
Methoxy benzene Phenol Iodomethane
CH2 O C2H5 CH2I
HI + C2H5OH
(iii) 373 K
Benzyl ethyl ether Benzyl iodide Ethanol
16. Write mechanism of the reaction of HI with methoxymethane.

Solution
Step 1 : Ether molecule gets protonated
H
.. +
CH3 O
.. CH3 + H I CH3 O CH3 + I−
fast
Dimethyl oxonium ion
Step 2 : The protonated ether undergoes SN2 attack by I− ion

H
− + SN2
I + CH3 O
.. CH3 CH3I + CH3OH
Slow
Methyl iodide Methanol
17. Explain the fact that in aryl alkyl ethers (i) the alkoxy group activates the benzene ring towards
electrophilie substitution and (ii) it directs the incoming substituents to ortho and para position in
benzene ring.
Solution
The alkoxy group increase the electron density on the benzene ring and therefore, activates the aromatic
ring towards electrophilic substitution reaction as given below
.. .. +
.. +
.. +
..
:OR :O R OR OR OR
.−. .
−.
..
−
(I) (II) (III) (IV) (V)
As is clear, structures III, IV and V show high electron density at ortho and para positions and therefore,
direct the incoming substituents to o- and p-position in the benzene ring.
18. Write the reactions of anisole with
(i) Br2 / acetic acid [March 2018, July 2018]
(ii) a mixture of conc. HNO3 and conc. H2SO4 (iii) CH3Cl / anhydrous AlCl3
(iv) CH3COCl / anhydrous AlCl3 [March 2017]
51
2PBBBCCM7AS
Solution OCH3 OCH3 OCH3

CH3COOH Br
(i) 2 + 2Br2 + + 2HBr
Br
OCH3 OCH3 OCH3
(ii) conc. H2SO4 NO2
2 + 2HNO3 + + 2H2O
heat
conc.
NO2
OCH3 O CH3 OCH3
Anhydrous AlCl3 CH3
(iii)
2 + 2 CH3Cl + + 2HCl
CH3
OCH3 OCH3 OCH3
2 4
Anhydrous AlCl3
CO CH3 3
(iv) 2 + 2CH3 CO Cl 1 + + 2HCl
2
1
CO CH3
19. Predict the products of the following reactions:
(i) CH 3 − CH 2 − CH 2 − O − CH 3 + HBr  →
OC2H5 OC2H5
Conc. H2SO4
(ii) + HBr (iii)
Conc. HNO3
(iv) (CH3)3C–OC2H5 + HI →
Solution
(i) CH3 CH2 CH2 OCH3 + HBr CH3 CH2 CH2 OH + CH3Br
1-Methoxypropane Propan-1-ol Methyl bromide
OC2H5 H
(ii) + HBr + C2H5Br
Ethoxybenzene Phenol Bromoethane
OC2H5 OC2H5
OC2H5 (H2SO4)
+ HNO3 NO2 +
(iii) Nitration
Ethoxybenzene NO2
o-Nitroethoxy p-Nitroethoxy
benzene benzene
CH3 (Minor) (Major)
CH3
.. ..
(iv) CH3 C O
.. C2H5 + HI CH3 C I + :O C2H5
CH3 CH3 H
Ethanol
tert-Buty ethyl ether tert-Butyl iodide
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2PBBBCCM7AS
12. Aldehydes, Ketones and Carboxylic Acids

Exercise
Unit I
1. Write the IUPAC name of the following compounds:
(i) CH3CH(CH3)CH2CH2CHO (ii) (CH3)2CHCH2CHO
(iii) CH3–CH=CH−CHO (iv) (CH3)3C CH2COCH3
(v) CH3CH2COCH(C2H5)CH2CH3
(vi) CH 2 = CH − CHO [July 2017]
(vii) CH3COCH2CH2CH3 [July 2018]
(viii) CH3CHO [July 2014]
O
(ix) CH3 C CH3 [September 2020]
(x) CH3CH2COCH(C2H5)CH2CH2C1
(xi) CH3COCH2COCH3
(xii) CH3CH(CH3)CH2C(CH3)2COCH3
(xiii) OHCC6H4CHO-p
Solution
(i) 4-Methylpentanal (ii) 3-Methylbutanal
(iii) But-2-enal (iv) 4, 4-Dimethylpentan-2-one
(v) 4-Ethylhexan-3-one (vi) Prop-2-enal
(vii) Pentan-2-one (viii) Ethanal
(ix) Propanone
(x) 6-Chloro-4-ethylhexan-3-one
(xi) Pentane-2, 4-dione
(xii) 3,3,5-Trimethylhexan-2-one
(xiii) Benzene-1,4-dicarbaldehyde
2. Write the structures of the following compounds:
(i) α-Methoxypropionaldehyde (ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentanecarbaldehyde (iv) 4-Oxopentanal
(v) Di-sec-butyl ketone (vi) 4-Fluoroacetophenone
(vii) 3-Methylbutanal
(viii) p-Nitropropiophenone
(ix) p-methylbenzaldehyde
(x) 4-Methylpent-3-en-2-one
(xi) 4-Chloropentan-2-one
(xii) p,p-Dihydroxybenzophenone
Solution
CHO
O 2 1
1
α 3 2 OH
(i) CH3CH C H (ii) CH3 CH CH2 C H (iii)
OCH3 OH O
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2PBBBCCM7AS
COCH3
1
5 4 3 2 1 2
(iv) CH3 C CH2CH2 C H (v) CH3 CH2 CH C CH CH2 CH3 (vi) 3
4
O O CH3 O CH3
F
4 3 2 1
(vii) CH3 CH CH2 CHO (viii) O2N COCH2CH3
CH3
1 2 3 4 5
(ix) CH3 CHO (x) H3 C C CH C CH3
O CH3
O Cl O
1 2 3 4 5
(xi) CH3 C CH2 CH CH3 (xii) HO C OH
3. Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also common
names.
(i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2CH(CH3)CHO
(iii) CH3(CH2)5CHO (iv) Ph–CH=CH–CHO
CHO
(v) (vi) PhCOPh
Solution
O Br
6 5 4 3 2 1
(i) CH3 C CH2 CH2 CH2 CH2 CH3 (ii) CH3CH2 CH CH2 CH CHO
Heptan-2-one
CH3
(Methyl n-pentyl ketone)
4-Bromo-2-methylhexanal
(γ-Bromo-α-methylcaproaldehyde)
(iii) CH 3 − CH 2 CH 2 CH 2 CH 2 CH 2 CHO (iv) C6H5CH CH CHO
Heptanal
3-Phenylprop-2-enal
(β-Phenyl acrolein)
CHO
(v) (vi) PhCOPh
Diphenyl methanone
Cyclopentanecarbaldehyde (Benzophenone)
(cyclopentane carbaldehyde)
4. Name the following reaction: [July 2015]

O O
C Cl H2 C H
Pd-BaSO4 + HCl
Solution
Rosenmund reduction
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2PBBBCCM7AS
5. Give the reaction of acetaldehyde with hydrogen cyanide. [July 2016]

Solution
O OH
CH3 C H + HCN CH3 C CH3
CN
Acetaldehyde Acetaldehyde cyanohydrin
6. Complete the following chemical reaction:

C O + NH2OH + H2O
[March 2014, 2016]
Solution
C N OH + H2O
oxime
7. Which oxidising agent is used in Etard reaction? [July 2015, March 2018]
Solution
Chromyl chloride or CrO2Cl2
8. Complete the reaction: [March 2014, 2017, June 2019]
CO, HCl
anhydrous
AlCl3 / HCl
(or)
CHO
CO, HCl
Anhyd AlCl3/CuCl
Name the above reaction.

Solution
CHO
CO, HCl
anhydrous
AlCl3 / HCl
Benzaldehyde
(or) Gatterman Koch reaction

9. Write the organic compound formed in the following equations: [July 2014]
anhydrous CH3
(i) + CH3COCl (ii) C O + NH2OH
AlCl3 CH3
Solution COCH3
H3C
(i) acetophenone or (ii) acetoxime or C N OH
H 3C
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2PBBBCCM7AS
10. Identify ‘A’ in the reaction: [June 2020]

Zn-Hg
C O A + H2O
HCl
Solution
A + is CH2
Hydrocarbon
11. Ethanal undergoes aldol condensation reaction. Give reaction. [March 2018]
Solution
Ethanal (CH3CHO) undergoes aldol condensation reaction due to the presence of α-H atom.
12. Acetaldehyde does not undergo Cannizzaro’s reaction. Why? [July 2015]
Solution
As it contains α- hydrogen atoms
13. Write equation for the reaction between formaldehyde and conc. KOH [March 2014]
Solution
(conc)
∆
2HCHO + KOH  → CH 3OH + HCOOK
14. Complete the reaction: [July 2017]
CHO HNO /H SO
3 2 4
273 - 283 K
Solution
CHO
CHO
conc. H2SO4
conc. HNO3 + H2O
283 K
NO2
4-Nitrobenzaldehyde

15. How would you prepare acetaldehyde from acetyl chloride? Name the reaction.
[March 2014, 2018, July 2015]
Solution
Acetyl chloride on reduction with H2 in presence of Pd-BaSO4 give acetaldehyde,
O O
Pd-BaSO4
CH3 C Cl + H2 CH3 C H
Name of the reaction: Rosenmund reaction
16. Aldehydes are generally more reactive than ketones towards nucleophilic addition reactions. Given two
reasons. [July 2016]
Solution
Aldehydes are more reactive towards nucleophilic addition than ketones due to
(1) electronic reason
(2) stearic reason
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17. Explain the mechanism of addition of HCN to a carbonyl group in presence of a base. [March 2016]
Solution
HCN + OH −  → H 2 O + CN −
O− OH
H+
C O + CN− C
C
CN CN
Carbonyl Nucleophile tetrahedral Addition
group intermediate product
18. What happens when carbonyl compounds are treated with hydrazine? Write the reaction. [March 2014]
Solution
Carbonyl compounds reacts with hydrazine to form respective hydrazone
C O + H2N NH2 C N NH2 + H2O
Carbonyl hydrazine Hydrazone

compound
(Or)
How does propanone reacts with hydrazine? Give reaction. [March 2018]
Solution
Propanone reacts with hydrazine to form propanone hydrazone.
H3C heat H3C
C O + H2N NH2 C N NH2 + H2O
H3C H3C
Hydrazine
Propanone Propanone hydrazone
19. Name the reagent used in the conversion of ketones to hydrocarbon. Name the reaction.
[March 2019, July 2015]
Solution
Zn-Hg/Conc. HCl, Clemmensen reduction
20. Explain Clemmensen reduction with an example. [March 2017]
Solution
Aldehydes and ketones react with zinc amalgam in conc. HCl to form respective hydrocarbon. This
reaction is called Clemmensen reduction.
Example :
O
Zn-Hg Conc. HCl
CH3 C H CH3 CH3
Ethanal Ethane
21. Explain the following reactions with an example:

(i) Aldol condensation [July 2014, June 2019]
(ii) Cross aldol condensation
(iii) Cannizzaro’s reaction [March 2017, July 2018, June 2019]
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2PBBBCCM7AS
Solution
(i) Aldehydes and ketones having alpha hydrogen when treated with dilute NaOH undergo self
condensation to form β-hydroxy compound which on heating give α, β-unsaturated aldehyde or
ketone. This reaction is called aldol condensation.
Example:
OH
NaOH ∆
CH3 C O + CH3 CHO CH3 C CH2 CHO CH3 CH CH CHO + H2O
H H
Ethanal α-hydrocy α, β-unsaturated
aldehyde aldehyde
(ii) Aldol condensation between two different aldehydes or two different ketones or an aldehyde and a
ketone is called cross aldol condensation.
O O
α
Example: CH3 C H + CH3 CH2 C H dil.NaOH
heat
Ethanal Propanal
H 3C CH CH CHO + CH3 CH2 CH C CHO

But-2-enal CH3
2-Methylpent-2-enal
self aldol products
O CH3 O
CH3 CH2 CH CH C H + CH3 CH C C H
Pent-2-enal 2-Methylbut-2-enal
cross aldol products

(iii) Aldehyde which does not have α- hydrogen when reacts with conc. NaOH undergo
disproportionation to form alcohol and sodium salt of carboxylic acid. The reaction is called as
Cannizzaro reaction.
Example:
∆
2C6H5 CHO + NaOH C6H5 CH2 OH + C6H5 COONa
Benzaldehyde conc Benzyl alcohol Sodium
benzoate
22. What is the action of dilute NaOH on ethanal (acetaldehyde) and name the reaction? [March 2016]
Solution
O OH
dil NaOH
CH3 C H + HCH2 CHO CH3 C CH2 CHO
H
β-hydroxy
Ethanal
aldehyde
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2PBBBCCM7AS
23. How does benzene reacts with acetyl chloride in presence of anhydrous AlCl3? Give equation.
Solution
Benzene react with acetyl chloride in the presence of anhydrous AlCl3 to form acetophenone.
O
C
anh AlCl3 CH3
+ CH3 C Cl + HCl
O
Benzene Acetyl Acetophenone
chloride
24. How does benzaldehyde react with acetophenone in presence of dilute alkali? [July 2016]
Solution
Benzaldehyde reacts with acetophenone in the presence of dilute alkali to form β-hydroxyketone which
upon heating forms benzalace to phenone (α, β-unsaturated ketone).
O O
C O + H2CH C 293 K
OH− CH CH C + H2O
H
Benzalacetophenone
25. Identify A and B in the following reaction: [March 2015]

CHO
2 + conc. NaOH A+B
Solution
A: Benzyl alcohol, B: Sodium benzoate

26. Write the structures of products of the following reactions:
O
C Anhyd.AlCl3
(i) + C2H5 Cl (ii) (C6 H 5CH 2 ) 2 Cd + 2CH 3COCl 
→
CS2
CH3
2+
Hg , H 2SO 4 1. CrO2Cl2
(iii) H 3C − C ≡ C − H  → (iv)
2. H3O+
O NO2
Solution
Anhyd. AlCl3 C
(i) + C2H6C Cl C2H5
CS2
O
Propiophenone
Dry ether
(ii) (C6H5CH2)Cd + 2CH3COCl 2CH3 C CH2C6H5 + 2HCl
O
1-Phenylpropanone
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2PBBBCCM7AS
Hg2+, H2SO4 Tautomerism

CH3 C CH + H2O CH3 C CH2 CH3 C CH3
(iii)
OH O
Propanone
OCrCl2OH
2CrO2Cl2 H2O+
(iv) NO2 CH3 NO2 CH NO2 CHO
CS2
OCrCl2OH
(Etard reaction) p-Nitrobenzaldehyde
27. Arrange the following compounds in the increasing order of their boiling points:
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Solution
The molecular mass of all these four compounds are comparable: CH3CHO(44), CH3CH2OH (46),
CH3COCH3(46), CH3CH2CH3(44). Among these CH3CH2OH undergoes extensive intermolecular
H-bonding and it exists as associated molecule and hence its boiling point is the highest (351 K).
CH3CHO is more polar than CH3OCH3 and therefore, dipole-dipole interactions are stronger in CH3CHO
than in CH3OCH3. Hence the boiling point of CH3CHO is higher than that of CH3OCH3. In CH3CH2CH3,
there are only weak van der Waal’s forces and hence its boiling point is the lowest. The order of boiling
points is CH3CH2CH3 < CH3OCH3 < CH3CHO < CH3CH2OH
28. Arrange the following compounds in increasing order of their reactivity towards nucleophilic addition
reactions:
(i) Ethanal, Propanal, Propanone, Butanone
(ii) Benzaldehyde, p-Tolualdhyde, p-Nitrobenzaldehyde, Acetophenone
Solution
(i) From ethanal to propanal, propanone and butanone, the +I inductive effect of alkyl group increases.
As a result, the positive charge on the carbon atom of the carbonyl group progressively decreases
and hence attack by nucleophile becomes slower and slower.
CH3 δ+ δ− CH3CH2 δ+ CH3 CH3 δ+
δ− δ−
C O C O C O C O
H H CH3 CH3CH2
Ethanal Propanal Propanone Butanone
Thus, the order of reactivity is butanone < propanone < propanal < ethanal
(ii) Among these compounds, acetophenone is a ketone while all others are aldehydes, therefore,
accetophenone is least reactive. In p-tolualdehyde, there is a methyl (CH3) group at the para position
w.r.t. the carbonyl group which decreases positive charge on carbonyl carbon group by
hyperconjugation effect, thereby making it less reactive than benzaldehye.
−
H O H+ O
H C C H H C C H , etc.
H H
On the other hand, in p-benzaldehyde, the −NO2 is an electron withdrawing group. By inductive and
resonance effect. Thereby increasing positive charge on carbonyl carbon. This facilitates the attack
of the nucleophile and hence makes it more reactive than benzaldehyde.
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O O
O + O− +
N C H N + C H , etc.
O −O
Therefore, the order of reactivity is

acetophenone < p-tolualdehyde < benzaldehyde < p-nitrobenzaldehyde.
29. Arrange the following compounds in decreasing order of their property as indicated:
Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards HCN)
Solution
The reactivity towards HCN addition decreases as +I effect of alkyl group (or groups) increases and /
or as steric hindrance to the nucleophilic attack by CN– at the carbonyl carbon increases.
Thus, the order of reactivity is:
CH3 O CH3 O CH3
CH3 CH3
C O > C O > CH3 C C CH3 > CH3 C C C CH3
H CH3
Acetone
Acetaldehyde CH3 CH3 CH3
tert-Butyl methyl ketone Di-tert-butyl ketone
30. Complete the following equation: [July 2018]

CONH2 H O +
(i) H3C C O
Zn Hg (ii) 3
conc. HCl ∆
H3C
NaOH + CaO
(iii) CH 3COONa →
∆
Solution
H3C Zn Hg CONH2 H O+ COOH
(i) C O CH3CH2CH3 + H2O (ii) 3
H3C conc. HCl ∆ + NH3
propane
Benzoic acid
NaOH + CaO
(iii) CH 3COONa →
∆
CH 4 ↑ + Na 2CO3
Sodium acetate Methane
31. (i) Complete the following equation:

1. alk. KMnO4
R CH2OH
2. H3O+
(ii) What is formalin solution? [June 2019]

Solution
[O], alk. KMnO4 H3O+
R CHO R COOK R COOH
(i)
Aldehyde Carboxylic acid
(ii) 40% solution of formaldehyde in water
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32. Write the name of the following reactions: [March 2020]

CH3 CHO
1. CrO2Cl2
(i)
2. H3O+
CHO
CO / HCl
(ii)
Anhyd AlCl3 / CuCl
Solution
(i) Etard reaction (ii) Gatterman-Koch reaction
33. Predict the products of the following reactions:
O H+
(i) + HO NH2
O2N
O
(ii) + NH2 NH NO2
O
H+
(iii) R CH CH CHO + NH2 C NH NH2
O
C CH3
H+
(iv) + CH3CH2NH2
Solution
O H+ NOH
(i) + HONH2
O2N
O2N
O N NH NO2
(ii) + NH2 NH NO2
(iii) R CH CH CH O + H2 N NHCONH2 R CH CH CH N NHCONH2 + H2O
CH3 CH3
C O C NCH2CH3
H+
(iv) + CH3CH2NH2
34. What is meant by the following terms? Give an example for each case.
(i) Cyanohydrin (ii) Acetal (iii) Semicarbazone (iv) Aldol
(v) Hemiacetal (vi) Oxime (vii) Ketal (viii) Imine
(ix) 2,4-DNP-derivative (x) Schiff’s base
Solution
(i) Compounds containing hydroxyl and cyano group on the same carbon atom are called
cyanohydrins.
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CH3 OH
Example: C
H CN
Acetaldehyde
cyanohydrin
(ii) Acetals are dialkoxy compounds in which two alkoxy groups are present on the terminal
carbon atom.
CH3 OCH2CH3
Example: C
H OCH2CH3
Acetaldehyde diethylacetal
(iii) Semicarbazones are the derivatives of aldehydes and ketones obtained by the action of
semicarbazide on them.
O
CH3
Example: C 5 NNHCNH2
CH3
Acetaldehyde semicarbazone
(iv) Aldols are hydroxyaldehydes or ketones which are produced by the condensation of two
molecules of aldehydes or ketones containing α-hydrogen atoms in the presence of a dilute
aqueous base.
OH H H
Example: CH C C C O
3
H H
3-Hydroxy butanal
(aldol)
(v) Gem-alkoxy alcohols are called hemiacetals.

CH3 OH
Example: C
H OCH3
1-Hydroxy-1-methoxy
methanal (Hemi acetal)
(vi) Oximes are formed when aldehydes or ketones react with hydroxyl amines.
CH3
Example: C NOH
H
Acetaldoxime
(vii) Gem-dialkoxy alkanes are called ketals. In these compounds, the two alkoxy groups are present on
the same carbon within the chain.
CH3 O CH2
Example: C + H2O
CH3 O CH2
Acetone ethylene ketal
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2PBBBCCM7AS
(viii) Imines are the compounds containing –CH=N−group and are produced when aldehyes and
ketones react with ammonia derivatives.
C O + H2 N Z C N Z + H2 O
Imines
Z = –NH, –OH, –NHC6H5, –NHNHCONH2, etc.

(ix) 2,4-Dinitrophenyl hydrazones are produced when aldehydes or ketones react with
2,4-dinitrophenyl hydrazine.
NO2
CH3
C NNH NO2
Example: CH
3
Acetone 2,4-dinitro
phenyl hydrazone
(x) Aldehydes and ketones react with primary aliphatic or aromatic amines to form
azomethines which are also called Schiff’s bases.
Example: CH 3CH = NCH 2 CH 3
Ethylidene ethanamine
C6 H 5 CH = NC6 H 5
Benzylideneaniline
35. Draw structures of the following derivatives:

(i) 2,4-dinitrophenylhydrazone of benzaldehyde (ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal (iv) semicarbazone of cyclobutanone
(v) ethylene ketal of hexan-3-one (vi) methyl hemiacetal of formaldehyde
Solution
NO2
(i) CH NNH NO2 (ii) NOH
CH3 OCH3 NNH CONH2

(iii) C (iv)
H OCH3
H3C CH2 C CH2CH2CH3

O O H OH
(v) (vi) C
CH2 CH2 H OCH3
36. Give plausible explanation for each of the following:

(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not
(ii) There are two –NH2 groups in semicarbazide. However, only one is involved in the formation of
semicarbazones
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2PBBBCCM7AS
Solution
(i) Cyclohexanone forms cyanohydrin in good yield.
O OH
HCN CN
Cyclohexanone Cyclohexanone
cyanohydrin
However, 2,2,6-trimethylcyclohexanone does not give cyanohydrin as

O
CH3 CH3
HCN No reaction
CH3
This is because of the presence of three methyl groups at O-positions with respect to carbonyl
group which hinder the nucleophilic attack of CN– group due to steric hindrance. However, there is
no such steric hindrance in cyclohexanone and therefore, the nucleophilic attack by CN ion occurs
readily to form cyanohydrin.
(ii) Semicarbazide has two –NH2 groups but one of these which is directly attached to C=O is
involved in resonance as shown below:
O O O
.. .. + .. .. +
H2N C NHNH2 H2N C NH NH2 H2N C NH NH2
As a result of resonance, electron density on NH2 group decreases and hence it does not act as a
nucleophile. In contrast, the lone pair of electrons on the NH2 group (i.e., attached to NH) is not
involved in resonance and is therefore, available for nucleophilic attack on the C=O group of the
aldehydes and ketones.
37. Predict the product formed when cyclohexanecarbaldehyde reacts with following reagents:
(i) PhMgBr and then H3O+ (ii) Tollen’s reagent
(iii) Semicarbazide and weak acid (iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid
Solution
OMgBr OH
CH O C C
PhMgBr H3O+ H
(i) H
Dry ether Ph Mg(OH)Br Ph
Cyclohexane Cyclohexylphenyl
carbaldehyde carbinol
CH O COO
(ii) + [Ag(NH3)2]+ + 3OH + 2Ag + 4NH3 + 2H2O
Tollen's reagent Silver mirror
Cyclohexane
carboxylate ion
O
CH O O CH NNHCNH2
(iii) weakly
+ H2NNH CNH2 Acidic + H2 O
Semicarbazide
Cyclohexanecarbaldehyde
semicarbazone
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OC2H5
CH O C
HOC2H6
(iv) + OC2H5
H
HOC2H5
Ethanol excess Cyclohexanecarbaldehyde
diethylacetal
CH O CH3
Zn/HgHCl
(v) Clemmensen
reduction
Methyl cyclohexane
38. Which of the following compounds would undergo aldol condensation, which the Cannizzaro reaction
and which neither? Write the structures of the expected products of aldol condensation and Cannizzaro
reaction.
(i) Methanal (ii) 2-Methylpentanal
(iii) Banzaldehyde (iv) 1-Phenylpropanone
(v) Cyclohexanone (vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde (viii) Butan-1-ol
(ix) 2,2-Dimethylbutanal
Solution
(ii) 2-Methylpentanal (v) 1-Cyclohexanone, (vi) 1-Phenylpropanone and (vii) phenylacetaldehyde
contain one or more α-hydrogen atom and therefore, undergo aldol condensation.
CH3 OH CH3
dil. NaOH 7 6 5 4 3 2
(ii) CH3CH2CH2 CH CHO + CHCH2CH2CH3 CH3CH2CH2 CH CH C CH2CH2CH3
1
CH3 CHO CH3 CHO
2-Methylpentanal 3-Hydroxy-2,4-dimethyl-2-propylheptanal
O
dil. NaOH
(v) O + O 1 2
OH
2-(1-Hydroxy-1-cyclohexyl)
cyclohexan-1-one
O CH3 OH CH3
(vi) dil. NaOH 3 2 1
C + CH2 C C CH C
5 4
CH2CH3 O H3C CH2 O
3-Hydroxy-2-methyl
3-diphenylpentan-1-one
CHO OH CHO
dil. NaOH
(vii) CH2CHO + CH2 CH2 CH CH
Phenyl acetaldehyde 3-Hydroxy-2,4-diphenylbutanal
(i) Methanal (iii) benzaldehyde and (ix) 2,2-dimethylbutanal do not contain α-hydrogen and therefore,
undergo Cannizzaro reaction.
Conc.NaOH
(ii) HCHO + HCHO → CH 3OH + HCOONa
Methanol Sodium methanoate
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(iii) CHO + CHO Conc. NaOH CH2OH + COONa

Benzyl alcohol Sodium benzoate
(ix)
CH3 CH3 CH3 CH3
Conc. NaOH
CH3CH2 C CHO + CH3CH2 C CHO CH3CH2 C CH2OH + CH3CH2 C COONa
CH3 CH3 CH3 CH3
2-2-Dimethylbutan-1-ol Sodium 2,2-dimethyl
butanoate
(iv) Benzophenone is a ketone having no α-hydrogen and (viii) butan-1-ol is an alcohol. These neither
undergo aldol condensation nor Cannizzaro reaction.
39. How will you convert ethanal into the following compounds:
(i) Butane-1,3-diol (ii) But-2-enal
Solution
(i) Butane-1,3-diol
OH O OH
OH− LiAlH4
2CH3CHO CH3CH CH2 C H CH3CH CH2CH2OH
Aldol condensation
Aldol Butane-1,3-diol
(ii) But-2-enal
OH
OH− H+
2CH3CHO CH3CH CH2CHO CH3CH CH CHO
Aldol condensation Heat
Aldol But-2-enal
40. Write structural formulas and names of the four possible aldol condensation products from propanal and
butanal. In each case, indicate which aldehyde serves as nucleophile and which as electrophile.
Solution
(i) Propanal as electrophile as well as nucleophile
OH
5 4 3 2 1
CH3CH2CHO + CH3CH2CHO CH3CH2 CH CH CHO
CH3
3-Hydroxy-2-methylpentanal
(ii) Propanal as electrophile and butanal as nucleophile

OH
5 4
3 2 1
CH3CH2CHO + CH3CH2CH2CHO CH3CH2 CH CH CH2CH3
(Electrophile) (Nucleophile)
CHO
2-Ethyl-3-hydroxypentanal
(iii) Butanal as electrophile and propanal as nucleophile

OH
6 5 4 3 2 1
dil. OH
CH3CH2CH2CHO + CH3CH2CHO CH3CH2 CH2 CH CH CHO
(Electrophile) (Nucleophile)
CH3
3-Hydroxy-2-methyl hexanal
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2PBBBCCM7AS
(iv) Butanal as electrophile as well as nucleophile

OH
6 5 4 3 2
dil. OH
CH3CH2CH2CHO + CH3CH2CH2CHO CH3CH2 CH2 CH CH CH2CH3
1
CHO
2-Ethyl-3-hydroxy hexanal
41. An organic compound with the molecular formula C9H10O forms 2,4-DNP derivative, reduces Tollens’
reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-benzenedicarboxylic
acid. Identify the compound.
Solution
The given compound forms 2,4-DNP derivative. Therefore, it is an aldehyde or ketone. Since it reduces
Tollen’s reagent, it must be an aldehyde. The compound undergoes Cannizzaro reaction, so it does not
contain α-hydrogen. On vigorous oxidation, it gives 1,2-benzendicarboxylic acid, it means that it must
be containing alkyl group at 2-position with respect to CHO group on the benzene ring.
CHO
CH2CH3
The molecular formula suggests that the compound is 2-Ethylbenzaldehyde
CHO COOH
COO
CH2CH3 COOH
CH2CH3 + Ag Tollen's reagent [O]
[Ag(NH3)2]+OH Vigorous
Silver
mirror 1,2-Benzene dicarboxylic
2-Ethyl benzoate
2,4 DNP acid
NO2
CH N NH NO2
CH2CH3
2,4-DNP derivative
42. An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid to
give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on
dehydration gives but-1-ene. Write equations for the reactions involved.
Solution
(a) Since the given compound on hydrolysis with dil. H2SO4 gives carboxylic acid (B) and an alcohol
(C), it must be an ester.
(b) Since the oxidation of alcohol (C) gives the acid B, therefore, both the carboxylic acid B and alcohol
C must contain same number of C atoms.
(c) Since ester (A) contains 8 carbon atoms, therefore, both carboxylic acid (B) and the alcohol (C) must
contain 4 C atoms each.
(d) Alcohol (C) on dehydration gives but-1-ene and therefore, C must be a straight chain alcohol i.e.,
butan-1-ol.
(e) (B) is obtained by the oxidation of (C) and therefore, B must be butanoic acid.
This also suggests that the ester (A) must be butyl butanoate.
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The relevant reactions are:

O O
dil. H2SO4
CH3CH2CH2C OCH2CH2CH2CH3 CH3CH2CH2C OH + CH3CH2CH2CH2OH
Hydrolysis
Butanoic acid Butanol
Butyl butanoate (A)
(C)
(M.F C8H16O2) (B)
CrO3 / CH3 COOH Dehydration

CH 3CH 2 CH 2 COOH ←
Oxidation
 CH3CH 2 CH 2 CH 2 OH → CH 3CH 2 CH = CH 2
Butanoic acid Butanol But −1− ene
(B) (C)
43. Give simple chemical tests to distinguish between the following pairs of compounds
(i) Propanal and propanone (ii) Acetophenone and Benzophenone
(iii) Pentan-2-one-and pentan-3-one (iv) Benzaldehyde and Acetophenone
(v) Ethanal and propanal
Solution
(i) (a) Propanal gives silver mirror with Tollen’s reagent, whereas propanone does not
CH 3CH 2 CHO + 2[Ag(NH 3 ) 2 ]OH → CH 3COONH 4 + 2Ag + H 2 O + 3NH 3
Propanal Tollen 's reagent Silver
mirror
(b) Propanal gives red ppt. with Fehling solution, while propanone does not answer this test.
CH 3CH 2 CHO + 2Cu(OH) 2 + 2NaOH  → CH 3COONa + Cu 2 O + 3H 2 O
Re d ppt.
Fehling solution
(ii) (a) Acetophenone gives yellow ppt. with alkaline solution of iodine (iodoform test).
Benzophenone does not give the test.
I2 , NaOH
C6 H 5 COCH 3  → CHI3 ↓ + C6 H 5 COONa
Acetophenone (Yellow ppt.)
(iii) (a) Pentan-2-one forms yellow ppt. with alkaline solution of iodine (iodoform test) but pentan-3-
one does not give ioctoform test.
CH 3COCH 2 CH 2 CH 3 + 3I2 + 4NaOH  → CH 3CH 2 CH 2 COONa + CHI3 + 3H 2 O + 3NaI
Pen tan − 2 − one
(b) Pentan-2-one gives white ppt. with sodium bisulphite, while pentan-3-one does not give.
OH
CH3COCH2CH2CH3 + NaHSO3 CH3CH2CH2C SO3Na
Pentan-2-one CH3
(White ppt.)
(iv) (a) Benzaldehyde forms silver mirror with ammoniacal silver nitrate solution (Tollen’s reagent).
Acetophenone does not react.
C6 H 5 CHO + 2[Ag(NH 3 )2 ]OH → C6 H 5COONH 4 + 2 Ag + 3NH 3 + H 2 O
Benzaldehyde Tollen 's reagent Silver
mirror
(b) Acetophenone forms yellow ppt. of iodoform with alkaline solution of iodine (iodoform test).
Benzaldehyde does not react.
(v) Ethanal gives yellow ppt. of idodoform with an alkaline solution of iodine (idodoform test).
Heat
CH 3CHO + 3I 2 + 4NaOH  → HCOONa + CHI3 + 3NaI + 3H 2 O
Sod. formate Iodoform
Propanal does not give yellow ppt.

I 2 , NaOH
CH 3CH 2 CHO  → No yellow ppt. of CHI3
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2PBBBCCM7AS
44. Write the steps involved in the preparation of p-Nitrobenzaldehyde from benzene.
Solution
CH3 CH3
CH3
Conc. HNO3+
CH3Cl H2SO4 NO2
+
Anhyd. AlCl3 ∆
NO2
(Major product) (Major product)
(Solid) (Liquid)
Separated by
filtration
CHO CH3
(i) CrO2Cl2, CS2
or CrO3 / (CH3CO)2O
(ii) H3O+
NO2 NO2
p-Nitrobenzaldehyde
45. How will you bring about the following conversions in not more than two steps?
(i) Propanone to propene (ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal (iv) Benzene to m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone (vi) Bromobenzene to 1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
Solution
O
NaBH4, CH3OH Conc. H2SO4
(i) CH3 C CH3 CH3 CH CH3 CH3CH CH2
Reduction 443 K
Propanone OH Propanone
COOH COCl CHO

SOCl2 H2, Pd, BaSO4
(ii) −SO2, −HCl quinoline
Benzoic acid Benzaldehyde
OH
Cu, 573 K dil. NaOH
(iii) CH3CH2OH CH3CHO CH3CH CH2CHO
Aldol condensation
Ethanol 3-Hydroxybutanal
COCH3 COCH3
(iv) (CH3CO)2 Conc. HNO3

Anhyd. AlCl3 Conc. H2SO4
NO2
Benzene
m-Nitro acetophenone
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2PBBBCCM7AS
K 2 Cr2 O7 SOCl2 C6 H 6
(v) C6 H 6 CHO  H+
→ C6 H5 COOH  → C6 H 5 COCl 
Anhyd. AlCl3
→ C6 H 5COC6 H 5
Benzophenone
Mg, dry ether (i) CH3CHO

(vi) C6H5Br C6H5MgBr C6H5CH CH3
(ii) H3O+
Bromobenzene OH
1-Phenylethanol
CHO CH CHCHO CH2CH2CH2OH
dil. NaOH, ∆ H2, Ni

(vii) + CH3CHO
Cross aldol Catalytic
condensation hydrogenation
Benzaldehyde 3-Phenylpropan-1-ol
46. Complete each synthesis by giving missing starting material, reagent or products:
O
C
H 2 NCONHNH 2
(i) C6 H 5CHO → (ii)
O
[Ag(NH3)2]+ CHO
(iii) (iv) NaCN/HCl
CHO COOH
dil.NaOH (i) NaBH 4

(v) C6 H5 CHO + CH3CH 2 CHO  → (vi) CH3COCH 2 COOC 2 H 6 
(ii) H +
→
CrO3
(vii) OH (viii) CH2 CHO
(i) O3
(ix) 2 O
(ii) Zn-H2O
Solution
H 2 NCONHNH 2
(i) C6 H 5CHO → C6 H 5CH = NNHCONH 2 + H 2O
Benzaldehyde semicarbazone
O
COCl C
Anhyd. AlCl3
+ + HCl
(ii)
Benzophenone
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2PBBBCCM7AS
O O
[Ag(NH3)2]+
(iii)
CHO COO−
4-Oxocyclohexane
carboxylate anion
OH
CHO CH CN
NaCN
(iv) HCl
COOH COOH
2-(1-Hydroxycyanomethyl)
benzoic acid
CH3 CH3
dil. NaOH 3 2 1
(v) C6H5CHO + H2C CHO C6H5CH C CHO
2-Methyl-3-phenylprop-2-enal
OH
(i) NaBH4
(vi) CH3COCH2COOC2H5 CH3 CH CH2COOC2H5
(ii) H+
Ethyl 3-hydroxybutanoate
CrO3, H2SO4
(vii) OH O
Cyclohexanone
(viii)
B2H6/THF H2 O2 PCC
CH2 CH2 B CH2OH CHO
NaOH
3
Cyclohexanecarbaldehyde
(i) O3
(ix) 2 O
(ii) Zn, H2O
Cyclohexanone
47. An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass
of the compound is 86. It does not reduce Tollen’s reagent but forms an addition compound with sodium
hydrogen sulphite and give positive iodoform test. On vigorous oxidation, it gives ethanoic and
propanoic acid. Write the possible structure of the compound.
Solution
Step 1: To determine the molecular formula of the compound
% C = 69.77, %H = 11.63
% O = 100 – (69.77 + 11.63) = 18.60
Simple atomic ratio
69.77 11.63 18.6
C:H:O = : : = 5.88 : 11.63 : 1.16 = 5 : 10 : 1
12 1 16
Empirical formula = C5H10O
Empirical formula mass 5 × 12 + 10 × 1 + 1 × 16 = 86
72
2PBBBCCM7AS
Molecular formula mass = 86

Molecular formula mass
n=
E.F.mass
86
= =1 ∴ Molecular formula = C5H10O
86
Step 2 : To determine the structure of the compound
(i) Since the given compound forms sodium hydrogen sulphite addition product, it must
be an aldehyde or a ketone.
(ii) Since the compound does not reduce Tollen’s reagent, therefore, it cannot be an
aldehyde and it must be a ketone.
(iii) Since the compound gives iodoform test, therefore, the compound must contain be
methyl ketonic group.
(iv) Since the compound on vigorous oxidation gives a mixture of ethanoic acid and
propanoic acid, therefore, the methyl ketone is pentan-2-one i.e.
O
CH3 C CH2CH2CH3 (M.F. C6H10O)
The given reactions are:

O CH3 SO−3 Na+
CH3 C CH2CH2CH3 + NaHSO3 C
CH3CH2CH2 OH
Pentan-2-one Sodium hydrogen sulphite
addition product
O Iodoform test
reaction
CH3 C CH2CH2CH3 + 3I2 + NaOH CHI3 + CH3CH2CH2COONa + 3NaI + 3H2O
Pentan-2-one Yellow ppt. Sodium butanoate
O
[O]
CH3 C CH2CH2CH3 + CH3COOH + CH3CH2COOH
Pentan-2-one Vigorous Ethanoic acid Propanoic acid
oxidation
Unit II
1. Write the IUPAC name of the following compounds:
(i) PhCH2CH2COOH (ii) (CH3)2C=CHCOOH
NO2
COOH
(iii) (iv)
COOH
O2N NO2
CH3
(v) (CH3)3CCH2COOH
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2PBBBCCM7AS
Solution
(i) 3-Phenylpropanoic acid (ii) 3-Methylbut-2-enoic acid
(iii) 2-Methylcyclopentanecarboxylic acid (iv) 2, 4, 6-Trinitrobenzoic acid
(v) 3,3-Dimethylbutanoic acid
2. Write the structures of the following compounds:
(i) 3-Bromo-4-phenylpentanoic acid (ii) Hex-2-en-4-ynoic acid
Solution
5 4 3 2 1
(i) H3C CH CH CH2 COOH
C6H5 Br
6 5 4 3 2 1
(ii) CH3 C C CH CH COOH
O
C OH
[NaOH + CaO]
3. X. What is X? [June 2019]
heat
Solution
X:
dry ether
4. CH 3 − MgBr + CO 2 
H O+
→ [March 2015]
3
Solution
CH3COOH
5. Write equation for the reaction between carboxylic acid and PCl5. [July 2014]
Solution
RCOOH + PCl5  → RCOCl + POCl3 + HCl
6. What is the effect of electron withdrawing group on the acidity of carboxylic acid? [March, 2017]
Solution
Increases the acidic strength
7. What is the reagent ‘A’ used in the following equation? [March 2019]
A
RCOOH  → RCH 2 OH
Solution
Li Al H4/ether
R COOH R CH2OH
8. Write the general equation for the formation of carboxylic acid from Grignard reagent. [Sept. 2020]
Solution
(i) CO2
R − MgX (ii) H O+
→ R − COOH
3
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2PBBBCCM7AS

9. Give the preparation of an aliphatic monocarboxylic acid from a primary alcohol. [July 2016]
Solution
If a primary alcohol is heated with a powerful oxidizing agent like acidified KMnO4 or K2Cr2O7 solution,
its gets oxidised to respective carboxylic acid.
K 2 Cr2 O7 /H 2SO4
Example: CH 3 CH 2 − OH + 2[O]  heat
→ CH 3 − COOH + H 2O
10. How are carboxylic acids prepared from nitriles? [July 2014]
Solution
Nitriles on acid hydrolysis gives amides which on further hydrolysis gives carboxylic acids.
O
H + / H2 O H+ / H2 O
R C N R C NH2 R COOH
Example:
O
H+ / H2O H+ / H2O
CH3 C N CH3 C NH2 CH3 COOH
Ethanenitrile Ethanamide Ethanoic
acid
11. Among formic acid and acetic acid, which is more acidic? Give reason. [July 2016]
Solution
Formic acid is more acidic than acetic acid. In acetic acid, due to +I effect of CH3− group the acidic
strength decreases.
12. Explain HVZ [Hell-Volhard-Zelinsky] reaction with an example. [March 2015]
Solution
Carboxylic acids with α-H, reacts with halogen in presence of red phosphorus to give
α-halocarboxylic acid. This reaction is called Hell-Volhard-Zelinsky reaction.
Re d P/heat
Example: CH 3 − COOH + Cl 2  → ClCH 2COOH + HCl
Monochloroacetic acid
13. How is benzoic acid converted to following products?

(i) Benzoyl chloride (ii) Benzamide [March 2016]
(iii) Methyl benzoate (iv) Benzyl alcohol

(v) m-Bromobenzoic acid [March 2017] (vi) m-Nitrobenzoic acid
Solution O O
C OH C Cl
(i) heat
+ PCl5 + POCl3 + HCl
O O O
C OH C O NH4 C NH2
heat
(ii) + NH3
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2PBBBCCM7AS
O O
C OH conc. H2SO4 C O CH3
(iii) + CH3OH + H2O
heat
O
C OH CH2 OH
LiAlH4/ether
(iv) + 4[H] + H2O
heat
COOH COOH
anhydrous FeBr3
(v) + Br2 + HBr
Br
COOH COOH
conc. H2SO4
(vi) + HNO3 + H2 O
conc. heat NO2
14. (i) Write general equation for esterification reaction.

(ii) Name the product obtained when benzoic acid is heated with ammonia. [March 2019]
Solution
Conc.H2SO4
(i) R COOH + HOR' R COOR' + H2O
Carboxylic acid Alcohol Ester
(ii) Benzamide

15. Although phenoxide ion has more number of resonating structure than carboxylate ion, carboxylic acid is
a stronger acid than phenol. Why?
Solution
The phenoxide ion has more number of resonating structures but carboxylic acid is more stronger acid
than phenol. This is because the negative charge of the carboxylate ion is more dispersed in comparison
to phenate ion since there are two electronegative atoms in carboxylate ion as compared to only one
oxygen atom in phenate ion.
δ−
O
δ−
O
R C δ−
δ−
O
Resonance hybrid of Resonance hybrid of

carboxylate ion carboxylate ion
In other words, carboxylate ion is relatively more stable as compared to phenate ion. Thus, the release of
H+ ion from carboxylic acid is comparatively easier and therefore, it behaves as stronger acid than
phenol.
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16. Among 4-nitrobenzoic acid and 4-methoxybenzoic acid, which is more acidic? Give one reason.
[March 2020]
Solution
4-nitrobenzoic acid is more acidic because electron withdrawing NO2 group increases the acidic strength
by increasing stability of carboxylate ion.
17. Which acid of each pair shown here would you expect to be stronger?
(i) CH3CO2H or CH2FCO2H
(ii) CH2FCO2H or CH2C1CO2H
(iii) CH2FCH2CH2CO2H or CH3CHFCH2CO2H
(iv) F3C COOH or H3C COOH
Solution
(i) CH2FCOOH
(ii) CH2FCOOH
(iii) CH3CHFCH2COOH
(iv) F3C COOH
18. Arrange the following compounds in increasing order of their property as indicated:
(i) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH (acid
strength)
(ii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid strength)
Solution
(i) +I effect decreases the acid strength of carboxylic acid while –I effect increases the acid strength of
carboxylic acid. The +I effect of isopropyl group is more than that of n-propyl group, therefore
CH3CHCOOH is a weaker acid than CH3CH2CH2CH3.
CH3
Since –I effect decreases with distance, therefore, CH3CH2CH(Br)COOH is a stronger acid than
CH3CH(Br)CH2COOH.
Thus, the overall increasing order of acid strength is:
CH3CH COOH < CH3CH2CH2COOH < CH3CHCH2COOH < CH3CH2CH COOH
CH3 Br Br
(ii) Electron donating groups decrease the acid strength and therefore, 4-methoxy benzoic acid is a
weaker acid than benzoic acid.
Since electron withdrawing groups increase the acid strength, both 4-nitrobenzoic acid and
3,4-dinitrobenzoic acids are stronger acids than benzoic acid. Further because of the presence of
additional −NO2 group at m-position w.r.t. –COOH group, 3,4-dinitrobenzoic acid is a slightly more
stronger acid than 4-nitrobenzoic acid.
Thus, the increasing order of acid strength is 4-methoxybenzoic acid < benzoic acid < 4-nitrobenzoic
acid < 3,4-dinitrobenzoic acid.
77
2PBBBCCM7AS
19. Show how each of the following compounds could be converted to benzoic acid:
(i) Ethylbenzene (ii) Acetophenone
(iii) Bromobenzene (iv) Phenylethene (Styrene)
Solution
C2H5 COO−K+ COOH
KMnO4, KOH H3O+

(i)
∆
Ethylbenzene Benzoic acid
COCH3 COO−Na+ COOH

I2 / NaOH H3 O+
(ii)
Iodoform
reaction
O O
Br MgBr C OMgBr C OH
Mg O C O H3O+
(iii)
Dry ether (dry ice) Mg(OH)Br
Bromobenzene Benzoic acid
(iv)
CH CH2 COO K+ COOH
KMnO4, KOH H3O+
∆
+ HCOOK + HCOOH
Methanoic
Phenylethene Benzoic acid acid
(Styrene)
20. How will you convert ethanal to But-2-enoic acid?

Solution
But-2-enoic acid
OH
OH− H+, H2O LiAlH4, H+
2CH3CHO CH3CHCH2CHO CH3CH CH CHO CH3CH CHCH2OH
Aldol Heat
condensation
KMnO4, H+
CH3CH CHCOOH
But-2-enoic acid
78
2PBBBCCM7AS
21. Give simple chemical tests to distinguish between the following pairs of compounds:
(i) Phenol and Benzoic acid (ii) Benzoic acid and Ethyl benzoate
Solution
(i) (a) Benzoic acid reacts with NaHCO3 to give effervescence due to the liberation of CO2.
C6 H 5 COOH + NaHCO3  → C6 H 5COONa + H 2 O + CO 2
Benzoic acid
Phenol does not give effervescence.

(b) Phenol gives violet colour with FeCl3 solution but benzoic acid does not.
(ii) (a) When treated with NaHCO3 solution, benzoic acid gives brisk effervescence while ethyl
benzoate does not
C6 H 5 COOH + NaHCO3  → C6 H 5 COONa + CO 2 ↑ + H 2 O
Benzoic acid Sodium benzoate
C6 H 5 COOC 2 H 5 + NaHCO3 
→ No effervescence due to evolution of CO 2
Ethyl benzoate
(b) Ethyl benzoate on boiling with excess of NaOH gives ethyl alcohol which on heating with iodine
gives yellow ppt. of iodoform.
Boil
C6 H 5 COOC 2 H 5 + NaOH  → C6 H 5 COONa + CH 3CH 2 OH
Ethanol
Heat
CH 3CH 2 OH + 3I 2 + 4NaOH 
→ CH 3COONa + CHI3 + 3H 2 O
Yellow ppt
22. How will you prepare the following compounds from benzene?
(i) Methyl benzoate (ii) m-Nitrobenzoic acid
(iii) p-Nitrobenzoic acid (iv) Phenylacetic acid
Solution
Br MgBr COOH COOCH3
CH3OH
Br2, FeBr3 Mg (i) CO2 (excess)
(i) Dry ether (ii) H3O+ H2SO4, ∆
Benzene Methyl benzoate
(ii)
Br MgBr COOH COOH
Br2, FeBr3 Mg (i) CO2 Conc. HNO3

Dry ether (ii) H3O+ Conc. H2SO4, ∆
NO2
Benzene m-Nitrobenzyl alcohol
(iii)
CH3 CH3 CH3
NO2
CH3Cl Conc. HNO3
+
Anhyd. AlCl3 Conc. H2SO4, ∆
Benzene
NO2
79
2PBBBCCM7AS
(Major product) (Minor product)

COOH CH3 (Solid) (Liquid)
(i) KMnO4, KOH, ∆ Separated by

(ii) dil. H2SO4 filtration
NO2 NO2
p-Nitrobenzoic acid
CH3 CH2Br CH2CN CH2COOH
CH3Cl Br2, hv alc. KCN H+ , H2 O

(iv) Anhyd. AlCl3 ∆
Benzene Phenylacetic acid
23. How will you bring about the following conversions in not more than two steps?
(i) Benzaldehyde to α-hydroxyphenylacetic acid
(ii) Benzoic acid to m-Nitrobenzyl alcohol
Solution
NaCN, HCl H+, H2O
(i) C6H5CHO pH 9-10
C6H5CH CN
Hydrolysis
C6H5 CHCOOH
Benzaldehyde
OH OH
α-Hydroxyphenyl
acetic acid
COOH COOH COCl CH2OH
Conc. HNO3 SOCl2 (i) NaBH4

(ii)
Conc. H2SO4, ∆ –SO2, –HCl (ii) H3O+
NO2 NO2 NO2
Benzoic acid m-Nitrobenzyl alcohol
24. Describe the following:

(i) Acetylation (ii) Decarboxylation
Solution
(i) The replacement of an active hydrogen of alcohols, phenols or amines with acetyl group to form
corresponding esters or is called acetylation. It is carried out by using acid chlorides or anhydrides
in the presence of a base such as aniline, dimethyl aniline, etc.
Pyridine
CH 3COCl + CH 3CH 2 OH → CH3COOC 2 H5 + HCl
Acetyl chloride Ethyl alcohol Ethyl acetate
( CH 3CO )2 O + C6 H 5OH 
→ CH 3COOC6 H 5 + CH 3COOH
Acetic anhydride Phenol Phenyl acetate
(ii) The process of removal of carboxyl group from carboxylic acid is called decarboxylation. It is
carried out by heating sodium salt of carboxylic acid with soda lime (NaOH + CaO).
CaO
CH 3CH 2 COONa + NaOH  ∆
→ CH 3CH 3 + Na 2 CO3
Sodium propanoate Ethane
COONa
CaO
+ NaOH + Na2CO3
∆
Sodium benzoate Benzene
80
2PBBBCCM7AS
25. Complete each synthesis by giving missing starting material, reagent or products:
CH2CH3 COOH
KMnO4 SOCl2
(i) (ii)
KOH, Heat heat
COOH
Solution
CH2CH3 COOK
KMnO4
(i) KOH, Heat
Potassium benzoate
COOH COCl
SOCl2
(ii) ∆
COOH COCl
Phthaloyl chloride
26. Give plausible explanation for each of the following

During the preparation of esters from a carboxylic acid and an alcohol in the presence of an acid catalyst,
the water or the ester should be removed as soon as it is formed.
Solution
The formation of esters from carboxylic acid and an alcohol in the presence of an acid catalyst is a
reversible reaction.
H+
RCOOH + R 'OH ↽ ⇀ RCOOR '+ H 2 O
Carboxylic acid Alcohol Ester
Therefore, to shift the equilibrium in the forward direction, the water or ester formed should be removed
as soon as it is formed.
***
81

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CHEMISTRY

Topics Page No.

10. Haloalkanes and Haloarenes 12

11. Alcohols, Phenols and Ethers 27

12. Aldehydes, Ketones and Carboxylic Acids 53

8. What is the coordination number of chromium in the complex, [Cr ( NH 3 ) 3 ( NO 2 ) 3 ] ?

O2N NH3 H3N NO2

O2N NH3 O2N NO2

18. Write the structure of trans isomer of [Co(NH3)4Cl2]+. [July 2017]

Short answer questions (SA)

Used to estimate the hardness of water

31. What is an ambidentate ligand? Explain with an example. [March 2018]

32. What is a chelating complex? Give an example.

40. Explain hydrate isomerism with an example.

44. Explain linkage isomerism with an example.

Long answer questions (LA)

While forming the complex, electrons in d-orbitals remains unpaired.

While forming the complex, electrons in 3d-orbitals are paired.

In this complex, cobalt is in the +3 oxidation state

While forming the complex, electrons in d-orbitals are paired.

In this complex, nickel is in the +2 oxidation state

While forming the complex, electrons in 3d-orbitals remains unpaired.

10. Haloalkanes and Haloarenes

Cl CH3 I CH3 C CH3

(ii) CH3 CH C CH3 + HBr

(iii) CH3 CH2 CH CH2 + HBr peroxide

(iv) CH3 CH CH2 + HI

(ii) CH3 CH2 C CH3

(iii) CH3 CH2 CH2 CH2 Br

(iv) CH3 CH CH3

8. Arrange the following in the order of increasing boiling points:

10. Complete the following reactions:

(i) CH3CH2CH2Cl + NaI acetone (ii) CH3CH(Br)CH2CH3 + NaOH water

(iii) CH3 C CH2

21. Write the general formula of Grignard reagent. [March 2016]

Short answer questions (SA)

30. Explain Finkelstein reaction with an example.

(ii) C2H5Br + C2H5ONa+ ethanol C2H5 O C2H5 + NaBr

CH2 C CH2 CH3

KBr + Conc. H2SO4 alcoholic KCN

Solution to Long answer questions (LA)

Compound A is CH3 CH CH2 Br (isobutyl bromide)

red P NaI CHI

6. Write the preparation of iodobenzene from benzenediazonium chloride.

8. The dipole moment of chlorobenzene is lower than that of chloroethane. Why?

Hybridised state of carbon atom

(ii) Chlorobenzene reacts with nitrating mixture on heating to form a mixture of

12. Explain Wurtz-Fittig reaction with an example. [March 2016]

13. What is Fittig reaction? Give an example.

Long answer questions (LA)

Unit III Polyhalogen compounds

11. Alcohols, Phenols and Ethers

(iii) CH3 CH CH CH3 (iv) CH2 CH CH2

3. Write structures of the following compounds:

(iii) HOCH2 CH2 C CH2 C CH3 (iv) CH2OH

CH3 CH2 CH CH2 CH2OH

(b) Identify allylic alcohol in the above examples.

13. What is molasses?

Short answer questions (SA)

1-Methylcyclohexan-1-ol 1-Methylcyclohexene 1-Methylcyclohexene

The desired alcohol can be obtained by addition of H2O to either of these,

CH3 H+ CH3 H+ CH3

4-Methylheptan-4-ol 4-Methyl heptan-3-ene

Addition of water in the presence of an acid gives the desired alcohol.