Full Organic Chemistry Flow Charts and Brief Theory

GOC-I
1. KEKULE’S PRINCIPLE
 Carbon has four valencies.

 Carbon has a property of catenation. It can make a large chain with addition of other carbons.
 A carbon atom can share 2, 4 or 6 electrons with other carbons & can form single, double or triple bond.
 For a carbon atom, it is not possible to make more than 3 bonds with adjacent carbon atom because a carbon atom
complete its octet from overlapping which consists directional property.
2. THE FOUR VALENCIES OF CARBON ATOM CAN BE REPRESENTED BY FOLLOWING WAY
Structure  bonds  bonds Hybridisation Shape Bond Angle No. of Bond

angles
4 0 sp3 Tetrahedral 109º28' 6
C (Non planar)
3 1 sp2 Planar (Trigonal) 120º 3
C
C 2 2 sp Linear 180º 1
C 2 2 sp Linear 180º 1
3. CLASSIFICATION OF CARBON
There are four types of carbon present in organic compounds. The carbon which is directly attached with one, two,
three and four carbon atoms are known as primary, secondary, tertiary and quarternary carbon atom respectively.
On the basis of carbon atom, hydrogen atoms bonded with 1º, 2º or 3º are named as primary, secondary or
tertiary hydrogen atom respectively.
3ºC C 4ºC
C–C–C–C–C
1ºC
2ºC C C
4. CLASSIFICATION OF ORGANIC COMPOUNDS

Organic compounds
Open chain compounds Closed chain

or or ring compounds
Acyclic compounds or cyclic compounds
Saturated Unsaturated
Homocyclic Heterocyclic
or
Carbocyclic
Alicylic Aromatic
Alicylic Aromatic
Benzenoid Non-benzenoid
SPECIAL POINTS :
 Saturated compounds having carbon-carbon single bonds.
e.g. CH4, CH3–CH3, CH3–CH2–CH3, CH3–CH2–Br, CH3–OH, CH3–O–CH3 etc.
 Unsaturated compounds having atleast one carbon-carbon multiple bond (= or )
e.g. CH2=CH2, HCCH, HCC–CH3, H2C=CH–CH3, CH2=C=CH2, CH2=CH–CCH, HCC–CCH etc.
 Homocyclic compounds having similar types of atoms in the complete cycle. Whereas heterocyclic compounds
having atleast one different atom (O, S, N) in the cycle.
 Alicyclic = Aliphatic + homo/hetero cyclic i.e. The cyclic compounds which have same properties as aliphatic compounds.
(Alipher = Fats)
O
O O
O
O
O NH
e.g. O
Homocyclic Heterocyclic
 Aromatic compounds having sweet smell (aroma), cyclic resonance and follow Huckle's rule (4n + 2 =  electrons)
e.g. Benzenoid compounds : n = whole no. = 1,2,3,4…………..
Benzene Naphthalene Anthracene Phenanthrene
e.g. Non-Benzenoid compounds :
Azulene
e.g. Heterocyclic compounds :
O S N N
Furane Thiophene Pyrrole Pyridine
5. HOMOLOGOUS SERIES
The organic compounds which are structural ly similar having same functional groups, combinedly gives a series
known as homologous series and the members as homologues. The homologous series is characterised by :
(i) The two adjacent members are differ by a – CH2 – group or 14 atomic mass unit.
(ii) All the members of a series have same general formula, general methods of preparation and similar chemical
properties due to same functional group.
(iii) The homologues shows difference in physical properties due to change in molecular mass and structural
arrangement of molecule.
SOME STANDARD HOMOLOGOUS SERIES ARE :
S.No. Name of Series General Formula I-homologue II-homologue
1. Alkane CnH2n+2 CH4 CH3–CH3
2. Alkene CnH2n CH2=CH2 CH2=CH–CH3
3. Alkyne CnH2n–2 HCCH HCC–CH3
4. Halo alkane CnH2n+1X CH3–X CH3–CH2–X
5. Alcohol CnH2n+2O CH3–OH CH3–CH2–OH
6. Ether CnH2n+2O CH3–O–CH3 CH3–O–CH2–CH3
7. Aldehyde CnH2nO H–CHO CH3–CHO
8. Ketone CnH2nO CH3–C–CH3 CH3–C–CH2–CH3

O O
9. Carboxylic acid CnH2nO2 H–COOH CH3–COOH
10. Ester CnH2nO2 H–C–O–CH3 H–C–O–CH2CH3

O O
or CH3–C–O–CH3
O
11. Amide CnH2n+1NO H–CONH2 CH3–CONH2
12. Nitro alkane CnH2n+1NO2 O O

CH3–N CH3–CH2–N
O O
13. Amine CnH2n+3N CH3–NH2 CH3–CH2–NH2
6. NOMENCLATURE OF ORGANIC COMPOUNDS

Mainly three system are adopted for naming of an organic compound :
(a) Common Name or Trivial Name System
(b) Derived Name System
(c) IUPAC Name or Jeneva Name System
6.1 SOME COMMON NAMES BASED ON SOURCE :
S.No. Compound Common Name Source
1. CH4 Marsh gas (Fire damp) Marshy places
2. CH3OH Wood spirit (Carbinol) Destructive distillation of wood
3. CH3CH2OH Grain alcohol Grain
4. NH2–C–NH2 Urea (Carbamide) Urine

O
5. HCOOH Formic acid Formica (Red ants)
6. CH3COOH Acetic acid Acetum (Vinegar)
7. HOOC–COOH Oxalic acid Oxalis plant
8. CH3–CH–COOH Lactic acid Lactum (Milk)

OH
9. CH3CH2CH2COOH Butyric acid Butter
10. HO–CH–COOH Tartaric acid Tamarind
HO–CH–COOH
11. HO–CH–COOH Malic acid Malum (Apple)

CH2–COOH
12. CH2–COOH Citric acid Citron (Lemon)
HO–C–COOH
CH2–COOH
6.2 SOME FREQUENTLY USED COMMON NAMES (TO BE REMEMBER) :

S.No. Common Name Structure Formula
1. Isooctane CH3
CH3–CH–CH2–C–CH3
CH3 CH3
2. Triptane CH3
CH3–CH–C–CH3
CH3 CH3
3. Ethylene H2C = CH2
4. Acetylene HC  CH
5. Allylene HCC–CH3
6. Crotonylene CH3–CC–CH3
7. Allene CH2=C=CH2
8. Ketene CH2=C=O
9. Acetone or Dimethyl Ketone CH3–C–CH3
O
10. Pavaldehyde CH3
CH3–C–CHO
CH3
11. Chloral Cl3C–CHO
12. Acrolein or Acryl aldehyde CH2=CH–CHO
13. Acetophenone or Methyl phenyl Ketone
CH3–C
O
14. Benzophenone or Diphenyl Ketone
C
O
15. Pinacol CH3 CH3
CH3–––C–––C–––CH3
OH OH
16. Pinacolone
CH3
CH3–C–––C–––CH3
O CH3
17. Mesityl oxide (Dimer of acetone)

CH3–C=CH–C–CH3
CH3 O
18. Phorone (Trimer of acetone) CH3–C=CH–C–CH=C–CH3

CH3 O CH3
19. Oxalic acid HOOC–COOH
20 Malonic acid HOOC–CH2–COOH
21. Succinic acid HOOC–(CH2)2–COOH
22. Gluteric acid HOOC–(CH2)3–COOH
23. Adipic acid HOOC–(CH2)4–COOH
24. Pimelic acid HOOC–(CH2)5–COOH
25. Maleic acid H–C–COOH

(cis)
H–C–COOH
26. Fumeric acid H–C–COOH

(trans)
HOOC–C– H
27. Cyanic acid HO–CN
28. Isocyanic acid (Tautomer of cyanic acid) O=C=NH
29. Isourea (Tautomer of urea) H2N–C=NH

OH
30. Chloroform (Anaesthatic agent) CHCl3
31. Chloropicrin (Nitro Chloroform) Cl3C–NO2
32. Chloretone CCl3

(Chloroform + acetone) CH3–C–CH3
OH
33. Pyrene (Fire - extinguisher) CCl4
34. Westrosol
Cl H
or Triclene C=C
Cl Cl

35. Westron Cl Cl
CH – CH
Cl Cl
36. Tetraclene Cl Cl
C=C
or Perclene Cl Cl
37. Isoprene CH2=C–CH=CH2

CH3
38. Chloroprene CH2=C–CH=CH2

(Monomer of Neoprene Polymer) Cl
39. AAE (Aceto acetic ester) CH3–C–CH2–C–OC2H5

or EAA (Ethyl aceto acetate) O O
40. Acrylic acid CH2=CH–COOH
41. Crotonic acid CH3–CH=CH–COOH
42. Cinnamic acid

CH=CH–COOH
43. Glycol CH2–OH

CH2–OH
44. Glycerol CH2–OH

CH–OH
CH2–OH
45. Phosgene Cl–C–Cl

or Carbonyl chloride
O
46. Glyceraldehyde CH2–OH

CH–OH
CHO
47. Glyceric acid CH2–OH
CH–OH
COOH
48. Glyoxal CHO
CHO
49. Glycine H2N–CH2–COOH
50. -Alanine
H2N–CH–COOH
CH3
51. Tilden reagent Cl–N=O
52. Grignard reagent R–MgX
53. Frankland reagent R–Zn–R
54. Hinsberg reagent (used in N-compounds)

SO2Cl
55. Mustard Gas Cl–CH2–CH2–S–CH2–CH2–Cl

(Explosive used in I-world war)
56. Lewisite (Explosive used in II-world war) Cl–CH=CH–AsCl2
57. Semicarbazide H2N–NH–C–NH2

O
58. Schiff's Base or Anil R–CH=N–R
59. Methylal OCH3

CH3–CH
OCH3
60. Ethylal OCH2CH3

CH3–CH
OCH2CH3
61. Mercaptal R SR
C
H SR
62. Mercaptol R SR
C
R SR
63. Mercaptan R–SH
64. Mercaptide R–S–R
65 Mesitylene CH3
H3C CH3
66. Toluene
CH3
67. Cummene
or Isopropyl benzene CH–CH3
CH3
68. Acetanilide
CH3–C–NH
O
69. Benzanilide
C–NH
O
70. Anisole
OCH3
71. Phenetole
OC2H5
72. Azo benzene

N=N
73. Hydrazo benzene

NH–NH
74. Phthalic acid COOH
COOH
75. Phthalic anhydride CO
O
CO
76. Phthalimide CO
NH
CO
77. Anthranilic acid COOH
NH2
78. Sulphanilic acid SO3H

(Forms zwitter ion)
NH2
79. Aspirin (Analgesic) COOH

or
o-Acetoxy benzoic acid O–C–CH3
O
80 Salol (Antiseptic)
or OH
Methyl salicylate C–OCH3
O
81 Oil of wintergreen OH
or C–OPh
Phenyl salicylate
O
82. o-Cresol OH
CH3
83. o-Toluic acid

COOH
CH3
84. o-Toluidene NH2

CH3
85. p-Benzoquinone
O O (Antiaromatic)
86. Gammexane Cl
or Lindane Cl Cl
(Alicyclic)
or BHC (Benzene hexachloride)
Cl Cl
Cl
87. Salicylaldehyde OH
CHO
88. Salicylic acid OH

COOH
89. Picric acid OH

O2N NO2
NO2
90. Tosyl chloride

CH3 SO2Cl
91. Styrene
CH=CH2
92. o-Xylene
CH3
CH3
6.3 SYSTEMATIC COMMON NAMES OF HYDROCARBONS :
CH3
CH3–CH2–CH2–CH2–CH3 CH3–CH–CH2–CH3 CH3–C–CH3

CH3 CH3
n-Pentane Isopentane Neopentane
CH3–CH2–CH2–CH3 CH3–CH–CH3 CH3–CH2–CH3
n-Butane CH3 Propane
Isobutane
CH2=CH–CH2–CH3 CH3–CH=CH–CH3 CH2=C–CH2

-Butylene -Butylene CH3
Isobutylene
SPECIAL POINTS :
 prefix "n" is used for unbranched carbon chain.
 prefix "iso" is used when one methyl group is attached on 2nd carbon from either terminal
 prefix "neo" is used when two methyl groups are attached on 2nd carbon from either terminal.
 Prefix "/" is used to locate the position of double bond.
6.4 COMMON NAMES OF HYDROCARBON RADICALS :
n-Pentyl CH3–CH2–CH2–CH2–CH2–
n-Propyl CH3–CH2–CH2–
s-Pentyl CH3–CH2–CH–CH2– CH3
Iso propyl CH3–CH– |
|
CH3 |
Active s-pentyl CH3–CH–CH2–CH2–CH3
Isopentyl CH3–CH–CH2–CH2–
|
n-butyl CH3–CH2–CH2–CH2– CH3
Active isopentyl CH3–CH–CH–CH3
Isobutyl CH3–CH–CH2– | |
| CH3
CH3
CH3
s-butyl CH3–CH2–CH–CH3 |
| Neopentyl CH3–C–CH2–
CH3 |
| CH3
t-Butyl CH3–C–
| |
CH3 t-Pentyl CH3–C–CH2–CH3
|
CH3
Active pentyl –CH2–CH–CH2–CH3

|
CH3
CH2–CH2 Ethylene
Vinyl CH2=CH–
Allyl CH2=CH–CH2– CH3–CH Ethylidene
Propargyl HCC–CH2– CH3–C Ethylidyne

Phenyl or Ph–
Benzyl CH2–
Benzal or Benzylidene CH
Benzo or Benzylidyne C
6.5 COMMON NAMES OF HYDROCARBON DERIVATIVES :
For systematic common names of these compounds we are dividing whole functional groups in following two
systems :
6.5.1 SYSTEM - I :
In this system prefix is decided by hydrocarbon radical (as discussed above) and suffix is given by following table:
S. No. Functional Group Suffix
1 –SO3H sulphonic acid
2 –OH alcohol
3 –SH thioalcohol
4 –NH2 /–NH– / N amine
5 –O– ether
6 –S– thioether
7 –X halide
8 –C– ketone
||
O
9 – CN cyanide
10 − N==C isocyanide
e.g.
CH3 *
| CH3 –CH–CH–CH3 CH3–O–CH2CH3
CH3–CH–SO3H CH3–C–OH | |
| | CH3 NH2
CH3 CH3
Isopropyl sulphonic acid t-Butyl alcohol Active isopentyl amine Ethyl methyl ether
or
Active isoamyl amine
→
CH3–C–CH–CH3 CH3–N=C
CH2 –Br || |
CH3CH2–N–CH2CH3 O CH3
|
CH2CH3 Benzyl bromide Methyl isocyanide
Isopropyl methyl ketone
Triethyl amine
CN
CH3–C–CH3
CH CH2–CH2–CH2
CH2=CH–S–CH2–CCH O
CN Cl Cl
Dimethyl ketone
Trimethylene or
Propargyl vinyl thioether Benzal (di) cyanide chloride Acetone
6.5.2 SYSTEM II :
In this system prefix is decided by total number of carbon atoms in the compound
If total carbon  One Two Three Four Five
Prefix  Form Acet Propion Butyr Valer
And suffix is given by following table :
S. No. Functional Group Suffix
1 ––COOH ic acid
2 –CO ic anhydride
O
–CO
3 –C– OR Alkyl …… ate

||
O
4 –COX yl halide
5 –CONH2 amide
6 –CHO aldehyde
7 – CN onitrile
8 − N==C oisonitrile
e.g.
CH3
|
H–COOH CH3 –C–Cl CH3 –CH–CHO CH3 –C–CONH2
|| | |
O CH3 CH3
Formic acid Acetyl chloride Isobutyraldehyd Neovaleramide
e
O
O ||
|| CH3–C
CH3 –C–O–CH3 CH3–C O
|| O CH3–CH––C–O–C2H5
O CH3–CH2–C
CH3–C ||
|| O CH3 O
Methyl acetate O
Acetic propionic anhydride Ethyl isobutyrate
Acetic anhydride
SPECIAL POINTS :
 Prefix "Acryl" is used for the compounds which have total three carbon atoms and double bond is on 2 nd carbon.
(only for system II groups)
e.g CH2 = CH–COOH Acrylic acid
CH2 = CH–CHO Acryl aldehyde
CH2=CH–CONH2 Acrylamide
 Prefix "Croton" is used for the compounds which have total four carbon atoms and double bond is on 2 nd carbon
(only for system II groups)
e.g CH3–CH = CH–COOH Crotonic acid
CH3–CH = CH – CHO Croton aldehyde
CH3–CH = CH – COCl Crotonyl chloride
 Prefix "Pyruv" is used when CH –C– is directly attached with (system II) functional groups.
3
O
e.g.
CH3–C—COOH CH3–C—CHO CH3–C—COBr
CH3–C—CONH2
O O O
O
Pyruvic acid Pyruvaldehyde Pyruvamide Pyruvyl bromide
 –CN and –NC groups are considered in both systems.

e.g.
System (I) System (I)
Isopropyl isocyanide Isopropyl cyanide
→ CH3–CH–CN
CH3–CH–N= C
| |
Isobutyroisonitrile CH3 Isobutyronitrile
CH3 System (II) System (II)
System (I) System (I)

Vinyl cyanide Vinyl isocyanide
→
CH2=CH–CN CH2=CH–N= C
Acrylonitrile Acryloisonitrile
System (II) System (II)
7. DERIVED NAME SYSTEM
According to this system name of any compound is given according to the representative compound of the
homologous series. This system is reserved for following homologous series :
Series Name of Homologous series Name of Representative Structure of group

compound
1 Alkane Methane
–C–
2 Alkene Ethylene >C=C<
3 Alkyne Acetylene –CC–
4 Alcohol Carbinol
–C– OH
5. Aldehyde Acetaldehyde
–C– CHO
6. Ketone Acetone
–C–C –C–
O
7. Carboxylic acid Acetic acid

–C– COOH
e.g.
H H CH3
| | |
CH3–C– CH3 CH3–CH2–C–CH3 CH3–C– CH3
| | |
CH3 CH3 CH3
Trimethyl methane Ethyl dimethyl Tetramethyl methane
CH3 H CH3 O
CH3–C––CH2––CH–CH3
CH3–CH2–C–OH CH3–C–––C–H
CH3 CH3
CH3 CH3
Isobutyl Isopropyl methane Ethylmethyl carbinol Trimethyl acetaldehyde
H O H O
CH3–CH2–C––C–H H CH3
CH3–C–C–OH
CH3 C=C
CH3 CH3 H
Ethylmethyl acetaldehyde Dimethyl acetic Symmetrical dimethyl ethylene

acid
CH3 H CH3 CH3 CH3 CH3
C=C C=C C=C CH3–CC–CH3
CH3 H CH3 H CH3 CH3
Unsymmetrical dimethyl ethylene Trimethyl ethylene Tetramethyl ethylene Dimethyl acetylene

8. IUPAC NAME SYSTEM OR GENEVA NAME SYSTEM
(International union of pure and applied chemistry)
8.1 Parts and format of IUPAC name :
Secondary prefix + Primary Prefix + Root word + Primary suffix + Secondary suffix
It represents substituents It is used in cyclic It represents number of It represents saturation or It represents (main)
or branches compounds (cyclo) carbon atoms in selected unsaturation in principle functional group.
principle carbon chain carbon chain
e.g. ane, ene, yne
e.g.
1C → Meth 11C → Undec
2C → Eth 12C → Dodec
3C → Prop 13C → Tridec
4C → But 14C→ Tetradec
5C → Pent 15C → Pentadec
6C → Hex 16C → Hexadec
7C → Hept 17C → Heptadec
8C → Oct 18C → Octadec
9C → Non 19C → Nonadec
10C → Dec 20C → Eicos
8.2 Rules for IUPAC nomenclature :
Rule – 1 : Select the longest continuous chain of carbon atoms which have maximum number of substituents,
multiple bonds and functional groups.
Priority order : Functional group > Multiple bond (= or ) > Substituent
Rule – 2 : Selected principle carbon chain is numbered from the side where substituent or multiple bond or
functional group is nearer (lowest possible number):
Priority order : Functional group > Double bond > Triple bond > Substituent
e.g.
3 2 1 7 6 5 4 3 CH3
CH3–CH–CH2–COOH CH3–CH2 –CH2–CH2–CH–CH3 4 3| 2
| CH3–CH–C–CH2–CH3
4 CH2 CH2–CH3 ||
2 1 CH2
5 CH3 1
3-Methyl heptane
3-Methyl pentanoic acid
2-Ethyl-3-methyl-1-butene
SPECIAL POINTS :
 If the compound contain more than one similar alkyl groups, their positions are indicated separately and an
appropriate numerical prefix di, tri, tetra......, is attached to the name of the substituent. The positions of the
substituents are separated by commas
CH3 CH3
CH3 CH3 1
e.g. 1 CH3– C– CH2– CH–5CH3
2 3 4
CH3–2CH–3CH–4CH2–5CH3
CH3
2,3 – Dimethyl pentane 2,2,4- Trimethyl pentane
 If there is different alkyl subsitituents present in the compound, their names are written in the alphabetical order.
However, the numerical prefixes such as di, tri etc, are not considered for the alphabetical order. For example ,
C2H5
1
CH3– CH– C–4CH2–5CH3
2 3
CH3 CH3
3 –Ethyl-2,3-dimethyl pentane
 If two different alkyl groups are located at the equivalent positions, then numbering in the carbon chain is done in
such a way that the alkyl group which comes first in alphabetic order gets the lower position.
C2H5 CH3
1
CH3– CH2– CH–4CH–5CH2–6CH3
2 3
3 –Ethyl-4-methylhexane
 If a compound has two or more chain of the same length, then principle chain is selected in such a way that greater
number of substituent works as prefix.
5
CH3–4CH2–3CH–CH2–CH3
2
CH–CH3
1
CH3
3 –Ethyl -2- methyl pentane
 In case some functional group (other than C=C and C  C) is present in molecule, it is indicated by adding
secondary suffix after the primary suffix. The terminal ‘e’ of the primary suffix is generally removed before
adding the secondary suffix. The terminal ‘e’ of the primary suffix is removed if it is followed by a suffix begining with
‘a’, ‘i’, ‘o’, ‘u’ or ‘y’ .
e.g. 4 3 2 1 4 3 2 1
CH3–CH–CH–CH3 CH2=CH–CH2–COOH
CH3 OH But-3-enoic acid
3-Methyl butan-2-ol
 Some of functional group always works as prefix
Functional group Prefix name
–X Halo
– OR Alkoxy
–C–C– Epoxy
O
– NO2 Nitro
– NO Nitroso
3 2 1 1 2 3 4
CH3CH2CH2–O–CH3 CH2–CH–CH2–CH3
1-Methoxy propane O
1, 2-Epoxy butane
 If the molecule contains more than one dissimilar functional groups, the numbering of the parent chain is done in
such a way that the functional group of higher priority gets the lower number. The order of priority of various
groups for the sake of numbering is given in following table :
S.No. Functional group Prefix Suffix

1 –C–OH carboxy oic acid
||
O
2 – SO3H sulpho sulphonic acid
3 –C–O–C– × oic anhydride

|| ||
O O
–C–O–R alkoxy carbonyl alkyl ....... oate

4 ||
O or
carbalkoxy
5 –C–X halo formyl oyl halide

||
O or
halo carbonyl
6 –C–NH2 carbamoyl amide

||
O or
amido
7 CN cyano nitrile
8 C
– N= carbyl amino isonitrile
or
isocyano
val
9 –C–H formyl
||
O or
oxo
10 –C– keto one

||
O or
oxo
11 – OH hydroxy ol
12 – SH mercapto thiol
13 – NH2 amino amine
14 –O– alkoxy ×
e.g.
CH3 Suffix
|
4 3 2 1
CH3– C— C— CH3
| ||
OH O 3
CH3 –2C–1CH=O 3
CH2 –2CH2–1COOH
Prefix || |
O CN
3-Hydroxy-3-methylbutan -2- one 2-keto propanal 3-cyano propanoic acid

8.3 Sometimes a special suffix is used for given functional groups :
S.No. Functional group Suffix
1 –COOH Carboxylic acid
2 –COOR Alkyl …. carboxylate
3 –COX Carbonyl chloride
4 –CONH2 Corboxamide
5. –CN Carbonitrile
6. –NC Carbo isonitile
7. –CHO Carbaldehyde

It is used in acylic compounds when 3 or more functional groups are presents.
e.g.
CH2 — CH — CH2 CH2 — CH — CH2— CH — CH3
| | | | | |
COOH COOH COOH CHO CHO CHO
Propane –1,2,3,-tricarboxylic acid Pentane –1,2,4,-tricarbaldehyde
CN CH2–CH–CH2
CH3–C–CH2–CH2 CN CH2 CN
CN CN CN
Butane-1,3,3-tricarbonitrile 3-Cyanomethyl pentane-1,5-dinitrile
  It is used in cyclic compound when functional group is directly attached to the cycle.
e.g. C–O–CH2–CH3
COOH
O
Cyclopropane carboxylic acid Ethyl cyclobutane carboxylate
CHO
Cl C Cl
CHO
O
CHO
4-Chloro cyclohexane carbonyl chloride Cyclohexane-1,2,4-tricarbaldehyde
NH2
OH
CONH2
COOH
2-Hydroxy benzene carboxylic acid 3-Amino benzene carboxamide

or or
2-Hydroxy benzoic acid 3-Amino benzamide
8.4 IUPAC NOMENCLATURE ALICYCLIC COMPOUNDS :

  Names of alicyclic compounds are given by putting another prefix ‘cyclo’ before the root word which depends
upon the number of carbon atoms in the ring. The suffixes ane, ene or yne are written depending upon saturation or
unsaturation in the ring.

  If some substituent or functional group is present, it is indicated by some appropriate prefix or suffix and its
position is indicated by numbering the carbon atoms of the ring. The numbering is done in such a way so as to
assign least possible number to the functional group or substituent in accordance with the rules already discussed.
e.g.
OH NO2
1 3
4 2 4 2
5 3 1
5
CH3 CH3
6 6
Cyclohexane Cyclopentene 3-Methylcyclo hexanol 1-Methyl-3-Nitrocyclohexene
CH3 O
5 4 3 2 1
CH3 2 CH3 1
4
3
6
2 CH3–CH–CH=CH2
1
1 5 3
4
3 2 C2H5 4
OH
1,5-Dimethylcyclopentene 1-Ethyl-2-Methylcyclobutene 3-Hydroxycyclohexanone 3-Cyclopentyl-1-butene
8.5. IUPAC NOMENCLATURE OF COMPOUNDS WITH BOND LINE FORMULA
In this representation of organic molecules, carbon and hydrogen atoms are not shown and the lines representing
carbon – carbon bonds are drawn in zig-zag manner. A single line (–) represents a single bond, two parallel lines
(=) represents a double bond and three parallel lines () represent a triple bond. The only atoms specitically written
are those that are neither carbon nor hydrogen bound to carbon. The intersection of lines represent carbon atoms
carrying appropriate number of hydrogen atoms.
e.g.
1 6 3 1 OH
2 4 2
4 O
3 5
1 3 5 5
4 6
4-Methylpenta-1,3-diene 6-Ethyl-1-methylcyclohexa-1,3-diene 2,6-Dimethylhept-2,5-dien-oic acid
Br
2 4 23 2 4
OH 3
1 1 5
4
1 3 5 5 O
Hexa-1,3,5-triene Pent-1-en-3-ol 2-Bromopentan-3-one
8.6 IUPAC NOMENCLATUERE OF BRIDGED BICYCLIC HYDROCARBONS
  Saturated bicyclic systems having two or more atoms in common are named by prefixing ‘bicyclo’ to the name of
the cyclic parent hydrocarbon system containing the same total number of carbon atoms in the skeleton. The
number of carbon atoms in each of the three bridges, connecting the two tertiary carbon atoms is indicated in
parentheses, in descending order and arabic numerals are used to indicate the number of carbon atoms and the
numbers are separated by commas or full stops.
  The bicyclic system is numbered starting with one of the tertiary bridging cabon and proceeding through longest
bridge to the second bridging carbon continuing back to the first bridging carbon through the second longest chain.
Numbering is completed by numbering the shortest bridge beginning with the atom next to the first bridging
carbon.
e.g.
1
1
6 2 2
7 8 3
5 3 9 OH
6
4 5 4
Bicyclo [2,2,1] heptane Bicyclo [3,2,2] Nonan–3–ol
8.7. IUPAC NOMENCLATURE OF SPIRO BICYCLIC HYDROCARBONS
  Spiro bicyclic hydrocarbons contain two rings consisting of carbon atoms only and the two rings are linked by a
common carbon. These compounds are named by placing prefix ‘spiro’ before the name of the acyclic parent
hydrocarbon with same number of skeletal carbon atoms. The numbers of skeletal atoms linked to the spiro atom
are indicated by arabic numbers, separately by commas or fullstop. The numbers are written in ascending order
and enclosed in square brackets.
  Numbering of a spiro bicyclic hydrocarbon starts with a ring carbon next to the spiro atom and proceeds first
through the smaller ring and then through the spiro atom and around the second ring.
e.g.
9 10 1 2 CH3
1 7 6 5
8
3 3
4 5 7 6 4
2
Spiro [2,4] 2-Methylspiro [4, 5] deca-1, 6-diene

GOC-II
LECTRONIC DISPLACEMENT IN ORGANIC COMPOUNDS
.
INDUCTIVE EFFECT
• It involve partial displacement of − electrons towards more electronegative atom or group.
It is permanent effect.
1
• I − effect 
dis tance
• I-effect is of two types : + I-effect and I-effect
(1) –I effect : The atoms or groups which attracts -electrons as compare to the hydrogen shows this effect.
Order of – I-effect of some standard species is :
 
– OH 2 > – NH 3 > –NO2 > –CN > –COOH > –COOR > –CHO > –COR >
–F > –OH > –OR > – Cl > –Br > –NH2 > –Ph > –CH=CH2 > –H
(2) +I effect : The atoms or groups which repels -electrons as compare to the hydrogen shows this effect.
Order of +I-effect of some standard species is :
CH3
–NH > –O > –C–CH3 > –CH– CH3 > –CH2CH3 > –CH3 > –D > –H
CH3 CH3
APPLICATIONS OF INDUCTIVE EFFECT :

(1) Stability of intermediates:
+I –I
Stability of carbocatio n  Stability of carbanion 
–I +I
   
e.g. (i) CH3–C–CH3 > CH3–CH–CH3 > CH3–CH2 > CH3
CH3
(ii) CH3–C–CH3 < CH3–CH–CH3 < CH3–CH2 < CH3

CH3
  
(iii) ClH 2 C – CH 2 > Cl 2 HC – CH 2 > Cl 3C – CH 2
(iv) CH3–CH2–CH–CH2 > CH3–CH–CH2–CH2 > CH2–CH2–CH2–CH2
F F F
(v) HCC > H2C=CH > H3C–CH2

sp-carbon sp3–carbon
sp2–carbon
more EN due to more s- character
Most stable
(2) Acidic strength:

The proton donating tendency of any compound is called as acidic strength.
Generally acidic strength  stability of anion
e.g. (i) CH3OH > CH3CH2OH > CH3–CH–OH
–H –H CH3

–H
(Stability) CH3O– > CH3CH2O– > CH3–CHO–
CH3
–H –H –H –H
(Stability) CH3–O > HCC > CH3–NH > CH2=CH
EN = 3.5 EN = 3.25 EN = 3.0 EN = 2.75

(sp-carbon) (sp2–carbon)
–I
Result : Acidic Strength 
+I
(iii) H–COOH > CH3–COOH > C2H5–COOH > CH3–CH–COOH

CH3
(iv) FCH2–COOH < F2CH – COOH < F3C–COOH
(v) CH3–CH–COOH > CH2–CH2–COOH > CH3–CH2–COOH

F F
(vi) COOH > COOH > H2C–COOH

COOH CH2 H2C–COOH
COOH
(3) Basic Strength :

The lone-pair donating tendency of the atom in any compound is called as basic strength.
+I
Generally Basic strength 
–I
e.g.
.. .. ..
(i) CH3–NH2 > NH3 > Cl–NH2
CH3
.. .. ..
(ii) CH3–C–NH2 > CH3–CH–NH2 > CH3CH2CH2–NH2
CH3 CH3
.. .. ..
(iii) CH3–CH–OH > CH3–CH2–OH
.. > CH3–OH
..
..
CH3
RESONANCE EFFECT
When a molecule or ion can be represented by two or more structures which have the same arrangement of
atomic nuclei but differ in distribution of electrons, the phenomenon is called as Resonance. The various
structures are called contributing or resonating structures. None of these structures truly represents all the
properties of that molecule or ion. The actual structure is a resonance hybrid of several contributing structures.
Resonance generally occurs when there is a conjugation of -bonds (alternate double - single - double bond
arrangement) known as conjugated system.
Conjugate positions of the molecule:
Alternate positions of the molecule having  bond with positive charge or negative charge or odd electron or lone
pair of electrons are known as conjugative positions.
CH 2=CH– CH =CH– CH =CH2

1 3 5
1, 3 and 5 are conjugate positions


CH 2 =CH– CH =CH–CH –CH3
1 3 5
1, 3 and 5 are conjugate positions.

••
CH 2 =CH– CH =CH– CH =CH– NH 2
1 3 5 7
1, 3, 5 and 7 are Conjugate positions

Note : Compound having at least two conjugate positions is known as conjugated compound.
Type of Conjugation :
(1) ,  conjugation: If all conjugate positions have  bonds, then conjugation is known as ,  conjugation
1
e.g. CH 2=CH– CH =CH2 CH3–CH2– CH =CH– CH =CH– CH =CH2
1 3 1 3 5 3 5
(2) Positive charge,  conjugation: In this case all conjugate positions have  bonds and only one conjugate position
has positive charge. If this is the case, then conjugation is known as positive charge,  conjugation.
 
e.g. CH 2=CH– C H 2 CH2=CH–CH=CH– C H 2
1 3
(3) Negative charge,  conjugation: If all conjugate positions have  bonds and only one conjugate position has
negative charge, then conjugation is known as negative charge,  conjugation.
e.g. CH2=CHCH2 CH2=CH–CH=CH–CH2
(4) Odd electron,  conjugation: If all conjugate positions have  bonds and one conjugate position has odd
electron, then conjugation is known as odd electron,  conjugation.
• •
e.g. CH2=CH– C H 2 CH2=CH–CH=CH– C H 2
(5) Lone pair,  conjugation: If all conjugate positions have  bonds and only one conjugate position has p then
conjugation is known as p,  conjugation.
••
e.g. CH2=CH– N H 2 CH2=CH–X CH 2=CH– CH =CH– CH =CH–CH3
1 3 5
7
MESOMERIC EFFECT (M-effect).
The complete delocalization of  electrons with conjugate  bond, loan pair of electrons, charge,  charge
(vacant p-orbital) or odd electron is called as M-effect.
e.g.
 CH
  + +
(i) CH2=CH–CH2 CH 2– CH =CH 2 2 CH CH2
Resonance Hybrid
–
 CH
 +
(ii) CH2=CH–CH=O CH2–CH=CH–O 2 CH CH O
Resonance Hybrid
(iii) CH2=CH–CH=CH2

CH2–CH=CH–CH2 CH2–CH=CH–CH2

 CH 2 CH CH CH2
Resonance Hybrid
– –
(iv) CH2=CH–CH2 CH2–CH=CH2  CH 2 CH CH2
Resonance Hybrid
. • •
(v) CH2=CH–CH2
. CH2–CH=CH2  CH 2 CH CH2
Resonance Hybrid
–
O O O
 +
(vi) H–C–O–H H–C=O–H  H–C O–H
Resonance Hybrid
–
O O O
 +
(vii) H–C–NH2 H–C=NH2  H–C N–H
H
Resonance Hybrid
+ +

O–H  O–H  O–H O–H O–H O–H O–H
– –
(viii)  or –
–
I II III IV V Resonance Hybrid
  +

NH2 NH2 NH2 NH2 NH2 NH2
(ix)  –
Resonance Hybrid
+
Cl Cl Cl  Cl  Cl  Cl
(x)  –
Resonance Hybrid
– –
O O O O O O O O O O O O
C C C C C C

 + +
(xi) 
 +
Resonance Hybrid
– –
O  O O  O O  O O  O O  O O + O
N N N N N N
  
(xii) +

Resonance Hybrid
(xiii)
Mesomeric effect are of following two types :
(1) – M effect : The group which attracts -electrons from carbon chain shows this effect.
O
e.g. N (–M-effect of NO2 group)
O
CH2=CH––CH=O (–M–effect of CHO group)
 order of –M–effect of some standard species is :

O
–N > –CN > –C–OH > –C–H > –C–R
O
O O O
(2) +M effect : The group which repells -electrons towards carbon chain shows this effect.
e.g. CH3=CH–––NH2 (+M-effect of –NH2 group)

OH (+M-effect of –OH group)
 Order of +M-effect of some standard species is :

• • • • • • • • • •
–NH > –O > – NH 2 > – NHR > – NR 2 > – OH > – OR > –NH–C–R > –O–C–R
• • • •
O O
APPLICATION OF MEOSMERIC EFFECT :
(1) Stability of Intermediates :
Generally more delocalized charge, charge or odd electron is more stable than localized species.
e.g.

 
(i) > CH2 > CH2
(ii) CH2=CH–CH–CH=CH2 > CH2=CH–CH–CH3 > CH3–CH–CH3
(iii) CH2=CH–C–CH=CH2 > CH2=CH–CH–CH=CH2 > CH3–CH2

CH
CH2
+M
Stability of C  
 For Benzylic carbocation/carbanions : –M
–M
Stability of C –O 
+M
e.g.
   
CH2 CH2 CH2 CH2
(iv) > > >
OMe Me COOH
CH2 CH2 CH2 CH2
(v) > > >
NO2 CH3 NH2

   
CH2 CH2 CH2 CH2
OH
(vi) > > >
OH
OH
CH2 CH2 CH2 CH2
NO2
(vii) > > >
NO2
NO2
(2) Acidic Strength :
Generally acidic strength  stability of anion
e.g. (i) CH3–C–OH > CH3CH2OH

O –H
–H
CH3–C–O > CH3CH2O
O
More stable Less stable
(ii) C–OH > C–O–OH

O O

–H –H
C–O > C–O–O

O O
More stable due to Less stable
delocalized charge due to localized
charge
–M
For phenolic compounds and benzoic acid : Acidic strength 
+M
e.g.
OH OH OH OH
(iii) > > >
H–C=O CH3 NH2

OH OH OH OH
NO2
(iv) > > >
NO2
NO2 Due to
Intramolecular
H-bonding
COOH COOH COOH COOH
(v) > > >
NO2 C OMe
O CH3
(3) Basic Strength :
Generally delocalized lone pair containing compounds are less basic than localized lone pair containing
compounds.
e.g.
(i) CH3CH2–NH2 > CH3–C–NH2

O
(localized l.p.) (delocalized l.p.)
CH2–NH2 NH2
(ii) > (iii) >

N NH
+M
For aromatic amines : Basic strength 
–M
e.g.
NH2 NH2 NH2 NH2
(iv) > > >
OMe Me CHO
NH2 NH2 NH2 NH2

NO2
(v) > > >
NO2
NO2
(4) Aromaticity :
In general aromatic compounds are those which are
(i) Cyclic (ii) Planar
(iii) Containing (4n + 2) electrons where n may be 0, 1, 2, 3, ...........
Third condition is well known as Huckle rule.
e.g. :
(i) (ii) (iii)
4n + 2 = 6 4n + 2 = 10 4n + 2 = 10
n=1 n=2 n=3
 Aromatic  Aromatic  Aromatic
H H sp3
(iv) (v)
4n + 2 = 10 4n + 2 = 0 (vi)
n = 3/2 n = 1/2
 Not aromatic  Anti aromatic 4n + 2 = 2
n=0
It should be aromatic but is not,
because it is not planar and does
not have cyclic resonance
sp2
 O
(vii) (viii) (ix)

x
4n + 2 = 2 4n + 2 = 4 4n + 2 = 2
n=0 n = 1/2 n=0
 Aromatic  Anti aromatic  Aromatic
(Because it is planar)


(x) (xi) (xii)

4n + 2 = 2 4n + 2 = 4 4n + 2 = 6
n=0 n = 1/2 n=1
 Aromatic  Anti aromatic  Aromatic
sp2 sp2
(xiii) O (xiv) N–H (xv)
sp2
N
4n + 2 = 6 4n + 2 = 6
n=1 n=1 4n + 2 = 6
 Aromatic  Aromatic n=1
 Aromatic
sp3
(xvi) (xvii) (xviii)

N
N 4n + 2 = 6 4n + 2 = 8
n=1 n = 3/2
4n + 2 = 6
 not aromatic  Anti aromatic
n=1
 Aromatic
sp2

(xix) (xx)
4n + 2 = 6
n=1
 Aromatic
Aromatic
O O

(xxi) (xxii) (xxiii)
Aromatic 4n + 2 = 10
It is Aromatic because
n=2
only peripheral  electrons
should be considered  Aromatic
(xxiv) (xxv) (xxvi)
4n + 2 = 10 4n + 2 = 10 4n + 2 = 18
n=2 n=2 n=4
But not aromatic because  Aromatic (because it is planar also)  Aromatic
not planar
Note : Despite the wide utility of the Huckel's rule a number of systems are known which do not contain (4n + 2) 
electrons but are still aromatic. Well-known examples of these anomalous cases are heptalene, acenaphthene, etc.,
and they posses considerable delocalization energies.
heptalene acenaphthene
HYPER-CONJUGATION EFFECT
When (C–H) sigma electrons are in conjugation to pi bond, this conjugation is known as
 (C–H),  conjugation, No bond resonance or hyper-conjugation.
Structural requirement for hyper-conjugation:
(A) Compound should have at least one sp2-hybrid carbon of either alkene or alkyl carbocation or alkyl free radical.
(B) -carbon with respect to sp2 hybrid carbon should have at least one hydrogen.
If both these conditions are fulfilled then hyperconjugation will take place in the molecule.
(C) Hyper-conjugation is of three types :
(i)  (C–H),  conjugation : This type of conjugation occurs in alkenes.
CH3
 
CH 3 – CH=CH 2 CH3–CH–CH=CH2 CH3
–C–CH=CH2
CH3 CH3
(ii)  (C–H), positive charge conjugation : This type of conjugation occurs in alkyl carbocation.
  
  CH3–CH–CH3   
CH3–CH2 CH3–C–CH3
 CH3
(iii)  (C–H), odd electron conjugation : This type of conjugation occurs in alkyl free radicals –
  
CH3–CH2 CH3–C–CH3
 CH3
(D) Resonating structures due to hyperconjugation may be written involving “no bond” between the alpha carbon and
hydrogen atoms.

H H H H

H–C–CH=CH2 H–C=CH–CH2 H C=CH–CH2 H–C=CH–CH2
H H H
H 
In the above resonating structures there is no covalent bond between carbon and hydrogen. From this point of
view, hyperconjugation may be regarded as “no-bond resosnance ”.
APPLICATION OF HYPERCONJUGATION :
(1) Stability of Alkenes : Hyperconjugation explains the stability of certain alkenes over other alkenes:
Stability of alkenes  Number of alpha hydrogens  Number of resonating structures
e.g. CH3–CH=CH2 > CH3–CH2–CH=CH2 > CH3–CH–CH=CH2

CH3
CH3 CH3 CH3 CH3

C=C > C=CH–CH3 > C=CH2
CH3 CH3 CH3 CH3
(2) Stability of Alkyl Carbocations :
Stability of alkyl carbocations  number of resonating structures  number of hydrogens.
   
e.g. CH3 < CH3–CH2 < CH3–CH–CH3 < CH3–C–CH3
CH3
(3) Stability of Alkyl free radicals : Stability of alkyl free radicals can be explained by hyperconjugation. Stability
depends on the number of resonating structures.
e.g. CH3 < CH3–CH2 < CH3–CH–CH3 < CH3–C–CH3
CH3
(4) Electron releasing (or donating) power of R in alkyl benzene : CH3– (or alkyl group) is
+R group, ortho-para directing group and activating group for electrophilic aromatic substitution reaction because
of the hyperconjugation.
H H H H
H–C–H H–C H H–C H H–C H
The electron donating power of alkyl group will depends on the number of resonating structures, this depends on
the number of hydrogens present on -carbon. The electron releasing power of some groups are as follows –
CH3
CH3– > CH3 – CH2– > CH3–CH–CH3 > CH3–C–
CH3
Special point : Reverse Hyperconjugation :
The phenomenon of hyperconjugation is also observed in the system given below :
X
–C–C=C Where X-halogen atom
In such system the effect operates in the reverse direction. Hence the hyperconjugation in such system is known as
reverse hyperconjugation.
Cl Cl Cl Cl
  
Cl–C–CH=CH2 Cl–C=CH–CH2 Cl C=CH–CH2 Cl–C=CH–CH2
Cl Cl Cl Cl
The meta directing influence and deactivating effect of –CX3 group for electrophilic aromatic substitution reaction
can be explained by this effect.
X X X
X–C–X X–C X X–C X

ELECTROMERIC EFFECT
Electromeric effect is a temporary effect in which a shared pair of electrons (−electron pair) is completely
transfered from a double or a triple bond to one of the atoms joined by the bond at the requirement of attacking
reagent.
If the attacking reagent is removed, charge disappears and substrate attains its original form. Thus this effect is
reversible and temporary.
The electromeric effect can be by other permanent effects in various conditions as follows.
CASE  - Electromeric effect may be decided by −effect as –
Reagent 
e.g. CH3→–CH=CH2 CH3–CH– CH2
Reagent 
Cl3C–CH=CH2 Cl3C–CH– CH2
CASE II - If the multiple bond is present between two different atoms, the electromeric shift will take place in the
direction of the more electronegative atom.

>C=O ⎯⎯⎯
⎯→ >C–O
Reagent
e.g.

–CN ⎯⎯⎯
⎯→ –C=N
Reagent
BOND FISSION
Breaking of covalent bond of the compound is known as bond fission. A bond can be broken by two ways -
(1) HOMOLYTIC FISSION :
Occurs in gas phase or in non-polar solvents and is catalysed by reagents. In such fission free radicals are formed.
Here the bond pair is equally shared after the fission.
A–B ⎯→ A• + B• (free radicals)

Condition for Homolytic Bond Fission : Homolysis takes place in the presence of peroxide, UV light, heat
( 500°C), presence of electricity and free radical. The process is known as initiation of free radical reaction.
A : B ⎯(⎯ ⎯⎯⎯
i ) Peroxide
⎯→ A• + B•
(ii) h
(iii) 
(iv) Electricity
or
( v ) Free Radical
h • •
CH3 – H ⎯⎯→ C H 3 ( methyl free radical) + H
(i) Homolytic bond fission gives free radical as the reaction intermidiate.
(ii) Reaction mechanism of the reaction is known as free radical or homolytic mechanism.
(2) HETEROLYTIC FISSION :
Occurs in polar solvents, catalysed by acids or bases, greatly influenced by polarity of solvents. Here, the ions are
formed. In an organic compound such as R - G, two types of ions are formed.
R–G ⎯→R+ + G– (R+ is known as carbocation ion )

R–G ⎯→R– + G+ (R– is known as carbanion ion )
The factor which favours heterolysis is a greater difference of electronegativity between A and B.
Thus,
(i) Heterolytic bond fission gives carbocation or carbanion as reaction intermediate.
(ii) Mechanism of the reaction in which heterolytic bond fission takes place is known as heterolytic mechanism or
ionic mechanism.
(iii) The energy required for heterolytic bond fission is always greater than that for homolytic bond fission due to
electrostatic force of attraction between ions.
REACTION INTERMEDIATES
In the study of organic chemistry following intermediates are important.

(i) Carbocation (ii) Carbanion (iii) Carbon free radical
(iv) Carbene (v) Nitrene
PROPERTY CARBOCATION CARBANION CARBON FREE
RADICAL
Representation C C C
Bond fission Heterolysis Heterolysis Homolysis
Electrically nature Positive Negative Neutral
No. of electrons in 6 8 7
valence shell
Hybridisation sp2 sp3 sp2
Shape Planar Pyramidal Planar
Carbene and Nitrene are of following two types :

PROPERTY SINGLET TRIPLET SINGLET TRIPLET
CARBENE CARBENE NITRENE NITRENE
Representation
C C N N
Electrically nature Neutral Neutral Neutral Neutral
No. of electrons in 6 6 6 6
valence sheet
Hybridisation sp2 sp sp2 sp
Shape V-shape Linear Linear Linear
Stability Less More Less More
REACTION REAGENTS
Organic reagents can be classified in two categories :

(A) Electrophile : Electron deficient species or electron acceptor is electrophile.
(B) Nucleophile : Electron rich species or electron donor is nucleophile.
(A) Electrophiles : It can be classified into two categories :
(I) Charged electrophiles (E)
(II) Neutral electrophiles (E)
(I) Charged electrophiles : Positively charged species in which central atom has incomplete octet is charged
electrophile.
 O  
H  , X  R , N , N =O, SO 3 H
O ••
Note : All cations are charged electrophiles except cations of A, A group elements, Al+++ and NH4.
(II) Neutral electrophiles : It can be classified into three categories :
(i) Neutral covalent compound in which central atom has incomplete octet is neutral electrophile,
• •• ••
BeCl2, BH3, ZnCl2, AlX3, FeX3, C H 3 , C H 2 , C X 2
(ii) Neutral covalent compound in which central atom has complete or expended octet and central atom has
unfilled -d-subshell is neutral electrophile
SnCl4, SiCl4, PCl5, SF6, F7
(iii) Neutral covalent compound in which central atom is bonded only with two or more than two
electronegative atoms is neutral electrophile.
••
BeCl2, BX3, AlX3, FeX3, SnCl4, PCl3 ; PCl5, NF3, C X 2 , CO2, SO3,CS2, CX4
Note :
(i) Cl2, Br2 and I2 also behave as neutral electrophiles.
(ii) Electrophiles are Lewis acids.
(B) Nucleophiles :
Nucleophiles can be classified into three categories :
(I) Charged nucleophiles : Negatively charged species are charged nucleophiles.
H, OH , R–O, CH3, X, SH, R–S

(II) Neutral nucleophiles : It can be classified into two categories :
(i) Neutral covalent compound, in which central atom has complete octet, has at least one lone pair of
electrons and all atoms present on central atom should not be electronegative, is neutral nucleophile.
•• •• •• •• ••
NH 3 , R– NH 2 , R2 NH , R3 N , NH 2 –NH2 (Nitrogen nucleophile)
•• •• ••
H– O –H, R– O –H, R– O
••
–R (Oxygen nucleophiles)
•• ••
•• •• ••
H– S –H, R– S –H, R – S – R (Sulphur nucleophiles)
•• •• ••
•• •• •• ••
PH 3 , R P H2, R2 P H, R3 P (Phosphorus nucleophiles)
(ii) Organic compound containing carbon, carbon multiple bond/bonds behave as nucleophile.
Alkenes, Alkynes, Benzene,
CH2=CH–CH=CH2, CH2=CH–CCH
(III) Ambident nucleophile : Species having two nucleophilic centres, one is neutral (complete octet and has at
least one lone pair of electrons) and other is charged (negative charge) behaves as ambident nucelophile.
O
CN, O–N=O, O–S–OH
O
Note :
(a) Organometallic compounds are necleophiles.
(b) Nucleophiles are Lewis bases.
 Organic compounds which behave as electrophile as well as nucleophile :
Organic compound in which carbon is bonded with electronegative atom (O, N, S) by multiple bond behaves as
electrophile as well as nucleophile.
O O O O O O

R–C–H , R–C–R , R–C–OH , R–C–Cl, R–C–OR , R–C–NH2 , R–CN, R–NC
Note : During the course of chemical reaction electrophile reacts with nucleophile.
NUCLEOPHILICITY AND BASICITY IN
If the nucleophilic atoms are from the same period of the periodic table, strength as a nucleophile parallels
strength as a base e.g. H2O < NH3
H2O < ROH < R–C–O < H–O < R–O

O
increasing base strength
increasing nucleophile strength
 Nucleophile strength increases down a column of the periodic table

(in protic solvents that can have hydrogen bond, such as water and alcohols).
RO < RS & F < Cl < Br < I
e.g.
increasing nucleophilic strength
& decresing base strength
In aprotic solvents such as DMF, DMA, DMSO, HMPA.
I < Br < Cl < F
Increasing basic strength increasing
nucleophilic sterngth
 Steric bulk decreases nucleophilicity .
CH3
e.g. H3C–C–O < HO
CH3
weaker nucleophile stronger nucleophile
Stronger base weaker base
TYPES OF REACTION
In organic chemistry the following types of reactions are important.

(1) Addition reactions
(2) Substitution reactions
(3) Elimination reactions
(1) ADDITION REACTIONS :
The reaction in which reagent adds to a multiple bonds to give less unsaturated or completely saturated product
are known as addition reactions.
e.g.
(i) CH2=CH2 ⎯H
⎯→2
CH3–CH3
Cl
(ii) CH3–CH=CH2 ⎯⎯
⎯→ CH3–CH–CH3
HCl
(iii) CH2=CH2 ⎯HOCl

⎯⎯→ HO–CH2–CH2–Cl
(2) SUBSTITUTION REACTIONS :
Reaction proceeding by the replacement or substitution of one or more atoms or groups of a compound by other
atoms or groups are referred to as substitution reaction.
i.e. C–X + A–B C–A + BX
e.g.
Cl 2 Cl 2 Cl 2 Cl 2
(i) CH4 ⎯⎯⎯ → CH3Cl ⎯⎯⎯ → CH2Cl2 ⎯⎯⎯ → CHCl3 ⎯⎯⎯ → CCl4
h h h h
Cl 2
(ii) CH3–CH2–H ⎯⎯⎯ → CH3–CH2–Cl + HCl
O
Br
NBS
(iii) CH3–CH=CH2 ⎯⎯⎯→ CH2 – CH = CH2 here N.B.S. is N–Br
O
AgNO 3 AgNO 3
(iv) CHCH ⎯⎯⎯⎯ ⎯→ AgCCH ⎯⎯⎯⎯ ⎯→ AgCCAg
NaNH 2 
(v) CHCH ⎯⎯ ⎯ ⎯
⎯→ CHCNa
R −MgX 
(vi) R–CCH ⎯⎯⎯⎯ ⎯→ R–CCMgX + R– H
(vii) CH3 – Cl ⎯KCN
⎯⎯→ CH3 – CN + KCl
(viii) CH3–CH2–OH ⎯⎯→HI
CH3 –CH2–I
aq. KOH
(ix) CH3 –CH2–Cl ⎯⎯ ⎯ ⎯ ⎯→ CH3 –CH2–OH
KNO 2
(x) CH3 –CH2–Cl ⎯⎯ ⎯⎯ → CH3–CH2–O–N=O
(3) ELIMINATION REACTIONS :

Elimination reaction is formally the reverse of addition reaction and consist in removing the two group from one
or two atoms of a molecule to form an unsaturated linkage or centre i.e.,
A B
–C–C– ⎯⎯→ –C=C– + AB
H Cl
alc. KOH
e.g. (i) CH2–CH2 ⎯⎯⎯⎯⎯→ CH2=CH2
H OH
H SO4
(ii) CH2–CH2 ⎯⎯2⎯⎯ → CH2=CH2
conc.
(iii) CH3–CH–O ⎯⎯→ CH3–CH=O
Cu

H H
DISSOCIATION CONSTANTS OF ORGANIC ACIDS

compound Ka compound K a1 K a2
H–COOH 17.7 × 10–5 HOOC–COOH 5400 × 10–5 5.2 × 10–5

CH3–COOH 1.75 × 10–5 HOOC–CH2–COOH 140 × 10–5 0.20 × 10–5
Cl–CH2–COOH 136 × 10–5 HOOC–(CH2)2–COOH 6.4 × 10–5 0.23 × 10–5
Cl2HC–COOH 5530 × 10–5 HOOC–(CH2)3–COOH 4.5 × 10–5 0.38 × 10–5
Cl3C–COOH 23200.7 × 10–5 HOOC–(CH2)4–COOH 3.7 × 10–5 0.39 × 10–5
HOOC COOH
C=C
F–CH2–COOH 260 × 10–5 H H 1000 × 10–5 0.055 × 10–5
HOOC H
C=C
Br–CH2–COOH 125 × 10–5 H COOH 96 × 10–5 4.1 × 10–5
I–CH2–COOH 67 × 10–5
OH
1.1 × 10–10
OH
NO2 1000000 × 10–10
NO2
OH
O2N NO2 10.5 × 10–2
(very large)
NO2
COOH
6.3 × 10–5
DISSOCIATION CONSTANTS OF AROMATIC ORGANIC ACIDS
Ka of Benzoic acid = 6.3 × 10–5 (pKa = 4.20)

compound ortho meta para
Me–C6H4–COOH 12.4 × 10–5 5.4 × 10–5 4.2 × 10–5
O2N–C6H4–COOH 670 × 10–5 32 × 10–5 36 × 10–5
H2N–C6H4–COOH 1.6 × 10–5 1.9 × 10–5 1.4 × 10–5
HO–C6H4–COOH 105 × 10–5 8.3 × 10–5 2.6 × 10–5
MeO–C6H4–COOH 8.2 × 10–5 8.2 × 10–5 3.3 × 10–5

F–C6H4–COOH 53.7 × 10–5 13.4 × 10–5 7.2 × 10–5
Cl–C6H4–COOH 120 × 10–5 15.1 × 10–5 10.3 × 10–5
Ka of Phenol = 1.1 × 10–10 (pKa = 9.98)
Me–C6H4–OH 0.63 × 10–10 0.98 × 10–10 0.67 × 10–10
O2N–C6H4–OH 600 × 10–10 50 × 10–10 690 × 10–10
H2N–C6H4–OH 2 ×10–10 69 × 10–10 0.5 × 10–10
HO–C6H4–OH 3.31×10–10 3 × 10–10 1.1 × 10–10
MeO–C6H4–OH 1.05 × 10–10 2.24 × 10–10 0.62 × 10–10
F–C6H4–OH 15 × 10–10 5.2 × 10–10 1.1 × 10–10
Cl–C6H5–OH 77 × 10–10 16 × 10–10 6.3 × 10–10
DISSOCIATION CONSTANTS OF ALIPHATIC ORGANIC BASES
compound Kb
CH3–NH2 4.5 × 10–4
CH3CH2–NH2 5.1 × 10–4
CH3–CH–NH2
| 4 × 10–4
CH3
CH3
|
CH3–C–NH2 5 × 10–4
|
CH3
5.4 × 10–4
CH3–NH–CH3
CH3CH2–NH–CH2CH3 10 × 10–4
CH3–N–CH3
| 0.6 × 10–4
CH3
CH3CH2–N–CH2CH3
| 5.6 × 10–4
CH2CH3
CH2–NH2 0.2 × 10–4
NH2 4.2 × 10–10
Me 11.7 × 10–10
N
Me

Me–C6H4–NH2 2.6 × 10–10 5 × 10–10 12 × 10–10
O2N–C6H4–NH2 0.00006 × 10–10 0.029 × 10–10 0.001 × 10–10
H2N–C6H4–NH2 3 × 10–10 10 × 10–10 140 × 10–10
MeO–C6H4–NH2 3 × 10–10 2 × 10–10 20 × 10–10
Cl–C6H4–NH2 0.05 × 10–10 0.3 × 10–10 1 × 10–10

PURIFICATION & CHARACTERIZATION OF ORGANIC COMPOUNDS
PURIFICATION OF ORGANIC COMPOUNDS
The methods to be employed depend on the physical state of the compound.
CRYSTALLISATION :
This method is based on the differences in the solubility of the organic compound and its impurities in a solvent.
(a) Preparation of the solution : Organic substance is powdered and is dissolved in a suitable solvent by heating.
The amount of solvent should be just sufficient to dissolve the whole of the solid on heating.
Choice of Solvent. The choice of solvent is very important in the crystallisation process. The main conditions of
the solvent are:
(i) The organic substance should dissolve in the solvent upon heating and it should get separated on cooling.
(ii) The solvent should not dissolve the impurities.
(iii) The solvent should not react chemically with the substance.
e.g., suppose we want to purify sugar containing an impurity of common salt. This can be done by treating the
mixture with ethanol around 350 K. The sugar will dissolve whereas common salt remains insoluble.
(b) Filtration of the solution. The hot saturated solution is filtered preferably through a fluted filter paper placed in a
glass funnel. The use of the fluted filter paper makes the filtration rapid. The jacketer of the hot water funnel is
heated from outside and this keeps the solution hot in the glass funnel. This will prevent the formation of crystals
during filtration.
(c) Crystallisation. The hot filtration is allowed to cool slowly and undisturbed in a beaker or in a crystallising dish.
After some time the crystals of the pure compound are formed.
(d) Separation of the crystals. The crystals formed are separated from the mother liquor by filtration. The filtration is
normally done by use of Buckner funnel and a suction pump. This enables the filtration under reduced pressure
and is therefore, quite fast.
(e) Drying of crystals. The crystals are dried by pressing between the folds of filter paper and then placed in a steam
of air oven for some time. The crystals are finally dried over sulphuric acid or calcium chloride in a desiccator.
SUBLIMATION
Certain organic solids directly change from solid to vapour state on heating. This process is called sublimation. The vapours
on cooling change back to the solid form
Heat
Solid Vapours
Cool
The sublimation process is used for the separation of those solids which sublime on heating from non-volatile
solids. The process is generally used for the purification of camphor, naphthalene, anthracene, benzoic acid, etc.
containing non-volatile impurities.
DISTILLATION
This method is used for the purification of liquids which boil without decomposition and contain non-volatile impurities.
The simple distillation involves its boiling point so that it is converted into vapours. On cooling the vapours, pure
liquid is obtained.
The distillate contains pure liquid while the impurities are left behind in the distillation flask
e.g.Ether from ethyl alcohol.
FRACTIONAL DISTILLATION
This process is used to separate a mixture of two or more miscible liquids which have boiling points close to each other.
The fractionating column is a long tube provided with obstructions to the passage of the vapours moving upwards
and liquid moving downwards. This method may be used to separate a mixture of acetone (b.p. 330K) and methyl
alcohol (b.p. 338. K).
DISTILLATION UNDER REDUCED PRESSURE (VACCUM DISTILLATION)

Certain liquids have a tendency to decompose at a temperature below their boiling points. Such liquids cannot be purified
by ordinary distillation. Therefore vacuum distillation is used for liquids which decompose at a temperature below
their normal boiling points.
e.g.. glycerol boils with decomposition at 563K.
STEAM DISTILLATION
The process of steam distillation is used for the separation and purification of liquid which is appreciably volatile in steam,
from non-volatile components of a mixture. Thus, the process of steam distillations is used to purify the substances which
(i) are volatile in steam but are not miscible with water
(ii) possess sufficiently high vapour pressure at the boiling point temperature of water (1000C)
(iii) contain non-volatile impurities.
The process of steam distillation can be applied for the separation of a mixture of o-nitrophenol and p-nitrophenol.
In this process, water vapours carry along with them vapours of o-nitrophenol which is more volatile and they get
condensed in the receiver ;p-nitrophenol with higher b.p. remains in the distillation flask. The method can also be
used for the purification of impure sample of aniline.
CHROMATOGRAPHY
This method is based on the differences in the rates at which the components of a mixture are adsorbed on a suitable
adsorbent. There are many forms of chromatography such as column chromatography, paper chromatography, thin
layer chromatography (TLC), gas chromatography, etc. The simplest method is column chromatography.
Applications of chromatographic method. This method has been used
(i) To separate ortho and para nitro-anilines.
(ii) To separate blue and red dyes.
(iii) To separate and purify plant pigments and other natural products.
Types of chromatography :
Based on the principle involved chromatography is classified into different categories. Two of these are.
(a) Adsorption chromatography, and
(b) Partition chromatography
(a) Adsorption chromatography :
Adsorption chromatography is based on the fact that different compounds are adsorbed on an adsorbent to
different degrees. Commonly used adsorbents are silica gel and alumina, When a mobile phase is allowed to move
over a stationary phase (adsorbent), the components of the mixture move by varying distances over the stationary
phase. Following are two main types of chromatographic techniques based on the principle of differential
adsorption.
(i) Column chromatography :
Solvent
Mixture of compound (a + b + c)
a a
Adsorbent(stationary phase) b+c b
c
Glass wool
c
Different stages of separation of components of a mixture
Column chromatography involves separation of a mixture over a column of adsorbent (stationary phase) packed in
a glass tube. The column is fitted with a stopcock at its lower end. The mixture adsorbed on adsorbent is placed on
the top of the adsorbent column packed in a glass tube. An appropriate eluant which is a liquid or a mixture of
liquids is allowed to flow down the column slowly. Depending upon the degree to which the compounds are
adsorbed, complete separation takes place. The most readily adsorbed substances are retained near the top and
others come down to various distances in the column
(ii) Thin layer chromatography :
solvent front
jar
adsorbent coated on glass plate spot
Base line sample dot y base line
solvent x
Developed chromatogram
Thin layer chromatography (TLC) is another type of adsorption chromatography, which involves separation of
substances of a mixture over a thin layer of an adsorbent coated on glass plate. A thin layer (about 0.2 mm thick)
of an adsorbent (silica gel or alumina) is spread over a glass plate of suitable size. The plate is known as thin layer
chromatography plate or chromaplate. The solution of the mixture to be separated is applied as a small spot about
2 cm above one end of TLC plate. The glass plate is then placed in a closed jar containing the eluant. As the eluant
rises up the plate, the components of the mixture move up along with the eluant to different distances depending
on their degree of adsorption and separation takes place. The ralative adsorption of each component of the mixture
is expressed in terms of its retardation factor i.e. Rf value
D is tance moved by the subst ance from base line (x)

Rf =
Dis tan ce moved by the solvent from base line (y)
The spots of coloured compounds are visible on TLC plate due to their original colour. The spots of colourless
compounds which are invisible to the eye but fluorescence, can be detected by putting the plate under ultraviolet
light. Another detection technique is to place the plate in a covered jar containing a few crystals of iodine spots of
compounds, which adsorb iodine will show up as brown spots. Sometimes an appropriate reagent may also be
sprayed on the plate. For example, Amino acids may be detected by spraying the plate with ninhydrin solution
(b) Partition Chromatography :
card board card board

chromatography paper chromatography paper
jar jar
Spot spot
base line base line
solvent Solvent
Paper chromatography chromatography paper in two different shapes
Partition chromatography is based on continuous differential partitioning of components of mixture between

stationary and mobile phases. Paper chromatography is a type of partition chromatography. In paper
chromatography, a special quality paper known as chromatography paper is used. Chromatography paper contains
water trapped in it, which acts as the stationary phase.
A strip of chromatography paper spotted at the base with the solution of the mixture is suspended in a suitable
solvent or a mixture of solvents. This solvent rises up the paper by capillary action and flows over the spot. The
paper selectively ratains different components according to their differing partition in the two phases. The paper
strip so developed is known as a chromatogram. The spots of the separated coloured compounds are visible at
different heights from the position of initial spot on the chromatogram. The spots of the separated colourless
compounds may be observed either under ultraviolet light or by the use of an appropriate spray reagent as
discussed under thin layer chromatography.
QUALITATIVE ANALYSIS
The qualitative analysis of an organic compound involves the detection of all the elements present in it.
Detection of Carbon and Hydrogen

A small amount of the dry and powdered substance is mixed with about double the amount of pure and dry copper oxide.
The mixture is heated in a well dried hard glass tube (fig) delivery tube is packed with glass wool containing anhydrous
copper sulphate (white). When the mixture is heated , the carbon present in the compound is oxidised to carbon dioxide
which turns lime water milky. The hydrogen present in the organic compound is oxidised to water which turns anhydrous
copper sulphate in the bulb to blue.
Anhydrous copper sulphate
lime water
organic compound
+
copper oxide
Detection of carbon and hydrogen in an organic compound

C + 2CuO ⎯⎯→ CO2 + 2Cu

2H + CuO ⎯⎯→ Cu + H2O
CO2 + Ca(OH)2 ⎯⎯⎯

⎯→ CaCO3  + H2O
CuSO4 + 5H2O ⎯⎯⎯

⎯→ CuSO4 . 5H2O
(white) (Blue)
This method is known as copper oxide test.
Detection of Nitrogen
Nitrogen in an organic compound is detected by the following tests :
Soda lime test

A pinch of an organic compound is heated strongly with soda lime (NaOH + CaO) in a test tube. If ammonia gas evolves, it
indicates nitrogen.
CaO
CH3CONH2 +NaOH CH3COONa + NH3

acetamide
Limitation : This method has a limitation. A large number of organic compounds such as nitro and diazo
compounds do not liberated ammonia on heating with sodalime.
Lassaigne’s method
A small piece of a dry sodium metal is heated gently in a fusion tube till it melts to a shining globule. Then , a small amount
of organic substance is added and the tube is heated strongly till it becomes red hot. The red hot tube is then cooled
and filtered. The filtered liquid is known as sodium extract or Lassaigne’s extract.
The Lassaigne’s extract is usually alkaline. If not, it may be made alkaline by adding a few drops of a dilute
solution of sodium hydroxide added to a part of sodium extract a small amount of a freshly prepared ferrous
sulphate solution is and the contents are warmed. A few drops of ferric chloride solution are then added to the
contents and the resulting solution is acidified with dilute hydrochloric acid. The appearance of a bluish green or a
blue colouration confirms the presence of nitrogen in the organic compound. The following chemical reactions
occur during the test :

Na + C + N ⎯⎯→ NaCN

2Na + S ⎯⎯→ Na2S

Na + X ⎯⎯→ NaX (X = Cl, Br or I)
FeSO4 + 2NaCN ⎯→ Fe(CN)2 + Na2SO4
Fe(CN)2 + 4NaCN ⎯→ Na4[Fe(CN)6] sodium ferrocyanide
3Na4[Fe(CN)6] + 4FeCl3 ⎯→ Fe4[Fe(CN)6]3 + 12NaCl
ferric ferrocyanide (Prussian blue colour)
Detection of Sulphur
The sulphur in the compound reacts with sodium metal to form sodium sulphide.
2Na + S ⎯→ Na2S
from organic compound

The Lassaigne’s extract is divided into two parts and following tests are performed.
Sodium nitroprusside test.

The one portion of the extract, a few drops of sodium nitroprusside are added. The appearance of violet
colouration indicates sulphur.
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NO.S]
sod. nitroprusside violet colouration
Lead acetate test

The other part of the Lassaigne’s extract is acidified with acetic acid and then lead acetate solution is added. Formation of
black precipitate confirms the presence of sulphur.
Na2S+Pb(CH3COO)2 PbS + 2CH3COONa

lead acetate black
Detection of Halogens :
Lassaigne’s test.
Sodium extract is prepared as already. During fusion , sodium will combine with the halogen (from the organic compound)
to form sodium halide
Na + X ⎯Fusion
⎯⎯→ NaX (X=Cl, Br, I)
(i) A white precipitate soluble in ammonium hydroxide solution indicates the presence of chlorine in the organic
compound
NaCl + AgNO3 ⎯→ AgCl + NaNO3
white ppt.
(ii) A dull yellow precipitate partially soluble in ammonium hydroxide solution indicates the presence of bromine in
the organic compound.
NaBr + AgNO3 ⎯→ AgBr + NaNO3
dull yellow ppt.

(iii) A bright yellow precipitate, completely insoluble in ammonium hydroxide solution, indicates the presence of
iodine in the organic compound.
NaI + AgNO3 ⎯→ AgI + NaNO3
bright yellow ppt
Special test for bromine and iodine.

2NaBr + Cl2 ⎯→ 2NaCl + Br2
(turns CS2 layer orange)
2NaI + Cl2 ⎯→ 2NaCl + I2
(turns CS2 layer violet)
Test of phosphorus :
The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the compound is
oxidised to phosphate. The solution is boiled with nitric acid and then treated with ammonium molybdate. A
yellow colouration or precipitate indicates the presence of phosphorus.
Na3PO4 + 3HNO3 ⎯→ H3PO4 + 3NaNO3
H3PO4 + 12(NH4)2 MoO4 + 21HNO3 ⎯→ (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O

Ammonium molybdate Ammonium phosphomolybdate
Quantitative analysis
Estimation of Carbon and Hydrogen :

Principle. A known weight of the given dry organic compound is heated strongly with dry cupric oxide in an
atmosphere of air or oxygen free from CO 2. The carbon and hydrogen of the organic compound are oxidised to
CO2 and water vapour as :
C + 2CuO –––––→ CO2 + 2Cu
(from compound)
2H + CuO –––––→ H2O + Cu
(from compound)
Procedure :
Let the mass of organic compound taken = mg
Mass of water formed = m1g
(increase in CaCl2 in U-tube)
Mass of carbon dioxide formed = m 2g
(increase in potash tubes)
Percentage of Carbon
We know that 1 mole of carbondioxide (44 g) contains 1 gram atom of carbon (12g).
CO2C
44 g of CO2 contain C = 12g
12
m2 g of CO2 contains C = × m2 g
44
12m 2
Hence, Percentage of carbon = × 100
44  m
Percentage of Hydrogen
We know that one mole of water (18g) contains 2 gram atom of hydrogen (2g)
H2O=2H
18g of H2O contain H = 2g
2
 m1 g of H2O contains H = × m1 g
18
2m1
Percentage of hydrogen = × 100
18  m
Percentage of C
12 Mass of CO 2 formed
= × x 100
44 Mass of compound taken
Percentage of H
2 Mass of H 2 O formed
= × x 100
18 Mass of compound taken
ESTIMATION OF NITROGEN :
There are two methods for the estimation of nitrogen
(i) Duma’s method (ii) Kjeldahl’s method
Duma’s method :
Principle of the method. A known mass of an organic compound is heated with dry cupric oxide in an
atmosphere of carbon dioxide. The carbon and hydrogen are oxidised to carbon dioxide and water respectively
while nitrogen is set free. If any oxide of nitrogen is produced during this process, it is reduced to nitrogen by
passing over a heated copper gauze. The gaseous mixture is collected over an aqueous solution of KOH when all
the gases except nitrogen are absorbed. The volume of nitrogen produced is measured at room temperature and
atmospheric pressure. From the volume of N2 produced, percentage of nitrogen in the sample can be calculated.
C + 2CuO ⎯→ CO2 + 2Cu

2H + CuO ⎯→ H2O + Cu
2N + CuO ⎯→ N2 + oxides of nitrogen
Oxides of nitrogen + Cu → CuO + N2
Let the mass of organic compound = wg

The volume of nitrogen collected = Vcm3
Atmospheric pressure (from barometer) = P mm of Hg
Room temperature = tºC
Aqueous tension at tºC = a mm of Hg
Pressure of dry nitrogen = (P – a) mm of Hg
Let us first convert the volume of nitrogen to volume at S.T.P.
Experimental conditions S.T.P. conditions
P1 = (P – a)mmHg P2 = 760 mm
T1 = (273 + t)K T2 = 273
V1 = V cm3 V2 = ?
P1V1 PV
Applying gas equation = 2 2
T1 T2
P1V1T2 (P − a )  V 273
 V2 = = = x cm3 (say)
P2 T1 760(273 + t )
Now 22400 cm3 of N2 at S.T.P. weight = 28 g
28
x cm3 of N2 at S.T.P. will weigh = × xg
22400
Mass of nitrogen 28 100

 Percentage of nitrogen = × 100 =
Mass of organic compound 22400  w
Kjeldahl’s method
This method cannot be used for
(i) Organic compounds containing nitrogen in the ring such as pyridine, quinoline, etc.
(ii) Organic compounds containing nitrogen (-NO2) and diazo (-N = N-) groups.
Principle : A known weight of the organic compound is heated with conc. H 2SO4 so that nitrogen is quantitatively
converted into ammonium sulphate. The solution is then heated with excess of sodium hydroxide. The ammonia
gas evolved is passed into a known but excess volume of standard acid (HCl or H2SO4). The acid left unused is
estimated by titrating the solution with standard alkali. From the amount of acid left unused the amount of acid
used for neutralisation of ammonia can be calculated. From this percentage of nitrogen can be calculated.
⎯⎯⎯⎯ ⎯ →
Conc.H SO
C, H, S 2 4
CO2 + H2O + SO2
(from organic compound)
⎯⎯⎯⎯ ⎯ →
Conc.H SO
N 2 4
(NH4)2SO4
(from organic compound) (ammonium sulphate)
(NH4)2SO4 + 2NaOH ⎯Heat

⎯⎯→ Na2SO4 + 2NH3 + 2H2O
2NH3 + H2SO4 ⎯→ (NH4)2SO4
NH3 + HCl ⎯→ NH4Cl
Calculations
Let the mass of organic compound = w g
Volume of standard acid taken = V cm3
Normality of acid = N1
Let vol. of standard alkali used for neutralisation of unused acid = V 2 cm3
Normality of standard alkali = N2
N1V1 = N 2 V2
 
alkali acid
Let this volume of v cm3

 Vol. of acid used for neutralisation of ammonia
= (V – v) cm3 of N1 normality
 Ammonia liberated = (V – v) cm3 of N1 solution
Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g
14(V − v)x N1
(V – v) cm3 of N1 NH3 solution contains nitrogen = g
1000
Mass of nitrogen
Percentage of nitrogen = x 100
Mass of organic compound
14(V − v)x N1 100 1.4(V − v)x N1
= × =
1000 w w
ESTIMATION OF HALOGENS :
Carius method :
Principle : A known mass of the organic substance is heated with fuming HNO 3 in a Carius tube. The silver
halide so obtained is separated, washed, dried and weighed. From the weight of silver halide formed, the
percentage of halogen can be calculated.
X + AgNO3 ⎯→ AgX
Halogen
Carbon, hydrogen or sulphur present in the compound will be oxidised to CO 2, H2O and H2SO4 respectively.
C + 2O ⎯HNO
⎯⎯ 3
→ CO2
2H + O ⎯HNO
⎯⎯ 3
→ H2 O
S + H2O + 3O ⎯HNO
⎯⎯ 3
→ H2SO4
Calculations :
Let the mass of organic compound be w g
Mass of silver halide formed = a g
Now, AgX = X
108 + X parts by weight of silver halide contains X parts by weight of halogen (X is its atomic mass)
(108 + X) g of silver halide give halogen = X
X
a g of silver halide will give halogen = × ag
(108+ X)
Mass of halog en
 Percentage of halogen = x 100
Mass of organic compound
X a 100
= ×
(108+ X) w
Here X is the atomic mass of halogen, e.g.
Cl = 35.5 , Br = 80 (79.9 exact),
I = 127 (126.9 exact)
Atomic mass of halogen  Mass of silver halide
Percentage of halogen = ×100
(108 + At. mass of halogen)  Mass of organic substance
ESTIMATION OF SULPHUR :
Sulphur is estimated by Carius method.
Principle : A known mass of the organic compound is heated with fuming HNO 3 in a sealed tube when sulphur is
quantitatively converted into sulphuric acid. It is then precipitated with barium chloride as barium sulphate. The
precipitate is filtered, washed, dried and weighed. From the weight of BaSO 4 formed, the percentage of sulphur
can be calculated. The main reactions are :
S + H2O + 3O ⎯HNO
⎯⎯ 3
→ H2SO4
H2SO4 + BaCl2 ⎯→ BaSO4
ppt.
Calculations :
Let the mass of organic compound = w g
Mass of BaSO4 formed = ag
BaSO4S
137 + 32 + 64 = 32
233 = 32
233 g of BaSO4 contain sulphur = 32 g
32  a
ag of BaSO4 will contain sulphur = g
233
Mass of sulphur 32a 100
Percentage of sulphur = × 100 = ×
Mass of organic compound 233 w
ALKANE
GENERAL INTRODUCTION :
• These are the hydrocarbons in which Carbon - Carbon contains single bond. (Saturated hydrocarbon).
• These are also called as ‘Paraffins’ (Parum + Affinis i.e. less reactive).
• In alkane if chiral carbon or unsymmetrical carbon is present, then it shows optical isomerism.
• General reagents such as dil. and conc. HCl, dil. and conc.H2SO4, dil. and conc. HNO3, acidic and basic KMnO4
and K2Cr2O7 usually does not react with alkane.
• General formula is CnH2n+2 .(n = 1, 2, 3, 4..............)
• Hybridisation state of carbon is sp3.

• Geometry of carbon is tetrahedral.
• Bond angle is 109º28’.
• Number of bond angle in methane are six, while in ethane are twelve.
H H H
H 4
3 1 2
1 6 5 5
2 3 6
2
H 1 3
4 5 4
H 6 H H H H
Methane Ethane
• C–C bond length is 1.54 Å while C–H bond length is 1.12 Å.

• C–C bond energy is 84 kcal/ mole while C–H bond energy is 98 kcal /mole.
• Alkane shows only chain, position isomerism.
• First three members methane, ethane and propane does not exhibit any isomerism, while butane and pentane
shows only chain isomerism.
H
|
H– C –H CH3–CH3 CH3–CH2–CH3 CH3–CH2–CH2–CH3 CH3–CH –CH3
| |
H CH3
Methane Ethane Propane n-Butane Isobutane
CH3
|
CH3–CH2–CH2–CH2–CH3 CH3–CH –CH2–CH3 CH3–C–CH3 CH3–CH2–CH2–CH2–CH2–CH3
| |
CH3 CH3
n-Pentane IsoPentane NeoPentane n-Hexane
CH3
CH3–CH2–CH–CH2–CH3 CH3–C–CH2–CH3 CH3–CH–CH2–CH2–CH3 CH3–CH–CH–CH3
CH3 CH3 CH3 CH3 CH3
3-Methyl pentane Neohexane Isohexane 2, 3-Dimethyl butane

• The molecules of alkanes are angular , so carbon chains in these molecules are zig- zag type (not straight) which
may be branched or unbranched as shown below.
(Unbranched) (branched)
PHYSICAL PROPERTIES :
• Alkanes are colourless, odourless and tasteless.
• Physical state:
C1–→ C4 Gaseous state
C5 –→ C17 Liquid state (except neo pentane)
C18 & above –→ Solid like wax
• Alkanes are lighter than water, so it floats over water.
• Solubility : [Like dissolves like]
Alkanes are non-polar or weakly polar compounds so these are soluble in non-polar solvents (benzene, ether,
chloroform, carbontetrachloride etc.) and are insoluble in polar solvents (water etc.).
• Boiling point :
For homologues B.P.  Molecular weight
because Mol. wt.  = Surface area  = Intermolecular Vander wall's interaction  = B.P. 
1
For isomers B.P. 
No. of branches
because Branches  = Spherical shape  = Surface area  = B.P. 
• Melting point :
The melting point of alkanes depends upon molecular weight as well as packing in crystal lattice
Variation of boiling point and melting point in alkanes
Name Formula Molecular mass B.P. (ºC) M.P. (ºC)

Methane CH4 16 –162 –183
Ethane CH3CH3 30 –88.5 –172
Propane CH3CH2CH3 44 –42 –187
n-Butane CH3(CH2)2CH3 58 0 –138
Isobutane (CH3)2CHCH3 58 –12 –159
n-Pentane CH3(CH2)3CH3 72 36 –130
Isopentane (CH3)2CHCH2CH3 72 28 –160
Neopentane (CH3)4C 72 9.5 –17
n-Hexane CH3(CH2)4CH3 86 69 –95
n-Heptane CH3(CH2)5CH3 100 98 –90.5
n-Octane CH3(CH2)6CH3 114 126 –57
• Graphical representation :
[regular graph] [Irregular or zig-zag graph]

B.P. M.P.
No. of carbon atoms No. of carbon atoms
 M.P. (odd to even) >  M.P. (even to odd)
Ques. Boiling point order ?

(i) CH4 < CH3CH3 < CH3CH2CH3
CH3 CH3
(ii) CH3–C–CH3 < CH3–CH–CH2–CH3 < CH3CH2CH2CH2CH3
CH3
Ques. Melting point order ?
(i) CH3CH2CH3 < CH4 < CH3CH3
CH3 CH3
(ii) CH3–CH–CH2–CH3 < CH3CH2CH2CH2CH3 < CH3–C–CH3
CH3
 Maximum packing due to

symmetrical spherical shape
CHEMICAL PROPERTIES OF ALKANE :
Halogenation
R–X
X2/h or UV light
(F2 > Cl2> Br2 > I2)
O
Nitration
R–N
HNO3/400ºC O
Sulphonation
R–SO3H
H2S2O7
Reed reaction
R–SO2Cl
SO2 + Cl2/h
SO2Cl2/h
R–Cl
R–H
Isomerisation
or Branched alkane
R–R AlCl3/HCl
Pyrolysis or Cracking
Alkenes + CH4 or C2H6
500º–700ºC
Cr2O3 + Al2O3
Aromatic compound
500ºC
CH2N2/
Higher alkane
step up reaction
O2
CO2 + H2O + HC (exothermic)
combustion
O2 / Cu R–CH2OH
Catalytic Mo2O3
R–CHO
Oxidation (AcO)2 Mn
R–COOH
PREPARATION METHODS OF ALKANE :

NaOH + CaO/
RCOOH
Soda lime
Kolbe's electrolysis
RCOONa
Na / ether
R–X
Wurtz reaction
Zn / Ether
R–X
Frankland's reaction
(i) Li (ii) CuX (iii) R–X

R–X
Corey-House synthesis
R–H
Zn/HCl or LiAlH4
R–X or
Reduction
R–R
HOH or ROH
R–Mg–X
or NH3 or RNH 2
HI / red P / 140ºC
RCOOH or ROH or R–C–R or RCHO
Reduction
O
Zn–Hg/HCl
R–C–R or R–C–H
Clemmenson's reduction
O O
H2N–NH2 / KOH
R–C=O or R–C=O
Wolff Kishner reduction
R H
200–300ºC, H2/Ni
R–CCH or R–CH=CH2
Sabatier Senderen's reaction
SPECIAL POINTS :
• LPG is called as liquefied petroleum gas or kitchen gas which is a mixture of propane and butane.
• CNG (compressed natural Gas) mainly contains CH4.
• A mixture of n-butane and isobutane is called as Calore gas.
• Methane reacts with ozone to make formaldehyde.
• When methane is heated (at about 1500º C) in presence of nickel it makes acetylene.
• Sabetier Senderen's reaction :
Ni/200ºC
CO + 3H2 CH4 + H2O
Ni/200ºC
CO2 + 3H2 CH4 + 2H2O
• Preparation of synthesis gas :
CH4 + H2O ⎯Ni
⎯/1000
⎯⎯ ⎯ºC
→ CO + 3H2
ALKENE
::
• These are the acyclic hydrocarbons in which unsaturation (C=C) is present.
• These are also known as olefins (i.e. oleum, oil + fines, forming) because lower alkene react with halogens to form
dihalides which are oily substances.
• General formula is CnH2n(n = 2, 3, 4, 5..........).
• Hybridisation of unsaturated ‘C’ atoms are sp2

• Geometry of unsaturated ‘C’ carbon is trigonal planar.
• Bond angle on sp2 carbon is 120º.
• C=C bond length is 1.34 Å.
• C–H bond length is 1.10 Å.
• C=C bond energy is 142 kcal/mol
• C–H bond energy is 106 kcal/mol
• Alkene shows chain, position, functional (ring chain), optical & geometrical isomerism.
(i) Chain isomers → CH3–CH2–CH=CH2 and CH3–C=CH2

|
CH3
(ii) Position isomers → CH2=CH–CH2–CH3 and CH3 – CH = CH – CH3

(iii) Functional isomers (ring chain isomerism) → CH3–CH2–CH=CH2 and CH2– CH2
| |
CH2– CH2
(iv) Geometrical isomers → CH3–C–H and CH3–C–H
|| ||
CH3–C–H H–C–CH3
(cis -2-butene) (trans-2-butene)
*
(v) Optical isomerism → CH3CH2–CH–CH=CH2
CH3
Special Point : Cumulated polyene can exhibit geometrical as well as optical isomerism.
CH3 H
C=C=C
H CH3
This molecule is simplest example of cumulated polyene which can exhibit optical isomerism. Because this is a
chiral molecule. Similarly suitably substituted polyene containing odd no. of double bond can exhibit geometrical
isomerism as
CH3 CH3
C=C=C=C
H H
Because this is a planar molecule.
a
• Cumulated polyene having even no. of double bonds which has = C system at the both end can exhibit optical
b
isomerism but cannot exhibit geometrical isomerism.
a
• Cumulated polyene having odd no. double bonds which have = C system at both end can exhibit geometrical
b
isomerism but cannot exhibit optical isomerism.
• Alkenes are colourless and odourless.
• These are insoluble in water and soluble in organic solvents.
• Physical state :
C2—C4 ––→ gaseous
C5—C15 ––→ liquid
C16 and above––→ solid like wax
Molecular weight
Boiling and Melting point 
No. of branches
Name Formula B.P.(ºC) M.P.(ºC)

Ethylene CH2 =CH2 –102 –169
Propylene CH3 –CH=CH2 –48 –185
1-Butene CH3 CH2 –CH=CH2 –6.5 –171
cis-2-Butene cis–CH3 –CH=CH–CH3 4 –139
trans-2-Butene trans–CH3 –CH=CH–CH3 1 –106
Isobutylene (CH3 )2 C=CH2 –7 –141
• B.P and M.P. decreases with increase in branches in alkene.
• The melting points of cis isomers are lower than trans isomers because isomer is less symmetrical than trans. Thus
trans packs more tightly in the crystal lattice and hence has a higher melting point.
• The boiling points of cis isomers are higher than trans isomers because cis–alkenes has greater polarity (Dipole
moment) than trans one.
• These are lighter than water.

CHEMICAL PROPERTIES OF ALKENES :
HX
R–CH–CH3
X
HBr/Peroxide
R–CH2–CH2–Br
X2
R–CH–CH2–X (Br2/CCl4 gives test of
unsaturation)
HOCl
X
R–CH–CH2–Cl
dil. H2SO4
OH
or H2O/H  R–CH–CH3
OH
Conc. H2SO4 R–CH–CH3
or HO–SO2–OH
OSO2OH
(i) (AcO)2Hg (ii) H2O
R–CH–CH3
(iii) NaBH4 H2O/H
OH R–CH2CH3
Hydrolysis
BH3 or B2H6/THF (RCH2CH2)3B
Hydroboration
or
R–CH2–CH2–BH2 H2O2/OH
H2/Ni R–CH2CH2–OH
R–CH2–CH3 Oxidation
200–300ºC
OsO4/H3O
R–CH–––CH2
OH OH
Baeyer reagent OH
R–CH=CH2 R–CH–––CH2 (Test of unsaturation)
1% alkaline KMnO4
OH OH OH
OH
mCPBA H3O OH
R–CH–––CH2 R–CH–––CH2
Prelischave's reaction
O OH
O3 + H2O + Zn
R–CHO + HCHO
ozonolysis
O3 + H2O
RCOOH + HCOOH
ozonolysis
Strong oxidant
RCOOH + CO2 
K2Cr2O7 or KMnO4/H
O2
combustion
Cl2
Allylic substitution product (Cl–H2C–CH=CH2)
500ºC
NBS/
Allylic substitution product (Br–H2C–CH=CH2)
Al2(SO4)3
Isomerisation
200–300ºC
PREPARATION METHODS OF ALKENE :
conc. H2SO4/170ºC
R–CH2–CH2–OH
–H2O
alc. KOH
R–CH2–CH2–X
–HX
NaNH2
R–CH2–CH2–X
–HX
Zn dust
R–CH–CH2
–X2
X X R–CH=CH2
H2
R–CCH
Pd + BaSO4/CaCO3
Kolbe's electrolysis
R–CH–COOK
R–CH–COOK
R 
R 
N OH
Pyrolysis
R CH2–CH2–R

R–C–O–CH2–CH2–R
Pyrolysis
O
R

R–N O
Pyrolysis
CH2–CH2–R
SPECIAL POINTS :
• Ethene is used in the artificial ripening of fruits.
• Water solution of sodium or pottasium salt of succinic acid on electrolysis gives ethene at anode.
• Ethene react with sulpher monochloride (S2Cl2) to form poisonous mustard gas (, -dichloro diethyl sulphide).
Gas is used as a war gas. (Used in 1st world war)
CH2 Cl Cl CH2 ClCH2 CH2Cl

|| + | | + || ⎯→ | | +S
CH2 S–S CH2 H2C––S––CH2
Mustard gas ( , ’-dichloro diethyl sulphide)
• Some other reactions of ethene are :
NOCl
Cl–CH2–CH2–N=O
Tilden's reagent
CH2N2/ (Cyclopropane)
N2O3
O2N–CH2–CH2–N=O (Ethylene nitrosite)
N2O4
O2N–CH2–CH2–NO2 (Ethylene nitrosate)
CH3COCl/AlCl3
CH2=CH2 CH3–C–CH2–CH2–Cl
CH3
O
CH3–C–Cl/AlCl3
CH3
CH3
CH3–C–CH2–CH2–Cl
CH3
CH3–O–CH2–Cl/AlCl3
CH3–O–CH2–CH2–CH2–Cl
CO + H2/Catalyst
CH3–CH2–CHO
Hydrofomylation
CO + H2O/H
CH3–CH2–COOH
Hydrocarboxylation
ALKYNE
GENERAL INTRODUCTION
• These are the acyclic hydrocarbons in which unsaturation (CC) is present.
• Hybridisation state of triple bonded carbon in alkyne is sp.
• Geometry of unsaturated carbon is linear in alkynes.
• Bond angle in alkyne on sp carbon atom is 180º.
• Their general formula is CnH2n–2 (n = 2, 3, 4, 5 ..........................)
• C–C triple bond length is 1.20 Å.
• C–H bond length is 1.08 Å.
• C–C triple bond energy is 200 kcal/mol.
• C–H bond energy is 121 kcal/mol.
• Alkyne shows chain, position and functional isomerism. They are functional isomer with cycloalkene and
alkadiene.
e.g. : Isomers of C4H6 are :
CH3–CC–CH3 CH3–CH2–CCH CH3–CH=C=CH2CH2=CH–CH=CH2
2-Butyne 1-Butyne 1,2 –Butadiene 1,3-Butadiene Cyclobutene
CH3 CH2
CH3
1-Methyl cyclopropene 3-Methyl cyclopropene Methylidene cyclopropane Bicyclobutane
PHYSICAL PROPERTIES
• Alkynes are colourless, odourless and tasteless.
• Lower alkynes are partially soluble in H2O.(It is due to its polarisibility).
• Higher alkynes are insoluble in water due to more % of covalent character.
• Completely soluble in organic solvents.
• Melting point and boiling point increases with molecular mass and decreases with number of branches.
• Physical state :
C2–C4 → Gaseous C5–C11 → Liquids C12 & above → Solids
Molecular weight
Boiling point and Melting point 
No. of branches
Name Formula B.P. (ºC) M.P. (ºC)

Acetylene HC  CH –75 –82
Propyne CH3 –CCH –23 –101.5
1-Butyne CH3 CH2 –CCH 9 –122
2-Butyne CH3 –CC–CH2 27 –24
CHEMICAL PROPERTIES OF ALKYNE
Br
HBr HBr
R–C=CH2 R–C–CH3
Br Br
HBr/Peroxide HBr
R–CH=CH R–CH–CH2
Peroxide
Br Br Br
Br Br
Br2
R–C––CH (Test of unsaturation)
Br Br
OH OH Cl Cl
HOCl HOCl –H2O
R–C=CH R–C––CH R–C––CH
Cl OH Cl O Cl
Unstable
BH3/H2O2/OH T
R–CH=CH R–CH2–C–H
OH O
H2/Ni
R–CH2–CH3
H2/Pd+BaSO4
R–CH=CH2
H2O/Hg+2 T
R–CCH R–C=CH2 R–C–CH3
OH O
OCH3
CH3OH
R–C–CH3
(BF3–HgO)
OCH3
CN
HCN/Ba(CN)2
R–C–CH3
CN
OCOCH3
CH3COOH/Hg+2
R–C–CH3
OCOCH3
NaNH2
R–CC–Na
AgNO3 + NH4OH
R–CC–Ag Only for terminal alkyne
(Tollen's Reagent)
Cu2Cl2+ NH4OH
R–CC–Cu
Baeyer Reagent
R–C–CHO (Test of unsaturation)
O
O3/H2O/Zn
R–C–C–H
ozonolysis
O O
K2Cr2O7 or KMnO4/H
R–COOH + CO2 
Strong oxidant
Combustion
PREPARATION METHODS OF ALKYNE
alc KOH or NaNH2
CH2–CH2
Br Br
Br alc KOH or NaNH2

CH3–CH
Br
Cl
Ag powder
HC Cl

Cl
Br Br Zn dust HCCH
CH–CH or
Br Br CH3–CC–R
Zn dust
Br–CH=CH–Br
alc. KOH or NaNH2

CH2=CH–Cl

HC–COONa Kolbe's electrolysis
HC–COONa
(i) Na
CH3–CCH
(ii) R–X
(i) CH3MgI
CH3–CCH
(ii) R–X
SPECIAL POINTS
• Ethyne is used in oxy-acetylene flame (2800-3200ºC) which is used for cutting and welding of metal.
• Ethyne is used in carbide lamps for lightning (is a illuminating agent in hawker's lamp)
• When hydrogen is passed in atmosphere of electric arc between carbon electrode, a mixture of H 2 & ethyne is
formed (Berthelot Method).
• Mixture of ethyne and nitrogen in electric spark converted into HCN.
• Ethyne burns with sooty flame due to presence of high % of carbon.
• Acetylene is used in artificial ripening of fruits.
• Pure acetylene (NARCYLENE) is odourless and impure acetylene has odour like garlic. It is due to impurities of
Arsene (AsH3) & Phosphine (PH3).
• Acetylene & 1- alkyne are acidic in nature. It is due to greater electronegativity of sp hybridised carbon.
• Acetylene has two acidic hydrogen atoms. It can neutralise two equivalents of base at the same time. So it is also
called as dibasic acid. But the base should be very stronger as NH2 or CH3etc.
• Some other reactions of acetylene are.
Cl AsCl2
AsCl3
HC=CH (Lewisite)
CO + H2
CH2=CH–CHO
Hydroformylation
CO + ROH
CH2=CH–COOR
CO + H2O
CH2=CH–COOH
(Hydrocarboxylation)
H2O/Hg+2
HCCH CH3–CHO
Kuchrov's reaction
Dimerisation HCCH
CH2=CH–CCH CH2=CH–CC–CH=CH2
Cu2Cl2 + NH4Cl/ Trimer
Trimerisation
Red hot Fe tube
Tetramerisation
Ni(CN)2
cN)
(conc.) H2SO4 HSO4
CH3–CH
HSO4
• Lewisite is Highly explosive as which was used in IInd world war. British anti-Lewisite (B.A.L.) is an organic
compound whose structure is CH2–CH–CH2
OH SH SH
• Hydrolysis of metal carbides gives following hydrocarbons :
Al4C3 + 12 H2O ⎯→ 3CH4+ 4 Al(OH)3
Be2C + 4H2O ⎯→CH4 + 2 Be(OH)2
CaC2+ 2H2O ⎯→ C2H2 + Ca(OH)2
Mg2C3 + 4H2O ⎯→ C3H4 + 2 Mg(OH)2

AROMATIC HYDROCARBON
::
• These are also called arenes.
• General formula is CnH2n–6y. Where y is the number of benzene ring in molecule.
Illustrate example :
CH3 CH2CH3 CH3 CH3 CH3
CH3
CH3
Benzene Toluene Ethyl CH3
benzene
o/m/p-xylene
• Following reactions are important in the determination of the structure of benzene.
H /
(i) C6H6 ⎯⎯2 ⎯→
Pt
O O
|| ||
(ii) C6H6 ⎯⎯ ⎯ ⎯→ H–C–C–H
1. O 3
2. H O / Zn
2
(iii) C6H6 ⎯⎯⎯

⎯→ No reaction (no decolourisation)
KMnO 4
cold & dil.
(iv) C6H6 ⎯Br

⎯2 ⎯⎯
/ CCl4
→ No reaction
(v) C6H6 ⎯HCl
⎯⎯→ No reaction
On the basis of (i) and (ii) reactions Kekule in 1865 suggested that benzene is equilibrium mixture of
cyclohexatrienes [(I) and (II)] as follows
(I) (II)
But reaction (iii), (iv) and (v) can not be explained by Kekule's structure.
THE RESONANCE HYBRID STRUCTURE :
::
According to the resonance theory, benzene is a resonance hybrid of the following canonical forms.

 
KEKULE structures DEWAR'S structures

Contribution : Total 80% Total 20%
20
40% each i.e., % contribution by each
3
It should be noted that the concept of resonance is imaginary and the canonical forms mentioned above actually do
not exist. It is the hybrid structure which is a reality.
RESONANCE THEORY CAN EXPLAIN :
(i) Stability of -electrons.
(ii) Equal bond energies of all C–C bond.
(iii) Equal bond lengths of all C–C bond.
(iv) Lower value of heat of combustion.
(v) Lower value of heat of hydrogenation.
THE MOLECULAR ORBITAL STRUCTURE OF BENZENE :
According to this theory, all of the six carbon atoms in benzene ring are in sp 2 hybridised state.
By overlapping of hybrid orbitals these six carbon atoms form a planar hexagonal ring. Now each of 'p' orbital on
the six carbon atoms can overlap on either side with adjacent 'p' orbitals. These result in a molecular orbital which
is actually made of two continuous rings, one ring above and another below the plane of hexagon.
sidewise
overlaping
• Benzene is a colourless volatile liquid. It has characteristic smell.
• Its boiling point is 80oC and freezing point is 5.5o C.
• It is highly inflammable and burns with sooty flame.
• It is lighter than water.Its specific gravity at 20oC is 0.8788.
• It is immiscible with water but miscible with organic solvents such as alcohol and ether.
• It is a non - polar compound and its dipole moment is zero.
• It is extremly poisonous substance. nhalation of vapours or absorption though skin has a toxic effect.
CHEMICAL PROPERTIES OF BENZENE :
Cl2/AlCl3
Cl
Halogenation
HNO3+ H2SO4
NO2
Nitration
H2SO4
SO3H
Sulphonation
CH3CH2–Cl/AlCl3
CH2CH3
Friedal-Craft alkylation
O
O
CH3–C–Cl/AlCl3
C–CH3
Friedal-Craft acetylation
(CO + HCl)/AlCl3
CHO
Gattermann-Koch reaction
(HCN +HCl)/AlCl3 H3O

CH=NH CHO
Gattermann reaction
(HCHO + HCl)/ZnCl2 HCl

CH2OH CH2Cl
Blace reaction ZnCl2
O3/H2O/Zn CHO
(Glyoxal)
Ozonolysis
CHO
Benzene
Cl Cl
Cl2/sunlight
Cl Cl (Gammexane or BHC or 666)
Cl Cl
H2/Pd or Pt or Ni
H.T.P.
Na/liq. NH3
Birch reduction
(i) CrCl3 + AlCl3 Sandwitch

Cr
(ii) Na2S2O4 (reduction) Compound
V2O5/300ºC
OH (Phenol)
Oxidation
O O
V2O5/400º-500ºC OH –H O
2
O (maleic anhydride)
Oxidation OH
O O
Combustion
6 CO2 + 3 H2O + HC (exothermic)
PREPARATION METHODS OF BENZENE :
NaOH + CaO / 
COOH Sodalime
H 2O / 
SO3H
H2 O
Mg – Br
Benzene
Zn
OH
reduction
Cr2O3 + Al2O3
500ºC
red hot Fe tube

HC  CH
Polymerisation
CH2
(i) CH2 = CH2
HC
(ii) Pt/
HC
CH2
PREPARATION METHODS & CHEMICAL PROPERTIES OF TOLUENE :

O CH3 CH3
CH3–C–Cl/AlCl3 C–Cl
+
F.C.R. O
C–Cl
O
CH3 CH3
CH3
COONa NaOH + CaO C2H5Cl/AlCl3 C2H5 +
 F.C.R.
C2H5
CH3
CH3 CH3
OH Zn HNO3 + H2SO4 NO2 +

Nitration
NO2
CH3
CH3 O 2N NO2

HNO3 + H2SO4 T.N.T. (explosive)
SO3H H2O/H
H.T.P Fuming
. NO2
CH3–Cl/AlCl3 CH3
CH3
F.C.R.
H2SO4 SO3H +
CH3 Sulphonation
SO3H
Cl
CH3 CH3
CH3–Cl/2Na/ether Toluene
Wurtz-Fitting Cl2/AlCl3 Cl
+
reaction
Cl
CH2–Cl
MgCl Cl2/h
(Free radical substitution)
CH3–Cl
CCl3
Cl2/h
excess
CHO
Cr2O3 + Al2O3
CrO2Cl2
500ºC
ETARD oxidation
COOH
 
KMnO4/HorOH

Strong oxidation
CH3
H2/Pd
Hydrogenation
PETROLEUM :
Petroleum (from Latin : petra meaning rock and oleum meaning oil) is a dark viscous oily liquid and is
considered to be of biological origin. It is believed to be formed by the decomposition of marine animals under
high pressure and temperature. Petroleum or crude oil as it is obtained is a complex mixture of hydrocarbons
(mainly aliphatic but lesser amount of aromatic hydrocarbons) along with small amounts of nitrogen & sulphur
containing organic compounds.
REFINING OF PETROLEUM
The process of separating petroleum into different fractions having different boiling ranges is called refining. The
important petroleum fractions obtained by fractional distillation along with their approximate composition boiling
range and uses are given in Table.
refinery gas
petrol/gasoline
kerosene
bubble cap
(each tray has many bubble caps)
diesel oil
heater residue
crude oil
Fractional distillation of crude oil
FRACTIONS OF PETROLEUM :
Approximate Boiling range

S.N. Fraction Uses
composition (in K)
1. Gaseous hydrocarbons C1 – C4 Upto 303 As fuel gas after liquefaction, carbon black
2. Crude naphtha C5 – C10 303 – 423 As solvent in varnish and rubber industries,
(i) Petroleum ether C5 – C7 303 – 363 for dry cleaning
(ii) Petrol or gasoline C7 – C9 363 – 393 As motor fuel, dry cleaning
(iii) Benzene C9 – C10 393 – 423 for dry cleaning
3. Kerosene oil C10 – C13 423 – 513 Fuel for stoves, manufacture of oil gas,
illuminant
4. Fuel oil C13 – C18 513–623 Fuel for diesel engine and tractors, cracking
(i) Gas oil stock for gasoline
(ii) Diesel oil
(iii) Furnace oil
5. Lubricant oil C15–C18 Above 543 Paint oil, transformer oil,
(i) Medicinal oil lubrication, sizing paper
(ii) Motor oil
(iii) Grease
6. Paraffin wax C18–C30 673 upward Ointments, candles, paraffin wax, for
(i) Petroleum jelly matches, paints, water proofing, solid fuel,

protecting paints
(ii) Petroleum wax
(iii) Petroleum coke
7. Heavy fuel oil and C30 onwards Forms Paints, road surfacing
Bitumen residue
CRACKING : Cracking is the process of breaking down the less volatile higher molecular mass hydrocarbons
from petroleum into different types of more volatile lower molecular mass hydrocarbons by heating in the
presence of a catalyst.
e.g.
C12H26 ⎯973
⎯⎯ ⎯⎯ ⎯→ C7H16 + C5H10
K / catalyst
Dodecane Heptane Pentene
(B.P. 489 K) (B.P. 371 K) (B.P. 309 K)
REFORMING : In this process alkanes containing 6-8 carbon atoms are heated at about 873 K in presence of a
catalyst (platinum, palladium or nickel) leading first to cyclization and then to aromatization or dehydrogenation.
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SYNTHETIC PETROL OR GASOLINE :
In view of the depleting crude oil reserves, synthetic methods have been developed for the manufacture of petrol.
These are :
(i) FISHER-TROPSCH PROCESS : In this process, water gas (a mixture of CO and H 2) produced by passing
steam over heated coal is mixed with excess hydrogen and heated to 473–523 K at 1–10 bar in the presence of Co
or Ni. under these conditions, a mixture of hydrocarbons is obtained which is fractionally distilled.
(ii) BERGIUS PROCESS : In this process, finely powdered coal is made into a paste with heavy oil. the paste is
then heated in the presence of hydrogen at 773-873 K at 200–250 bar using iron oxide as catalyst.
QUALITY OF PETROL :
(i) OCTANE NUMBER : Octane number is a scale which is used to determine the knocki ng quality of a fuel in
an internal combustion engine. The two pure hydrocarbons heptane and isooctane have been selected as standards.
• Heptane (CH3–CH2–CH2–CH2–CH2–CH2–CH3) is a straight chain hydrocarbon having very high knocking

property when used as fuel, has been orbitrarily assigned an octane number zero. Isooctane (2,2,4-
trimethylpentane) having lowest knocking property is given an octane number 100.
• The octane number is defined as the percentage of isooctane present in a mixture of isooctane and heptane, when
the mixture has the same knocking performance in the experimental engine as the gasoline under examination.
• A sharp metallic ratting sound produced in an internal combustion engine is known as knocking. Generally
knocking tendency decreases as in the order :
straight chain alkane > branched chain alkane > cycloalkane > aromatic hydrocarbon.
Knocking can be reduced by adding antiknock compound as (C2H5)4Pb [T.E.L.] which is a source of free radical
•
( C 2 H 5 ). The free radical convert the straight chain alkanes to branched chain alkanes.
ORGANIC COMPOUNDS WITH THEIR OCTANE NUMBER :
Compound Octane number Compound Octane number
Methane 122 CNG 130
Ethane 101 Benzene 122
Propane 96 Toluene 120
Butane 89 Xylene 118
Triptane 125
(ii) CETANE NUMBER : The quality of diesel fuel is expressed in terms of a unit called cetane number.
hexadecane, C16H34 also known as cetane, ignites rapidly and has been given a rating 100, while
1-methyl naphthalene, which ignites slowly is given a rating zero.
CH3
CH3(CH2)14–CH3
Cetane
1-Methylnaphthalene
The cetane number is defined as percentage of cetane by volume in a mixture of cetane and
1-Methylnapthalene, which has same ignition quality as the sample fuel under examination.
FRACTIONS OF COALTAR DISTILLATION :

Fraction Name Temperature range (K) Major components
1. Light oil Up to 443 Benzene, toluene, xylene etc.
2. Middle oil or Carbolic oil 443 – 503 Phenol, naphthalene, pyridine
3. Heavy oil or Creosote oil 503 – 543 Methyl and higher alkyl phenols,
naphthalene, napthols etc.
4. Green oil or Anthracene oil 543 – 633 Anthracene, phenanthrene
5. Pitch (residue) Non – volatile Used for making black paints,
varnish for wood for water
proofing and construction of roads
ENVIRONMENTAL CHEMISTRY
Environmental pollution may be defined as any undesirable change in the physical, chemical or biological
characteristics of air, water and soil which may cause any harm to man and other living organisms of the
environment.
TYPES OF POLLUTANTS
The agents causing pollution are termed as pollutants.

(A) On the basis of form of their occurence, pollutants are divided into two categories.
(i) Primary pollutants – These are present in the same form in which they are produced. eg. carbon monoxide,
DDT.
(ii) Secondary pollutants – These are formed by reaction between the primary pollutants in the presence of
sunlight eg. PAN, Ozone, HNO3 H2SO4 etc. Nitrogen oxides and hydrocarbons react photochemically to
produce peroxyacetyl nitrates (PAN) and ozone.
The secondary pollutants may be more toxic than the primary once. The phenomenon is called synergism.
(B) On the basis of their degradation, pollutants are divided into two categories.
(i) Biodegradable Pollutants – Pollutants which are decomposed or degraded by biological ormicrobial action
are called biodegradable pollutants e.g. domestic sewage.
(ii) Non-biodegradable Pollutants – Pollutants which are not decomposed or degraded by living organisms or
micro organisms are are called non-biodegradable pollutants eg. DDT, glass, plastics, aluminium cans,
phenolic compounds, pesticides, radioactive substances, heavy metals like mercury, lead, cadmium etc.
(C) On the basis of their existance in nature, pollutants are divided into two categories.
(i) Quantitative pollutants – These are naturally present in nature and are also added by man. These become
pollutants only when their concentration reaches beyond a threshold value in the environment.
e.g. CO2.
(ii) Qualitative pollutants – These are not present in the nature but are added in nature only due to human
activities e.g. insecticides, fungicides, herbicides etc.
KINDS OF POLLUTION
On the basis of environmental study pollution is of following types.
(1) Air pollution

(2) Water pollution
(3) Soil pollution
(4) Noise pollution
(5) Radioactive pollution
AIR POLLUTION
• It is mainly caused by industries and automobiles. Automobiles are the greatest pollutior of the atmosphere
and are responsible for 75% of noise pollution and about 60-80% of air pollution of big cities.
• The combustion of fossil fuels (coal, oil, gas etc.) releases CO, CO2, nitrogen oxides, fluorides, hydrocarbons
etc. into atmosphere usually in the form of smoke causing air pollution.
• Particulate matters released by mills, factories and mines also cause air pollution.
• Some of the natural air pollutants are pollen grains, spores, volcanoes etc.
MAJOR AIR POLLUTANTS –

(1) Carbon monoxide –
• It is formed by incomplete combustion of fuels in various industries, automobiles etc.
• CO accounts for about 50% of total air pollution. It is largest pollutant in Delhi's air.
• CO combines with haemoglobin, produces carboxyhaemoglobin and therefore decreases oxygen carrying
capacity leading to hypoxia, headache, decreased vision, muscular weakness, nausea, exhaustion etc.
• When 50% of haemoglobin has been transformed into carboxyhaemoglobin, then death occurs due to CO-
poisoning leading to anoxia (oxygen starvation)
(2) Carbon dioxide (CO2) –

• It is a green house gas. It is produced due to combustion of fuels, volcanic eruptions and during the process
of respiration.
• Its average concentration in the atmosphere is 300 ppm (0.03%) .
• It is normally not an atmospheric pollutants, but under very high concentration it may act as a pollutant.
• It causes Global warming .
(3) Sulphur dioxide (SO2) –

• It is produced during combustion of fossil fuels (mainly coal) and smelting of sulphur containing ores.
• It causes acid rain (gaseous SO2 oxidises to SO3, which on combination with water forms H2SO4).
• Acid rain is 60-70% due to SO2 and SO3, and 30-40% due to NO2 and NO3.
• Due to acid rain the leaves develop chlorotic and necrotic spots.
• SO2 corrodes stones, metals, leather, paper and fabrics. There is deterioration of colour and lusture of fabries,
stones and painted surfaces.
• Tajmahal of Agra is affected by gases (SO2, H2S etc.) discharged from oil refinery of Mathura.
• Lichens (e.g. Usnea) are extremly sensitive to SO2 and could be regarded as indicators of SO2 pollution.
(indicators of air pollution)
• Garden pea is another SO2 pollution indicator.
• Lichen vegetation (parmelia, usnea, cladonia,) Garden pea and mosses are completely destroyed due to SO2.
• SO2 causes chlorosis (destruction of chlorophyll) and necrosis of vegetation, membrane damage and yeild
reduction.
• In plants and animals, SO2 destroys all membrane systems.
• In human beings SO2 increases the chances of occurence of asthma, bronchitis and emphysema. (xv) It
produces eye irritation, damage respiratory tract.
(4) Hydrocarbons –
• They are produced naturally (e.g. marsh gas CH4) and by burning of petroleum.
• Benzene (C6H6) is a major constituent of petrol and automobile exhaust.
• Hydrocarbons are carcinogenic, cause irritation of eyes and mucous membrane.
• Benzene is a known carcinogen causing leukemia.
• Ethylene (C2H4) causes premature senescence and abscission in many plants especially in orchids and cotton,
• Methane (marsh gas) has the potential of destroy ozone.
(5) Nitrogen oxides –
• There are three oxides of nitrogen which act as air pollutants : Nitric oxide (NO), nitrogen dioxide (NO2) and
nitrogen trioxide.
• Nitrogen and oxygen combine together at high temperature in any combustion process to produce nitrogen
oxides.
• These are also released by furnaces, forest fires, industries and denitrifying bacteria.
• NO is less toxic but NO2 is a poisonous gas.
• Nitrogen oxides are responsible for forming photochemical smog.
• They also cause acid rain due to formation of HNO3.
• They produce lesions, necrosis, defoliation, dieback and death of many plants.
• Like SO2, they corrode metals and deteriorate paints, textiles as well as various articles.
• They cause eye irritation, dilation of arteries, injury of lungs, liver and kidneys.
(6) Fluorides –
• Fluorides are emitted during refinement of aluminium and rock phosphates .
• Fluorides cause necrosis and chlorosis of leaf tips and leaf margins.
• In human fluorides cause mottling of teeth, weak bones, boat-shaped posture, knocking knees etc.
• Disease caused by fluoride is known as fluorosis.
(7) Particulate matter –
• It is the non-gaseous matter in the atmosphere.
• It consists of soot, dust, mist, fibres, fly ash, fur, spores, pollen grains etc.
• It is of two types settleable (larger than 10 m) and suspended (less than 10m)
• SPM (suspended particulate matter) is classified into 3 categories –
(a) Aerosols (less than 1 m)
(b) Dust (solid particles with more than 1 m diameter)
(c) Mist (liquid particles with more than 1 m diameter)
• It is added in the atmosphere by burning of fuels.
• Particulate matter causes about 10-15% of air pollution.
• Under condition of high humidity, the particulate matter causes corrosion and erosion of surfaces.
• In human beings, it may cause respiratory problems.
• Particulate matter from processing industries (eg. cotton dust, iron mill dust, flour mill dust, mine dust) causes
pneumoconiosis, byssinosis, siderosis, emphysaema and other pulmonary problems.
• The asbestos fibers cause asbestosis which is a type of cancer.
• Dust and smoke produce smog.
• The ill effects of different kinds of dusts are listed below –
(a) Coal dust – Anthracosis
(b) Silica – Silicosis
(c) Asbestos – Asbestosis, Lung cancer
(d) Iron – Siderosis
(e) Cotton dust – Byssinosis
(f) Hay or grain dust – Farmer's lung
(8) Aerosols –
• These are chemicals released in the air with force in the form of mist or vapour by jet planes.
• Aerosols contain CFC (chlorofluor-ocarbons) which destroy ozone layer in the stratosphere. This permitting
some more harmful
• U.V. radiations to reach the earth surface, U.V. radiations cause skin cancer and increases mutation rates.
• Ozone acts as preventive shield against the U.V. rays.
• Freons are several CFMS (chlorofluoromethanes) released into troposphere where they dissociates and
release free chlorine that causes depletion of ozone.
• Freon or CFC also used in refrigerator, air conditioners and in making plastic foams.
Effect of air pollutants – Air pollutants are involved in causing four major environmental effects :
(i) Smog (ii) acid rain (iii) global warming and (iv) ozone layer depletion.
(1) Smog –
• The term smog was coined by Des Voeux.
• It is produced by the combination of smoke and fog.
• It causes silvering/glazing and necrosis in plants, allergies and asthma/bronchitis in human.
• Smog is of two types :
(a) Classical or London smog or sulphurous smog –
It occurs at low temperature andcontainsH2S, SO2, smoke and dust particles. It was first observed in winter months
at London in 1905. It is formed due to domestic and industrial combustion of coal.
(b) Photochemical smog or Los Angeles smog – It was first observed in the mid day at Los Angeles in 1943.
The cause of this smog was thought to be due to combustion of petroleum in automobiles. Photo chemical smog
occurs at high temperature over cities and towns. It is formed by the reaction of two air pollutants nitrogen oxides
(mainly NO2) and hydrocarbons (HC) that react with one another in the presence of UV radiations of sunlight to
produce ozone (O3) and PAN (peroxy acetyl nitrate) which constitute the photochemical smog.
Nitrogen oxides + Hydrocarbons ⎯⎯→ PAN + Ozone
Ozone and PAN are commonly referred to as oxidants.
Breathing ozone affects the respiratory and nervous system, resulting in headache, respiratory distress and
exhaustion. It also causes irritation in eyes and asthma. The ozone is known to destroy crops of potato, alfalfa and
spinach to the extent of 50%. It also damages leaves of tobacco, tomato and pine as also the grape fruits. Besides,
the PAN also blocks Hill reaction of photosynthesis.
(2) Acid rain –
• The coal and oil burned by power plants release SO2 into the air.
• Automobile exhaust puts NO2 in the air.
• Both SO2 and NO2 are converted to acids ( H2SO4 and HNO3 respectively) when they combine with water
vapour in the presence of O2 in the atmosphere. These acids return to the earth as acid rain.
NO + O3 ⎯⎯→ NO2 + O2
NO2 + O3 ⎯⎯→ NO3 + O2
NO2 + NO3 ⎯⎯→ N2O5
N2O5 + H2O ⎯⎯→ 2HNO3
2SO2 + O2 ⎯⎯→ 2SO3
• The pure rain has a pH of about 5.6 while the acid rain has pH below 5.6.
• Acid rain is actually a mixture of H2SO4 and HNO3 ( usually 60-70% H2SO4 and 30-40% HNO3)
• Acid rain affects the ability of the trees to tolerate cold temperatures and the weakened trees are killed by
cold conditions or become more susceptible to diseases.
• Acid rain leaches lead, mercury and calcium, from the soils and rocks and discharges them into rivers and
lakes. The metals may become concentrated in fish and then passed on to people through food chain.
• Acid rain also damages building materials, including steel, paint, plastics, cement and marble.
(3) GREEN HOUSE EFFECT and Global warming –

• The sunlight that reaches to the earth, warms both atmosphere and the earth surface. The earth's atmospheric
system then reradiates the heat as infra-red radiations.
• Gases like CO2 , CH4, CFCs, NO2 are strong absorbers of long-wave or infra-red radiations emitted by the
surface of the earth, and warm the earth's atmosphere. This is called the green house effect because it is like
the glass panel of a green house that allows sunlight to pass through and then traps the resulting heat inside the
structure.
• CO2 in the principal green house gas responsible for warming of the earth.
• CO2 is rising into the atmosphere slowly as a result of large scale burning of fossil fuels (coal, oil etc),
volcanic activities and respiration
• 50% of the increase in earth's temperature in due to CO 2, 20% is due to CFCs and remaining 30% is due to
other gases.
• Some ecologists visualise that the green house effect shall lead to global warming. In the next fifty years time
the temperature of earth shall rise by 2° –5°C.
• A rise of global temperature by 2 to 5°C may lead to
(a) Melting of glacies and polar ice caps.
(b) Flooding of low lying coastal plains.
(c) Increase in the flow of rivers and change in rainfall pattern.
(d) Possible submersion of islands.
• The UNEP (United Nations Environment Programme) has appropriately choosen the slogan "Global
Warming : Global Warning" and since 1989, 5th june is celebrated as World Environment Day.
Sunlight
Green
Ho use
G ases
Atmosphere
Radiant heta Trapped
by CO2
(4) Ozone layer depletion –

• The ozone layer present in the stratosphere acts as an ultraviolet absorbant thus protecting the earth from its
harmful effect.
• Depletion/destruction of ozone layer is primarily caused by CFCs (Chlorofluoro carbons) and halons
(halocarbons
CxFx Brx )
• CFCs are heat transfer agents used in refrigerators, air conditioners, fire extinguishers.
• Halons are antifire agents used in fire extinguishes .
• The CFCs react with ozone and thus cause thining of ozone layer which permits more UV radiations to reach
the surface of earth.
• UV radiations cause mutations that can develop skin cancer and cause eye cataracts. UV rays also affect our
immune system.
• Severe depletions of ozone layer are commonly called ozone holes.
• A hole in the ozone layer has been discovered in the Antarctica region. There was a severe depletion of some
40–50% above the Antarctica region.
• The ozone layer depletion is caused by chlorine atoms. These chlorine atoms comes from the break down of
CFCs. These atoms combine with ozone and remove the oxygen atoms one by one.
Cl + O3 ⎯⎯→ ClO + O2
ClO+O ⎯⎯→ Cl + O2
• One atom of chlorine can destroy upto 100,000 molecules of ozone.
• Most countries of the world have agreed to stop using CFCs by the year 2000.
BHOPAL GAS TRAGEDY
Occured on 2nd December 1984, when a poisonous gas MIC (methyl isocynate) was leaked in the atmosphere
from a fertilizer plant of union carbide company. MIC was used to manufacture an insecticide marked in the name
of SAVIN. The gas caused death of about 2500 persons. December 2 is recalled as National Pollution Prevention
Day.
IMPORTANT DAYS :
• Hiroshima day – 6th August –
• World earth day – 22nd April
• World environment day – 5th june
• International day for preservation of ozone layer [OR] Ozone day – 16th September
• Bhopal gas tragedy – 2 December,1984
nd
IMPORTANT ABBREVIATIONS :
• N.E.E.R.I. – National Environmental Engineering Research Institute, Nagpur.
• I.U.C.N. – International Union for Conservation of Nature and Natural Resources, Switzerland.
• C.P.C.B. – Central Pollution Control Board.
• U.N.E.P. – United Nations Environment Programme.
• O.D.P. – Ozone Deplecting Potential. (It is maximum in CFCs)
• I.A.P. – Indices of Atmospheric Pollution. [prepared with the help of lichens (sensitive to SO 2)]
• C.N.G. – Compressed Natural Gas
• C.T.B.T – Comprehensive Test Ban Treaty
• C.S.E. – Centre for Science and Environment.
IMPORTANT ACTS TO CONTROL AIR POLLUTION
• National Environment Policy Act, 1969
• Air ( Prevention and Control of Pollution )Act, 1981 (water act, 1974)
• Environment Protection Act, 1986
• Motor Vehicle Act, 1988
IMPORTANT POINTS :
• Benzpyrene/polycyclic hydrocarbon is a powerful carcinogen (cancer causing agent). It is emitted by
cigarette smoking, combustion of petrol, diesel etc.
• Carbon monoxide (CO) accounts for about 50% of total air pollution .
• Sulphur dioxide (SO2) accounts for 6% of total air pollution.
• Particulate matter accounts for 10 -15% of total air pollution.
• First Earth Summit of United Nations Conference on Environment and Development (UNCED) was held at
Rio-de-Janerio ( Brazil) in 1992.
• First International Conference on “Environment and Development” was held at Stockholm in 1972.
• Second International Conference on “ Environment and Development ” was held at New Delhi in 1985.
• Cyclon collector is used for minimising air pollution.
• Most polluted city of the world – Tokyo (Japan)
• Most polluted city of India – Kolkata.
• In Delhi and Kolkata pollution is mainly due to automobiles and fire.
• In Mumbai pollution is mainly due to industries.
• Cotton dust is main source of air pollution in Surat and Ahmedabad.
• Level of suspended particulate matter (SPM) concentration is highest in the atmosphere of Kolkata.
• In Bihar and Andhra Pradesh major source of air pollution is thermal power plants.
• Pittsburg city (USA) was once named as “Smoke city ”.
• The automobile emission can be reduced by adding barium salts in the petrol.
• CFCs have maximum Ozone Depleting Potential (ODP)
• Ozone, PAN, HNO3 and H2SO4 are secondary pollutants.
• Green Charter– Drawn by the World Wildlife Fund for Nature for India in December , 1997. It states that “
Protection of environment is crucial for human survival and well being now and in future”.
• Excessive inhalation of manganese causes pneumonia.
• Methane is released by cud–chewing domestic animals.
• Excess of pollen causes allergic reactions in several human beings. The common reactions are collectively
called hay fever.
• The smoke reduces visibility. To visualise the extent of darkness caused due to smoke Ringelmann charts are
used.
• Tocofarol produces resistance against carcinogen.
• Formation of ozone hole is maximum over Antarctica.
WATER POLLUTION
Water pollution is defined as the addition of some substances (organic, inorganic , biological, radio logical) or
factor (eg. heat) which degrades the quality of water so that, it either becomes health hazard or unfit for use.
(1) Kinds of water pollution –
The water pollution may be physical, chemical or biological.
(a) Physical pollution – It involves the changes in the physical properties of water eg. colour, taste, adour,
temperature, turbidity etc.
(b) Chemical pollution – It is caused due to change in the chemical properties of water. They mainly include the
pH, dissolved O2, inorganic or organic chemicals, heavy metals etc.
Inorganic chemicals include fluorides, chlorides, phosphates and nitrates. Organic chemicals include phenols,
dyes, pesticides and chlorocompounds.
(c) Biological pollution – It is caused due to the presence of living organisms in water such as algae, fungi,
bacteria, viruses, protozoans, insects etc.
(2) Sources of water pollution and effects of water pollutants –
Water pollution is a serious health hazards in India, especially in villages. It is estimated that 50-60% of Indian
population suffers from diseases caused by it. 30-40% of all deaths are believed to be due to it.
The principal sources of water pollution and effects of water pollutants are as follows.
Domestic wastes and sewage
• Sewage containing human faeces, urine, kitchen and cloth washings, organic waste, industrialwaste etc. is
usually poured into water bodies which cause water pollution.
• The villagers often wash their animals, cloths and take bath in the same pond. Such water get contaminated
with infectious agents for cholera, typhoid, dysentery, Jaundice and skin diseases.
• Sewage provide food for decomposers, so the population of decomposers increases.
• Decomposers/microorganisms causing decomposition of sewage take up most of the oxygen present dissolved
in water. So in this water BOD (Biological oxygen demand or Biochemical oxygen demand) increased very
much.
• BOD is the amount of oxygen in milligrams required by microorganisms for five days to metabolise waste
present in one litre of water at 20°C .
• A weak organic waste will have BOD below 1500 mg/litre, medium organic waste between 1500 – 4000
mg/litre while in strong waste above 4000 mg/litre.
• The degree of pollution is directly proportional to BOD.
• In sewage phosphorous and nitrogen compounds are present which are necessary for the growth of algae. In
polluted water these are accumulated which result into excessive growth of algae on water surface. Excessive
growth of algae is called water bloom .
• The phosphates present in detergents stimulate algal growth in the water bodies and cause eutrophication.
• Presence of extra nutrients brings about dense growth of plants and animals life. The phenomenon is called
eutrophication.
• Eutrophication leads to organic loading, depletion of oxygen,death of animals and fouling of water.
• Sewage produces foul odour and makes the water brownish and oily.
Industrial effluents (or industrial discharges)
Industries usually discharge waste water into ponds, lakes and rivers. Industrial waste water contains heavy
metals (mercury, lead, copper, arsenic and cadmium), inorganic pollutants (acids, alkalies and bleaching liquors),
organic pollutants (phenol, naphtha, proteins, aromatic compounds, cellulose fibres etc.) Industrial effluents are the
most hazardous pollutants on land and water.
(A) Mercury (Hg) –
• It is released during combustion of coal, smelting of metallic ores, paper and paint industries.
• Mercury is highly persistent . In water it gets changed into water soluble dimethyl form [(CH 3)2Hg and enters
the food chain (undergoes biomagnification).
• It kills fish and poisons the remaining fauna. Human beings feeding on such poisoned animals develop a
crippling deformity called minamata disease which is characterised by impairment of
various senses, diarrhoea, haemolysis, meningitis and death.
• The minimata disease was first detected in Japan.
• Mercury inhibits chromosomal disjunction during gamete formation. So it brings about genetic changes also.
(B) Lead (Pb) –
• The sources of lead pollution are smelters, battery industry, paint, chemical and pesticide industry,
automobiles exhausts etc.
• Lead is pollutant of air, soil and water.
• It is used as anti-knock reagent in petrol and released by automobile exhausts.
• Lead is a persistant pollutant and may show biological amplification or biomagnification.
• It is a mutagenic and causes anemia, headache, vomitting, colic, loss of muscle power, bluish lines around the
gums, loss of appetite and damage of liver, kidney and brain.
(C) Cadmium (Cd) –
• It is added to the environment by metal industries, welding and electroplating, pesticides and phosphate
industries.
• Cd shows biological amplification and accumulates inside kidneys, liver, pancreas and spleen.
• It causes hypertension, anemia, diarrhoea and damages liver and kidneys.

(3) Oil
• During extraction and transportation of oil from the sea to different parts, some of the oil spreads over the
surface of water. Refineries also discharge a lot of oil present in their effluents into rivers.
• Oil spreading on the surface of water prevents its oxygenation and inhibits photosynthetic activity of aquatic
plants. Animal life is destroyed due to reduced availability of oxygen , food and toxic effects of oil.
• Oil spilled over the surface of water may catch fire and hence kill all organic life.
(4) Thermal pollution

• Hot water is produced by many industries , power generation plants and thermal power plants.
• Thermal pollution is caused by addition of hot water effluents in water bodies, it bring about rise in water
temperature.
• Warmer water contains less oxygen. Therefore, there is decrease in the rate of decomposition of organic
matter.
• In hot water green algae are replaced by less desirable blue green algae.
• Many organisms fail to reproduce in hot water e.g. Salmon, Trout.
(5) Radioactive wastes
• The nuclear tests performed into sea pollute the water.

• The animals and plants are affected by the remaining radioactivity of the wastes. Radioactive elements (eg.
cesium –137, strontium –90, Iodine – 131) enter the human system.
• Cesium–137 accumulates inside body muscles, strontium–90 in bones while Iodine–131 in thyroid.
• Cesium – 137 brings about functional and genetic changes.
• Strontium – 90 causes blood and bone cancer.
• Iodine – 131 affects normal functioning of thyroid.
IMPORTANT POINTS RELATED TO WATER POLLUTION
• Some organism like Daphnia, Trout and fishes are sensitive to water pollution, they are indicator of water
pollution.
• I.W.P.– Indices of Water Pollution.
• Drinking water rich in nitrates cause methaemoglobenemia.
• Faecal pollution is indicated by Escherichia coli. MPN is Most Probable Number of E-coli. It is indicator of
water pollution.
• Algal Genus Index – High organic pollution is indicated by presence of 20 or more genera of algae in a water
body. Growth of less than 5 genera of algae is indication of clear water. It is called as Algal Genus Index
(AGI)
• Water (Prevention and control of pollution) Act, 1974. It has been amended in 1988.
• Putriscibility – Decay and decomposition of organic matter present in water by bacteria and micro-organisms.
• Silent spring– Novel written by Rachel Carson (1962) mentioning the effect of DDT on birds. DDT use has
been banned in USA since then.
• In India, DDT banned for agricultural use in 1985. It is a chlorinated hydrocarbon and show biomagnification.
• Fluorosis –13 states of India possess high fluoride content in drinking water (more than 1.5 mg/l) which
causes fluorosis in human.
• ABS (Alkyl Benzene Sulphonate) – It is most harmful component of detergents causing water pollution.
• Maize (Zea mays) is sensitive indicator of fluoride pollution.
• Ganga Action Plan started in 1985 for controlling pollution in Gangas.
• Reed plants yellow iris are used to purify water. This method of purifying water is called “Green method of
water cleaning”. Yellow iris plant is less affected by herbicides, so reed beds are highly effective in those
areas where pesticides are in use and provides microbiological methods of pesticie detoxification. These
plants filter out the particulate matter, while the microbes living in association with the plants,
decompose the organic wastes.
• Endrin is most toxic amongst chlorinated hydrocarbons.
• Aldrin in most persistant insecticide in the water and soil.
• Water hyacinth (Eicchornia) popularly known as Jalkumbhi or Kaloi, can purify water polluted by biological
or chemical wastes. It can also filter out heavy metals like cadmium , mercury, lead and nickel as well as other
toxic substances found in industrial waste waters.
• Biotic index :- It gives an idea of pollution of a particular water body. Any water body with a biotic index of
more than 15 is clean, while index lower than 10 is polluted.
• C.O.D. (Chemical Oxygen Demand) – It is amount of oxygen required to oxidise all pollutant materials is one
litre of water at 20°C in five days. The value of COD is much higher than BOD. (xx) B.O.D. of pure drinking
water - Less than 1ppm or mg/l
• Soil salinity can be measured by conductivity meter.
SOIL POLLUTION
• Unfavourable alteration of soil by addition or removal of substances and factors which decrease soil
productivity, quality of plant products and ground water is called soil pollution.
• The soil pollutants include pesticides, fertilizers, industrial wastes, salts, radio-nuclids , tin, iron, lead, copper,
mercury, aluminium, plastics, paper, glass, broken bottles, discarded food etc.
• Soil pollution is of two main tyes
(1) Negative soil pollution –
• It includes over use of soil and erosion .
• Soil erosion is caused by water and wind.
• Water erosion of soil is found near the hills where high speed flooding removes top soil.
• Soil erosion also occurs by high speed winds which bring sand particles from dry desert.
(2) Positive soil pollution – It is caused by addition of undesirable substances (eg. pesticides, fertilizers, industrial
waste, air pollutant washed down from atmosphere through rain)
(A) Pesticides –
• These include insecticides (kill insects), fungicides (kill fungi), algicides (kill algal
blooms), weedicides or herbicides (kill weeds), rodenticides (kill rodents).
• Pesticides are generally broad-spectrum and affect other animals, man and even plants. They are hence, also
called biocides.
• DDT (dichloro diphenyl trichloroethane), BHC (benzene hexachloride or gamaxine), aldrin, dieldrin, endrin,
heptachlor etc. are chlorinated hydrocarbons used as pesticides.
• Dieldrin is five times more toxic than DDT when ingested and 40 times more poisonous when absorbed.
• Endrin in the most toxic amongst chlorinated hydrocarbons.
• Chlorinated hydrocarbons are persistent, fat soluble and show biomagnification.
• DDT and other chlorinated hydrocarbons affect CNS, cause softning of brain, cirrhosis of liver (liver cancer),
cerebral haemorrhage, cancer, hypertension, thinning of egg shells in birds, malformation of sex hormones,
failure of gonad development.
• The population of certain birds (e.g. Bald eagle) has declined due to these biocides.
• DDT also affects the photosynthetic activity of plants, especially phytoplankton.
• DDT was banned in 1985 for agricultural purpose in India.
• In India concentration of DDT in fat tissue of people is 18-31 ppm.
• The weedicides (or herbicides) are usually metabolic inhibitors which stop photosynthesis and other metabolic
activities and hence kill the plants.
• 2,4-D, 2,4,5 -T, DCMU and CMU are weedicides.
(B) Fertilizers –
• The fertilizers contain plant nutrients particularly N,P and K , but the soil also gets polluted mainly due to
organic pollutants present as impurities.
• Excessive use of fertilizers cause soil deterioration through decrease of natural microflora ( nitrogen fixing,
nitrifying bacteria)
• Fertilizers added to soil enter the crop plants. Nitrogen fertilizers produce toxic concentration of nitrate in the
leaves and fruits. When these leaves and fruits are eaten, nitrates changed into nitrites by the activity of
bacteria in the alimentary canal. The nitrites enter the blood and combine with haemoglobin to form
methaemoglobin. As a result oxygen transport is reduced. It gives rise to disease known as
methaemoglobinaemia. In infants it produces cyanosis (blue baby syndrome)
(C) Industrial wastes –
• Wastes of the industries are dumped over the soil. They contain a number of toxic substances including
cyanides, acids, chromates, alkalies and metals like mercury, copper, zinc, lead, cadmium etc.
• The industrial pollutants increase the toxicity level of the soil.
• Heavy metals destroy useful micro organisms of the soil.
• In 1970 some 200 people died in Japan by Cd pollution of soil due to itai–itai disease.
NOISE POLLUTION
• Various kinds of undesirable loud sounds, which disturb our environment are called noise pollutants.
• Noise pollution is produced by loud sounds of various machines, loudly played radio, automobiles, thundering
of jet planes, loud speakers etc.
• The intensity of noise is measured in decibels (or dB).
• The sound above 80 dB causes noise pollution.
• Moderate conversation produces 60 dB sound, loud conversation 70dB.
• Scooter, buses, trucks etc. create noise of about 90 dB, Jet aeroplanes 150 dB, rocket 180 dB.
• Noise pollution may cause hypertension (high B.P), respiratory and cardiac problems.
• Noise stimulates the secretion of adrenaline which increases irritability, nervousness , neuromuscular tension
and feeling of fatigue, so decreasing the working efficiency.
• Noise has an adverse effect on mind health and behaviour of man.
• Noise may damage ear drum and eye sight.
• Noise brings about interference in conversation and hearing.
• The first effects of noise are anxiety and stress.
• Noise can impair the development of nervous system of unborn babies which leads to abnormal behaviour in
later life.
• Plantation of trees is very essential for reducing the noise pollution.
• Green plants are being planted along the road sides to check the noise pollution. This is called as Green
muffler.
RADIOACTIVE POLLUTION
• It is a special type of physical pollution of air, water and soil with radioactive materials.
• Nuclear explosion results into production of radioactive substances as Sr 90, U235. I131 and cause pollution of
air, water and soil.
Sources of Radioactive pollution
(1) Natural (Background) radiations –
• These include cosmic rays that reach the earth surface from outer space and terristrial radiations from
radioactive elements(radium–224, thorium –232, uranium–235, uranium – 238, radon –222, carbon–14,
potassium – 40 etc.) present in the earth's crust. These radioactive elements are present in rocks, soil and
water.
• Maximum back ground radiation is found in Kerala beach where 75% of thorium deposits of the world are
found.
• Monazite is the source of thorium.
(2) Man-made radiations – Man made sources of radiations include mining and refining of plutonium, uranium and
thorium, production and explosion of nuclear weapons, nuclear power plants, nuclear fuels and preparation of
radioactive isotopes.
GREEN CHEMISTRY IN DAY TO DAY LIFE
(i) Dry Cleaning of Clothes
Tetra chlroroethene (Cl2C=CCl2) was earlier used as solvent for dry cleaning. The compound contaminates the
ground water and is also a suspected carcinogen. The process using this compound is now being replaced by a
process, where liquefied carbondioxide, with a suitable detergent is used. Replacement of halogenated solvent by
liquid CO2 will result in less harm to ground water.
These days hydrogen peroxide (H2O2) is used for the purpose of bleaching clothes in the process of laundary,
which gives better results and makes use of lesser amount of water.
(ii) Bleaching of paper
Chloring gas was used earlier for bleaching paper. These days, hydrogen peroxide (H 2O2) with suitable catalyst,
which promotes the bleaching action of hydrogen peroxide, is used.
(iii) Synthesis of Chemicals
Ethanal (CH3CHO) is now commercially prepared by one step oxidation of ethene in the presence of ionic catalyst
in aqueous medium with an yield of 90%.
Catalyst
CH2 = CH2 + O2 ⎯Pd
⎯( III
⎯) /⎯ ⎯ ⎯ ⎯⎯→ CH3CHO(90%)
Cu ( II )( in water )
Green chemistry, in a nutshell, is a cost effective approach which involves reduction in material, energy
consumption and waste generation.
HALO-ALKANE
• These are the organic compounds in which halogen atom is directly linked with carbon atom.
• These are also called as Haloalkanes.
• Their general formula is CnH2n+1X , (X = F, Br, Cl, I).
• The carbon that bears functional group is sp3 hybridized in alkyl halides.
• In these compounds, geometry of carbon is tetrahedral.
• Central carbon atom has a bond angle of 109º 28’.
• On the basis of no. of halogen atom(s), these are of following types -

(i) Monohalides – They possess only one halogen atom. eg. CH3Cl, CH3CH2Br
(ii) Dihalides – They possess only two halogen atoms.These are of following three types
eg. gem dihalide, vicinal dihalide and , or terminal dihalide

(iii) Trihalides – They possess three halogen atoms. eg. CHCl3 / CHI3
(iv) Tetrahalides – They possess four halogen atoms. eg. CCl4

• Alkyl halide shows chain and position isomerism. If unsymmetrical or chiral carbon is present then it shows
optical isomerism also.
• Alkyl halides do not show functional isomerism, metamerism, tautomerism, geometrical isomerism.
• Alkyl halides are colourless with sweet smell or pleasant smell oily liquid, whereas CH 3F, CH3Cl, CH3Br,
CH3CH2F, CH3CH2Cl are gaseous in nature.
• Although carbon-halogen bond is polar in nature therefore alkyl halides are partial soluble in H2O.
• These are completely soluble in organic solvents.
molecular weight
• Boiling po int 
No. of Branches
• Ques. order of boiling point will be -

(i) CH3I > CH3Br > CH3Cl > CH3F
(ii) CH3CH2CH2Cl > CH3CH2Cl > CH3Cl
CH3
(iii) CH3CH2CH2CH2–Cl > CH3–CH–CH2–CH3 > CH3–C–CH3
Cl Cl
Cl
(iv) CH2–CH2–CH2 > CH3–CH–CH2 > CH3–C–CH3
Cl Cl Cl Cl Cl
• Chloroform is colourless and pleasant smelling liquid while iodoform is yellow crystaline solid.
• Chloroform is used as an anaesthatic agent
• Iodoform is more reactive than chloroform due to large size of iodine atom.
CHI3 + AgNO3 → AgI (Yellow ppt)
CHCl3 + AgNO3 → No white ppt of AgCl
• Carbon tetrachloride is colourless liquid and used as FIRE EXTINGUISHER under the trade name PYRENE
• Chloroform is kept in dark coloured bottles to avoid following oxidation.
CHCl3 ⎯[⎯
O]
→ COCl 2 (Phosgene) + HCl
air & light ( Poisonous)
• TEST OF CHLOROFORM (BEFORE ANAESTHATIC USE) : -
Sr.No. Test Pure CHCl3 [COCl2 + HCl]
(i) Litmus paper Blue → Blue Blue → Red
(ii) AgNO3 No ppt While ppt (AgCl)
(iii) H2SO4 No Colouration Yellow colour
• Polarity order is RF > RCl > RBr > RI
• Reactivity order is RI > RBr > RCl > RF
• For same halide group reactivity order is 3º halide > 2º halide > 1º halide
• Fluorides and Chlorides are lighter than water whereas bromides and iodides are heavier than H 2O due to more
density of bromine than oxygen. CH2I2 is heavier liquid after Hg.
• All haloalkanes burn on copper wire with green flame (BELESTEIN TEST for halogens)
CHEMICAL PROPERTIES OF HALO-ALKANE :
(Wurtz reaction) Na/dry ether

R–R
(Frankland reaction) Zn/dry ether
R–R
Corey-House reaction
R–R
(i) Li (ii) CuX (iii) R–X
Reduction
R–H
LiAlH4 or NaBH4 or Ph3SnH
R–MgX or RLi or RNa or R2Zn

R–R
or R2CuLi (Organo metallic reagents)
R–CH=CH–MgX
R–CH=CH–R
R–CC–Na or R–CC–MgX
R–CC–R
(Finkelstein reaction) NaI/acetone
R–I
(Swart reaction) AgF/DMSO

R–F
(Williamson reaction) RONa
R–O–R
(Streker reaction) Na2SO3
R–X R–SO3Na
ROH or dry Ag2O
R–O–R
H2O or aq. NaOH or moist Ag2O
R–OH
RCOONa or RCOOAg
R–COOR
••
N H3 ••
R– N H 2
••
R– N H 2 ••
R– N H –R
••
R– N H –R •• R–X 
R3 N R4N X
KCN/(Ionic)
R–CN
AgCN (covalent) 
R–N = C
KO–N=O (Ionic)
R–O–N=O
Ag–O–N=O (covalent) O
R–N
O
CHEMICAL PROPERTIES OF ARYL HALIDE :
CH3CH2–Cl/2Na /Ether
CH2CH3
Wurtz-Fittig Reaction
Cl/2Na/Ether
Fittig Reaction
OH
NaOH/300ºC
Aromatic N.S.R. (carbanion intermediate)
NH2
NaNH2/NH3(liq.)
(Benzyne intermediate)
Elimination + Addition
Cl Cl
Cl
Cl2/AlCl3
+
Cl Halogenation (E.S.R.)
Cl
Aryl Cl Cl
Chloride CH3Cl/AlCl3 CH3
+
Friedel-Craft Reaction
(E.S.R) CH3
O
O Cl Cl
C
CH3–C–Cl/AlCl3 CH3
+
Friedel-Craft Reaction
(E.S.R) C
O CH3
Cl Cl
HNO3 + H2SO4 NO2
+
Nitration (E.S.R.)
NO2
Cl Cl
SO3H
H2SO4/
+
Sulphonation
(E.S.R.) SO3H
PREPARATION METHODS OF HALO-ALKANE :

X2/h
R–H
HX
Alkene
HBr/Peroxide
Alkene
Cl–N=O
R–NH2
(Tilden reagent)
Darzen reaction
R–OH
SOCl2/Pyridine
R–X
PCl3 or PCl5
R–OH
HI or HBr or
R–OH
NaBr + H2SO4
HCl + ZnCl2
R–OH
(Lucas reagent)
Br2/CCl4
R–C–OAg
Hunsdiecker reaction
O
CHEMICAL PROPERTIES & PREPARATION METHODS OF DIHALIDES:

aq. NaOH CH 2 − OH
|
CH 2 − OH
Cl2
H2C=CH2
alc. KOH/
HCCH
CH 2 − Cl or NaNH2
CH 2 − OH PCl5 |
| CH 2 − Cl
CH 2 − OH
Vicinal dihalide Zn
PCl5 H2C=CH2
CH2–CH2
O O
||
(i) alc. KCN CH2– C
(ii) H3O | O
CH2– C
(iii)  ||
O
OH
aq. NaOH –H2O
CH3–CH CH3–CHO
(Unstable) OH
alc. KOH/
2HCl HCCH
HCCH or NaNH2
Cl
CH3–CH
PCl5
CH3–CH=O Cl
Zn
CH3–CH=CH–CH3
Gem dihalide
(i) alc. KCN

CH3–CH2–COOH
(ii) H3O (iii) 
aq. NaOH
CH2CH2CH2CH2
OH OH
alc. KOH or
PCl5 CH2=CH–CH=CH2
CH2CH2CH2CH2 NaNH2
CH2CH2CH2CH2
OH OH
Cl Cl
Cl2/h
,−dihalide Zn
(i) alc. KCN O

(ii) H3O (iii) 
CHEMICAL PROPERTIES & PREPARATION METHODS OF CHLOROFORM :

O
aq. NaOH
H–C–ONa (salt)
(excess)
O
OH
CH3–C–CH3
CH3–C–CH3 Chloretone
Lab. Method (Hypnotic)
CH3– CH − CH3 CCl3
| (CaOCl 2 + H2O)/ Cl
OH HO–NO2/
O2N–C Cl +H2O Chloropicrin or
(–H2O) Cl Nitro chloroform
(Tear Gas)
Ind. Method
CH 3 − CH − H
| aq. NaCl/electrolysis Cl
OH H–C Cl (i) alc. KOH 
Cl ••
R–N = C (Hoffmann's Isocyanide Test)
(ii) R–NH2
NaOH
H – C – CCl 3 Chloroform
||
O
(Chloral ) air & light
COCl2 + HCl
(Oxidation) Phosgene (Poisonous)
3Cl2/h
CH4 Zn+HCl
CH2Cl2
Reduction (–HCl)
Zn+H2O
CH4
(–3HCl)
Ag/
HCCH
CHEMICAL PROPERTIES & PREPARATION METHODS OF CARBON TETRACHLORIDE :

aq. NaOH
Na2CO3
Cl2/h (excess)
CHCl3 (salt)
(–HCl)
3Cl2/AlCl3 2HF/SbCl5
CS2 Cl Cl CF2Cl2+ 2HCl
(–S2Cl2)
C (Freon-012)
Cl Cl 
Refridgerent
4Cl2/h Carbon tetra Oxidation
CH4 COCl2+2HCl
(–4HCl) chloride H2O[Steam] Phosgene (Poisonous)
9Cl2/500ºC
CH3–CH2–CH3 Reduction
(–C2Cl6) CHCl3
Fe/H2O
(–8HCl)
OXYGEN COMPOUNDS
ALCOHOL
::
• The organic compounds in which – OH group is directly attached with carbon.
• These are hydroxy derivatives of alkanes and mono alkyl derivatives of water.
• Their general formula is CnH2n+1OH or CnH2n+2O.
• The hybridisation state of carbon, with which – OH group is directly attached, is sp3. Therefore geometry around
this carbon atom is tetrahedral.
• In these compounds C-O bond length is 1.42 Å.
• Depending on the no of –OH groups alcohols are classified into following –
(i) Monohydric alcohol :- Contains only one –OH group, For example – Ethanol
(ii) Dihydric alcohol :- Contains two –OH groups. For example – Ethylene glycol
(iii) Trihydric alcohol :- Contains three –OH groups For example – Glycerol
• Alcohols shows chain, position and functional group isomerism. If chiral carbon atom is present, they shows
optical isomerism.
• The alcohols are neutral substances : lower members containing upto 12 carbon atoms are liquids, and have a
distinctive smell and a burning taste. The higher members are solids and are almost odourless.
• The lower alcohols are soluble in water and the solubility diminishes as the molecular mass increases. Their
solubility in water is to be expected, since the oxygen atom of hydroxyl group in alcohols can form hydrogen
bonds with water molecules.
• Melting point and boiling point  molecular mass.
• Boiling point of alcohols are higher than ethers of comparable molecular masses because intermolecular hydrogen
bonding is present in alcohols.
Molecular weight
• Boiling point of alcohols  .
No. of branches
• Boiling point order :

(i) CH3OH < CH3CH2OH < CH3CH2CH2OH
OH OH
(ii) CH3CH2CH2OH > CH3–CH–CH2CH3 > CH3–C–CH3
CH3
CH2–OH
CH2–OH
(iii) CH–OH > > CH3CH2OH
CH2–OH
CH2–OH
(Max. H–Bond)
• Order of solubility in water :
(i) CH3OH > CH3CH2OH > CH3CH2CH2OH
OH OH
(ii) CH3–C–CH3 > CH3–CH–CH2–CH3 >CH3CH2CH2CH2OH
CH3
CH2OH
CH2–OH
(iii) CH–OH > > CH3CH2OH
CH2–OH
CH2–OH
(Max. H-bond)
• Boiling point of alcohols are higher than ethers of comparable molecular masses because intermolecular
hydrogen bonding is present in alcohols.
• Alcohols are poisonous in nature. Poisonous character increases with increment in molecular mass or
branching. Ethanol is exception, which is non–poisonous in nature. Methanol cause blindness.
• Isopropyl alcohol is called as rubbing alcohol.
• Cholestrol is also alcohol, it causes heart attack. Hence it is also called as notorious alcohol.
• Ethanol is liquid while glucose is solid because of more intermolecular H–bonding in glucose.
CHEMICAL PROPERTIES OF ALCOHOL :
PCl3 or PCl5 or SOCl2

R–Cl
Lucas reagent
R–Cl
(H–Cl + ZnCl2)
H–NH2/Al2O3/
R–NH2
(–H2O)
H–O–NO2/100ºC
R–O–NO2 (Alkyl nitrate)
(–H2O) Inorganic esters
H2SO4/100ºC
R–HSO4 (Alkyl hydrogen sulphate)
(–H2O)
O
O
R'–C–OH/H
R'–C–OR (Esterification)
(–H2O)
O
O
CH3–C–Cl
CH3–C–OR'
(–HCl)
R–O–H (i) Na (ii) R'–X

R–O–R'
Alcohol Williamson synthesis
CH2=C=O
CH3–C–OR
Ketene
O
HN=C=O H–NH2
H2N–C–OR H2N–C–NH2
Isocyanic acid (–ROH)
O O
(Urea)
R'MgX
R'–H
Grignard reagent
O
O
Ph–C–Cl
Ph–C–OR
Schotten-Baumann reaction
HI + red P
R–H
reduction
CH2N2/
R–O–CH3
H2SO4/170ºC
Alkene
H2SO4/140ºC
R–O–R (Williamson etherification)
Oxidation [O]
aldehyde/ketone Carboxylic acid
PREPARATION METHODS OF ALCOHOL :

H2O/H
CH2 = CH2

BH3/H2O2/OH
CH2 = CH2
(AcO)2 Hg/H2O/NaBH4
CH2 = CH2
aq. NaOH
CH3CH2–Cl
CH3MgBr/H3O
H–C–H
||
O H2/Pd or Na/EtOH
or LiAlH4/H
CH3–CH=O
reduction
LiAlH4/H
CH3–C–Cl CH3CH2OH
|| reduction
O Ethyl alcohol
LiAlH4/H
CH3–C–OCH2CH3
|| reduction
O
NaOH
CH3–C–OCH2CH3
||
O
H3O
CH3–C–OCH2CH3
|| reversible reaction
O
NaNO2 + HCl
CH3CH2–NH2
or HNO2
o INDUSTRIAL PRODUCTION OF ALCOHOL :

(A) Preparation of methanol : - Methanol is also called as carbinol or wood spirit.
(1) From Water Gas :-
[CO + H2] + H2 ⎯⎯ ⎯ ⎯→ CH3OH (90 %)

2 3Al O
ZnO / CrO 3
200 º −300 º C
(2) From Methane : - CH4 gives methanol on partial oxidation in Cu tube.
CH4 + 1/2 O2 ⎯Cu

⎯tube
⎯
⎯→ CH3OH (90%)
200 º C
(3) By destructive distillation of wood : -

When wood is heated in absence of air in iron retorts at 400ºC then following products are formed.
(i) Wood Gases : - These are mixture of natural gases like CH4, N2, H2 , CO2, SO2 etc.
(ii) Pyroligneous acid : - It is also called as pyro acid. It is brownish sticky liquid.
(iii) Wood tar : - Blackish viscous liquid used in formation of road and also for preservation of wood.
(iv) Wood coke : - It is used as a fuel.
(4) By Pyroligneous Acid : -
It contains acetic acid ( 8-10%) acetone (0.5 - 2%), methanol(2 - 5%) and remaining water.
(i) Removal of Acetic acid : - Acetic acid is separated by adding base Ca(OH)2. It forms calcium acetate with
acetic acid.
(ii) Removal of Acetone : - We can remove acetone by fractional distillation because boiling point of acetone is
56ºC and boiling point of methanol is 65ºC.
(iii) Removal of water : - We can remove impurities of water by using anhydrous calcium chloride or anhydrous
magnesium chloride or anhydrous CuSO4. These form additional crystal salt with methanol.
anhy.CaCl2 + CH3OH ⎯⎯→ CaCl2.4CH3OH
anhy.MgCl2 + CH3OH ⎯⎯→ MgCl2 .6CH3OH
anhy.CuSO4 + CH3OH⎯⎯→CuSO4.2CH3OH
we get pure methanol on steam distillation or we can use oxalic acid to separate water impurities.
O=C–O–H H–O–CH3 ⎯⎯⎯→ O=C–OCH3
⎯2⎯ ⎯⎯→ 2CH 3OH + O=C–ONa
NaOH
O=C–O–H H–O–CH3 O=C–OCH 3 ( Pure )

O=C–ONa
oxalic acid Methanol methyl oxalate(solid)
(B) Preparation of Ethanol : -
(1) From Ethene : - By hydration with dil. H2SO4
CH2=CH2 + H–OH ⎯dil ⎯⎯ ⎯

⎯→ CH3–CH2–OH
. H 2SO4
(2) Formation of ethanol by fermentation –
(i) Cane sugar ⎯Crystalliz

⎯⎯⎯ation ⎯→ Molasses ⎯INVERTASE
⎯⎯⎯⎯→ Invert sugar ⎯ZYMASE
⎯⎯⎯→ C2H5OH
Sucrose hydrolysis Fermentati on
(ii) Grain → Starch ⎯DIASTASE

⎯ ⎯⎯ ⎯→ Maltose ⎯MALTASE
⎯⎯⎯ ⎯→ Glucose ⎯ZYMASE
⎯⎯⎯→ C2H5OH
HOH hydrolysis Fermentati on
General Definitions : -
(i) Fermentation : - In presence of microbes like yeast break down of complex organic compounds into
simple compounds is called fermentation. It is an exothermic process. The term 'Fermentation' was
proposed by Lebeig.
(ii) Yeast is unicellular living parasite plant.
(iii) Enzymes : - Nitrogenous high molecular mass complex compound which converts complex organic
compound into simple organic compound without taking part in reactions is called enzymes. They are
also called as biocatalyst. They are made of proteins.
(iv) They are sensitive for temperature, concentration and pH.
(v) Temperature at which enzymes are maximum efficient is called optimum temperature. For yeast
optimum temperature is 20 – 35ºC.
(vi) Temperature at which enzymes are destroyed, is called thermal death point (TDP) > 60º. At low
temperature they becomes inactive.
(vii) They always work in dilute solution. They cannot work in conc. solution.
(viii) Their working pH range is 6.5 - 7.5 ( slightly acidic slightly basic).
(ix) Boric acid and mercuric salt are inhibitors.
(x) Food of yeast cell is ammonium phosphate or ammonium sulphate.
(3) Preparation of ethanol from sugar :-
(i) Molasses : - Waste product in sugar industry is called molasses. It is a mixture of sugar (30%) and invert
sugar (32-40%).
(ii) Invert sugar : - Combine form of glucose and fructose is called as invert sugar.
C12H22O11+H2O ⎯⎯ ⎯⎯⎯→ C6H12O6 (glucose) + C6H12O6 (fructose)
yeast cell
invertase enzyme
C6H12O6 ⎯⎯ ⎯⎯⎯→ C2H5OH + CO2 + H2O

yeast cell
Zymase enzyme
NOTE : Glucose and fructose are functional isomers.

(4) Preparation of ethanol from starch :-
(i) Starch solution is technically called 'Mash'
(ii) Crushed germinated barley solution is called 'Malt'.
2(C6H10O5)n starch + nH2O ⎯diastase
⎯⎯ ⎯→ nC12H22O11 maltose (wort)
C12H22O11 maltose + H2O ⎯maltase

⎯⎯ ⎯→ 2 C6H12O6 glucose
2C6H12O6 ⎯zymase
⎯⎯ ⎯→ C2H5OH + CO2 + H2O + energy
(iii) From both of the above methods conc. of ethanol achieved is 10-12% which is called 'Wash'.
(iv) Distillation of wash is done in special apparatus 'Coffee's still', which is based on counter current method.
From this distillation yield of alcohol is 90%, which is called Raw spirit.
Raw spirit ⎯Fractional
⎯⎯⎯distillati
⎯⎯⎯ on
→ 95.5% C2H5OH (rectified spirit) + 4.5% H2O
(v) Further purification is done in the following ways : -
95.5%C2H5OH + 4.5% H2O ⎯Fractional

⎯⎯⎯distillati
⎯⎯⎯
on
→ C 6 H 6 + H 2 O + C 2 H 5 OH + Remaining C 6 H 6 + CH 3CHO
(64 º C) (78.5 º C) (68 º C) (99.7 %)
−3 days
C 2 H 5 OH + Ca ⎯2⎯ ⎯⎯→ C 2 H 5 OH + Ca(OH) 2
(99.7%) (100%)
C 2 H 5 OH + anhy. CuSO 4 ⎯→ C 2 H 5 OH + CuSO 4 5H 2 O
(99.7%) white (100%)
(5) Preparation of ethanol from wash :

Wash [10-15% EtOH]
Distillation
Raw spirit [90% EtOH]

Fractional distillation
20–21ºC 78ºC
Mainly CH3CHO Rectified spirit [95.5% EtOH] Fusel oil

Azeotropic distillation [Glycerol + CH3COCH3
Excess benzene
65ºC + Higher alcohol]
C6H6 + C2H5OH + H2O 68ºC 78.3ºC

C6H6 + EtOH Absolute alcohol
(74.1%) (18.5%) (7.4%)
(80%) (20%) [100% EtOH]
(Ternary mixture)
(Binary mixture)
ALCOHOLIC BEVERAGES :- Liquors used for drinking purposes containing ethyl alcohol as the principal
constituent are called alcoholic beverages. Besides alcohol, these contain large amounts of water, colouring and
flavouring materials. Alcoholic beverages are of two types :
(i) Undistilled beverages : These are prepared from fruit juices and grains. Those prepared from grapes and other
fruit juices are known as wines.Wines contain 18–20% of ethyl alcohol and are used as such after fermentation,
i.e., without distillation. The natural wines when made stronger by the addition of rectified alcohol are known as
fortified wines.
Undistilled Beverage
Name % of Alcohol Source

Beer 3–6 Barley
Cider 2–6 Apples
Wine (Champagne) 8–10 Grapes
Claret 7–13 Grape juice
Port and Sherry (Fortified) 14–24 Grape juice
(ii) Distilled beverages : These are prepared by the fermentation of molasses, barley, maize, etc. The fermented liquor
is then distilled. These contain a higher percentage of ethyl alcohol which may be as high as 50%.
Distilled Beverage
Name % of Alcohol Source
Whisky 35–40 Malt
Rum 45–55 Molasses
Gin 40–45 Maize
Brandy 40–45 Grape juice
Cognac 40–50 Grape juice
DIFFERENCE BETWEEN PRIMARY, SECONDARY & TERTIARY ALCOHOLS :

(1) By Oxidation Reaction : - Primary alcohol gives aldehyde on oxidation, secondary alcohol gives
ketone and tertiary alcohol is resistant to oxidation.
Dichromate test :
H  / K Cr O
1º-alcohol ⎯⎯⎯2⎯2+⎯
6
7
→ aldehyde + Cr+3 [green colour]
orange[ Cr ]
H  / K Cr O
2º-alcohol ⎯⎯⎯2⎯2+⎯
6
7
→ Ketone + Cr+3 [green colour]
orange [ Cr ]
H  / K 2Cr2 O7
3º-alcohol ⎯⎯⎯⎯+⎯
6
→ No oxidation [No green colour]
orange [ Cr ]
(2) By Catalytical Oxidation / Dehydrogenation :

Primary alcohol gives aldehyde on oxidation, secondary alcohol gives ketone and tertiary
alcohol gives alkene (dehydration takes place in tertiary alcohols.)
(3) LUCAS TEST : - A mixture of (anhydrous ZnCl2 + Conc. H2SO4) is called as Lucas Reagent.
(i) 3º alcohol gives white ppt. with Lucas reagent in 2-3 seconds only.
(ii) 2º alcohol takes 5–10 minutes.
(iii) 1º alcohol does not gives white ppt. at room temperature.
(4) VICTOR MEYER TEST : -This test is also known as RBW ( Red, Blue, White) test.
R
R–CH2–NO2 O=N–OH NaOH
⎯⎯⎯⎯→ R–CH2⎯
–I⎯−⎯⎯ →
Re d P / I 2 AgNO 2
(a) R–CH2–OH Agl
C=N–OH red solution
(–H2O) (salt)
NO2
(Nitrolic acid)
R NO2 R NO2
(b) R2CH–OH⎯Re ⎯⎯⎯
d P / I2
→ R2CH–I ⎯⎯⎯ ⎯→
AgNO 2
C HO–N=O C ⎯NaOH
⎯⎯→ No reaction
R H
R N=O
(pseudo nitrole)
blue
(c) R3C–OH ⎯Re
⎯⎯⎯
d P / I2
→ R3C– ⎯⎯⎯ ⎯→ R C – NO
AgNO 2
⎯HNO
⎯⎯ 2
→ No reaction
3 2
(white)
(5) Difference between Methanol and Ethanol : - (STA TE PMT)
Methanol Ethanol
1. When CH3OH is heated on Cu coil it gives 1. It does not give formalin like smell.
formalin like smell.
2. When CH3OH is heated with salicylic acid in 2. No such odour is given.

H2SO4 (conc.) then methyl salicylate is formed
which has odour like winter green oil
3. It does not give Iodoform test 3. It gives Iodoform test
4. Boiling point = 65ºC 4. Boiling point = 78ºC
oCHEMICAL PROPERTIES AND PREPARATION METHODS OF GLYCOL :

Na Metal CH2–ONa
|
CH2–ONa
Baeyer PCl5 or HCl CH2–Cl

CH2=CH2 |
reagent CH2–Cl
HI CH2–I –I2
CH2–Cl aq. NaOH CH2 HI CH3
| | ||
CH2–Cl excess CH2–I CH2
O CH2–I
Unstable
CH2–OH ||
CH3–C–OH or CH2–O–COCH3
CH2–OH |
CH3–C–Cl CH2–O–COCH3
Glycol ||
O
CH2–NH2 HNO2 HNO3/ CH2–O–NO2
| |
CH2–NH2 CH2–O–NO2
HIO4
CHO LiAlH4/H 2 HCHO
| (oxidation)
CHO
Anhy. ZnCl2/ Tautomerise
CH2=CH CH3CHO
(–H2O) |
OH
Conc. H2SO4
O O
(–H2O)
oCHEMICAL PROPERTIES AND PREPARATION METHODS OF GLYCEROL :
Na (excess) CH2–CH–CH2
| | | (2ºH is weak acidic)
ONa OH ONa
HCl or PCl5 CH2–CH–CH2

| | |
Cl Cl Cl
(i) NBS
CH2= CH–CH3 HI CH3–CH–CH3
(ii) HOBr excess |
(iii) aq. NaOH
I
P + I2
CH2 ⎯ CH ⎯ CH2 NaOH CH2=CH–CH2–I
| | |
OCOR OCOR OCOR (excess) O OCOCH3
CH2 – CH – CH2 || |
| | | CH3–C–OH/H
CH2⎯ CH⎯CH2
OH OH OH or CH3–C–Cl | |
Glycerol || OCOCH3
O OCOCH3
HNO3/ CH2 –– CH –– CH2

| | |
Fermentation
C6H12O6 ONO2 ONO2 ONO2
(sugar) COOH
|
COOH/110°C
HCOOH (formic acid) + Glycerol
COOH (Reused)
|
COOH/260°C
CH2=CH–CH2–OH (allyl alcohol)
KHSO4 Tautomerise
CH2=C=CH CH2=CH–CHO
(–2H2O) |
OH
Acrolein test (pungent smell)
HIO4 (aq.)
2 HCHO + HCOOH
COOH
KMnO4/H | + CO2 + H2O
COOH
(oxalic acid)
FENTON REAGENT
CHO CH2–OH
| |
H2O2/FeSO4 CH–OH + C=O
| |
CH2–OH CH2–OH
(Glyceraldehyde) (Dihydroxy acetone)
CH2 – CH – CH2
| | | OXIDATION COOH COOH
OH OH OH | |
dil. HNO3
CH–OH + CH–OH
Glycerol | |
CH2–OH COOH
(Glyceric acid) (Tartaric acid )
COOH
Conc. HNO3 |
CH–OH (Glyceric acid)
|
CH2–OH
COOH
Bismuth nitrate |
C=O (Mesoxalic acid)
Bi(NO3)2 |
COOH
oSPECIAL POINTS :
• Glycol is used as an antifreeze for automobile radiators and as a coolant for aeroplane aviation petrol under the
name prestone.
• Glyceryl trinitrate is an inorganic ester.
• Glyceryl trinitrate is colourless, oily liquid insoluble in water and is called Nobel's oil.
• On detonating it explodes violently giving CO2, N2, O2 as gaseous products.
CH2–ONO2
4 CH–ONO2 ⎯→ 12CO2 + 10H2O + 6N2 + O2
CH2–ONO2
• It is a safer explosive when adsorbed on keiselguhr and is known as DYNAMITE.
• Its mixture with cellulose nitrate is known as blasting galetin or gelignite.
• Its mixture with cellulose nitrate (gun cotton) and vaseline is called cordite. It is a smokeless powder.
• Noble's oil is also used in the treatment of angina pectoris and asthma.
• Dunstan's test for glycerol. A drop of phenolphthalein is added to approx. 5ml of borax solution. The pink colour
appears. On adding 2-3 drops of glycerol, the pink colour disappears. The pink colour reappears on heating and
disappears on cooling again.
PHENOL
::
• It is also called as carbolic acid.
• The compounds in which —OH group is directly attached with benzene ring are called as 'Phenols'
• It is discovered by the scientist 'Runge'
• The scientist 'Hofmann', prepared it first from 'coal tar'.
• Aromatic hydroxy compounds in which a single –OH group is attached with benzene ring are called phenols.
OH CH3 CH3 CH3 OH OH OH OH

OH OH
e.g. OH ; ; ; ;
; ; ; OH
OH OH
OH OH
phenol o-cresol m-cresol p-cresol pyrogallol resorcinol
catechol quinol
• The physical property of phenol are strongly influenced by the hydroxyl group which permits phenols to form
hydrogen bond with other phenol molecules as well with water
• Thus , phenol have higher melting points (40ºC) & boiling points (132ºC).
• Phenol are more soluble in water than arenes and aryl halides of comparable molecular weight.
• Some ortho-substituted phenols, such as ortho-nitro phenol, have boiling point that are significantly lower than
those of the meta & para isomers.
Reason : The intermolecular hydrogen bond that form between the hydroxyl group & substituent partially
compensates states for the energy required to go from the liquid state to the vapour.
• Resonance in phenol and phenoxide ion –
+

O–H  O–H  O–H O–H O–H O–H
– –

–
Resonance Hybrid
–
O O O O O O
– –

–
Resonance Hybrid
It is evident from the above structures that — OH group of phenol is o & p-directing as there are electron richer
places so electrophile attack at these places.
• Phenoxide ion is resonance stabilised that is why phenol shows acidic character.
• The hydroxyl oxygen is less basic, and the hydroxyl proton is more acidic in phenol than in alcohol.
CHEMICAL PROPERTIES OF PHENOL :
:: OH
H2O
Br Br
(White ppt)
ONa
Br2 Br
Na or OH OH
NaOH Halogenation CCl4 or Br
+
CS2
No reaction NaHCO3
Br
NH2 OH OH
dil. HNO3
NH3/Al2O3/ NO2
+
(–H2O) Nitration NO2
OH
Zn HNO3
O2N NO2
H2SO4
Reduction
Cl NO2
PCl5 OH
+ Ph3PO4 25ºC SO3H
(Mixture) Sulphonation
O H2SO4 OH
HO OH CH3–C–CH3 / H2SO4 100ºC
CH3–C–CH3 (–H2O) SO3H

(Bis-Phenol- A)
OH OH
O CH3Cl / AlCl3
OH CH3
O O C C O +
O C C Friedel – Craft
H2SO4
OH reaction
–H2O CH3
(Phenolphthalein)
O OH OH
O
O
C–Cl CH3–C–Cl / AlCl3 COCH3
C–O +
Schotten Baumann Friedel – Craft
OH reaction OH reaction
COCH3
60º / AlCl3 O OH
OH
O–C–CH3
O
Phenol CHCl3 / KOH (alc.) CHO
COCH3 Fries CH3–C–Cl +
Rearrangement
Reimer-Tiemann
(–HCl)
reaction Major
CHO
OH H OH
100ºC/AlCl3 OH
COCH3 OH
CCl4 / KOH COOH
H2 / Pd +
Reimer-Tiemann
reaction Major
COOH
(Cyclohexanol)
OH OH
FeCl3
Voilet colour (i) HCN + HCl / AlCl3 CHO
Neutral +
(ii) H3O
OH Gattermann Reaction CHO
K2S2O8 / KOH OCOONa OH

(Quinol) (i) NaOH
Elb's pursulphate (ii) CO2 / 140ºC H rearranged COONa
oxidation
OH Kolbe-schmidt
reaction
OH
COOH
 Liebermann nitroso test
H OH KMnO4 / H H2SO4 H2O NaOH
Green Red Blue
H OH oxidation NaNO2 + H2SO4
HO–N=O GRB
COOH
N=O test
(mesotartaric acid)
O OH OH
Lederer Mannase
NaOH
(Pink colour)
air & light Reaction CH2OH
CH2=O/H +  BAKELITE
POLYMER
O CH2OH
PREPARATION METHODS OF PHENOL :
::
V2O5 / 300ºC
Oxidation
Cl
aq. NaOH / 300ºC
OH COOH
Sodalime/
SO3H
NaOH (excess)
OH

MgBr
(i) [O] Phenol

(ii) H3O
Raschig process
(i) HCl + ½ O2 / Cu – Fe / 200ºC
(ii) SiO2 / 450ºC
Cl
Dow process
aq. Na2CO3 / Cu– Fe / 300ºC / 200 atm
CH3
CH3 – C –H
(i) O2 / 60ºC
(ii) H2SO4
ETHER
::
• The compounds which contain an oxygen atom bonded to two alkyl groups. R–O–R'.
When R and R' are same, they are called as symmetrical ethers and when both are different, they are called mixed
or unsymmetrical ether.
• Ether have general formula CnH2n+2O. where n = 2, 3.....
• These may be considered as dialkyl derivatives of water.
• The oxygen atom in ethers is sp3 hybridised.
• In IUPAC system ethers are named as alkoxyalkanes.
• Ether show chain, positional, functional isomerism and metamerism. Ether are functional isomers of alcohols.
• Dimethyl ether and ethyl methyl ether are gases. All others are colourless liquids with pleasant smell.
• They are sparingly soluble in water, but readily soluble in organic solvents.
• They are lighter than water. Lower ethers are highly volatile and inflammable.
• Boiling points of ethers show a gradual increase with increase in molecular mass. Ethers have low boiling points
than isomeric alcohols, as there is association between the alcohol molecules due to hydrogen bonding. The
boiling points of ethers are close to the boiling points of alkanes.
• Due to bond angle of 110º, ethers are partial polar.
• Lower ethers act as anaesthetics.
• Test of ether before anaesthetic use :
(i) ether (peroxide) + Fe+2 ⎯⎯→ Fe+3 ⎯KCNS

⎯⎯→ Red colour [Fe(CNS)3]
(ii) ether (peroxide) KI ⎯starch

⎯⎯→ Blue colour [I2]
• Reacton of HI with ether is used to estimate alkoxy group (mainly CH 3O) in organic compound. This method is
called Zeisel method.
• Mixture of diethyl ether & ethyl alcohol is known as NATALITE used in place of petrol.
• CROWN ether is the cyclic polyether which have atleast 4 oxygen atoms.
• These are mainly used as an antibiotic.
e.g. :
O O O
O O O
O O O
O O O O O O
12-Crown-4 15-Crown-5 18-Crown-6

CHEMICAL PROPERTIES OF ETHER :
::
H2SO4 
[CH3CH2–OH–CH
•• 2CH3] HSO4
BF3 CH3CH2 O
••
BF3
CH3CH2
••
CH3CH2 – O –CH2CH3
RMgX
R–Mg–X Salt formation
Grignard reagent
CH3CH2–O–CH
•• 2CH3
HF 
[CH3CH2–OH–CH
•• 2CH3] F
HCl 
[CH3CH2–OH–CH
•• 2CH3] Cl
HI or HBr
CH3CH2I + CH3CH2OH (ZIESEL REACTION)
(Cold and conc.)
•• HI or HBr
CH3CH2 –O– 2 CH3CH2I + H2O
•• CH2CH3 (Hot and cond.)
Diethyl ether
BCl3
3 CH3CH2–Cl + (CH3CH2)3BO3
PCl5 / 
2 CH3CH2–Cl + POCl3
CH3COCl /AlCl3
CH3CH2–Cl + CH3–C–OCH2CH3
O
CO / BF3 / HgO /  CH3CH2–C–O–CH2CH3
O
dil.H2SO4 / 
2 CH3CH2–OH
Cl2 / dark
CH3–CH–O–CH–CH3 (,'-dichloro ether)
Cl Cl
Cl2 / sunlight
CCl3–CCl2–O–CCl2–CCl3 (Per chloro ether)
Air and light •• long time
CH3–CH2–O–CH–CH3 (Ether peroxide) Explosion
O=O ••
O–O–H
PREPARATION METHODS OF ETHER :

::
CH3CH2ONa
CH3CH2Cl
Williamson reaction
(–NaCl)
H2SO4 / 140ºC
CH3CH2 –OH
Williamson reaction
CH3CH2–O–CH2CH3
(–H2O) Diethyl Ether
dry Ag2O / 
CH3CH2 –Cl
–2AgCl
CH3MgCl
CH3CH2 –O–CH2Cl
CARBONYL COMPOUNDS
::
• Organic compounds in which – C – group is present are called ‘Aldehyde & Ketone’.
||
O
• The group – C – is called as carbonyl group so, compound are also called carbonyl compounds. If H atom is
||
O
attached with this carbonyl group, then compound is called aldehyde and if alkyl group is present on both side
then compound is called Ketone.
• In ketone if both alkyl group are same then they are called simple ketone, if different then called mixed ketone.
• Their general formula is CnH2nO. Hybridization state of carbon is sp2 and C=O bond length is 1.23 Å.
• The ratio of C,H & O in formaldehyde is 1: 2 :1 (CH2O).
• Aldehyde shows chain and functional isomerism.
• Ketone shows chain, position, functional and metamerism also. Aldehyde and ketone both are functional isomer
with each other.
• Aldehydes are colourless with pungent smell liquid, while ketones are pleasant smell liquids but formaldehyde is
gaseous in nature.
• Lower carbonyl compounds are soluble in water. It is due to polarity in carbonyl group.
• Higher carbonyl compounds are insoluble in water due to more covalent character.
1
• Boiling point  Molecular mass 
No. of branches
• Aldehyde & ketone have higher boiling points than those of non-polar compounds of comparable molar mass , but
have lower boiling points than those of alcohols & carboxylic acids due to the absence of H-bonding
Order of boiling point
(a) Aldehyde < Ketone
(b) The boiling point of unbranched aldehydes increases with the increase in the molcular weight.
Methanal < ethanal < propanal
(c) Order of boiling point of methyl ketones
Propanone < butanone < 2-pentanone
(d) Branched carbonyl compounds < unbranched carbonyl compounds
3-methyl butanal < Pentanal
2-pentanone > 3-methyl-2-butanone
• 40% solution of formaldehyde is known as ‘FORMALIN’ (40% HCHO, 54-56% H2O, 4-6% methanol)
• Mixture of formaldehyde and lactose sugar is called ‘FORMAMINT’ which is used in medicine of throat
infection.
• Boiling point of carbonyl compounds are as under–
Compound Boiling Point

1. Formaldehyde – 21ºC
2. Acetaldehyde + 21ºC
3. Acetone + 56ºC
CHEMICAL PROPERTIES OF CARBONYL COMPOUNDS :


OH
H–CN / OH cat.
C (Cyanohydrin)
CN
(i) R–MgX OH
C
(ii) H3O  R
(alcohols)
(i) Br Zn CH2 COOR OH

(Reformatsky reaction)
C
(ii) H2O CH2–COOR
OH
(i) R–CC Na (Acetylinic alcohol)
C
(ii) H C  C–R
NaHSO3 OH
(White Crystal)
C
SO3Na
H2O / H OH
C (Unstable)
OH
2 RO–H / H OR
(Acetal or Ketal)
C
(–H2O) OR
C=O
Aldehyde 2 RS–H / H SR
Thioacetal or Thioketal
C
or (–H2O) SR
Ketone
H–O–CH2
 O–CH2
H–O–CH2 H
C (Cyclic acetal or ketal)
(–H2O) O–CH2
H2N–Z / H
C = N–Z (Z  CH3, NH2, OH, NH–Ph…..)
(–H2O )
aldol reaction
–Hydroxy aldehyde / Ketone
dil. NaOH
COOR
(i) H2C Pyridine
COOR
C = CH–COOH (Knoevenagel reaction)
(ii) H3O / 
Witting reaction
C = CH2 + Ph3P=O
Ph3P= CH2
H2 / Pd or LiAlH4 / H
CH–OH
Zn – Hg / HCl Reduction
CH2
NH2–NH2 / KOH
CH2

SOME OTHER REACTIONS OF ALDEHYDE & KETONE :
(1) Cannizzaro Reaction : Only  – H = Zero aldehyde shows this reaction

HCHO + HCHO ⎯50
⎯%⎯ ⎯→ HCOOK + CH3OH
KOH
PhCHO + PhCHO ⎯50 ⎯%⎯ ⎯⎯→ PhCOONa + PhCH2OH

NaOH
(2) Tischenko (esterification) Reaction : It is also called modified cannizzaro reaction because all aldehydes show
this reaction.
CH3CHO + CH3CHO ⎯⎯2 ⎯5 ⎯3⎯→ CH3–C–O–CH2CH3
(C H O ) Al
O
HCHO + HCHO ⎯⎯2 ⎯5 ⎯3⎯→ H–C–O–CH3
(C H O ) Al
O
(3) Oxidation by SeO2 :  – C of aldehyde/ketone is converted into C group
O
CH3–C–H ⎯⎯⎯→ H–C–C–H + Se + H2O
SeO2
O O O
CH3–C–CH3 ⎯⎯⎯→ H–C–C–CH3 + Se + H2O
SeO2
O O O
SeO2
CH3–C–CH2–CH3 H–C–CH2–CH3 + Se + H2O
O O
(4) Baeyer-villiger oxidation : Aldehyde is converted into acid but Ketone is converted into ester.
CF3CO3H
CH3–C–H CH3–C–OH + CF3CO2H
O O
CF3CO3H
CH3–C–CH3 CH3–C–OCH3 + CF3CO2H
O O
CF3CO3H
CH3–C–CH2–CH3 CH3–C–O–CH3–CH3 + CF3CO2H
O O
(5) Oxidation by strong oxidants :
KMnO4 / H
CH3–C–H CH3–C–OH
O O
KMnO4 / H
CH3–C–CH3  CH3–C–OH + CO2  + H2O
O O
KMnO4/H+
CH3–C–CH2–CH3 2 CH3–C–OH

O O
(6) Bimolecular reduction of acetone :
CH3 CH3 CH3 CH3
(i) Mg–Hg
CH3–C + C–CH3 CH3–C–—C–CH3
(ii) H3O
O O OH OH
(Pinacol)
(7) Formation of oximino acetone :

CH3–C–CH–H2+O=N–OH (–H2O) CH3–C–CH =N–OH
O O
(8) Pyrolysis :
H–CH2–C–CH3  CH2=C=O + CH4

O (Ketene)
(9) Reducing property of aldehydes :
(a) Tollen's reagent : Ammonical silver nitrate solution [Ag(NH3)2] OH
R–CHO ⎯T⎯
⎯
.R .
→ R–COOH + Ag (Silver mirror)
+
( Ag )
(b) Fehling's solution : It is a mixture of following two solutions.

F.S. (A) → Aqueous solution of CuSO4
F.S. (B) → Alkaline solution of Roschell's salt (sodium potassium tartarate)
.S.(A) + F.S.(B)
R–CHO ⎯F⎯ ⎯⎯⎯⎯→ R–COOH + Cu2O (Red ppt)
Cu +2 ( Blue colour )
(c) Benedict's solution : It is a mixture of copper sulphate sodium citrate and sodium carbonate.
R–CHO ⎯Benedict
⎯+2⎯⎯Solution
⎯⎯→ R–COOH + Cu2O (Red ppt)
Cu ( Blue colour )
(d) Corrosive sublimate (HgCl2) solution :

R–CHO ⎯[⎯ ⎯⎯→ [Hg 2 Cl 2 ] → R–COOH +
HgCl2 ]
Hg
( White ppt ) ( Black ppt )
(10) Test of aldehydes with Schiff's Reagent :

aqueous solution of
⎯⎯
⎯2 → Colourless solution ⎯RCHO
⎯⎯→ Pink colour
SO
p-Roseniline hydrochloride
gas
or magenta dye (Schiff's Reagent)
(pink colour)
(11) Aldehyde shows addition polymerization but ketone shows condensation polymerization.
evaporation
(a) n HCHO + H2O –CH2–O–n

( Formalin) paraformaldehyde
n = 6 to 100
White crystalline solid
dil.H2SO4 O
3 HCHO H2C CH2 Metaformaldehyde / trioxane
O O
CH2
Ba(OH)2 or (Ca(OH)2
6 HCHO CH2–CH–CH–CH–CH–CHO Formose / Hexose
OH OH OH OH OH
O
conc. H2SO4
(b) 3 CH3CHO CH3–HC CH –CH3 Paraldehyde used as Hypnotic
O O
CH
CH3
H3C CH3
HC O CH
dry HCl Metaaldehyde used as solid fuel
4 CH3CHO O O
HC O CH
H3C CH3
O CH3 dry HCl O CH3
(c) CH3–C–CH–H2 + O = C CH3–C–CH = C (Mesityl oxide)
CH3 CH3
O O
H3C CH3 H3C CH3
dry HCl
C=O + H2 CH–C–CH H2 + O = C C=CH–C–CH=C (Phorone)
H3C CH3 H3C CH3
O CH3
Conc. H2SO4 (Mesitylene)
3 CH3–C–CH3
H3C CH3
(12) Ammonia gives following types of products with aldehyde and ketone
N
H2C CH2 CH2 (CH2)6N4
(a) 6HCHO + 4NH3  N Urotropine or HNO3
–6H2O CH2 CH2 Aminoform or RDX
Oxidation
N N Hexamethylene tetramine
Research
used as urinary anticeptic
CH2 &
Development
Xplosive

(b) CH3CH=O + H2 =NH ⎯⎯→ CH3 – CH=NH (acetaldimine)
( − H 2O)
H–NH2 H3C NH2

(c) H3C  O
O (diacetone amine)
C=O+ O (–H2O)
H3C H3C CH2–C–CH3
H–CH2–C–CH3
H3C CH3 H3C CH3
NH
H3C CH3
C H–NH–H + C
 H3C C C
CH3
(d) O+ O (triacetone amine)
(–2H2O) H 2C CH2
H–CH2–C–CH2–H
C
O
O
Ph–CH=O + H2 N H  Ph–CH=N
(e) + O = CH–Ph –3H O CH–Ph (hydrobenzamide)
2
Ph–CH=O + H2 N H Ph–CH=N
PREPARATION METHODS OF CARBONYL COMPOUNDS :

O Nef reaction
CH–N (i) NaOH (ii) H3O
O
O3/ H2O / Zn
C=C
H2O / HgSO4
—CC—
BH3 / H2O2 / OH
—CC—
Cl aq. NaOH
C
Cl
C=O
oxidation Aldehyde
(1º/2º-alcohol) CH–OH PCC or collin's or
reagent Ketone
H3O
C=N–OH
OR H3O
C
OR
(i) RMgX
R–CN
(ii) H3O
(i) SnCl2 / HCl

R–CN
(ii) H3O
O
H2/Pd + BaSO4
R–C–Cl
Rosenmund
reduction
PREPARATION METHODS & CHEMICAL PROPERTIES OF BENZALDEHYDE :

(OIL OF BITTER ALMONDS)
OH
CO + HCl HCN
CH–CN
AlCl3
OH
NaHSO3
CH–SO3Na
LiAlH4/H
(i) HCN + HCl/AlCl3 CH2OH
(ii) H3O H2N–OH/H

CH=N–OH
(–H2O)
H2N–NH–CONH2/H
CH=N–NH–CONH2
CH3 (–H2O)
CrO2Cl2 OCH3
2 CH3OH/H
Oxidation CH
(–H2O) OCH3
COCl Zn–Hg/HCl CH3

Reduction
H2
K2Cr2O7/H
Pd + BaSO4 COOH
Oxidation
CHO 50% KOH
CHCl2 COONa + CH2OH
Cannizzaro
aq NaOH Al(OC2H5)3
CH2–O–C
Tischenko
O
CH2OH Tollen reagent
COOH + Silver
Cu/300ºC mirror
Or PCC Fehling solution
OH O
CN alc. KCN/ CHO
CH–C
(i) SnCl2 + HCl Benzoin condensation
(ii) H3O (CH3CO)2O/Basic med. CH=CH–COOH
Perkin Reaction
CHO
CH=CH2 Cl2/AlCl3
O3/H2O/Zn
Cl
CHO
HNO3+ conc. H2SO4
E.S.R
MgBr NO2
H–C–OR CHO
H2SO4 (Fuming)
O
SO3H
Friedel Craft
Reaction
SPECIAL POINTS :
1. Distinction between formaldehyde, acetaldehyde and acetone (STATE PMT) :
S.No. Reagent / Test HCHO CH3CHO CH3COCH3
1 Brady reagent / DNP Coloured crystal Coloured crystal Coloured Crystal
2 Tollen's reagent Silver mirror Silver mirror ×
3 Fehling's solution Red Red ×
4 Benedict's solution Red Red ×

Corrosive sublimate
5 Black Black ×
(HgCl2)
6 Schiff's reagent Pink Pink ×
7 Iodoform test × Yellow Yellow
8 Pyrogallol test White × ×

Legal test
9 × Red Red
(Sod. nitropruside / NaOH)
10 m-dinitrobenzaldehyde test × × Blue
2. Chloral (CCl3CHO) is an important intermediate in the manufacture of chloroform and D.D.T.
3. Popoff's rule : Oxidation of unsymmetrical ketones largely take place in such a way that the smaller alkyl group
remains attached to the CO group during the formation of two molecules of acids.
[O]
eg. CH3–C – CH2–CH3 ⎯⎯⎯→ CH3–COOH + CH3–COOH
4. Formaldehyde is used in preparation of urotropine (Hexamethylene tetramine), a urinary antiseptic and Bakelite
(phenol formaldehyde resin) polymer,formamint, throat lozengas (formalin + lactose).
5. Formaldehyde is used as disinfectant and preservative for biological specimens in the form of formalin
6. Acetaldehyde is used in preparation of polymers, dyes, metaldehyde is used as solid fuel and paraldehyde as mild
hypnotic, some more hynotics are.
R SO2–R H3 C SO2 –C2 H5 H5 C2 SO2 –C2 H5

|
|
|
|
C C C
|
|
|
|
R SO2–R H3 C SO2 –C2 H5 H5 C2 SO2 –C2 H5
sulphonal trional tetronal
7. Acetaldehyde is used as an antiseptic
8 Acetone is used as a solvent for cellulose, nail - polish, varnish and silk.
CARBOXYLIC ACID
• Saturated monocarboxylic acids have a general formula, CnH2n+1 COOH or CnH2nO2.
• The carboxylic carbon and the two oxygen atom in carboxylic acid are sp 2 hybridized.
• The C–O (single bond) of carboxylic group is shorter (1.36 Å) than normal C–O single bond (1.43 Å) in alcohols
and ethers, due to resonance.
• The C=O double bond in carboxylic group is slightly longer (1.23 Å) than the normal C=O double bond (1.20 Å)
in ketones and aldehyde.
• The carboxylic acid exhibit isomerism as illustrated below :
(a) Chain isomerism : (b) Position isomerism :
CH3 CH3 CH3
CH3CH2CH2CH2–COOH &CH3–CH2–CH– COOH CH3–CH– CH2–COOH & CH3–CH2–CH– COOH

pentanoic acid 2-Methyl butanoic acid 3-Methylbutanoic acid 2-Methyl butanoic acid
(c) Functional isomerism :
O O
CH3–CH2–COOH & CH3–C–OCH3 & H–C–OC2H5
propionic acid Methyl acetate Ethyl formate
(d) Optical isomerism : (e) Geometrical isomerism :
C2H5 C2H5
CH3 COOH CH3 H
CH3–C*–C3H7 C3H7–C*–CH3
C=C C=C
COOH COOH H H H COOH
2-Ethyl-2-methyl pentanoic acid cis-But-2–enoic acid trans-But-2–enoic acid
• Lower fatty acid upto C10 are colourless liquid. The higher ones are colourless waxy solids.
• The first three members have a sharp pungent odour but the middle one C4 to C9 have of rancid butter where as
higher member are odourless.
• Lower member are completely miscible with water because of the formation of the hydrogen bonds and solubility
decreases with increasing molecular weight because of increased effect of non-polar long carbon chain which
result in weak H-bonding or no H-bonding.
• Boiling point of carboxylic acid increase regularly with increase in molecular weight. B.P. of R–COOH > R–OH
due to hydrogen bonding and they exist as dimer.
H-Bond
O H––O
CH3––C C––CH3
O––H O
H-Bond
A dimer of a carboxylic acid
CHEMICAL PROPERTIES OF CARBOXYLIC ACID :
Sodalime Na 1
R–H  R–C–ONa + H2 
|| 2
O
(i) NaOH NaOH
R–R R–C–ONa + H2O
(ii) electrolysis ||
O
NaHCO3
R–C–ONa + H2O + CO2 
||
(i) AgOH O
R–Br
(ii) Br2/CCl4
CH2N2
R–C–OCH3 + N2 
||
Ca(OH)2 O
R–C–R 
O
O ||
R–C–Cl
R–C–OH R–C–O–C–R + HCl
|| || ||
MnO
R–C–R O O O
300°C
O
Carboxylic acid CH2=C=O
R–C–O–C–CH3
|| ||
O O
ROH/H
R–C–OR (Esterification)
(–H2O) ||
O
PCl3/PCl5/SOCl2
R–C–Cl
||
O
P2O5/
(–H2O)
R–C–O– C–R
H.V.Z Reaction || ||
R–CH–COOH Br2/red P/ O O
|
Br ●●
NH3  
R–C–ONH4 R–C–NH2
(–H2O) ||
||
-Halogenation product O
O
is obtained by Hell-Volhard-
Zelinsky reaction HI/red P/
reduction
R–CH3
LiAlH4/H
reduction
R–CH2OH
PREPARATION METHODS OF CARBOXYLIC ACID :
Cl
aq. NaOH
R–C Cl
Cl
R–MgCl (i) CO2

(ii) H3O
H2O/H
R–C–Cl
O
H2O/H
R–C–OR
O
COOH R–C–OH
H2C 
(–CO2) O
COOH
Carboxylic acid
H2O/H
R–CN

R–C–H KMnO4/H /
oxidation
O
KMnO4/H/
R–CH2OH oxidation
(AcO)2Mn
CH3–CH3 oxidation
O3/H2O
R–CH=CH2
O3/H2O
R–CCH
COMPARISON OF FORMIC ACID AND ACETIC ACID : (STATE PMT)
PROPERTY FORMIC ACID ACETIC ACID
1. Acidic nature
(i) With electro positive HCOOH + Na → HCOONa + ½ H2 CH3COOH + Na → CH3COONa + ½ H2
metals
(ii) With bases HCOOH + NaOH → HCOONa + H2O CH3COOH + NaOH → CH3COONa + H2O
(iii) With carbonates and HCOOH +NaHCO3 →HCOONa + H2O + CO2 CH3COOH + NaHCO3 → CH3COONa +
bicarbonates
H2O + CO2
2. Esterification HCOOH + C2H5OH → HCOOC2H5 + H2O H SO

CH3COOH + C2H5OH ⎯⎯2 ⎯
⎯4
→
Conc.
CH3COOC2H5 + H2O
3. Reaction with PCl5 HCOOH + PCl5 → HCOCl + POCl3 + HCl CH3COOH + PCl5 → CH3COCl + POCl3 +
CO + HCl HCl
4. Heating Amm. salts HCOONH4 → HCONH2 + H2O CH3COONH4 → CH3CONH2 + H2O
5. Heating alone HCOOH → CO2 + H2 Unaffected

6. Conc. H2SO4 H SO Unaffected
HCOOH ⎯⎯2 ⎯
⎯4
→ CO + H2O
Conc.
7. Cl2/ red P Unaffected Form ClCH2COOH; Cl2CHCOOH,

Cl3CCOOH
8. Action of heat on salts

(i) Calcium salt (HCOO)2Ca → HCHO + CaCO3 (CH3COO)2Ca→CH3COCH3+ CaCO3
(ii) Sodium salt COONa Unaffected

2HCOONa ⎯360
⎯⎯ ºC
→ | + H2
COONa
(iii) Sodium salt HCOONa + NaOH ⎯CaO
⎯⎯→ Na2CO3 + H2 CH3COONa + NaOH⎯⎯
⎯→ CH4+Na2CO3
CaO
(NaOH + CaO)
9. Electrolysis of Na or H2 CH3–CH3 formed

K salt
10. On heating with P2O5 Unaffected 2CH3COOH ⎯P⎯⎯→ (CH3CO)2O + H2O

2O5
11. Reducing nature
(i) Tollen’s reagent HCOOH + Ag2O→ 2Ag + CO2+ H2O Unaffected
(ii) Fehlings solution HCOOH + 2CuO → Cu2O + CO2+ H2O Unaffected
PROPERTY FORMIC ACID ACETIC ACID

(iii) Mercuric chloride HCOOH + HgCl2→ Hg2Cl2+ CO2+ 2HCl Unaffected
HCOOH + Hg2Cl2→ 2Hg + CO2+ 2HCl
12. Acid (neutral solution) Greenish blue colour Unaffected
+ NaHSO3 + sodium
nitroprusside
13. Acid (neutral solution) Red colour which changes to brown ppt. on Wine red colour
+ neutral ferric chloride heating.
14. Uses (i) For preparation of CO2 in laboratory (i) As solvent and a laboratory reagent.
(ii) In the preservation of fruits. (ii) For making various organic compound
such as CH3COCH3; (CH3CO)2O;
(iii) In the preparation of nickel formate,
CH3COCl, CH3CONH2 and CH3COOR.
which is used as catalyst the
hydrogenation of oil. (iii) For making various useful acetate, of
Cu, Al, Fe, Cr, Pb.
(iv) As a reducing agent
(a) (CH3COO)2Cu; Making green paints.
(v) In the manufacture of oxalic acid
(b) Al, Fe & Cr acetate; mordant in dying
(vi) As an antiseptic and in the treatment of
gout. (c) (CH3 COO)4 Pb : oxidizing agent
(vii) As coagulating agent for rubber latex (iv) Basic (CH3COO)2Pb : manufactore
of white lead
(viii) In lather tanning.
(v) Aluminium acetate; water proof
fabrics
(vi) Alkali acetate : Diuretics
(vii) Cellulose acetate : Artificial silk and

Celluloid
CARBOXYLIC ACID'S DERIVATIVES
R–C–OH
O
Carboxylic acid
R–C–X R–C–O–R R–C–O–C–R R–C–NH2

O O O O O
Acid halide Ester Acid anhydride Acid amide
• Dervatives are characterized by Nucleophilic Substitution Reaction which take place at the acyl carbon
(carbonyl group).
Leaving group
R
R R
C=O•• + ••Nu Nu–C–L C=O + L
••
L O Nu
(L : Cl, OCOR’ , NH2 or OR’ or even –OH in acid)
• Relative reactivity of acyl compounds :
R–C–Cl > R–C–O–C–R' > R–C–OR' > R–C–NH2

O O O O O
This overall order of reactivity can be accounted for in terms of the following three factors -
1. Effects of the basicity on Leaving group
• Weaker bases are good leaving group.
• Hence acid derivative with weaker bases as leaving group are more reactive.
• Chloride ion being weakest base, acyl chloride are most reactive of the acid derivatives.
• Amines are the strongest bases (as compared to Cl , OOCR, OR) hence are least reactive.
2. Rsonance effect
• The leaving group in each case has an atom with alone pair of electron adjacent to carbonyl group.
• The compound exists, therefore as resonance hybrid
O O
R–C R–C
••
L L

• The greater the stabilization, the smaller the reactivity of the acyl compound.
• Acyl chloride are least affected by resonance due to the ineffective overlapping(i.e.2p-orbital of carbon with
3p-orbital of Cl)
• Stabilization is achieved by acid -anhydride, ester and amide (due to effective overlapping of 2p-orbital of
carbon – oxygen & carbon - nitrogen.)
• The stabilization on particular carbon in acid anhydride is less than that of ester since the resonance effect is
shared between two carbonyl groups.
3. Inductive effect
• The inductive effect of oxygen in ester is greater than that of nitrogen in amide. Hence ester is more reactive
than an amide.
• Methyl acetate and ethyl acetate are Fruity smelling liquids.
• Acetamide is white crystalline solid having pungent smell of dead mouse.
• Generally acid derivatives are polar in nature. Therefore, they have higher boiling points than corresponding
hydrocarbons but lower boiling points than corresponding carboxylic acids. Primary amides have quite high
boiling point and melting points because they form strong intermolecular H-bonding.
Ques. Order of boiling point -
O
O O O
CH3 C
(1) CH3–C–NH2 > O > CH3–C–OC2H5 > CH3–C–Cl
CH3 C
O
[222ºC] [139ºC] [77ºC] [52ºC]
(2) CH3–C–NH2 > CH3–C–OH > CH3–CH2–CH2–OH > CH3–C–OCH3

O O O
[222ºC] [100.5ºC] [85ºC] [72ºC]

CHEMICAL PROPERTIES OF ACID CHLORIDE :
O
/AlCl3
CH3–C– + HCl
Friedal craft acylation
Acetophenone
H2O
CH3–COOH + HCl O
Acetic acid Hydrolysis H2/Pd/BaSO4
C2H5ONa Rosenmund reaction CH3–C–H + HCl
CH3–COOC2H5 + NaCl Ethanol
Sod. ethoxide
Ethyl ethanoate
LiAlH4/H2O
CH3–CH2–OH + HCl
CH3–COOC2H5 + HCl C2H5OH Complete reduction
Ethanol
Ethyl ethanoate Alcoholysis or
(Esterification)
O
NH3 CH3–C–Cl (CH3)2 Cd
CH3–CONH2 + HCl 3 CH –C–CH3 + CdCl2
Ammonolysis Dimethyl cadmium
Ethylamide O Propanone
Acetyl chloride 
Better than CH3MgBr
C2H5OC2H5
CH3COOC2H5 + C2H5Cl ZnCl2 O
Ethyl ethanoate
(i) CH2N2
CH3–NH2 CH3–CH2–C–OH [ARNDT-EIENSTERT]
CH3–CONHCH3 + HCl (ii) Ag2O (iii) H2O
Propanoic acid reaction
N-methylethanamide Methyl amine

 NH2–OH
CH3–C–ONa CH3–C–NH2–OH
CH3–CO–O–COCH3 + NaCl (–HCl)
Sod. Acetate
Acetic anhydride
KCN O
CH3COCN + KCl
CH3–CO–O–COCH3 + HCl CH3COOH Ethanoyl chloirde
Acetic anhydride Pyridine
PREPARATION METHODS OF ACID CHLORIDE :
HCl
CH2=C=O
CH3–C–OH
PCl5/PCl3/SOCl2 CH3–C–Cl

O
O
Acetyl
Chloride
PCl5/PCl3/SOCl2
CH3–C–ONa 
O
CHEMICAL PROPERTIES OF ESTER :

O O
500ºC H2O/H
CH3– C –OH + CH2=CH2 Pyrolysis CH3– C –OH + C2H5OH
Ethanoic acid Ethene Acid hyrolysis
Ethanoic acid
O
O NaOH
NH3 Alkaline hydrolysis CH3– C –ONa + C2H5OH
CH3– C –NH2 Sod. ethanoate
Ethanamide –C2H5OH
NaBH4/H2O
No reaction
Reduction
O O
CH3–NH2 LiAlH4/H2O
CH3– C –NHCH3 + C2H5OH CH3– C –OC2H5 2 C2H5OH
Reduction
N-Methyl Ethanamide Ethyl ethanoate Ethanol
O  Na/C2H5OH
C2H5ONa 2 C2H5OH
CH3– C –CH2COOC2H5 + C2H5OH Bouveault Ethanol
Ethyl aceto acetate Claisen Blanc reduction
(-ketoester) esterification
O PCl5/
C3H7–O–H/Alkoxide CH3COCl + C2H5Cl
CH3– C –O–C3H7 –POCl3
Trans esterification Ethanoyl chloride
Propyl ethanoate
H2N – OH
CH3– C –NH–OH + C2H5OH
OH Hydroxyl amine
CH3MgBr/H3O O
CH3–C–CH3 N-Hydroxy ethanamide
Grignard reagent
CH3 NH2–NH2
Tert. Butyl alcohol CH3– C –NH–NH2
Hydrazine
O
PREPARATION METHODS OF ESTER :

H–OCH2CH3/H2SO4
CH3–C–OH
|| (–H2O)
O
O
||
CH3–C–O
H–OCH2CH3
O
(–CH3COOH)
CH3–C–O
||
O
H–OCH2CH3
CH3–C–OCH2CH3
CH3–C–Cl ||
(–HCl) O
||
O Ethyl acetate
I /CCl
CH3–C–OAg 2 4
|| Bir n-Baum simonini reaction

O
Tischenko reaction
2 CH3–CH=O
Al(OEt)3
Baeyer villiger oxid.

CH3–C–CH2CH3
|| CF3CO3H
O
CH2=CH2
CH3–C–OH
||
O
CHEMICAL PROPERTIES OF ACID ANHYDRIDE :
H2O (i) LiAlH4 (ii) H3O
2CH3COOH Hydrolysis 2CH3CH2OH
Reduction Ethanol
Acetic acid
O O O
C2H5OH H2N–
CH3– C –OC2H5 –NH–C–CH3 + CH3–C–OH
–CH3COOH Aniline Acetanilide
Ethyl acetate (Acetic acid)
O O O O O
2 NH3 PCl5
CH3–C–NH2 + CH3–C–ONH4 CH3 – C –O– C –CH3 2CH3–C–Cl + POCl3
Ethanamide Amm.acetate Ammonolysis Acetyl chloride
Acetic O O
anhydride N–O–N O
O O
O
2CH3–C–O–N
O Nitrogen pentaoxide
Acetyl nitrate
C2H5NH2
O
CH3–C–NHC2H5 + CH3COOH O O
N-Ethyl ethanamide Acetic acid Dry HCl
CH3C–Cl + CH3–C–OH
Acetyl chloride Acetic acid
O
O CH3CHO/AlCl3
/AlCl3 CH3 O–C–CH3
Acetaldeyde C
C–CH3 + CH3COOH H O–C–CH3
Anhy. AlCl3
(Friedal Craft Acylation)
O
Acetophenone Ethylidene acetate
Perkin reaction
–CH=CH–COOH
–CHO/CH3COONa Cinnamic acid
PREPARATION METHODS OF ACID ANHYDRIDE :
CH3COOH
CH2=C=O
O O
|| ||
CH3–C–ONa
CH3–C–OH
(–NaOH) O
||
CH3–C
O
O O CH3–C
|| || ||
CH3–C–OH/Pyridine O
CH3–C–Cl (–HCl)
O Acetic
|| P2O5/ anhydride
2 CH3–C–OH
(–H2O)
O
||
O–C–CH3 Distillation/
CH3–CH (–CH3CHO)
O–C–CH3
||
O
CHEMICAL PROPERTIES OF ACID AMIDE :

P2O5/ H2O/H
CH3–CN CH3–C–OH + NH3
(–H2O)
O
CH3–C–NH2
Reduction NaOH
CH3–CH2–NH2 O CH3–C–ONa + NH3
Na/EtOH
or LiAlH4/H Acetamide O
Br2 + KOH NaNO2 + HCl

CH3–NH2 CH3–C–OH
Hoffmann or HNO2
bromamide O
reaction Cl
SOCl2 or H –2HCl
CH3–C–N CH3–CN
PCl5 H
Cl
(unstable)
AMPHOTERIC CHARACTER OF ACETAMIDE
Available for protonation
••
O O •
•• •
CH3–C CH3–C
•• 
NH2 N–H Available for deprotonation
H
O 
+ – O –H O–H
(i) CH3–C–NH2–HCl CH3–C CH3–C Cl
acid 
NH2 NH2
O O

(ii) CH3–C–NH + NaNH2 2 CH3–C–NH Na + NH3
H
base
O
O
CH3– C –NH
(iii)
2 CH3–C–NH2 + HgO Hg + H2O
base CH3–C–NH
O
Salt
PREPARATION METHODS OF ACID AMIDE :
••
NH3
CH3–C–Cl
|| (–HCl)
O
••
NH3
CH3–C–OCH3
|| (–CH3OH)
CH3–C–NH2
O ||
O
Acetamide
H2O/OH
CH3–CN
Partial hydrolysis
 
CH3–C–ONH4 (–H2O)
||
O
ALIPHATIC AMINE
• General formula  CnH2n+3 N
R–NH2 (1º/p-amine)
• Classification R–NH–R (2º/s-amine)
R–N–R (3º/t-amine)
R
• Shape : Pyramidal
• Hybridizaton of nitrogen sp3
• NOMENCLATURE :
NH2
CH3
(i) CH3–CH 2–CH 2–CH2–NH 2(ii) CH3–CH2–CH–CH3 (iii) CH3–CH2–CH–NH–CH3
1-Butanamine 2-Butanamine N-methyl butan-2-amine

CH3 OH OH
(iv) CH3–CH–N–CH2–CH3 (v) (vi)
N–CH3 NH2
CH3 O
CH3
N-ethyl-N-methyl 2-(N,N-dimethyl amino)-cyclohexanol 2-amino-3-hydroxy cyclohexanone.
propan-2-amine
• ISOMERISM :
(i) Chain isomerism : (ii) Position isomerism :
CH3–CH2–CH2–CH2–NH2 and CH3–CH –CH2–NH2 CH3–CH2–CH2–NH2 and CH3–CH –CH3
CH3 NH2
(iii) Functional isomerism :
CH3
CH3–CH2–CH2–NH2, CH3–CH2–NH–CH3 and CH3–N–CH3
(iv) Metamerism :
CH3–CH2–CH2–NH–CH3 , CH3–CH2–NH–CH2–CH3 and CH3–CH–NH–CH3
CH3
••
(iv) Optical isomerism : Although N type amines are chiral but they cannot exhibit optical activity because
R1 R2 R3
these are readily interconvertable in its mirror image. Thus exists as recemic mixture.
R1 R1
R2 N •• •• N R2
R3 R3
R4
However N type molecule can exhibit optical activity 1and are resolvable.
1 3
R R
R2
H3C H

H O N
e.g. (i) N (ii) N (iii)
H3C C3H7 H C2H5
C2H5 CH3 Cl
• These are colour less volatile compounds having ammonia like smell. Higher amines have fishy smell.
• CH3NH2 is gas but CH3CH2NH2 and higher members are liquids.
Molecular weight
• BOILING POINT : B.P. 
No. of Branches
Q. CH3CH2CH2NH2 > CH3CH2NH2 > CH3NH2
CH3
Q. CH3CH2CH2CH2NH2 > CH3–CH–CH2–NH2 > CH3–C–NH2
CH3 CH3
Q. CH3CH2CH2NH2 > CH3–NH–CH2CH3 > CH3–N–CH3
CH3
(1ºamine) (2ºamine) (3ºamine)
Q. CH3CH2–OH > CH3CH2–NH2
(More polar) (Less polar)
• SOLUBILITY IN WATER :
Lower amines are highly soluble in H2O due to intermolecular H-bonding ; solubility decreases as no. of carbon
atoms increases. All amines (even 3º) can act as proton acceptors in H-bonding to water molecules.
No. of Branches
Solub ility 
Molecular weight
Q. CH3NH2 > CH3CH2NH2 > CH3CH2CH2NH2
Q. CH3–CH2–CH2–CH2–NH2 > CH3CH2–NH–CH2CH3 > CH3–N–CH2CH3
CH3
Q. CH3–OH > CH3–NH2
(liquid) (Gas)
• COMPARISION OF BASIC STRENGTH OF 1º/2º/3º AMINES AND NH3 :
(I) In gaseous state : Basic strength  + I effect

•• •• •• ••
Q. R3N > R2NH > RNH2 > NH3
+ I effect
(II) In aqueous state : Basic strength 
Steric hinderance
Q.
Value of R Basic strength order
1. Methyl 2º> 1º > 3º > NH3
2. Ethyl 2º > 3º > 1º > NH3

3. Iso propyl 1º > NH3 > 2º > 3º
4. t-Butyl NH3 > 1º > 2º > 3º
CHEMICAL PROPERTIES OF AMINE :
O
||
 H2O Cl–C–Cl R–N=C=O
R–NH3 OH (–2 HCl) (Alkyl isocyanate)
O
O ||
 || CH3–C–OH CHCl3+alc.KOH
RNH3 O–C–CH3 R–N C
Hoffmann
n (Pungent smell)
Carbyl amine rx

R–NH3 Cl HCl CH3–CH=O/H CH3–CH=N–R
(Schiff's Base)

R–NH3 AuCl4 HAuCl4 Cl–N=O
R–NH2 R–Cl
Tilden reagent
NO2
 1
Na(Metal)
NO2 HO NO2 R–NHNa + H2

2
NO2
R–NH3 O NO2
Picric acid CH3 CH2–Cl
NO2 R–NH–CH2CH3
(–HCl)
O
 –2 || O
H2SO4 CH3–C–Cl ||
R–NH3 2 SO 4 R–NH–C–CH3
(–HCl)
O O
|| ||
 –2 Ph–C–Cl
 H2PtCl6 R–NH–C–Ph
Pt metal RNH3 PtCl6 (–HCl)
2
(Chloro platinate method)used in Cl
CH3MgCl
determination of molecular weight CH4 + Mg
of amine. NHR
Br2 + KOH
Halogenation R–NH–Br
TEST OF AMINES :
Chemical Reactions (difference between 1º/2º/3º amines) :
(1)Hoffmann's mustard oil reaction :
S S
 HgCl2
RNH–H + C=S RNH–C–SH R–N=C=S
(–2HCl)
Alkyl iso thiocyanate
(–HgS)
(Smell of mustard oil)
S S
 HgCl2
R2N–H + C=S R2N–C–SH No reaction
R 3N + CS2 No reaction
(2)Hoffmann's carbyl amine reaction/isocyanide test :
R–NH2 + (CHCl3 + 3KOH) ⎯⎯→ R–N C + 3KCl + 3H2O
(offensive smell)
R2NH and R3N does not give this test.
(3)Reaction with Hoffmann's reagent (Diethyl oxalate) :
2 RNH–H O=C–NH–R Oxamide
(–2C2H5OH) O=C–NH–R (solid)
O R
C–OC2H5 R2N–H O=C–N Oxamic ester
R (liquid)
C–OC2H5 (–C2H5OH)
O=C–OC2H5
O
R3N
No reaction
(4)Reaction with Hinsberg reagent (Benzene sulphonyl chloride).
RNH–H KOH Soluble
SO2NHR
(–HCl) –H2O
SO2–Cl
R2N–H R KOH Insoluble
SO2–N
(–HCl) R
R3N
No reaction
(5)Reaction with nitrous acid :
R–NH2 + HNO2 ⎯⎯→ R–OH + N2 + H2O
–H2O
R2N H + HO–N=O R2N–N=O (Nitroso amine)
Yellow oily liquid which also gives Leiber mann's nitroso test (G.R.B. colour)
Room temp.
No reaction
R3N + HNO2
H
0ºC 
R–N–R O–N=O (Soluble)
R
(6) Oxidation by KMnO4 :

[O] H 3O 
CH3CH2–NH2 CH3–CH=NH CH3CHO + NH3
(–H2O)
Acetaldimine (aldehyde)
CH3 [O] CH3 H 3O  CH3

CH–NH2 C=NH C=O + NH3
CH3 (–H2O) CH3 CH3
(ketone)
CH3 CH3
3[O]
CH3–C–NH2 (–H2O) CH3–C–NO2 (Nitro alkane)
CH3 CH3
CH3 [O] CH3 CH3

2 N–N (tetramethyl hydrazine)
N–H (–H O)
CH3
2 CH3 CH3
[O]
CH3–N–CH3 No reaction
CH3
(7) Oxidation by Caro's acid (H2SO5) or Fenton's reagent (FeSO4+ H2O2) :
CH3CH2–NH2 ⎯[⎯ → CH3CH2–NH–OH ⎯⎯→ CH3–CH=N–OH ⎯[⎯ → CH3–C–NH–OH

O] [O] O]
[– H 2 O ]
O
(Hydroxamic acid)
CH3 CH3 CH3

[O] [O]
CH3 CH–NH2 CH–NH–OH C=N–OH (Acetone oxime)
CH3 (–H2O) CH3
CH3 CH3
2[O]
H3C–C–NH2 CH3–C–N=O (Nitroso alkane)
CH3 CH3
CH3
CH3 [O]
NH N–OH (N,N-dimethyl hydroxyl amine)
CH3 CH3
CH3 CH3
[O]
H3C–N CH3 N→O (trimethyl amine oxide)
CH3 CH3
PREPARATION METHODS OF AMINE :

Br2 + KOH (excess)
R–C–NH2
|| Hoffmann bromamide reaction
O
N3H/H
R–C–OH
|| Schmidt reaction
O
(i) NaN3 (ii) H3O

R–C–Cl
|| Curtius reaction
O
H (i) dry HCl (ii) H3O

R–C–N
|| OH Lossen reaction
O
O
|| (i) KOH (ii) R–X (iii) H3O
C N–H
C Gabriel phthalimide reaction
||
O
(i) NH3/H (ii) H2/Pd

C=O Reductive amination
(ald./ketone)
R–NH2
or
Cl–NH2 R–CH2–NH2
R–MgCl (–MgCl2)
Alkyl amine
NH3/
R–X or R–OH
H 3O 
R–N C
Complete hydrolysis
2KOH
R–N=C=O
Wurtz reaction
O
|| LiAlH4/H2O
R–C–NH2 Reduction
LiAlH4/H2O
R–CN
Reduction
O LiAlH4/H2O
R–N O
Reduction
(Baryta water) Ba(OH)2

R–CH–NH2
| –BaCO3 , –H2O
COOH
(-amino acid)
ANILINE
• Structure of aniline is represented by NH2
• All six carbon atom in this compound and nitrogen atom are sp 2 hybridised.
• Lone pair on nitrogen atom is delocalised through out the ring.
• Due to delocalisation basic character is less than aliphatic amine.
• N–H bond of aniline exhibit acidic character.
• Electrophilic substitution usually takes place at ortho and para position.
• It is purified by steam distillation method (B.P. = 184ºC)
• It is a colourless oily liquid.
• It has a faint characteristic odour.
• It is partial soluble in water but complete soluble in organic solvents.
CHEMICAL PROPERTIES OF ANILINE :

[A] Reactions due to benzene ring (E.S.R.) :
(1) Bromination :
NH2 NH2
Br2 Br
+
CCl4 or CS2
Br
o-Bromo aniline p-Bromo aniline
NH2 NH2
Br2 Br Br (2,4,6-tribromo aniline)
H2O
Br
NH–C–CH3 NH–C–CH3 NH2
O O
CH3–C–O–C–CH3 O O 
⎯Br
⎯2 → ⎯H⎯ ⎯⎯→
2O / H
−CH3COOH
or CH3–C–Cl
O Br Br
(2) Nitration :
(a) Direct nitration gives meta product.
NH2 NH3 NH3 NH2

HNO 3
⎯⎯⎯⎯ → ⎯NO
⎯⎯ 2
→ HO (Major product)
H2SO4
NO2 NO2
(b) If-NH2 group is protected ortho/para product is obtained.
NH2 NH–C–CH3 NH–C–CH3 NH2 NH2
O O NO2
(CH CO ) O 
⎯⎯⎯3⎯⎯2⎯→ ⎯HNO
⎯⎯3 → ⎯H⎯ ⎯⎯→
2O / H +
H 2SO4 −CH3COOH
NO2 NO2
o-nitro aniline p-nitro aniline
(3) Sulphonation :
 •• 
NH2 NH3HSO4 NHSO3H NH2 NH3
⎯H⎯ ⎯→ ⎯⎯⎯→
160ºC
2SO4
⎯rearrangem
⎯⎯⎯ent ⎯→ ⎯
⎯→
160 ºC ( − H 2O )
H SO3H SO3
zwitter ion of sulphanilic acid
[B] Reactions due to NH2 group :

NH3Cl
HCl
••
NH–R
R–X
–HX
O O
NH2 C –Cl
NH–C
–HCl
Aniline
O=CH /H
N=CH
(–H2O)
Cl
C=O N=C=O
Cl
(–2HCl)
N C
CHCl3/alc. KOH
[C] Other reactions :
⎯⎯⎯
(1) Oxidation of aniline : –NH2  ⎯⎯⎯
⎯→ –NH–OH 
[ O] ⎯→ N=O 
⎯⎯⎯
⎯→ NO2
[ O] [ O]
2H 2H 2H
`
Oxidants Products
air & light p-Benzo quinone
CF3CO3H (per acid) Nitro benzene
KMnO4/H Aniline Black
KMnO4/OH Azo benzene
KMnO4 Azo benzene + Nitro benzene

H2SO5 (Caro's acid) Nitroso benzene + Nitro benzene
NaOCl p-amino phenol
(2) Formation of diazonium salt :

• When aniline is treated with HNO2(NaNO2 + HCl) in cold condition benzenediazonium chloride (salt) is obtained.
 •• 
NH2 N2Cl N=N–Cl
NaNO + HCl
+ HNO2 ⎯⎯ ⎯2 ⎯⎯→ or
0 º–5 º C
or
273 – 278 K
• If room temperature or high temperature is used than phenol is the major product.
• Benzene dizonium chloride is used in synthesis of following aromatic compounds :

H3PO2 or C2H5OH
reduction
CuCl
Cl
CuBr
Br Sandmeyer reaction (Good yield)
CuCN/
CN
KI
I
HBF4 or NaBF4
F (Beltz-Schiemann reaction)
Cu/HCl
Cl
Cu/HBr
Br Gattermann reaction

N2Cl Cu/HNO2
NO2
N=N
Benzene
diazonium OH
chloride
N=N OH
NH2 (Orange dye)
N=N NH2
Me Coupling reaction (ESR)
N (yellow dye)
Me
Me
N=N N
Me
(yellow dye)
OH N=N
OH
(Red dye)
-Naphthol
PREPARATION METHODS OF ANILINE :

Br2+KOH
C–NH2 (excess)
O
N3H/H
C–OH
(i) NaN3 (ii) H3O

C–Cl
(i) dry HCl (ii) H3O

C–NH–OH
••
NH2
O
(i) NaNH2
Cl Aniline
(ii) NH3(liq.)
H 3O 
N C
2 KOH
N=C=O
O Sn/HCl
N Reduction
O
NITRO BENZENE (OIL OF MIRBANE)
PREPARATION METHODS AND CHEMICAL PROPERTIES OF NITRO BENZENE :
NO2 NO2

Conc. HNO3 NO2
H2SO4 
NO2 NO2 NO2
E.S.R NO 2
. Fuming H2SO4
SO3H
NO2
Cl2/AlCl3
Cl NO2 NO2
HNO3 NaNH2 NH2 +
H2SO4
O
NH2
CH3–C–O–NO2/ NO2 NO2
NO2
(–CH3COOH) N.S.R OH
NaOH +
.
NH2
Nitro Benzene OH
CF3CO3H
Oxidation NO2 NO2
 CH3ONa
REDUCTION
OCH3 +
N2Cl
Sn/HCl
HNO2/Cu NH2
or LiAlH4/H2O OCH3
Gattermann reaction or H2/Pd
Zn+NH4Cl
NH–OH
Fe/H2O
N= O
dil.H2SO4
NH2
Electrolysis
rearranged
Conc.H2SO4 NH–OH HO NH2
CH3OH/NaOH O
or glucose/NaOH
N=N (Azoxy benzene)
or Na3AsO3
CH3OH/NaOH/Zn Bimolecular
N=N (Azobenzene) Reduction
or Na2SnO3
H2O/NaOH/Zn
NH–NH (Hydrazobenzene)
NITRO ALKANE
PREPARATION METHODS AND CHEMICAL PROPERTIES OF NITROALKANE :
Sn/HCl
CH3CH2–NH2
or H2/Pd
or Na/EtOH
or LiAlH4/H
Zn/NH4Cl
CH3CH2–NH–OH
H2O/H
CH3–CHO
AgNO2 Nef reaction
CH3CH2–Cl
O
CH3CH2–N
O NO2
Fuming HNO3 O==N–OH
CH3–CH3 colourless CH3–C N–OH (Nitrolic acid)
600°C
sweet
smelling
 liquid Tautomerism O
CH3–CH–COOH CH3–CH=N (aci-nitro form)
| (–CO2) OH
NO2 CH3MgBr
CH4
(-Nitro acid)
CH3
CH3CHO/OH |
CH3–CH–CH–NO2 (Nitro-alcohol)
|
OH
Cl2/NaOH/OH
CH3–CH–NO2
(–HCl)
Cl

CO2 + N2 + H2O
Pyrolysis
SPECIAL POINTS :
1. Selective reduction :-
NO2 NH2
(NH4)2S
or NH4 SH
NO2 NO2
(only m-dinitro benzene) (m-Nitro aniline)
2. Muliken - Barker Test :-
O Zn + NH4Cl Tollen
R–N R–NH–OH R–N=O + Silver mirror (Ag)
O reduction reagent
or or
O or
N NH–OH N=O
O
CYANIDE & ISOCYANIDE
PREPARATION METHODS AND CHEMICAL PROPERTIES OF ALKYL CYANIDE :
LiAlH4/H
KCN or H2/Pd
CH3–Cl reduction CH3CH2–NH2
Na/EtOH
CH3–CH2–NH2
Mendius
reduction
P2O5/ SnCl2/HCl H3O
CH3–C–NH2 CH3–CH=NH CH3–CHO
|| (–H2O) Stephen reduction
O
CH3–CN
Methyl cyanide (i) CH3MgBr CH3–C–CH3
(ii) H3O ||
O
P2O5/
CH3–CH==N–OH (i) ROH
(–H2O) CH3–C–OR
(ii) H3O ||
O
H2O/OH
CH3–C–NH2
||
O
Cl–CN H2O/H
CH3MgBr CH3–C–OH
||
O
PREPARATION METHODS AND CHEMICAL PROPERTIES OF ALKYL ISOCYANIDE :

AgCN H3O
CH3–Cl CH3NH2 + HCOOH
H2/Pd
CH3–NH–CH3
reduction
CH3–N C
P 2O 5 Na/EtOH
CH3–NH–C–H Methyl CH3–NH–CH3
||  reduction
isocyanide
O
O3/
CH3–N=C=O + O2
CHCl3 2HgO
CH3–NH2 CH3–N==C==O + Hg2O
alc. KOH
(MIC)
SPECIAL POINTS :
• In December 1984 (Bhopal tragedy) Methyl isocyanate (MIC) gas was responsible.
• Lower RCN and RNC are colourless liquid but higher members are crystalline solid.
• RCN have sweet smell but RNC have offensive smell.
• Lower RCN are soluble in H2O but RNC are insoluble.

UREA (only for STATE PMT)
INTRODUCTION :
O
• Structural formula : H2N–C–NH2
• Common name : urea, carbamide, diamino ketone
• Derived name : amino formamide
• IUPAC name : amino methanamide
• Urea is monoamide of carbamic acid and diamide of carbonic acid.
• Urea and ammonium cyanate are Functional group isomers.
• Urea and isourea are tautomers.
NH2–C–NH–H NH2–C=NH (Isourea)

O OH
• Urea is used as N-fertilizers (46.6% N).
• Urea is white crystalline solid.
• M.P. = 132ºC.
Resonance in Urea :
  + +
NH2=C–NH2 NH2 – C – NH2 NH2–C=NH2  NH2—C—NH2
O O O O–
(Resonance hybrid)
Urea an accept one H so urea is monoacidic base.
Due to resonance urea is more polar and highly soluble in H 2O.
Resonance in protonated urea :
  + +
NH2=C–NH2 NH2 – C – NH2 NH2–C=NH2  NH2—C—NH2

O–H OH OH HO+
(Resonance hybrid)
CHEMICAL PROPERTIES OF UREA :

1. Basic nature :
Conc. HNO3 (NH2CONH2)HNO3
O
Urea nitrate (White crystals)
H2N–C–NH2
(COOH)2 (NH2CONH2)(COOH)2
(Oxalic acid) Urea oxalate
2. Hydrolysis :
H2O + HCl
CO2 + NH4Cl
acidic medium
O H2O + NaOH NH + Na CO
3 2 3
alkaline medium
H2N–C–NH2
H2O
(NH4)2CO3
neutral medium
H2O
CO2 + NH3 [Used in estimation of urea]
Urease enzyme
3. Effect of heat :
(a) Slow heating at 132ºC
132ºC CuSO
NH2–C–NH2 + H–NH–C–NH2 NH2–C–NH–C–NH2 NaOH4 Violet colour ("Biuret test")
–NH3
O O O O
(Biuret)
• Compounds containing– CONH – group gives Biuret test

• RCONH2 does not give Biuret test.
• Protein also give Biuret test due to presence of peptide bond.
(b) Strong heating at 170ºC :
OH
C
T Trimerisation N N
NH2–C–NH2 170ºC NH=C=O NC–OH
–NH3 Isocyanic acid Cyanic acid
HO–C C–OH
O
N
Cyanuric acid
4. Reaction with HNO2 :

H H
H
N C N
H 2H2O + 2N2  + CO2  + H2O
O
O= N–OH HO–N =O
5. Reactiom with NaOBr :
H H
H
N C N
H 2H2O + 3NaBr + CO2  + N2 
O
Na — O–Br Na–O–Br Na – O–Br
• This is reaction is used in estimation of urea.
6. Formation of Uriedes :
(a) Acyclic uriedes :
O
NH2–C–NH2 CH3–C–Cl NH2–C–NH–C–CH3 (acetyl urea)

(–HCl)
O O O
(b) Cyclic uriedes :
Cl –C = O
Cl –C = O NH – C = O Oxalyl urea
Oxalyl chloride or
O=C
(–2HCl)
NH – C = O Parabonic acid
HO –C = O
HO –C = O NH – C = O Oxalyl urea
Oxalic acid
(–2H2O) O=C or
NH – H NH – C = O Parabonic acid
O=C
NH – H
O
Cl – C Malonyl
CH2 chloride
Cl – C
O
O Malonyl urea
NH – C or
O=C CH2
(–2HCl) NH – C Barbituric acid
O
• Enol form of barbituric acid is used as tranquiliser, sedative and hypnotic.
7. Reaction with endol form of Aceto Acetic Ester (AAE) :-
T
CH3–C–CH2–C–OC2H5 CH3–C=CH–C–OC2H5
O O OH O
(Keto form) (Enol form)
CH3 CH3
NH–H HO –C –H2O NH–C
O=C + CH –C H OH O=C CH (4-Methyl uracil)
2 5
NH–H C2H5O–C NH–C
O O
• 4-Methyl uracil is used as starting material for DNA synthesis.
PREPARATION METHODS OF UREA :
1. By 'Wholer' synthesis :-
 Rearranged
(NH4)2SO4 + KCNO ⎯⎯
⎯→ NH 4 CNO H2N–C–NH2
( − K 2SO4 ) ( Ammonium cyanate )
O
2. By Ammonolysis of carbonyl chloride :
Cl H—NH2 NH2
O=C O=C + 2HCl
Cl H—NH2 NH2
3. By Ammonolysis of ethyl urethane :
NH2 H–NH2 NH2
O=C O=C + C2H5OH
OC2H5 NH2
4. By Ammonolysis of diethyl carbonate :
OC2H5 2 H–NH2 NH2
O=C O=C + 2C2H5OH
OC2H5 NH2
BIOMOLECULES
CARBOHYDRATES :
1.1 INTRODUCTION
(i) Carbohydrates are naturally occuring organic substances present in both plants and animals.
(ii) Carbohydrates are formed in the plants by the process of photosynthesis
from carbon dioxide and water.
nCO2 + nH2O ⎯Chlorophy

⎯ ⎯⎯→
Sun light
ll
(CH2O)n + nO2
(iii) Carbohydrates are compounds composed of C,H, and O
(iv) Their general molecular formulae could be expressed in form of C x(H2O)y

Ex.
Glucose : C6(H2O)6 ⎯→ C6H12O6
Sucrose : C12(H2O)11 ⎯→ C12H22O11
Starch, cellulose : [C6(H2O)5]n ⎯→ (C6H10O5)n
Exception : Phamnone : C6H12O5 & 2-deoxyribose : C5H10O4
(v) All compound possessing the formula Cx(H2O)y are not necessarily carbohydrates e.g. Formaldehyde
[HCHO{C(H2O)}]; acetic acids [CH3COOH{C2(H2O)2}] etc.
(vi) Carbohydrates are polyhydroxy compound that has an aldehydes or a ketonic functional group either free or as
hemiacetal or acetal.
H OH
H O C
C
CHOH
HO–C–H
CHOH
H–C–OH O
CHOH
HO–C–H
HC
H–C–O–H
CH2OH
CH2–OH
Glucose (CHO group in free state) Glucose (an internal hemiacetal)

(vii)Hemiacetal is obtained by the reaction between alcoholic and carbonyl group.
H H
H3C–C=O + H–O–C2H5 H3C–C–OH
Acetaldehyde Ehyl alcohol OC2H5
Hemiacetal
1.2 CLASSIFICATION
1.2.1 Classification based on sugars
(a) Sugar – They are crystalline in structure sweet in taste & soluble in water.
e.g. Glucose : Fructose Sucrose
C6H12O6 C6H12O6 C12H22O11
(b) Non–sugar :– They are amorphous in structure and very less soluble in water, they are not sweet in taste.
e.g. Starch & Cellulose
1.2.2 Classification based on the no. of monosaccharides unit.
(a) Monosaccharides :
(i) They are single unit carbohydrates (polyhydroxy) aldehydes or ketones.
(ii) These carbohydrates can't be hydrolyzed further.
(iii) They have general formula CnH2nOn.
(iv) They are crystalline in nature, readily dissolves in water and are sweet in taste.
e.g.
Glucose C6H12O6 (Aldohexose)
Fructose C6H12O6 (Ketohexose)
(b) Oligosaccharides
These carbohydrates contain generally 2 to 9 monosaccharides units.
(i) Disaccharide – sucrose (C12H22O11)
They give two monosaccharides on hydrolysis

+
H
C12H22O11 (Sucrose) + H2O ⎯⎯⎯⎯→ C6H12O6(Glucose) + C6H12O6 (Fructose)
hydrolysis
(ii) Trisaccharides – Raffinose (C18H32O16)
They give three monosaccharides on hydrolysis.

+
C18H32O16 (Raffinose) + 2H2O ⎯H
⎯→
⎯ C6H12O6 (Glucose) + C6H12O6 (Fructose)+ C6H12O6(Galactose)
(iii) Majority of oligosaccharides are colourless, crystalline, solids, soluble in water and are sweet in taste.
(c) Polysaccharides
(i) These form a large number of monosaccharides units on hydrolysis. Ex. Starch, Cellulose, Insulin.
+
(C6H10O5)n + nH2O ⎯H
⎯→
⎯ nC6H12O6
Starch Glucose
(ii) These are colourless, amorphous solid having no taste.
(iii) They are insoluble in cold water.
(iv) These have long chain or are polymers of monosaccharides that may be either linear or branched in structure.
(v) If the polymer is made up from a single monosaccharides, the polysaccharide is called a homopolysaccharide.
(vi) If two or more different monosaccharides are found in polymer, it is called a hetropolysaccharide.
(vii) They are also called non-sugars.
NUT SHELL CLASSIFICATION of Carbohydrates
Sugars Non-Sugars
Polysaccharides
Monosaccharides Oligosaccharides
Triose Disaccharide
(Glyceraldehyde) (sucrose, Maltose, Homopolysaccharide Hetropolysaccharide
(Dihydroxyacetone) Lactose) (Starch, cellulose, glycogen (Hygluronic acid, chondritin sulphate,
chitin, dextrin, insulin) heparin, pectine, hemicellulose)
Tetrose Trisaccharide
D-Erythrose (raffinose)
Pentose Tetrasaccharide etc.

(D-Ribose)
Aldohexose
Hexose (Glucose)
Ketohexose
(Fructose)
1.3 MONOSACCHARIDES
(i) The monosaccharides are the basis of carbohydrates chemistry.

(ii) Since all carbohydrates are either monosaccharides or are converted into monosaccharides on hydrolysis.
(iii) They have the general formula CnH2nOn where n varies from 3 to 9 carbon atoms.
(iv) About 20 monosaccharides occur in nature.
(v) The simplest are triose (n = 3)
H O
C
H2C–OH
C3H6O3 H–C–OH C=O
Triose H2C–OH
CH2–OH
Glyceraldehydes Dihydroxy acetone
(vi) The aldoses and ketoses may be represented by the following general formula
H O CH2–OH
C C=O
(CHOH)n (CHOH)n
CH2–OH
CH2–OH
n = 1, 2, 3, 4 n = 0, 1, 2, 3, 4.....
1.3.1 Stereochemistry of monosaccharides

H O H O CH2–OH
C C
C=O
H–C–OH HO–C–H
CH2–OH
CH2–OH CH2–OH
L(–)–glyceraldehyde
D(+) – glyceraldehyde (L means left)
(i) If the hydroxy group of the asymmetric carbon atom farthest from aldehyde or ketone group project to the right the
compound is a member of D–family.
(ii) If the hydroxyl group on the farthest asymmetric carbon project to the left, the compound is a member of the L–
family.
(iii) The prefix (+) is used to designate a dextrorotatory compound (i.e., which rotate the plane–polarised light to the
right)
(iv) The prefix (–) is used to designate a laevorotatory compound (i.e., which rotate the plane polarised light to the left.)
(v) The letter D & L refer to absolute configuration around the asymmetric carbon atom.
(vi) The sign (+) & (–) refer to the direction of rotation of the plane polarised light, which is a measure of physical
constant and can't be obtain by looking at the formula.
(vii)A compound in the D–family may rotate the plane–polarised light to the right or it may rotate it to the left.
(viii) Except ketotriose (dihydroxy acetone) all aldoses & ketoses (monsaccharides) contain assymetric atom & are
optically active.
(ix) Maximum number of optical isomers = 2n where n = no. of asymmetric carbon atoms in molecules.
1.3.2 Configuration of monosaccharides
CHO CHO
H O HC–OH HO–C–H
C CH2–OH CH2OH
(i) Aldotriose H–C–OH ; n =1; isomer (2)1=2 D-glyceraldehyde L-Glyceraldehyde
CH2–OH
1 CHO
2 CHOH
(ii) Aldotetrose ; n = 2; isomer = (2)2 = 4
3 CHOH
4 CH2OH
CHO CHO
CHO CHO
H–C–OH HO–C–H HO–C–H H–C–OH
H–C–OH HO–C–H H–C–OH HO–C–H
CH2OH CH2OH CH2OH CH2OH
D (–) erythose L (+) erythose D (–) threose L (+) threose
Mirror image(enantiomers racemic pair) Mirror image(enartiomers racemic pair)
(a) D–erythose and L–threose are not mirror image that is, they are diastereomers (optical isomers that are
not mirror image) and the degree of rotation of each would probably differ.
Note :– Above formula clearly demonstrate that their is no relationship between D – sugar and the term
dextrorotatory, and an L–sugar and the term laevorotatory.
(iii) Aldopentoses
* * *
OHC–C HOH–C HOH–C HOH–CH2OH
n = 3; isomers (2)3 = 8
CHO CHO CHO CHO

HO–C–H H–C–OH H–C–OH HO–C–H
HO–C–H H–C–OH HO–C–H H–C–OH
D(–) xylose L(+)xylose D(–)xylose L(–) xylose
Mirror image Mirror image

(racemic pair) (racemic pair)
CHO CHO CHO CHO

HO–C–H H–C–OH H–C–OH HO–C–H
H–C–OH H–C–OH H–C–OH HO–C–H
D(–) arabinose L(–) arabinose D(–) ribose L(+) ribose
Mirror image Mirror image

(racemic pair) (racemic pair)
(iv) Aldohexose
* * * *
OHC–C H–OH–C HOH–C HOH–C HOH–CH2OH
n = 4;isomer (2)4 = 16
CHO CHO CHO CHO

H–C–OH H–C–OH HO–C–H HO–C–H
H–C–OH H–C–OH H–C–OH H–C–OH
CH2OH H2COH CH2OH CH2OH
D(+) Allose D(+) Altrose D(+) Glucose D(+) Mannose
CHO CHO CHO CHO

H–C–OH H–C–OH HO–C–H HO–C–H
HO–C–H HO–C–H HO–C–H HO–C–H
D(–) arabinose D(–) aldose D(+) Galactose D(+) Talose
1.4 PREPARATION OF GLUCOSE AND FRUCTOSE

(A) Glucose
(i) (C6H12O5)n + nH2O ⎯dil

⎯HCl⎯
⎯→ nC6H12O6
(ii) C12H22O11(Sucrose) + H2O ⎯4⎯ ⎯ ⎯⎯→ C6H12O6 (Glucose) + C6H12O6(Fructose)

% Alcoholic
HCl
(Glucose form precipitate in Alc. Soln it is separated by filtration)

(B) Fructose
(i) From sucrose
4% Alcoholic KOH
C6H12O11 (Sucrose) + H2O ⎯⎯⎯⎯⎯⎯⎯⎯⎯→ C6H12O6 (Glucose) + C6H12O6(Fructose)
The ppt. of glucose is separated by filtration & the filtrate contains fructose solution. This solution is
concentrated under reduced pressure.
(ii) From Insulin
Insulin contain fructose units join together in the form of a polysaccharide.
(C6H12O5)n + nH2O ⎯dil

⎯⎯ ⎯→ nC6H12O6
H 2SO4
Insulin Fructose
The excess of dil H2SO4 is removed by titration with Ba(OH)2. The ppt. of BaSO4 is removed by filtration &
the remaining solution is concentrated under reduced pressure.
1.5 PHYSICAL PROPERTIES
1.5.1 Glucose
(i) Glucose is a white crystalline solid.
(ii) It is soluble in water.
(iii) M.P. → 146ºC

(iv) It is sparingly soluble in alcohol but insoluble in ether.
(v) It is less sweeter than cane sugar.
(vi) It is optically active and the ordinary naturally occuring form is (+) glucose (or dextro form)
(vii) It shows mutarotation.
1.5.2 Fructose
(i) The anhydrated fructose is a colourless crystalline compound.
(ii) M.P. → 102ºC
(iii) It is soluble in water but insoluble in benzene and ether.
(iv) It is less soluble in water than glucose.
(v) It is the sweetest of all sugar.
(vi) It's solution is laevorotatory.
(vii)It also show mutarotation.
1.6 CHEMICAL PROPERTIES
(A) In the solid state, the two cyclic form of D–glucose (–D–glucose & –D–glucose) & D–Fructose (–D–Fructose
& –D–Fructose) are stable.
(B) However is solution each form is in equilibrium with other via the open–chain aldehyde form.
CH2OH CH2OH CH2OH
O OH OH O O H
H H H
H H H
OH H OH H H OH H
HO H HO HO OH
H OH H OH H OH
-D-glucose D-glucose -D-glucose
(open chain Aldehyde form)
H H H
O O–H OH O CH2OH
H H H
H H C=O H
H H OH HO H HO
HO CH2OH HO CH2OH HO OH
OH OH OH H OH H
-D Fructopyranose D-Fructose (open chain form) -D Fructopyranose (Not isolated)
[]p = – 133º []p = –92º
(C) The important characteristics reaction are of two type.

1.6.1 Reaction characteristic of the open chain form
1.6.1.1 Oxidation with Br2/water
H O
C COOH
[O]
(CHOH)4 (CHOH)4
Br2/H2O
CH2OH CH2OH
D–Glucose D-Gluconic acid
(a) The brown colour of Br2 disappears → Test for a glucose.
(b) Fructose does not give any reaction because of presence of ketonic group.
1.6.1.2 Oxidation with conc. HNO3
CHO COOH
[O]
(i) (CHOH)4 (CHOH)4
conc. HNO3
CH2OH COOH
D-Glucose D-glucoric acid
CH2OH COOH
C=O [O] CH2OH H–C–OH
+
CH–OH conc. HNO3 COOH H–C–OH
(ii)
(CHOH)2 COOH
CH2OH
D-Fructose Glucollic acid meso Tartaric acid
1.6.1.3 Action as a reducing agent
*(A)Tollen's reagent :–
2AgNO3 + 2NaOH ⎯
⎯→ 2AgOH + 2NaNO3
Unstable
⎯→ 2Ag2O + H2
2AgOH ⎯
Ag2O + 4NH4OH ⎯
⎯→ [Ag(NH3)2]+OH + 3H2O
[Diammine silver hydroxide (Tollen's reagent)]

(i) Glucose & Fructose both reduces an ammonical solution of Ag 2O (Tollen's reagent) to silver.
(ii) Glucose is an aldehyde & therefore it is a reducing agent.

(iii) Fructose is ketone & thus should not acts as reducing agent.
(iv) Fructose act as reducing agent because NH4OH present in Tollen's reagent rearrange fructose into a mixture
of Glucose, Fructose & Mannose.
(v) Glucose & mannose are epimers (having different configuration on 2 nd carbon atom)
(a) Test for Glucose
COOH
CHO
2Ag + (CH2OH)4 + 4NH3 + H2O
(CHOH)4+ 2[Ag(NH3)2] + OH ⎯
⎯→ Silver
CH2OH
CH2OH mirror
Gluconic acid
Glucose
(b) Rearrangement of Fructose
CHOH
CHO CH2OH CHO
C–OH
H–C–OH C=O HO–C–H
HO H
HO–C–H HO–C–H HO–C–H
H OH
H–C–OH H–C–OH H–C–OH
H OH
CH2OH CH2OH CH2OH
CH2OH
D-Glucose D-Fructose Common enolic form D-Mannose
(B) Fehling solution :–

(i) Fehling solution (A) contain aqueous solution of CuSO4 & Fehling solution (B) contains alkaline solution of
sodium potassium tartarate or Rochelle salt in NaOH solution.
(ii) Equal volumes are added to obtain Fehling solution.
(iii) Glucose & Fructose both reduce Fehling solution and red precipitate of Cu2O is obtained.

(a) C6H12O6 + 2CuO ⎯⎯ → C6H12O7 + Cu2O
Glucose or Fructose Gluconic acid Cuprous oxide (Red ppt.)

(b) Lobry de Bruyn & Van Ekenstein rearrangement : Dilute alkali solution changes glucose into a
mixture of glucose, mannose & Fructose. Similarly Fructose change into a mixture of glucose, fructose &
mannose.
CHO CHO CHO

H–C–OH HO–C–H C=O
H–C–OH dil. NaOH H–C–OH dil. NaOH H–C–OH
CH2OH CH2OH CH2OH
Glucose Mannose Fructose
Epimers
1.6.1.4 Reduction
(A) Mild reduction :– [NaBH4 or Na/Hg]
CHO CH2OH
(CHOH)4 + 2[H] ⎯⎯⎯⎯⎯⎯⎯
⎯→
Na / Hg or ( NaBH4 )
(i) (CHOH)4
CH2OH CH2OH
D glucitol (D sarbitol)
CH2OH
C=O CH2OH CH2OH
(ii) (CHOH)3 + 2[H] ⎯⎯⎯⎯⎯⎯
⎯→
Na / Hg or ( NaBH 4 ) H–C–OH HO–C–H
(CHOH)3 + (CHOH)3
CH2OH
CH2OH CH2OH
Fructose
Glucitol (D – Sorbitol) D-Mannitol
Both are epimers

(B) Drastic Reduction (HI/Red P)
CH2OH
CHO CH3
C=O
(CHOH)4 + HI ⎯⎯⎯→ ⎯⎯⎯ HI + (CHOH)
Re d P Re d P
(CH2)4
  3
CH2OH CH3 CH2OH
D-Glucose n-Hexane Fructose
*1.6.1.5 Reaction with hydrogen cyanide (cyanohydrogenation)
H O CN CN
C H–C–OH HO–C–H
H
(i) (CHOH)4 +
CN (CHOH)4 + (CHOH)4
CH2OH
CH2OH CH2OH
D-Glucose
D-Glucononitrile D-Manononitrile
CH2OH
CH2OH CH2OH
(ii) C=O H NC–C–OH HO–C–CN
(CHOH)3 CN (CHOH)3 + (CHOH)3
CH2OH CH2OH CH2OH
D-Fructose
2-Cyanosorbitol 2-Cyanomannitol
1.6.1.6 Reaction with hydroxylamine
H H
C= O + H2 –N–OH 
C=N–OH
H
(CHOH)4 (CHOH)4
(–H2O)
CH2OH CH2OH
D-Glucose Hydroxylamine D-Glucoseoxime
CH2OH CH2OH
H
C= O + H2 N– OH C=N–OH
(–H2O)
(CHOH)3 (CHOH)3
CH2OH CH2OH
D-Fructose D-Fructose oxime
1.6.1.7 Reaction with semicarbazide
H O
C O O
H
H
(CHOH)4 + H2N–NH–C–NH2 (–H2O) C=N– NH–C–NH2
CH2OH (CHOH)4
CH2OH
D-Glucose Semicarbazide D-Glucose semicarbazone
CH2OH CH2OH O
C=O O C=N–NH–C–NH2
H
(CHOH)3 + H2N–NH–C–NH2 (–H2O) (CHOH)3
CH2OH CH2OH
D-Fructose Semicarbazide D-Fructose semicarbazone

1.6.1.8 Reaction with phenylhydrazine (osazone formation)
H H H
C=O C=N NHC6H5 C=N–NHC6H5
H–C–OH H–C–O H C=N–NHC6H5
H2 N–NHC6H5 H2N–NH–Ph
(CHOH)3 (CHOH)3 (CHOH)3 + C6H5NH2
–H2O Oxidation
CH2OH CH2OH –PhNH2, –NH3 CH2OH
D-Glucose D-Glucosephenyl hydrazone D-Glucosazone Aniline

CH2OH CH2O H CH = NNH C6H5
C=O C=N–NH–Ph C=NNHC6H5
(CHOH)2 PhNHNH2 (CHOH)2 2C2H5NHNH2 (CHOH)3 + C6H5NH2
CH2OH CH2OH CH2OH
D-Fructose D-Fructose phenyl hydrazone D-Fructosazone

Mechanism :
Generally accepted mechanism was proposed by Weygand and Semyakin (1965)
(i) The first formed phenylhydrazone undergoes a rearrangement through a cyclic intermediate in which the
secondary hydroxyl group at C–2 becomes a ketone group.
(ii) This ketone group than condensed with phenyl hydrazine to form the osazone.
H O CH=N NHC6H5 CH–NH CH=NH
C NH C6H5
H C
C C=O
CHOH C6H5NHNH2 OH O H –C6H5NH2
(CHOH)3 (CHOH)3 (CHOH)3
(CHOH)3 –H2O
CH2OH CH2OH CH2OH
CH2OH
CH=NH CH=N NHC6H5
C=N NHC6H5 C=N NHC6H5
–C6H5NHNH2 –C6H5NHNH2
(CHOH)3 (CHOH)3 (Osazone)
–H2O –NH3
CH2OH CH2OH
Note : The reaction with phenyl hydrazine stop at the osazone stage apparently because hydrogen bonding permit
resonance stabilization in the form of a cyclic structure.
N CH
CH N
CH2OH–(CHOH)3–C N–C6H5 C6H5–N C–(CHOH)3–CH2OH
N H H N
NHC6H5 NHC6H5
1.6.2. Reaction characteristic of the cyclic form
1.6.2.1 Reaction with acetic anhydride (acetylation)
CH2OH CH2OAC
O O
H H H H
C5H5N H + 5 CH3COOH
H + 5 CH3–C–O–C–CH3
OH H 0°C ACO OAC H OAC
HO OH
H OH H OAC
–D–glucose Acetic anhydride –D–glucose pentaacetate

[]D = 102°; m.p. 113°C
CH2OH CH2OH CH2OAC

O O
H H H OH C5H5N H OAC
H H + 5 CH3–C–O–C–CH3 H + 5CH3COOH
OH H OH H 0°C OAC H
HO OH HO H ACO H
H OH H OH H OAC
–D–glucose –D–glucose Acetic anhydride –D–glucose pentaacetate

[]D = +4°; m.p. 134°C
H H
O O
H OH C5H5N H H OAC
H + 5CH3–C–O–C–CH3 + 5CH3COOH
H HO 0°C H ACO
HO CH2OH ACO CH2OAC
OH H ACO H
–D–Fructopyranose –D–fructopyranose pentaacetate
[]D = +121° m.p. 109°C
H H
O O
H CH2OH C5H5N H H CH2OAC
H + 5 CH3–C–O–C–CH3 + 5CH3COOH
H HO 0°C H ACO
HO OH ACO OAC
OH H ACO H
–D–Fructopyranose –D–Fructopyranose pentaacetate
[]D = +35° m.p. 70°C
1.6.2.2 Reaction with alcohols -
CH2OH CH2OH
H H HCl H H
H H + H2O
OH H OH H
HO OH + H OCH3 HO OCH3
H OH H OH
–D Glucose Methyl –D glucoside []0 = + 159° ; m.p. 166°C
CH2OH CH2OH CH2OH

H H H OH + H OCH3 H O–CH3
H H HCl H
H + H2O
OH OH H OH H
HO OH + H OCH3 HO H HO H
H OH H OH H OH
–D glucoside –D Glucose Methyl –D glucoside []0 = – 34° , m.p. 107°C
H H
H OH + H OCH3 H OCH3
H H
H HO HCl H HO
HO CH2OH HO CH2OH
OH H OH H
–D Fructopyranose methyl –D–Fructopyranoside
[]0 = –172° m.p. 120°C
H H
H CH2OH H CH2OH
H HCl H
H HO H HO
HO OH + H OCH3 HO OCH3
OH H OH H
–D–Fructopyranose methyl –D–Fructopyranoside
[]0 = +90° m.p. = 102°C
1.6.2.3 Reaction with Amines

(i) Instead of giving schifts bases amine condense with glucose to form N-glucoside analogous to the ordinary
glucosides from alcohols.
CH2OH CH2OH
H H H H
H HCl H
OH H OH H
HO OH + H N(CH3)2 HO N(CH3)2
H OH H OH
–D–Glucose N–Dimethyl –D glucoside
(N–Dimethyl–D–glucosylamine)
CH2OH CH2OH
H OH + H N(CH3)2 H N(CH3)2
H HCl H
OH H OH H
HO H HO H
H OH H OH
–D–glucose N–Dimethyl –D glucoside
(N–Dimethyl –D glucosylamine)
1.6.3 Mutarotation
(i) The two forms of – and –glucose exist as separate crystalline form & have different melting points and optical
rotations [–D–glucose(+112°); –D–glucose (+19°)]
(ii) When either form is placed in solution it slowly form the other via the open chain aldehyde form and the gradual
change in specific rotation is attributed to the establishment of equilibrium between the forms.
(iii) The final value +52.7° correspond to the equilibrium mixture of  &  forms. This change in optical rotation of a
solution with time to an equilibrium value is called Mutarotation (Latin muta means to change).
CH2OH CH2OH CH2OH

H
H OH H O H H
H H H
OH H OH H OH H
HO H HO OH
HO H
H OH H OH H OH
–D–glucose D glucose –D –glucose
m.p. 180°C []D = +19° (0.02%)[]D = 52.7° (36%) []D= + 112° m.p. 140°
112° –D–glucose(+112°)
[]D 52.7°
–D–glucose(+19°)
+19°
Time ⎯→
Note :- Equilibrium mixture does not contain equal amount of two anomers
Mechanism
(i) It involves a simultaneously attack by acid and a base (water is an amphoteric solvent) to yield the open chain
aldehyde form which then recrosses to give the other anomeric forms.
CH2OH–H– A CH2OH. . CH2OH H A

.. ..
H . . O H:B H .. O H .. H
H H H
OH H OH H OH H
HO H HO O H
HO H
:B
H OH H OH H OH
–D–glucose D– glucose –D –glucose
(open chain Aldehyde form)
1.6.4 Tests for Glucose and Fructose
(i) Glucose react with Br2 water, it decolourizes bromine. While colour retain in case of fructose.
(ii) Tollen's reagent react with glucose and fructose both to form silver mirror.
(iii) Glucose and fructose both reduce fehling solution to form red ppt. of cuprous oxide (Cu2O)
(iv) Glucose and fructose when treated with conc. H2SO4 then black sugar charcoal is obtained
1.6.5 Structure of Glucose and Fructose
1.6.5.1 Fischer projection formulae
OH HO H
H
C H–C=O C
H–C H–C–O–H H–C
CH2OH CH2OH CH2OH
–D–Glucose D–Glucose –D–Glucose
H 1 CH2OH
1 CH2OH H
1 CH2–OH 2C
2C
HO–C–H 2C =O HO–C–H
3
3 3
H–C–OH HO–C–H H–C–OH
4 4
4 H–C–OH
H–C–OH H–C–OH 5
5 5
H–C–OH 6 CH2
6 CH2
6 CH2O–H
–D–Fructose D–Fructose –D–Fructose
1.6.5.2 Haworth projection (pyranose structure) (pyran)
CH2OH 6 CH2OH CH2OH

.. H O
C O OH 5C O H C H
H H ..
+ – H
C
H
OH H *C 4C
H
OH H C=O C OH H *C
HO C C H HO C3 C2
1
H HO C C OH
H HO H HO H HO
–D–Glucose D–Glucose –D–Glucose
H H H
6 .. H O
C O OH C O H C CH2OH
H H ..
H H +– H
HO C
C H HO C C 5 H HO 2C = O
C H
C C CH2OH HO C
4 3
C
1
CH2OH HO C C OH
HO
OH H HO H OH H
–D–Fructose D–Fructose –D–Fructose
Note : In free state D–Fructose exist as a six membered ring or as pyranose ring. However in combined state as a
component of disaccharides, it exist in the furanose form (5 membered hemiketal).
(Furan)
The furanose structure can be obtained by internal ketal formation by combining keto group (of C 2) and
– OH group of C5.
CH2OH 1 CH2OH CH2OH OH
6 6
5 2 5 2
H HO H HO
H 4 3 OH H 4 3 1CH2OH
OH H OH H
–D–Fructose –D–Fructose
These cyclic structure can also be written in same way for glucose.
1.7 DISACCHARIDES
(i) Disaccharides are the carbohydrate which on hydrolysis give two same or different monosaccharides.
(ii) Their general formula is C12H22O11.
(iii) The important member belonging to disaccharides are sucrose, maltose and lactose.
H+or Invertase
C12H22O11 ( Sucrose) + H2O ⎯⎯⎯⎯⎯⎯⎯→ C6H12O6 (Glucose) + C6H12O6 (Fructose)
H+or Maltase
C12H22O11 (Maltose) + H2O ⎯⎯⎯⎯⎯⎯ ⎯→ C6H12O6 (Glucose) + C6H12O6(Glucose)
H+or Lactase
C12H22O11 (Lactose)+ H2O ⎯⎯⎯⎯⎯⎯ ⎯→ C6H12O6 (Glucose)+ C6H12O6 (Galactose)
(iv) In disaccharides, the two monosaccharides linked to each other by a bond called glycosidic linkage.
(v) A glycoside bond is formed when hydroxy group of the hemiacetate carbon of one monosaccharides condense
with a hydroxyl group of another monosaccharides giving –O–bond.
1.7.1 Sucrose
(i) It is the most common disaccharides and is present in the sugar cane juice & sugarbeets.
(ii) It is composed of –D–glucose and –D–fructose.
(iii) These units are held together by ,–glycoside linkage between C1 of the glucose unit (pyranose ring) and C2 of
the fructose unit (furanose ring)
Glucosidic linkage
H OH
H OH
CH2OH 1 CH2OH
HOH2C H
H HOH2C 3 4 OH H
H H OH H
H + OH H H
O
OH H 2 5 –H2O OH H
HO HO
OH HO CH2OH
CH2OH
H HO 6 H OH
–D–glucose –D–Fructose sucrose
1.7.2 Physical properties
(i) Sucrose is colourless, odourless, crystalline solid, Sweet in taste.
(ii) It is very soluble in water, but slightly soluble in alcohol.
(iii) An aqueous solution of sucrose is dextrorotatory. It does not exhibit mutarotation.
1.7.3 Chemical properties
1.7.3.1 Non-Reducing sugar
(i) Sucrose do not reduce Tollen's reagent & Fehling solution, because of absence of free aldehyde or ketone group.
(ii) Contain stable acetal or ketal group & fructose which can't be opened up into free carbonyl group.
1.7.3.2 Effect of heat
(i) Sucrose on heating slowly and carefully, melts and then if allowed to cool, it solidifies to pale yellow glassy mass
called "Barley sugar".
(ii) When heated to 210ºC, it loses water to form brown amorphous mass called Caramel.
(iii) On strong heating, it chars to almost pure carbon giving smell of burnt sugar.
1.7.3.3 Oxidation with conc. HNO3
COOH
C12H22O11 + 18[O] ⎯V
⎯ ⎯→ 6
2 O5
+ 5H2O
COOH
(from conc. HNO3) Oxalic acid
1.7.3.4 Hydrolysis (Invert sugar or Invertase)
(i) Hydrolysis of sucrose with hot dilute acid or by invertase, produces a mixture of equal molecule of D glucose and
D–fructose.
H⎯+
C12H22O11 + H2O ⎯⎯ → C H O + C6H12O6
Invertase 6 12 6
Sucrose[]D = +66.5º D–glucose D–fructose
[]D = +53º []D = –92º
(ii) Sucrose is dextrorotatory, its specific rotation is +66.5º.
(iii) D–glucose is also dextrorotatory, []D = +53º.
(iv) D–fructose has a large negative rotation []D = –92º.

(v) Therefore the net specific rotation of an equimolar mixture of D–glucose and D–fructose is,
+53 – 90
= = –19.7º
2
(v) Thus in the process of hydrolysis of sucrose. The specific rotation changes from +66.5º to –19.7° i.e., from dextro
it become laevo & it is said that inversion has taken place.
(vi) The process of the hydrolysis of sucrose is known as Inversion of sucrose.
(vii) The equimolar mixture of glucose and fructose is known as Invert sugar or Invertose.
1.7.4 Uses
(i) Used as sweetening agent in food preparations, jams, syrups, sweets etc.
(ii) In preparation of oxalic acid.
(iii) In preparation of glucose, fructose & ethyl alcohol.
(iv) In the manufacture of sucrose octa acetate requires to denature alcohol, to make paper transparent and to make
anhydrous adhesives.
1.8 POLYSACCHARIDES
(i) Polysaccharides are the natural polymers of many monosaccharides units joined together by glycoside linkages.
(ii) They have general formula (C6H10O5)n.
(iii) Most common polysaccharides are starch dextrins, glycogen, insulin and cellulose.
(iv) Starch and cellulose are the most important.
1.8.1 Starch or Amylum (C6H12O5)n
(i) It is most widely distributed in vegetable kingdom.

(ii) It occurs in the leaves, stems, fruits, roots & seeds.
(iii) Concentrated form of starch is present in wheat, corn, barley, rice, potatoes, nuts etc.
(iv) It is most important food source of carbohydrates.
(v) It can be obtained from starch substance like potato, wheat & rice etc.
1.8.1.1 Structure
(i) Starch is not a pure compound.
(ii) It is a mixture of two polysaccharides : Amylose and Amylopectin.
(iii) Amylose is soluble in water and give a deep blue colour with iodine.
(iv) Amylopectin is insoluble and give no colour.
(v) Natural starch consist of 10 to 20% amylose & 80 to 90% amylopectin.
(A) Amylose
(i) Amylose is a straight chain polysaccharide compound entirely composed of D–glucose units.
(ii) These units are joined by –glycoside linkage between C – 1 of one glucose units and
C–4 of the next glucose unit.
(iii) The molecular weight of amylose range from 10,000 to 50,000, (60 to 300 D–glucose unit.)
CH2OH CH2OH CH2OH
H H H H
4H
H
4H 1 1
OH H OH H OH H
3 2 3 2
H OH H OH H OH n
–1,4 Glycosidic linkage
Structure of Amylose
(B) Amylopectin
Amylopectin is a branched chain polysaccharides consist of D–glucose unit 300 to 600.
CH2OH 6 CH2OH CH2OH 6 CH2 CH2OH
H H H O H O H H O H H O H
5
H H 1 H H H
4
OH H OH H OH H OH H OH H
3 2 O O O O
O
H n H OH O H OH H OH H OH n
OH
–1,4 Glycosidic linkage

Structure of Amylopectin
1.8.1.2 Physical properties
(i) Starch is colourless amorphous powder.
(ii) It has no definite m.p.
(iii) It is insoluble in cold water, but an special water soluble form can be made.
(iv) When a suspension of starch in water is heated the starch granules swell and burst forming a viscous, opalescent
solution which on cooling sets to a jelly and can be used as starch paste.
1.8.1.3 Chemical properties
(i) It is non-reducing polysaccharide.
(ii) It gives blue colour with iodine.
(iii) Acid hydrolysis :
dil HCl
(C6H10O5)n ⎯dil
⎯HCl⎯→ (C6H10O5)n´ ⎯⎯⎯⎯→ n´C6H12O6
– nH 2O
Starch(here n > n´) Dextrin –D–glucose
(iv) Hydrolysis with enzymes :
(C6H12O5)n + nH2O ⎯Diatase

⎯⎯ ⎯→ C12H22O11
Starch Maltose
C12H22O11 + nH2O ⎯Maltase

⎯⎯ ⎯→ 2C6H12O6
Maltose –D–Glucose
1.8.1.4 Uses of starch

(i) In the manufacture of glucose, dextrine adhesive & alcohol.
(ii) As the most valuable constituent of food, rice, bread, potato and corn-flours etc.
(iii) In paper and textile industry.
(iv) In calico printing as thickening agent for colour.
(v) Nitro starch is used as explosive.
(vi) Starch acetate is a transparent gelatin like mass and is mainly used for making sweets.
1.8.2 Cellulose
(i) Cellulose is the main constituent of the cell walls of plants.
(ii) Wood is about 50% cellulose and rest is lignin.
(iii) Cotton and paper are largely composed of cellulose.
(iv) The general formula is (C6H10O5)n.
1.8.2.1 Structure
(i) Cellulose is a straight chain polysaccharides composed entirely of D–glucose units.
(ii) These units are joined by –glucosidic linkage between C–1 of one glucose units and C–4 of the next glucose
units.
(iii) The molecular weight of cellulose ranges from 50,000 to 500,000 (300 to 2500 D–glucose units).
CH2OH H HO CH2OH
H  H H  
 H
H OH H
OH H H OH H
   H H
H H
H OH CH2OH H OH
–1,4 glucoside linkage Structure of Cellulose
HOH2C OH CH2OH H HO
H H
OH H H OH H
H OH H H
H
H H
CH2OH H OH CH2OH
1.8.2.2 Physical properties

(i) Cellulose is a colour less amorphous solid.
(ii) It has no melting point and decomposes on strong heating.
(iii) It is insoluble in water and soluble in organic solvents.
(iv) It dissolves in ammonical copper hydroxide solution(schwitzer's reagent).
(v) Cellulose also dissolves in a solution of zinc chloride in hydrochloric acid.
(vi) It also get dissolves in mixture of sodium hydroxide solution and carbon disulphide.
1.8.2.3 Chemical properties
(i) Hydrolysis with dil H2SO4
dil H SO 4
(C6H10O5)n + nH2O ⎯⎯ ⎯ ⎯2 ⎯ ⎯ ⎯→ nC6H12O6 (–D–glucose)
Re duced pressure
(ii) Enzymes
(C6H10O5)n + nH2O ⎯Cellulase

⎯ ⎯ ⎯⎯→ nC6H12O6 ( –D–glucose)
catalyst
Note : Cellulase enzymes in cattle (grazing animals), not in man hence grass is digested by cattle not by man.
(iii) Cellulose does not reduce Tollen's reagent or Fehling solution.
(iv) When cellulose is heated with conc. NaOH solution then cotton cloth become silky in appearance this is called
Mercurization.
1.8.2.4 Uses
(i) Cellulose is the basic row material for textile industry.
(ii) Cellulose on nitration with conc. HNO3 and conc. H2SO4 form cellulose trinitrite, it is called cordite or gun
cotton. This gun cotton is used in making Blastingelatin.
(iii) Blasting gelatin contain mostly glycerol trinitrate and small amount of cellulose trinitrate Blasting gelatin is
highly explosive.
(iv) Pyroxylin is cellulose dinitrite and it is obtained by partial nitration of cellulose, when dissolved in acetone it form
nail polish.
(v) Pyroxylin is treated ethyl alcohol and ether and a thin film is obtained called collodian.
(a) Collodian is used for covering wounds.
(b) In purification of colloids.
(c) Pyroxylin is heated under pressure with camphor and ethyl alcohol then celluloid is formed. This celluloid is
used in making toys and photographic films.
(vi) Cellulose is acetylated with acetic anhydride in the presence of conc. H2SO4, cellulose triacetate is formed.
(a) This cellulose triacetate is dissolved in acetone solvent and sent into a warm chamber.
(b) Acetone is vaporized leaving behind cellulose acetate in the form of threads. It is called acetate rayon silk.
(c) Cellulose triacetate is used for making picture films.
(A) Viscous Rayon Silk

(i) Cellulose is treated with NaOH solution and carbon disulphide (CS 2), cellulose xanthate
(C6H9O4 (OCS2Na)n) is obtained.
(ii) This xanthate is dissolved in NaOH solution and viscous solution is obtained.
(iii) This viscous solution is sent into a chamber containing dil H 2SO4, through fine holes viscous rayon silk
fibre is obtained. It is cheapest method for producing silk from cellulose.
1.8.3 Glycogen (Animal starch)
(i) Glycogen in the reserve carbohydrate of animals.

(ii) it is found in liver and muscles, the former being a particularly rich source.
(iii) It also occur in yeast mushrooms and scallops.
(iv) The structure of glycogen is similar to amylopectin in that it has 1,6 as well as 1,4–glycosidic linkage.
(v) Glycogen has been found to be even more branched in structure with one branch for every 12 to 18 glucose units.
(vi) The molecular weight of glycogen is higher than amylopectin and it ranges from 1,000,000 to 5,000,000 (6,000 to
30,000 D–glucose units)
(vii) Glycogen is a colourless amorphous powder.
(viii) It is soluble in water and give a reddish brown colour with iodine solution.
(ix) Hydrolysis of glycogen with hot dilute acid yield D–glucose only.
(x) It does not reduce Fehling's solution & does not form an osazone with excess of phenyl hydrazine.
(xi) It is not fermented by yeast.
1.9 FUNCTION OF CARBOHYDRATES
(i) Carbohydrates are called bio fuels because they produce energy on burning in the body.
(ii) Carbohydrate act as reserve source of chemical energy for example - glycogen.
(iii) The plant cell membrane is made up of cellulose.
1.9.1 Importance of carbohydrate
(i) Carbohydrate are of great importance to our body because by slow combustion they produce energy which is
utilized by our body for doing work.
C6H12O6 + 6O2 ⎯→ 6CO2 + 6H2O + 2872 k Joule(energy)
(ii) Carbohydrates are essential metabolise for wide range of process in the body.
(iii) Free sugar, particularly glucose, are important energy fuel in the nervous system, muscles and many other tissues.
(iv) In combined form the pentose sugar contribute to the structure of nucleotide, coenzymes and polynucleotide of
DNA & RNA.
(v) Sugar may also combined with lipid forming glycolipids, which are of particular significance in myelin and other
membrane of nerves in the erythrocyte where they determine the blood group reaction.
(vi) Combined with protein as glycoprotein the sugar play a role in secretion & the external recognition properties of
cell membrance.
(vii) The sugar may polymerize among themselves to produce the storage energy substance glycogen or they may form
heteropolymers (glycominoglycans) of connective tissue ground substance.
Table – I Comparative study of glucose & fructose
Property Glucose Fructose
(a) Nature Polyhydroxy aldehyde Polyhydroxy Ketone

(b) Optical activity Dextrorotatory Laevorotatory
(c) Oxidation
(i) with Br2/water Gluconic acid No reaction
Glycollic acid + tartaric acid
(ii) with conc. HNO3 Saccharic acid
+ trihydroxy glutaric acid
(d) Reduction Sorbitol Sorbitol + mannitol
Calcium glucosate, soluble in Calcium fructosate insoluble
(e) Ca(OH)2
water in water
(f) Molisch's reagent Form a violet ring Form a violet ring
(g) Fehling solution Give red precipitate Red precipitate
(h) Tollen's reagent Ag mirror Ag mirror
(i) phenyl hydrazine form osazone Form osazone

(j) Resorcinol + dil HCl Give red or brown colours or
No colouration
(Selivanoff's test) precipitate
(k) Freshly prepared

ammonium molybdate Bluish green colour on
Light blue colour
sol+few drops of heating
CH3COOH (Pinoft's test)
(l) Alcoholic naphthol + A purple colour (violet) on
No colouration
conc HCl (furfural test) boiling
Table – II Distinction between glucose, sucrose & starch
Test Glucose Sucrose Starch
(a) With iodine solution No effect No effect Blue colour
(b) Tollen's reagent Silver mirror No effect No effect
(c) Fehling solution Red precipitate No effect No effect
(d) Phenyl hydrazine Yellow orange No effect No effect

(e) Solubility in water Soluble Soluble Insoluble
(f) Taste Sweet Sweet Sweet
Table – III Relative sweetness of some of the carbohydrate & other compound
Compound Relative sweetness Compound Relative sweetness
NH2 50,000 O 36,000

OC3H7 C
NH
O2N SO2
Nectarin Saccharin
H 71,00

NSO3Na
Fructose 173
Cyclamate
Invertase (Invertsugar) 123 Sucrose (table sugar) 100
Glucose 74 Xylose 40
Galactose 32 Maltose 32
Lactose 16
2. AMINO ACIDS :
2.1 INTRODUCTION
(i) Amino acids are organic compound of both an amino group and carboxylic group.
(ii) They are represented by the following general formula -
Side chain H carboxyl group

R–C–COOH
NH3
Amino group
R is different for different amino acid.
(iii) These amino acids are very important because these are the building blocks of proteins.
(iv) Protein is the natural polymer having –amino acid as the monomer.
(v) With the exception of glycine, all other –amino acid have chiral carbon atom & have two optically active
isomers.
(vi) All naturally occuring amino acid belong to L–series which have –NH2 group on the left as –OH group in L–
glyceraldehyde.
CHO COOH COOH
HO–C–H H2N–C–H e.g. H2N–C–H
CH2OH R CH3
L–Glyceraldehyde L–Aminoacid L–Alanine
2.2 CLASSIFICATION
2.2.1 Amino acid with non-polar side chain

NH3

NH3 CH3
CH–C–COO
CH3
(i) H–C–COO (ii)
H
H Valine (Val)
Glycine (Gly)
 
NH3 NH3
(iii) CH –C–COO (iv) CH3 CH–CH –C–COO
3 2
CH3
H H
Alanine (Ala) Leucine (Leu)
 
CH3 NH3 NH3
(v) CH3–CH2–CH–C–COO (vi) CH2–C–COO
Isoleucine* (Ile)
H
Phenyl alanine(Phe)
H2 C CH2
(vii) H2C CHCOO
NH
Proline (Pro)
2.2.2 Amino acid with polar but neutral side chain
e.g.
 
NH3 OH NH3
(i) HO–CH2–C–COO (ii) CH3–CH–CH–COO
H Threonine (Thr)
Serine (Ser)

NH3

–CH2–C–COO NH3
(iii) H (iv) HO CH2–C–COO
N
H H
Tryptophan (Typ) Tyrosine (Tyr)
 
NH3 NH3
(v) HS–CH2–CH–COO (vi) CH3–S–CH2–CH2–CH–COO
Cystein (Cys) Methionine (met)
 
O NH3 O NH3
(vii) H2N–C–C–COO (viii) H2N–C–CH2–CH2–C–COO
H H
Asparagine (Asn) Glutamine (Gin)
2.2.3Amino acids with acidic side chains :
NH2 NH2
e.g. (i) HOOC–CH2–CH–COOH (ii) HOOC–CH2–CH2–CH–COO
Glutamic acid (Glu)
Aspartic acid (Asp)
2.2.4 Amino acids with basic side chains

e.g.
NH2 NH2
HN
(i) H2N(CH2)4–CH–COOH (ii) C–NH(CH2)3–CH–COOH
H2N
Lysine (Lys) Arginine (Arg)
NH2
(iii) C C––CH2–CH–COOH
N NH
C
H
Histidine (His)
2.2.5 Amino acid from special source
(i) These amino acids do not occur in proteins but they may play some as yet unknown part in biosynthesis.
e.g.

O H NH3 NH2
(a) H2N–C–N–CH2–CH2–CH2–C–COO (b) H2N–CH2–CH2–CH2–C–COOH
H H
Citrulline (in water melon juice, liver) Ornithine (in liver)
HN H NH2
(c) H2N–CH2–CH2–COOH (d) H2N–C–N–O–CH2–CH2–C–COOH
–alanine (constituent of vitamin pentothenic acid) Conavanine(in soyabeans meals)
NH2 I I NH2
(e) HO CH2–C–COOH (f) HO CH2–C–COOH
OH H H
I I
Dihydroxy phenyl alanine (DOPA) Thyroxine
(in sprouts and seeding of velvet bean) 3, 5, 3´, 5´ – tetraiodothyronine
(in thyroid gland)
I I NH2 O NH2
(g) HO CH2–C–COOH (h) N2 = CH–C–O–CH2–C–COOH
I H H
3, 5, 3´ – tri iodothyranine (in thyroid gland) Azaserine

(From a streptomyces species; an
antibiotic and an anticancer agent)
2.3 ESSENTIAL AMINO ACIDS
(a) These must be supplied to our diet as are not synthesized invivo in body.
(b) These essential amino acids are required for the growth of our body.
(c) Lack of these essential amino acid in diet can cause diseases such as Kwashiorkor.
(d) These are as follows :
(1) Valine (2) Leucine (3) Isoleucine (4) Phenylalanine
(5) Tryptophan (6) Threonine (7) Methionine (8) Lysine
(9) Arginine (10) Histadine
Note : Histidine and Arginine are semi essential i.e., can be synthesized but not in quantities sufficient to permit normal
growth.
2.4 NON-ESSENTIAL AMINO ACIDS

(a) These amino acid are synthesized involve by body.
These are as follows:
(1) Glycine (2) Alanine (3) Tyrosine (4) Serine
(5) Cystine (6) Proline (7) Hydroxypropine (8) Cysteine
(9) Aspartic acid (10) Glutonic acid
2.5 SYNTHESIS OF  – AMINO ACID
2.5.1 By hydrolysis of proteins
(i) Protein can be hydrolyzed by refluxing with dilute hydrochloric acid to give a mixture of –amino acids. The
resulting mixture can be separated by
(a) Fractional crystallization.
(b) Fractional distillation of their ester followed by hydrolysis (Fischer's method).
(c) Selective precipitation as salt with phosphotungstic and picric acid.
(d) Distribution of amino acid between n–butanol saturated with water (Dakin's method).
(e) Column, paper and gas chromatography.
(f) Electrophoresis.
2.5.2 By amination of –halo acids
50  H+/H2O
(i) Cl–CH2–COOH + 3NH3 ⎯⎯⎯ ⎯→ H2N–CH2–COONH4 H2N–CH2–COOH Glycine
(– NH4Cl)
50°  H+/H2O
(ii) CH3–CH–COOH + 3NH3 (–NH Cl) CH3–CH–COO NH4 CH3–CH–COOH Alanine
4
Br NH2 NH2
2.5.3 By Gabriel synthesis :
O O
C C O

NK + Cl–CH2–COOC2H5 N–CH2–C–OC2H5
–KCl
C C
–C2H5OH
O O
H+/H2O
Potassium phthalimide Ethyl chloroacetate

O
C–OH
+ H2N–CH2–COOH
C–OH
O
Phthalic acid Glycine
2.5.4 By strecker synthesis
–
O OH NH2 NH2 O
|| 
H–C–H+H–CN⎯→ H–C–H NH3 H+/H2O
H–CH–CN H–CH–C–OH
(i) + –H2O
CN Glycine
Formaldehyde Cyanohydrin
–
O OH NH2 NH2
|| 
CH3–C–H+H–CN⎯→ CH3–C–H NH3 H+/H2O
CH3–CH–CN CH3–CH–COOH
(ii) + –H2O
CN Alanine
Acetaldehyde Cyanohydrin
2.5.5 By Koop synthesis
O NH NH2
H+
CH3–C–COOH+NH3 CH3–C–COOH H2/Pd or
CH3–CH–COOH
–H2O Na/C2H5OH
–ketopropionic acid Alanine
2.6 PHYSICAL PROPERTIES OF AMINO ACID

(i) Amino acids are generally, crystaline substance having sweet taste.
(ii) They melt with decomposition at higher temperature (more than 200ºC).
(iii) They are soluble in water but insoluble in organic solvents.
2.6.1 Zwitter ion
(i) Amino acids contain both acidic carboxyl group (–COOH) and basic amino group in the same molecules.
(ii) In aqueous solution, the acidic carboxyl group can lose a proton and basic amino group can gain a proton in a kind
of internal acid – base reaction.
O O
R–CH–C–O–H R–CH–C–O

H2N NH3
Dipolar ion or Zwitter ion
(iii) The product of this internal reaction is called a Dipolar or a Zwitter ion.
(iv) The zwitter ion is dipolar, charged but overall electrically neutral and contain both a positive and negative charge.
(v) Amino acid in the dipolar ion form are amphoteric in nature.
(vi) Depending upon the pH of the solution, the amino acid can donate or accept proton.
 NH3  NH3 O
(A) R–CH–C–O + H
+
R–CH–C–OH (B) An amino acid in basic solution
O O O
Positive ion (cation)
R–CH–C–O + OH R–CH–C–O + H2O

H2N–H NH2
Negative ion (Anion)
2.6.2 Isoelectric points
(i) When ionised form of amino acid is placed in an electric field it will migrate towards the opposite electrode.
(ii) Depending upon the pH of the medium following three thing may happen.
(a) In acidic medium, the cation move towards cathode.
(b) In basic medium, the anion move towards Anode.
(c) The zwitter ion does not move towards any of the electrodes.
(iii) At a certain pH (i.e., H+ concentration), the amino acid molecules show no tendency to migrate towards any of the
electrodes and exists as a neutral dipolar ion, when placed in electric field in known as Isoelectric point.
(iv) All amino acids do not have the same isoelectric point & it depend upon the nature of R–linked to  carbon atom.
Isoelectric point of some amino acid
Amino acid Isoelectric point
Neutral Amino acids (pH 5.5 to 6.3)
Glycine 5.7
Alanine 6.1
Valine 6.0
Serine 5.7
Threonine 5.6
Acidic amino acids (pH  3)
Aspartic acid 2.8

Glutamic acid 3.2
Basic Amino acids (pH  10)
Lysine 9.7
Arginine 10.8
(v) Amino acid have minimum aqueous solubility at their isoelectric point.
(vi) This fact has been made use in the separation of –amino acid from protein hydrolysies.
 
CATHODE CATHODE
+ – + –
O O
R–CH–C–OH R–CH–C–O
H3N  NH2
 
ANODE ANODE
Amino acid in acidic solution Amino acid in basic solution
Effect of electric field on an amino acid ion Acidic and Basic solution
2.7 CHEMICAL PROPERTIES
Amino acids show the following characteristic reaction.

2.7.1 Reaction of the carboxyl group
2.7.2 Reaction of the amino group
2.7.3 Reaction involving both the carboxyl and the amino group
2.7.1 Reaction of the carboxyl group
2.7.1.1 Reaction with base
 
(i) H3N–CH2–COO + NaOH ⎯→H2N–CH2–COONa + H2O
Glycine Sod. amino actate

(ii) CH3–CH–COO + NaOH ⎯→ CH3–CH–COONa + H2O
  
Sod. –amino propionate
2.7.1.2 Esterification
  C2H5OH  AgOH
H3N–CH2–COO HCl ClH3N–CH2–COOH ClH3N–CH2–COOC2H5 H2N–CH2–COOC2H5
–AgCl/–H2O
Glycine Ethyl––amino acetate
Note : HCl first convert the dipolar ion into an acid which is subsequently esterified.
2.7.1.3 Decarboxylation
H2N–CH2–COOH + Ba(OH)2  CH3NH2 + BaCO3 + H2O
Glycine Methyl amine
CH3

H2N–CH–COOH + Ba(OH)2 CH3–CH2–NH2 + BaCO3 + H2O
Alanine Ethyl amine
2.7.1.4 Reduction
O
LiAlH4
H2N–CH2–C–OH H2N–CH2–CH2–OH
4[H]
Glycine 2-amino ethanol
O
LiAlH4
CH3–CH–C–OH CH3–CH–CH2–OH
4[H]
NH2 NH2
Alanine 2-amino propanol
2.7.2 Reaction with the amino group
2.7.2.1 Reaction with strong acid
 
H3N–CH2–COO + HCl ClH3N–CH2–COOH
Glycine Glycine hydrochloride
CH3–CH–COO +HCl CH3–CH–COOH

 NH3  NH3Cl
Alanine Alanine hydrochloride

2.7.2.2 Acetylation
O H O
Base
CH3–C–Cl + H–N–CH2–COOH CH3–C–NH–CH2–COOH + HCl

Acetyl chloride Glycine N–acetylglycine
O O H O
Base
CH3–C–O–C–CH3 + H–N–CH–COOH CH3–C–NH–CH–COOH + CH3COOH

CH3 CH3
Acetic anhydride Alanine N–acetyl alanine
O H O
Base
C–Cl + H–N–CH2–COOH C–NH–CH2–COOH + HCl

Benzylchloride Benzoylglycine (hippuric acid)
2.7.2.3 Reaction with Nitrous acid


H3N–CH2–COO + HONO HO–CH2–COOH + N2 + H2O
Glycine Nitrous acid Glycollic acid
CH3–CH–COO + HONO CH3–CH–COOH + N2 + H2O

 NH3 OH
Alanine Nitrous acid Lactic acid
Note : (i) This reaction from the basis of the "van slyke method" for the estimation of amino acids.
(ii) The nitrogen is evolved (one half comes from the amino acid) quantitatively and its volum measured.
2.7.2.4 Reaction with Nitrosyl halide
(i) H2N–CH2–COOH + NOCl ⎯→ Cl–CH2–COOH + N2 + H2O
Glycine Chloroacetic acid
NH2 Br
(ii) CH3–CH–COOH + NOBr CH3–CH–COOH + N2 + H2O

Alanine –bromopropionic acid
2.7.2.5 Reaction with formaldehyde
H
(i) H C = O + H2N–CH2–COOH H2C=N–CH2–COOH + H2O
N–methylene glycine
Formaldehyde Glycine
Note : (i) Basic character of amino acid is lost & the product is acidic in nature which can be titrated with alkali.

H2C=N–CH2–COOH + NaOH ⎯→H2C=N–CH2–COONa + H2O
Sod. salt of N–methylene glycine
This reaction forms the basis of Sorenson formal titration method for the determination of neutrilization
equilvalent of amino acids.
2.7.2.6 Reaction with 2,4 –Dinitrofluorobenzene (DNEB)
NO2 NO2
H H H H
R–C–N–H+F NO2 R–C–N NO2 + HF
COOH COOH
DNFB (Sangar's reagent) Dinitrophenyl amino acid
(DNP) – amino acid
Note : (i) This reaction is very important in determination of structure of peptide & proteins.
(ii) The reagent react with the free amino group of terminal amino acid in a peptide or a protein & thus
identifies the end amino acid in structure.
2.7.3 Reaction involving both the carboxyl & the amino group
2.7.3.1 Effect of heat
(i)  amino acids undergo dehydration on heating (200ºC) to give diketo piperazines.
O O
CH2–C C
CH2
NH
OH  + 2H2O
H H HN NH
OH
NH C CH2
C CH2 2,5-Diketopiperazine
O
O Glycine (2 moles) (A cyclic diamide)
(ii) Amino acid lose ammonia to form , unsaturated acid.

NH2–CH2–CH2–COOH CH2=CH–COOH + NH3
 – Alanine Acrylic acid (2, propenoic acid)
(iii) –Amino acid & –Amino acid undergo intermoelcular dehydration to form cyclic amides called lactams.
 H2C–CH2 + H2O
CH2–CH2–CH2–C=O
HN–H OH H2C C=O
N
H
–aminobuytric acid –butyrolactam
2.7.3.2 Reaction with Ninhydrin
O O O
OH C C
C –H2O
C + R–CH–COOH C = N–C + R–C–OH
C OH C C
NH2 O
O O O
Ninhydrin (2 moles) –amino acid Purple complex
Note : Reaction is commonly used to test the presence of amino acid.
2.7.3.3 Reaction with cupric oxide
O O H2
2+  C O N CH2
H2N–CH2–C–OH + Cu Cu
H2 C N O C
(Glycine) H2 O
Cupric glycine (deep blue complex salts )
3.PEPTIDE & PROTEINS :
3.1 INTRODUCTION
(i) Proteins are formed by joining the carboxyl group of one amino acid to the –amino group of another acid.
(ii) The bond formed between two amino acids by the elimination of water molecules is called peptide linkage.
–C–OH+H–N– –C–N–
O H O H
Carboxyl group Amino group Peptide bond
of one amino of another
acid amino acid
(iii) The product formed by linking amino acid molecules through peptide linkage –CO–NH– is called a peptide.
(iv) When two amino acid combined in this way the resulting product is called a Dipeptide.
O Peptide linkage
H O O H O
–H2O
H2–N–CH2–C–OH+H–N–CH–C–OH H2N–CH2–C–N–CH–C–OH
CH3 CH3
Glycine Alanine A Dipeptide

(v) Peptide are further designated as tri, tetra or penta peptides accordingly as they contain three, four or five amino
acid molecules, same or different.
(vi) In a peptide the amino acid that contain the free amino group is called the N–terminal residue (written of L.H.S.).
(N–Terminal on left)
(vii) The amino acid that contain the free carboxyl group is called the C–terminal residue (written on R.H.S.). (C–
terminal on right)
O O O
H2N–CH2–C–NH–CH–C–NH–CH–C–OH
CH3 CH2
Glycylalanylphenylalanine (tripeptide) Abbriviated as : Gly – Ala – phe
(viii) If a large number of –amino acids (100 to 1000) are joined by peptide bonds, the resulting polyamide is called
polypeptide.
H2N–CH–CO–N–CH–CO–NH–CH–COOH
R H R R
n
(ix) By convention a peptide having molecular weight upto 10,000 is called polypeptide.
(x) While a peptide having a molecular weight more than 10,000 is called a protein.
(xi) Peptidyl transferase, catalyse the synthesis of peptide bond.
3.2 STRUCTURE OF PROTEINS
(i) Proteins have three dimensional structure.

(ii) There are number of factor which determine the exact shape of proteins.
(iii) Four levels of structural organisation are
Primary Secondary Tertiary Quaternary
3.2.1 Primary structure
(i) This type of structure was given by Friedrich Sanger in 1953 in Insulin.
(ii) Primary structure is conformed by single polypeptide chain in a linear manner.
(iii) All amino acid are attached in a straight chain by peptide bond.
3.2.2 Secondary structure
(i) The fixed configuration of polypeptide skeleton is referred to as the secondary structure of protein.
(ii) It gives information
(a) About the manner in which the protein chain is folded and bent.
(b) About the nature of the bond which stablise this structure.
(iii) This structure of protein is mainly of two types
–Helix Beta pleated sheet
(A) –Helix
(a) The chain of –amino acid coiled as a right handed screw (called –helix) because of the formation of
hydrogen bond.
(b) The spiral is held together by H–bonds between N–H & C = O group vertically abjacent to one another.
(c) X–Ray studies have shown that there are approximately 3.6 amino acid unit for each turn in helix.
(d) Such proteins are elastic i.e., they can be stretched.
(e) On stretching week H–bonds break up & the peptide act like a spring.
(f) The hydrogen bonds are reformed on releasing the tension.
eg. Myosin, Keratin, Tropomyosin.
(B) Beta – pleated sheet
(a) Polypeptide chains are arranged side by side.
(b) The chain are held together by a very large number of hydrogen bond between C = O & NH of different
chains.
(c) These sheets can slide over each other to form a three dimensional structure called a beta pleated sheet.
eg. Silk has a beta pleated structure.
3.2.3 Tertiary structure
(i) It refer to the arrangement and interrelationship of the twisted chain of protein into specific layer or fibres.
(ii) This tertiary structure is maintained by weak interatomic force such as, H–bonds hydrophobic bond, vander wall's
force & disulphide bonds (eg Insulin)
e.g. Protein of tobacco mosaic virus (TMV); Myoglobin; Haemoglobin
3.2.4 Quaternary structure
(i) When two or more polypeptide chain united by the force other than covalent bond i.e., not peptide & disulphide
bonds.
(ii) It refer to final three dimensional shape that results from twisting bonding and folding of the protein helix.
(iii) It is most stable structure.
3.3 CLASSIFICATION OF PROTEINS
There are two method for classifying proteins.

3.3.1 Classification According to Composition
3.3.2 Classification According to Functions
3.3.1 Classification According to Composition
3.3.1.1 Simple proteins
(i) Simple proteins are those which yield only –amino acids upon hydrolysis.
(ii) Simple proteins are composed of chain of amino acid unit only joined by peptide linkage.
e.g.
Egg (albumin); Serum (globulins); Wheat (Glutelin); Rice (Coryzenin); Connective tissue (Collagen);
Tenden, arteries (Elastin); Hairs (keratin)
3.3.1.2 Conjugated proteins
(i) Conjugated proteins are those which yield –amino acids plus a non protein material on hydrolysis.
(ii) The non protein material is called the prosthetic group
Example :–
Mucin in saliva (Prosthetic group, carbohydrate); Casein in milk (prosthetic group, phosphoric acid);
Haemoglobin (prosthetic group, Nucleic acid); Cholestrol (prosthetic group-lipid)
According to molecular shape, protein are further classified into two types.
(A) Fibrous protein
(a) These are made up of polypeptide chain that are parallel to the axis & are held together by strong
hydrogen and disulphide bonds.
(b) They can be stretched & contracted like thread.
(c) They are usually insoluble in water.
Example :–
(i) Collagens (tendens & bones);
(ii) Elastin (tendens, arteries & other elastic tissue);
(iii) Keratin (hair, wool, silk & nails)
(iv) Myosin (muscle)
(v) Ossein (bones & teeth)
(vi) Prolamine (zein from corn & gliadin from wheat) {Ex. : Glutatins (wheat)}
(B) Globular proteins
(a) These have more or less spherical shape (compact structure)
(b) –amino helix are tightly held bonding; H–bonds, disulphide bridges, ionic or salt bridges :
(c) These are usually soluble in water.
Examples :–
Albumin (egg, serum); Globulin (serum, globulin); ovoglubulin in egg – yolk, myosin of muscles,
fibrinogens, Histone (globin); Protamines (salmine from salaman & sturine).
3.3.2 Classification According to Functions
The functional classification includes following groups.
3.3.2.1 Structural proteins
These are the fibrous proteins such as collogen (skin, cartilage & bones) which hold living system together.
3.3.2.2 Contractive proteins
These are found in muscles. Examples are myosin, actin.
3.3.2.3 Enzymes
Protein of this group serve as biocatalysts, rendering specificity, Example : trysin, pepsin.
3.3.2.4 Harmones
Proteins of this group acts as messenger. Ex Insulin.
3.3.2.5 Antibodies (protective proteins)
(i) When the body is invaded by infectious species that releases foreign proteins or antigens.
(ii) Antibodies are produced to remove the invading species from the system.
Example :– Gamma globulins present in blood.
3.3.2.6 Blood proteins
(i) The major proteins constituent of the blood are albumin haemoglobin & fibrinogen.
(ii) There presence contribute to maintainance of osmotic pressure, oxygen transport system & blood coagulation
respectively.
3.3.2.7 Toxin
These are poisonous in nature.
Example :– Snake venom
3.4 TESTS OF PROTEIN

3.4.1 Biuret test
(i) On adding a dillute solution of copper sulphate to alkaline solution of protein, a violet colour is developed.
O
(ii) This test is due to the presence of peptide (–C–NH–) linkage .
3.4.2 Millon's test
(a) Millon's reagent consist of mercury dissolved in nitric acid (forming a mixture of mercuric & mercurous nitrates).
(b) When millon's reagent is added to a protein, a white ppt form, which turn brick red on heating.
(c) This test is given by protein which yield tyrosine on hydrolysis (due to the presence of phenolic group).
3.4.3 Ninhydrin test
(i) This test is given by all proteins.

(ii) When protein is boiled with a dilute solution of ninhydrin, a violet colour is produced.
O O O
HO
C OH C C
C + R–C–C–OH N = N–C
C OH C C
NH2
O O O
Ninhydrin amino acid Violet complex
3.4.4 Molisch test
(i) This test is given by those proteins which contain carbohydrates residue.
(ii) On adding a few drops of alcoholic solution of –naphthol & concentrated sulphuric acid to the protein solution a
violet ring is formed.
3.4.5 Hopkin–cole–test
(i) To a mixture of protein & a glyoxalic acid solution, concentrated sulphuric acid is added carefully down the sides
of the test tube form a layer.
(A) If tryptophan is present in protein, a violet ring will appear between two layers.
H H
H
O C
H2SO4 C–COOH
CH2–CH2–COOH + H–C–COOH
C=NH
NH2 N C
N H
H H H
Tryptophan Glyoxalic acid Violet complex
3.5 USES OF PROTEINS
(i) Protein consitute as essential part of our food, meat, eggs, fish, cheese provide protein to human beings.
(ii) Casein (a milk protein) is used in the manufacture of artificial wool & silk.
(iii) Amino acid needed for medicinal use & feeding experiment, are prepared by hydrolysis of proteins.
(iv) Gelatin is used in desserts, salad's, candies bakery goods etc.
(v) Leather is obtained by tanning the protein of animal hides.
(vi) Haemoglobin present in blood is responsible for carrying oxygen and CO 2.
(vii) Harmones controls various body process.

(viii) Enzymes are the proteins produced by living system & catalyse specific biological reaction.
e.g.
Ureases (Urea → CO2 + NH2)
Pepsin (Protein → Amino acid)
Trypsin (Protein → Amino acid)
Carbonic anhydrase (H2CO3 → H2O + CO2)
Nuclease (RNA, DNA → Nucleotides)

POLYMERS & CHEMISTRY IN EVERYDAY LIFE
POLYMERS
INTRODUCTION :
• Polymers are the compound of very high molecular masses formed by the combination of large number of simple
molecules.
• In Greek, poly means many and meros means units or parts.
• The simple molecules which combine to give polymer are called monomers.
• The process by which simple molecules (i.e. monomer) are converted into polymers is called polymerisation.
Polymerisa tion
e.g. nCH2=CH2 ⎯⎯⎯⎯⎯⎯⎯→ –(CH2–CH2–)n
Ethylene Polyethylene
(Monomer) (Polymer)
• These large molecules have relative molecular masses in the range 104 – 106.
• Where n is as large as 105. The number of monomers units in a polymer is called the degree of polymerisation.
• A polymer formed from one type of monomers is called HOMOPOLYMER.
e.g. Polyethylene (Monomer :- ethylene)
• A polymer formed from two or more different monomers is called COPOLYMER or mixed polymer.
e.g. Terylene (Monomers: Ethylene glycol and terephthalic acid)
CLASSIFICATION OF POLYMERS :
(1) Based on Origin :
(a) Natural Polymers : The polymers obtained from nature ( plants and animals) are called natural polymers.
• Polysaccharides : Starch and cellulose
• Proteins: These are polymer of -aminoacids. eg. wool, skin etc.
• Nucleic acid : These are polymers of various nucleotides eg. RNA and DNA are common nucleotides.
• Natural rubber : It is a polymer of unsaturated hydrocarbon, 2- methyl-1,3- butadiene also called isoprene.
It is obtained from latex of rubber tree.
Polymerisation
n CH2=C=CH–CH3 —CH2–C=CH–CH2—
CH3 CH3 n
Isoprene Polyisoprene (Natural ruber)

(2-methyl-1,3-butadiene)
Note : Polymers such as polysaccharides (starch, cellulose) Protein and nucleic acid etc. which control various life
process in plants and animals are also called BIOPOLYMERS.
(b) Synthetic Polymers : These are man- made polymers.

• Elastomer : Synthetic rubber (Neoprene, Buna-S)
• Plastics : Bakelite, Polyethylene, PVC, Acrylics
• Fibres : Nylon, Terylene
(2) Based on structure:
(a) Linear chain Polymers:
• These are polymer in which monomeric units are linked together to form linear chains.
• These linear polymers are well packed and therefore have high densities, high tensile (pulling) strength
and high melting points. eg. Polythene, Nylon and Polyesters.
(b) Branched Chain Polymers :
• These are polymers in which the monomers are joined to form long chain with side chain or branches of
different lengths.
• These branched chain, polymers are irregularly packed and therefore, they have low tensile strength and
melting points than linear polymers. e.g. Low density polythene, glycogens, starch etc.
(c) Cross linked Polymers :
• These are polymer in which monomer units are cross- linked together to form a three dimensional
network.
• These polymers are hard rigid and brittle because of network structure.
e.g. Bakelite, Melamine formaldehyde resin.
(3) Based on synthesis :
(a) Addition Polymers :
•: A polymer formed by direct addition of repeated monomer’s without the elimination of any by product
molecules.
• In this type, the monomers are unsaturated compounds and are generally derivative of ethene.
• The addition polymers have same empirical formula as their monomers.
e.g. n CH2=CH —–CH2–CH—–
Cl Cl n
Vinyl chloride Polyvinyl chloride (PVC)
(b) Condensation Polymers :

• A polymer formed by the condensation of two or more than two monomers with the elimination of simple
molecule like - H2O / NH3 / HCl/R-OH etc..
• In this type, each monomer generally contain two functional group.

O
–n H2O
e.g. n H2N–(CH2)6–NH2 + n HOOC–(CH2)4–COOH –NH–(CH2)6–NH–C–(CH2)4–C–
Hexamethylenediamine Adipic acid O
Nylon-66 n
(4) Based on reaction mechanism :

(a) Chain growth polymerization :
• There is a series of reaction each of which consume a reactive particle and produce another, similar
particle, each individual reaction thus depend upon the previous one.
• The reactive particle can be free radical, cations or anions.
• The polymerization start when a molecule of monomers react with an initiator to form an active
intermediate.
• This active intermediate is added to another monomer forming another intermediate. In this way chain
propagation continue and ultimately a polymer is formed.
O O O
–CO2
(i) Chain initiating step : Ph–C–O–O–C–Ph 2 Ph–C–O 2 Ph
Benzoyl peroxide
(ii) Chain propagating step : CH2=CH2 + Ph Ph–CH2–CH2
Ph–CH2–CH2 + CH2=CH2 Ph–CH2–CH2–CH2–CH2
(iii) Chain terminating step : Ph–CH2–CH2— CH2–CH2 + Ph–CH2–CH2— CH2–CH2 Ph–CH2–CH2—
n n n Ph
e.g. Polyethylene, Polypropylene, PVC, teflon etc.
(b) Step growth polymerisation :
• This type of polymerization involve a series of reaction each of which is essentially independent of the
proceeding one;
• A polymer is formed simply because the monomer happen to undergo reaction at more than one
functional group.
• In the case of polyester, a diol for example, react with a dicarboxylic acid to form an ester but each
moiety of the simple ester contain a group that can react to generate another ester linkage and hence a
large molecule, which itself can react further, and so on
OH OH O O
OH OH OH
CH2CH2 HO–C C–OH
CH2CH2 + HOOC COOH ⎯→ CH2–CH2–O–C COH CH2CH2–O–C C–OCH2CH2
1,2-Ethanediol Pthalic acid O O OH O O OH
O
HO–C C–O–CH2CH2–O–C C–OCH2CH2OH –OCH2CH2–O–C C–
O – nH2O O
O O O
Terylene or dacron
e.g. Nylon 66, Bakelite, Dacron etc.
(5) Based on Molecular Forces :
• The mechanical properties of polymers such as tensile strength, toughness, elasticity etc. depend upon
intermolecular forces like Vander Waal’s, hydrogen bonds and dipole -dipole interactions existing in macro
molecules.
• In the polymers these forces extend all along the chain resulting significant combined effect.
• Thus longer the length of the polymer chain stronger is the effect of intermolecular forces.
• Depending upon the intermolecular force, the polymers have been classified into four categories:
(A) Elastomers :
• The polymers that have elastic character like rubber.
• In elastomers the polymer chain are held together by weakest intermolecular forces.
• Because of the presence of weak forces the polymer can be easily stretched by applying small stress and
regain their original shape when the stress is removed.
• The elasticity of such polymers can be further modified by introducing few cross linked between the chains.
• Natural rubber, a gummy material has a poor elasticity. However when natural rubber is heated with 3-5%
sulphur, it become non- sticky and more elastic. This process is called vulcanization.
• The product formed is called Vulcanized Rubber which has better tensile strength, elasticity and resistance to
abrasion than natural rubber. This is due to sulphur cross linked between polymer chains.
• Thus, cross linked are introduced in natural rubber to -

(i) Impart the property of regaining the original position after stretching force is released.
(ii) Prevent the chain from slipping past each other when force is applied.
Sulphur cross linked
Sulphur
Heat
Natural rubber
Vulcanized rubber
(B) Fibres :
• These are the polymer which have strong intermolecular force between the chains.
• These force are either hydrogen bond or dipole- dipole interactions.
• Due to the strong forces, the chain are closely packed giving them high tensile strength and less elasticity, thus
have sharp melting points.
• These polymers are long, thin and thread like and can be woven in fabrics.
e.g. : Nylon-66, Dacron, silk etc.
(C) Thermoplastics :
• These are the polymer which can be easily softened repeatedly when heated and hardened when cooled with
little change in their properties.
• The intermolecular forces in these polymers are intermediate between those of elastomers & fibres.
• There is no cross linking between the chain.
• The softening occur as the polymer chain move more and more freely because of absence of cross links.
• When heated, they melt and form a fluid which can be moulded into any desired shapes and then cooled to get
the desired product.
e.g. : Polythene, polystyrene, polyvinyl chloride, teflon etc.
(D) Thermosetting Polymers :

• These are the polymer which undergo permanent change on heating.
• They become hard and infusible on heating.
• They are generally prepared from low molecular mass semi- fluid substances.
• When heated, they get highly cross linked to form hard infusible and insoluble products.
• The cross links hold the molecules in place so that heating does not allow them to move freely.
• A thermosetting plastic is cross linked and is permanently rigid.

e.g. : Bakelite, melamine formaldehyde etc.
Special Ponits :
(i) Plasticizers are the organic compound used to soften plastics.
e.g. Polyvinyl chloride (PVC) is very stiff and hard but it is made soft by adding n-butyl phthalate(a plasticizer)
(ii) Some other common plasticizers are dialkyl phthalate, cresyl phthalate.
NATURAL RUBBER :
• Natural rubber or plantation rubber is an important polymer obtained from latex found in inner bark of a
tropical tree Hevea brasiliensis.
(1) Extraction of Natural Rubber :

• An incision is given in a special way in the trunk of rubber trees ( not less than seven years old), which slopes
from left to right.
• At the lower end of incision is attached a metal spout below which is kept a pot for collection of latex.
• The latex is a colloidal dispersion of rubber particle in water and contains 30% to 40% of rubber.
• The latex is strained and diluted with water such that concentration of rubber particle falls to 12%, into this is
added 1% acetic acid solution.
• The acid coagulate rubber particle with 3 to 4 hours.
• The coagulated rubber look like sponge cheese.
• It is filtered out and then kneaded between warm roller so as to form homogeneous mass.
• This mass is finely rolled out to form rubber sheets.
(2) Chemical composition of natural rubber :
• Natural rubber is a polymer of monomer isoprene which is chemically 2-methyl 1,3-butadiene.

• Rubber is the linear polymer of 11,000 to 20,000 molecules of isoprene.
CH2=C–CH=CH2 + CH2=C–CH=CH2 (–CH2–C=CH–CH2–CH2–CH2–C=CH–CH2–)
CH3 CH3 CH3 CH3
Isoprene(Monomer) Isoprene(Monomer) Dimer
CH2=C–CH=CH2 –CH2–C=CH–CH2–
n
CH3 CH3 n
Isoprene (n-molecules) Natural rubber (n-11,000 to 20,000) (polyisoprene)
ADDITION POLYMERS
S.No. MONOMER POLYMER USES
Ethene Polythene
1. CH2=CH2 –CH2–CH2– Carry bags, toys, Bottles
Propene Polypropene
CH3 CH3
2. Ropes, Toys, Fibres, pipes
CH2=CH –CH2–CH–
n
Styrene Polystyrene
C6H5 Insulators, in toys,
3. C6H5
–––CH2–CH––– television & radio cabinets.
CH2=CH
n
–
Vinyl chloride *Poly vinyl chloride (PVC)
Cl Cl Rain coats, hand bags,
4.
CH2=CH –CH2–CH– water pipes
n
*Polyacrylonitrile (PAN)
Acrylonitrile or Acrylon or Orlon
5. CN CN Blankets, Carpets.
CH2=CH –CH2–CH–
n
Tetrafluoroethene *Teflon or PTFE

6. Nonstick utensils coating
CF2=CF2 –CF2–CF2–
n
Chloroprene *Neoprene
7. Cl Cl Conveyor belts
CH2=C–CH=CH2 ––CH2–C=CH–CH2––
n
Poly isoprene
Isoprene
CH3
8. CH3 Natural Rubber (cis)
––CH2–C=CH–CH2––
CH2=C–CH=CH2
n
Methyl methacrylate PMMA
CH3 CH3
9. Solar panels, skylights
CH2=C–C–OCH3 ––CH2–C–––––––
– COOCH
O 3
n
S.No. MONOMER POLYMER USES
Vinyl acetate Polyvinyl acetate
OCOCH3
10. OCOCH3 Latex points, adhesives
––CH2–CH––––––
CH2=CH –
n
Vinyl acetate
Polyvinyl alcohol
OCOCH3 OH
11. CH2=CH –––CH2–CH––– adhesives
 Vinyl alcohol is n
unstable
1,3-Butadiene
[CH2=CH–CH=CH2]
*Buna-N
&
CN
12. Acrylonitrile Oil seals, Tank linings
–CH2–CH=CH–CH2–CH2–CH–
CN n
CH2=CH
1,3-Butadiene
[CH2=CH–CH=CH2] *Buna-S or SBR
&
Styrene
Floor tiles, Foot wear
13.
–CH2–CH=CH–CH2–CH–CH2– components
CH=CH2
n
CONDENSATION POLYMERS
S.No. MONOMERS POLYMER USES

1. Adipic acid *Nylon–6,6 Sheets,
[HOOC–(CH2)4 –COOH] O O bristles
& ––NH–(CH2)6–NH–C–(CH2)4–C–– for brushes
n
Hexamethylenediamine
[H2N–(CH2)6–NH2]
2. Hexamethylene diamine *Nylon-6, 10 Sheet,
[H2N–(CH2)6–NH2] O O Textile
& –NH–(CH2)6–NH–C–(CH2)8–C– industry
n
Sebacic acid
[HOOC–(CH2)8–COOH]
3. Glycine Nylon-2-Nylon-6 Biodegradable polymer

[H2N–CH2–COOH] O O
& –NH–CH2–C–NH–(CH2)5–C–
Amino caproic acid
n
[H2N–(CH2)5–COOH]
4. Caprolactum *Nylon-6 Tyre cords, Fabrics and
NH O O ropes
––C–(CH2)5–NH––
n
5. Formaldehyde [HCHO] *Bakelite Electrical switches and
& handles of utensils
Phenol OH OH OH
CH2 CH2–
n
6. Phthalic acid Glyptal Paints and Lacquers
O O
HOOC COOH
––C C–OCH2–CH2––
n
&
Glycol [HO–CH2–CH2–OH]
7. Terphthalic acid Terylene or Dacron Fibres, Safety Belts
O O
HOOC COOH
–––C C–O–CH2–CH2––
n
&
Glycol [HO–CH2–CH2–OH]
S.No. MONOMERS POLYMER USES
8. O Urea formaldehyde Resin Unbrakable cups and
Urea H2N–C–NH2 O Laminated sheets
––NH–C–NH–CH2––
and n
Formaldehyde [HCHO]
9. 3-Hydroxy butanoic acid Poly -hydroybutyrate (PHBV) Orthopedic devices and
OH in controlled drugs
––O–CH–CH2–C–O–CH–CH2–C–– release
CH3–CH–CH2–COOH
CH3 O C2H5 O (Biodegradable
n
& 3-Hydroxy pentanoic Polymer)
acid
CH3–CH2–CH–CH2–COOH
OH
10. Melamine Melamine formaldehyde Resin Unbreakable crokery
N N
H2N NH2 ––HN NH–CH2––
N N N N
NH2 NH
& n
Formaldehyde [HCHO]
CHEMISTRY IN EVERYDAY LIFE
CHEMICAL IN MEDICINES
Chemotherapy :
The branch of science which deals with the treatment of diseases using suitable chemicals is known as
chemotherapy.
1.2Classification of Medicines :
Medicines are generally classified according to the purpose for which they are used. The different terms thus used
along with examples are given below :
1.2.1 Antipyretics :
Chemicals which are used to bring down the body temperature during high fever are called antipyretics. On taking
these medicines, the person gets a lot of perspiration. A few well known examples of antipyretics are Aspirin,
Phenacetin and Paracetamol,
OCOCH3 OH OC2H5
1
COOH
4
NHCOCH3 NHCOCH3 O N
N CH3
CH3
Aspirin Paracetamol 4-Ethoxyacetanilide Analgin

(Acetylsalicyclic acid) (4-Acetamidophenol) (Phenacetin)
Novalgin is another well known antipyretic. Quinine has also some antipyretic effect. Paracetamol is preferred
over asprin as an antipyretic since asprin gets hydrolysed to salicylic acid in the stomach. The salicylic acid thus
produced may cause ulcer in the stomach walls where from the bleeding may take place.
1.2.2 Antimalarials :
Chemical substances which are used to bring down the body temperature during malaria fever are called
antimalarials. Originally quinine (an alkloid) was the only drug known to be effective against malaria. Now a days,
a number of synthetic drugs are used for the purpose. These are Chloroquine, Paraquine, Primaquine etc.
1.2.3 Analgesics :
Medicines used for getting relief from pain are called analgesics. These are of two types
(i) Narcotics and (ii) Non-narcotics
(i) Narcotics : Drugs which produce sleep and unconciousness are called narcotics. These are mostly opium products.
Opium contains alkaloids such as morphine and codeine which are very effective analgesics. Morphine diacetate
(commonly known as Heroin) is the most widely used analgesic.
O
RO
C6H5 C–OC2H5
O
N
N–CH3
CH3
R= –H (Morphine) Pethidine hydrochloride
R= –CH3(Codeine)
(ii) Non-narcotics : The most important non-narcotic analgesics are butazolidine and brufen or ibuprofen.
CH2COONa Cl
CH3–CH–CH2 CH–COOH NH
CH3 CH3 Cl
Brufen or Ibuprofen Diclofenac sodium
Aspirin, Phenacetin, and Novalgin act both as antipyretic as well as analgesic. They are quite effective and give
immediate relief from pain and fever.
1.2.4 Antiseptics and Disinfectants :

(i) Antiseptics : The chemicals which kill or prevent the growth of micro-organisms are called antiseptics. These are
not harmful to living tissues and can be safely applied on wounds, cuts, ulcers, diseased skin surfaces. These are
also used to reduce odours resulting from bacterial decomposition of the body or in the mouth. They are, therefore
mixed with deodrants, face powders and breath purifiers.
(ii) Disinfectants : The chemical substances which are used to kill microorganisms but they cannot be applied on
living tissues are called disinfectants. These are commonly applied to inaminate objects such as floors,
instruments, etc.
The same substance can act as disinfectant as well as antiseptic depending upon its concentration. For example, a
0.2% solution of phenol acts as antiseptic and its 1% solution acts as disinfectant.
The common examples are :
(i) Cl2 is used for making water fit for drinking at a concentration 0.2 to 0.4 ppm.
(ii) Dettol is an antiseptic. It is a mixutre of chloroxylenol and terpenol in a suitable solvent.

(iii)Bithional is antiseptic which is generally added to medicated soaps to reduce the odour produced by bacterial
decomposition of organic matter on the skin.
(iv) Iodine is powerful antiseptic. It is used as a tincture of iodine which is 2 - 3% iodine solution of alcohol-water.
(v) Some organic dyes are also effective antiseptics. These are used for the treatment of infectious diseases. The
common examples of antiseptic dyes are gentian violet and methylene blue.
CH3 OH OH
Cl Cl
Cl
S
H3C OH Cl Cl
Chloroxylenol Bithional
1.2.5 Tranquilizers :
The chemical substances used to cure mental diseases are called tranquilizers. These are used to release mental
tension and reduce anxiety. These are the constituents of sleeping pills. They act on higher centres of nervous
system. These are also called psychotherapeutic drugs. These drugs make the patient passive and help to control
their emotional distress or depression. These also help to restore confidence and the patients work with full
capacities which they already have.
(i) Hypnotics : These are also known as tranquilizers and are used to reduce mental tension and anxiety. These
induce sleep. These are components of sleeping pills (sedatives)
Ex.
C3H7
O O O
C6H5 H3C–CH
N–H C2H5 N–H CH2=CHCH2 N–H
O N O N O N O
H H H
Barbituric acid Luminal Seconal
(ii) Non Hypnotics : They reduce tension and anxiety. These do not induce sleep.Equanil is also an important
tranquilizers used in depression and hypertension.
Ex.Chlorodiazepoxide, Meprobamate.
O CH3 O
H2N–C–O–CH2–C–CH2–O–C–NH2
CH3
Equanil
It may be noted that different terms are used for drugs which are used to cure mental diseases.
1.2.6 Antidepressants
These drugs are given to patients with shattered confidence. These produce a felling of well being and confidence in the
person of depressed mood. Therefore, these are also called mood booster drugs. The common examples are
Vitalin, Cocaine, Methedrine etc.
1.2.7 Antibiotics :
These are the chemical substances which are produced by micro-organisms (bacterial, fungi and moduls) and can
inhibit the growth or even destroy other micro-organisms. The first successful antibiotic produced was penicilin. It
was discovered by Alexander Fleming in 1920. The general formula of penicillin is C9H11O4 SN2R where R may
be different for different members. For example.
O
H H S CH3
R–C–NH CH3
N COOH
O H
General structure of Penicillin
With the subsitution of different R groups, about six natural penicillins have been isolated so far. for example.
Penicillin Nature of R
Penicillin G
CH2–
or Benzyl penicillin
Penicillin F CH3–CH2–CH=CH–CH2–
Penicillin K CH3–(CH2)6–
Ampicillin
CH–
NH2
Ampicillin and amoxycillin are some modifications of penicillins. It may be noted that many patients develop
allergy to penicillin. Therefore, it is essential to test the patient for sensitivity (allergy) to penicillin before it is
administered.
Penicillin has narrow spectrum. These can be used for curing sore throat, gonorrhoea, rheumatic fever, local
infections, etc.
In india the important centres which manufacture Penicillin are – Hindustan Antibiotics, Pimpri and Indian Drugs
and Pharmaceuticals, Rishikesh.
Streptomycin is also an antibiotic used for the treatment of tuberculosis, meningitis, pneumonia, local infections,
etc.
Broad spectrum antibiotics : These are the antibiotics which are effective against a variety of diseases. The
common examples are Tetracycline, Chloromycetin and Chloramphenicol which are effective against a variety of
diseases. Therefore, these can be used for curing typhoid, acute fever, dysentery, whooping cough, pneumonia, eye
infection, certain urine infection. The structure of chloramphenicol is :
NHCOCHCl2
O2N CH–CH–CH2OH
OH
Chloramphenicol
Sulpha drugs : These have great antibacterial powers and are used as medicines for various diseases. These are
also antibiotics and protect the body against micro-organisms. These are used against diseases such as pneumonia,
tuberculosis, diphtheria, etc. Some important sulpha drugs are sulphadiazine,sulphanilamide, etc.
N
H2N SO2NH2 H2N SO2NH
`
Sulphanilamide Sulphadiazine
Germicides :
These are the chemical substances used to kill germs, fungi and virus. The common examples of germicides are
phenol, cresol, formaldehyde, DDT, potassium permanganate solution, (1%) chlorine, bleaching power, hydrogen
peroxide, etc.
Anti–fertility drugs :
Chemical substances which are used to check pregnancy in women are called anti-fertility drugs or birth control
drugs or oral contraceptives.
All these drugs contain chemicals related to female sex harmones having a steroid ring structure. Most of these
contain a combination of an estrogen and a progesterone. For example, a common brand name Enovid E contains
norethindrone (a progestin) mestranol or ethenylestradiol monomethyl ether (an estrogen). All such drugs are
expected to have side effects and hence should be used only under proper medical advice.
OH OH
H3C CCH H3C CCH
H H H
H H
O CH3O
Norethindrone Mestranol
Antihistamines :
The drugs which have been used to fight allergy are called antihistamines. These are so called because they check
the production of histamines. Thus, antihistamines are widely used for treatment to hay fever, conjunctivitis, nasal
discharges, irradation sickness, motion sickness (air, sea, road), nausea in pregnancy and post operative vomiting.
The antihistamine drugs which are widely used are diphenlhydramine hydrochloride, Cetrizine,
Chloropheniramine, Promethazine hydrochloride etc. The structure of some of these are given below :
C6H5 CH3 Cl
CH3
CH–O–CH2–CH2–N .HCl
C6H5 CH3 CH–CH2–CH2–N
(CHCOOH)2 CH3
N
Diphenylhydramine hydrochloride Chlorpheniramine maleate
Antacids :
Antacids are substances that decrease gastric acidity by neutralising hydrochloric acid. They are compared
quantitatively in terms of their acid-neutralising capacity. These usually contain salts of Al, Mg and Na. These are
of the following two types :
(a) Systemic antacid (b) Non-systemic antacid
(a) Systemic antacids : Systemic antacids like sodium bicarbonate decrease acidity but cause systemic
alkalosis due to absorption of bicarbonate. Hence acid-base balance is disturbed. Further excess sodium may cause
oedema and cardiac failure in patients with renal or cardiac dysfunction.
(b) Non-systemic antacids : These may contain one or more of the following compounds : Al(OH) 3, Mg(OH)2,
MgCO3, CaCO3, magnesium trisilicate, magaldrate etc. These antacids are not absorbed after administration and
hence acid-base imbalance is minimal.
2. DYES
Dyes are chemical substances used to impart colours to the textiles, foodstuffs, silk, wool and other objects. The
discovery of dyes has provided glamour in our modern life. All coloured substances are, however, not dyes. A
substance can act an a dye if it satisfies the following conditions :
(i) It must have a suitable colour.
(ii) It must be able to fix itself permanently to the material being dyed.
(iii) When fixed, it must be fast to light and washing.
(iv) It must be resistant to the action of water, soap, acids and alkalies or other solvents used in dry cleaning etc.
2.1How a dye exhibits colour ? :

A dye is an organic compound which can absorb a certian portion of the visible light (400 – 750 nm) falling on it.
The rest of the light is reflected. The colour of the reflected light gives the colour of the dye which is
complementary to the colour of the light absorbed. The colour of the visible light absorbed and the complementary
colour reflected are given in Table.
WAVE LENGTH COLOUR ABSORBED COLOUR REFLECTED

(nm) (Complementary colour)
400–435 Violet Yellow green
435–480 Blue Yellow
480–490 Green-blue Orange
490–500 Blue-green Red
500–560 Green Purple
560–580 Yellow green Violet
580–595 Yellow Blue
595–605 Orange Green blue
605–750 Red Blue green
From the above table, it is clear that if a dye absorbs electromagnetic radiations corresponding to yellowish green,
it will appear violet which is the complementary colour of yellowish green. Similarly if a dye absorbs blue colour
it will appear yellow which is the complementray colour of blue. Thus dyes impart colour to a fabric by absorbing
the complementary colour.
(i) Chromopores : In general, the intrinsic colour of any compound is due to the presence of certain groups
containing multiple bonds. These groups which impart colour to a compound are called chromophores. Some
examples of chromophores are :
NO2 (nitro), N = O (nitroso), N=N (azo) quinoid structures etc.
(ii) Auxochromes : At the same time, there are certain groups which themselves are not chromophores but deepen the
colour when introduced into coloured compounds. Such groups which deepen the colour of a coloured compound
are called auxochromes. Some examples of auxochromes are :
OH, NH2, NHR, NR2, Cl, CO2H etc.
2.2Classification of Dyes :
Dyes can be classified in a number of ways as briefly described below :
2.2.1 Natural and synthetic Dyes :

Since early times, man has been trying to extract dyes from the plants for using them to beautify his cloths. Such
dyes are known as natural dyes. Two examples of natural dyes known since early times are indigo (a blue dye) and
alizarin (a red dye). India has been the main producer and exporter of indigo. However, natural dyes have only
limited shades. Hence, now a days, most of the dyes used are the synthetic dyes which can have a variety of
shades. Most of these dyes are aromatic compounds obtained from coal-tar. Hence these are also called coal-tar
dyes.
2.2.2 Classification of Dyes based on their Constitution (Chemical classification) :

On the basic of chemical constitution, the variety of dyes is so larger that a long list can be prepared. However
some important classes based on the characteristic structural units present in them are given in Table.
2.3Classification of dyes on the basis of their applications :

The dyes are classified into the following types on the basis of their applications :
2.3.1 Acid dyes :

The sodium salts of azo dyes containing sulphonic acid (–SO3H) and carboxylic acid (–CO2H) groups are called
acid dyes. These dyes are applied to the fabric from their acid solutions and are used to dye wool, silk, nylon and
acrylic fibres. These do not have affinity for cotton and hence connot be used to dye cotton. Typical examples of
acid dyes are orange–I, orange–II, methyl orange, methyl red and congo red. The dyeorange–I is prepared by
coupling diazotised sulphanilic acid with -naphthol.
Type Structural unit Example
1. Nitro dyes O OH
–N NO2
O
Nitro
NO2
(Martius yellow)
2. Azo dyes –N=N– 
(Azo) NaO3S N=N OH
(Orange-I)
3. Triphenylmethane dyes C 
C N(CH3)2
(Triphenylmethane)
N(CH3)2
(Malachite green)
4. Inigoid dyes O O
H
C C N
C= C=C
N N C
H H
(Indgoid) O
(Indigo)
5. Anthraquinone dyes O O OH
OH
O O
(Anthraquinone) (Alizarin)
6. Phhalein dyes O O
C C
O O
C
C
(Phthalein)
OH OH
(Phenolphthalein)
  OH
NaO3S 
N=NCl + NaO3S N=N OH
–HCl
Diazotised sulphanilic Orange-I
acid sodium salt -Napthol
The dye orange–II is similarly obtained by coupling diaxotised sulphanilic acid with  – naphthol.
OH
OH
  
NaO3S NNCl + NaO3S N=N
–HCl
Diazolised sulhaphanilic acid
-Naphthol Orange-II
sod. salt
Similarly, congo red is obtained by coupling tetrazotised benzinic (4, 4–diaminodiphenyl) with two molecules of
naphthionic acid (4–aminonaphthalene–1–sulphonic acid).
2.3.2 Basic dyes :
These dyes are the salts of the coloured bases containing amino groups (– NH2 or – NR2) as the auxochromes.
These include azo and triphenylmethane dyes. In the acid solution, these amino groups form water soluble cations
which then react with anionic sites present on the fabrics and thus get attached to them. Modified nylons and
polyesters can be dyed with these dyes. Some common examples of this class are aniline yellow, butter yellow,
chrysodine G (structures given below) and malachite green
N=N NH2 N=N N(CH3)2

Aniline yellow Butter yellow
NH2

N=N NH2 C N(CH3)2
Chrysodine G
N(CH3)2
(Malachite green)
Chrysodine G is an orange dye and is obtained by coupling benzenediazonium chloride (1 mole) with m-
phenylenediamine. It is generally used to dye silk, wool, cotton, leather and paper.
Methyl Orange and methyl red are obtained by coupling N, N–dimethylaniline with diazotised sulphanilic acid and
diazotised anthranilic acid respectively :
 NaOH
(i) HO3S NNCl + N(CH3)2 NaO2S N=N N(CH3)2
–NaCl, –H2O
Diazotised sulhpanilic Methyl orange
acid
COOH COOH

(ii) NCl + N(CH3)2 N=N N(CH3)2
–HCl
Diazotised anthranilic Methyl red
acid
2.3.3 Direct dyes :

As the name suggests, these are those dyes which can be directly applied to the fabric from an aqueous solution.
These are most useful for fabrics which can form hydrogen bonds with the dyes. Thus these are usually used for
dyeing cotton, wool, silk, rayon and nylon.
2.3.4 Disperse dyes :

These are water insoluble dyes and are applied to the fabric in form of a dispersion of the finely divided dye in a
soap solution in the presence of some stabilizing agent such as phenol, cresol or benzoic acid. These dyes are used
to dye synthetic fibres and as nylons, polyesters and polyacrylonitrile fibres.
These dyes belong to the class of monoazo dyes and anthraquinone dyes. Important examples of disperse dyes
(anthraquinone dyes) are :
(i) Cellitone fast pink B and (ii) Cellitone fast blue B
O NH2 O NHCH3
O OH O NHCH3
1-Amino-4-hydroxyanthraquinone 1-4-Di (methylamino) anthraquinone

(Celliton fast pink B) (Celliton fast blue B)
2.3.5 Fibre reactive dyes :

These are those dyes which contain a reactive group which combines directly with the hydroxyl or amino group of
the fibre. Because of the formation of permanent chemical bonds between the fibre and the dye, the colour of the
dyed fabric is fast and has a long life. Cotton, wool or silk can be dyes with this type of dyes. Dyes which are
derivatives of 2, 4 – dichloro – 1, 3, 5 – triazine are important example fibre reactive dyes.
N O–Fibre
N N
–HCl
Fibre – OH + Cl N –Fibre –OH + Cl– N
N N
Dye Dye
2.3.6 Ingrain dyes :

These are water insoluble azo dyes which are produced in situ on the surface of the fabric by means of coupling
reaction. The fabric to be dyed in soaked in an alkaline solution of a phenol or naphthol and is then treated witht he
solution of a suitable diazonium salt to produce an surface adsorption of the dye on the fabric, the colour is not
very fast.These dyes are generally used for dyeing cotton, silk, nylon and polyester. An example of this type of dye
is para red.
OH

 NaOH
O2N NNCl + O2N N=N
–HCl
p-Nitrobenzenediazonium chloride -Naphthol Para red
2.3.7 Vat dyes :

These are insoluble dyes which are first reduced to a colourless soluble from (leuco compound) in large vats with a
reducing agent such as alkaline sodium hyposulphite and then applied to the fabric. The fabric to be dyed is first
soaked in the alkaline solution of sodium hyposulphite and then oxidised to the insoluble coloured form by
exposure to air or by some oxidising agents such as chromic acid or perboric acid. These dyes are mainly used to
dye cotton fibres. A well known example of vat dyes is indigo.
2.3.8 Mordant dyes :

These dyes do not dye the fabric directly but require a mordant. The mordant, in fact, acts as the binding agent
between the fibre and the dye. For acid dyes, metal ions are used as mordants but for basic dyes, tannic acid is
used as the mordant. These dyes are primarily used to dye wool.
Soaps & Detergents

Introduction
(a) Sodium salts of higher fatty acids like stearic acid, oleic acid, palmitic acid etc. are called hard soaps and the
potassium salts of these fatty acids are called soft soaps.
(b) Soaps are prepared by hydrolysis of higher fatty acids.
(c) A higher proportion of salts of saturated acids (palmitic, stearic etc.) gives Hard soaps, while a higher proportion
of salts of unsaturated acids (oleic acid) yields soft soaps.
(d) Alkaline hydrolysis of oils or fats by NaOH or KOH gives glycerol and sodium or potassium salt of
the fatty acid. This reaction is known as saponification.
CH2OCOC17H35 CH2OH
CHOCOC17H35 + 3NaOH CHOH + 3C17H35COONa (sodium stearate)
CH2OCOC17H35 CH2OH
3. SOAPS
3.1 Types of soaps :
(a) Hard soaps – These are obtained from cheap oils and fats using sodium hydroxide. These contains free alkali and are
used for washing purposes.
(b) Soft soaps – These are obtained from good oils using potassium hydroxide. These do not contain free alkali and are
used as toilet soaps, shaving cream, in shaving sticks and shampoo.
(c) Transparent soaps : These are formed by dissolving toilet soaps in alcohol and evaporating the filtrate. They contain
glycerol.
(d) Medicated soaps : Toilet soaps containing some medicinal important substance are called medicated soaps.
(e) Metallic soaps : These are soaps of metals other than sodium and potassium.
3.2 Manufacture of soap :

Generally three processes are adopted for manufacture of soap.
(a) The cold process : The soap of good quality is not obtained by this method as glycerol, alkali and oil remain with
the soap. This is an expensive method. In this method oil is taken in an iron vessel and heated to about 50ºC.
Calculated amount of sodium hydroxide is added to it slowly by stirring the mixture. The whole mixture is kept
overnight which gets solidified and then is cut into pieces. Glycerol remains in the mixture in this method.
(b) The hot process : The following processes are involved in this method :
Saponification : A mixture of oil and alkali is heated in iron vessels by steam coils. The oil gets hydrolysed and a
mixture of soap, glycerol, oil and water is obtained.
Salting out of soap : A saturated solution of sodium chloride is added to the mixture obtained above. Due to
common ion effect soap separates out and floats on surface of the solution. Soap is separated from the solution and
glycerol is recovered from the mother liquour. The mother liquour is known as spent-lye. Soap so obtained is
washed with a small amount of water to remove the alkali. After some time it solidifies and then it is cut into
pieces.
(c) Modern method :– Glycerides of fatty acids are hydrolysed by water at higher temperatures in presence of
catalyst to give glycerol and higher fatty acids. These are separated and fatty acids are reacted with NaOH or
Na2CO3 at higher temperature to form its sodium salt. When lime or ZnO are used as catalyst, the method is
known as Itner process and if sulphuric acid or aromatic sulphonic acids are used as catalyst it is called Twitchell
method.
3.3Cleansing Action of Soap

When soap is rubbed with the greasy surface of clothes with water, it forms an emulsion and the dirt particles separate out
from the greasy surface. Soap forms colloidal solution with water, which separate the dirt particles by absorbing
them and escape out on washing with water.
4. DETERGENTS
The synthetic detergents, soapless, deter-gents, soapless soaps or syndets are substitutes of soaps. Unlike soaps,
they are derived from purely synthetic chemicals rather than from chemicals obtained form natural sources like
oils/fats. However, like soaps they contain both hydrophilic (water-soluble) and hydrophobic (oil-soluble) parts.
Synthetic detergents are mainly of two types.
4.1 Sodium alkyl sulphates

These are the half esters of an inorganic acid (H2SO4) rather than an organic acid and a higher primary alcohol, e.g. lauryl
alcohol (C12H25OH). Sodium lauryl sulphate is the most important detergent of this type.

Ex. CH3(CH2)10CH2OSO2ONa sodium lauryl sulphate
4.2 Sodium alkyl aryl sulphates

These are the sodium salts of long chain (linear) alkyl substituted benzene sulphonic acids (LAB) and are most widely used.
The most common is sodium dodecylbenzene sulphate.

Ex. CH3(CH2)10CH2 SO2ONa
Since in these detergents, the active portion is negatively charged, these are commonly known as anionic
detergents.
4.3 Activity of detergents
There are two parts in detergents – one is long chain hydrocarbon part and other is ionic part. Hydrocarbon part is soluble in
oils or greasy materials and insoluble in water while the ionic part is insoluble in oily or greasy substances and
soluble in water. Detergents form colloidal solution in water, the hydrocarbon part of which forms big clusters
with dirt particles and the ionic part goes into water. In this way on washing with water the whole part washes
away with water.
Water
OIL
circle ( ) represents polar group


(COONa) wavy line ( ) represents
non-polar group (R–)
4.4Types of detergents
Detergents are of three types :
,(i) Anionic detergents. These are so called because a large part of their molecules are anions. These are of two types.
(a) Sodium alkyl sulphates. example of this type of detergents is : sodium lauryl sulphate, C11H23CH2OSO3–Na+

C11H23CH2OH ⎯Conc.
⎯⎯→ C11H23CH2OSO3H ⎯NaOH
⎯⎯→ C11H23CH2OSO3Na
H 2SO4
n-Lauryl alcohol n-Lauryl hydrogen sulphate Sodium lauryl sulphate
(b) Alkylbenzenesulphonates. example

CH3–(CH2)11 SO3Na sodium 4-(1-dodecyl)benzenesulphonate (SDS).
Another important example is sod. 4-(2-dodecyl)benzensulphonate

CH3

CH3–(CH2)9–CH SO3Na Sod. 4-(2-dodecyl)bezensulphonate
(ii) Cationic detergents :
e.g.
CH3
 
[CH3(CH2)15N(CH3)3] Br or CH3–(CH2)15–N–CH3 Br Cetyltrimethylammonium bromide
(Cationic detergent used in hair conditioner)
CH3
cetyltrimethylammonium bromide, i.e.,
cetyltrimethylammonium bromide, i.e.,
(iii) Non-ionic detergents :
CH3(CH2)16COOH
e.g. HOCH2–CH2OH + nCH2–CH2 + HO(CH2CH2O)nCH2CH2OH CH3(CH3)16COO(CH2CH2)O)nCH2CHOH
–H2O
O Polyethylene glycol stearate
228

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GOC-I

 Carbon has four valencies.

2. THE FOUR VALENCIES OF CARBON ATOM CAN BE REPRESENTED BY FOLLOWING WAY

Structure  bonds  bonds Hybridisation Shape Bond Angle No. of Bond

4. CLASSIFICATION OF ORGANIC COMPOUNDS

Open chain compounds Closed chain

e.g. CH4, CH3–CH3, CH3–CH2–CH3, CH3–CH2–Br, CH3–OH, CH3–O–CH3 etc.

 Unsaturated compounds having atleast one carbon-carbon multiple bond (= or )

e.g. CH2=CH2, HCCH, HCC–CH3, H2C=CH–CH3, CH2=C=CH2, CH2=CH–CCH, HCC–CCH etc.

having atleast one different atom (O, S, N) in the cycle.

e.g. Benzenoid compounds : n = whole no. = 1,2,3,4…………..

Benzene Naphthalene Anthracene Phenanthrene

e.g. Non-Benzenoid compounds :

e.g. Heterocyclic compounds :

S.No. Name of Series General Formula I-homologue II-homologue

1. Alkane CnH2n+2 CH4 CH3–CH3

2. Alkene CnH2n CH2=CH2 CH2=CH–CH3

3. Alkyne CnH2n–2 HCCH HCC–CH3

4. Halo alkane CnH2n+1X CH3–X CH3–CH2–X

5. Alcohol CnH2n+2O CH3–OH CH3–CH2–OH

6. Ether CnH2n+2O CH3–O–CH3 CH3–O–CH2–CH3

7. Aldehyde CnH2nO H–CHO CH3–CHO

8. Ketone CnH2nO CH3–C–CH3 CH3–C–CH2–CH3

9. Carboxylic acid CnH2nO2 H–COOH CH3–COOH

10. Ester CnH2nO2 H–C–O–CH3 H–C–O–CH2CH3

11. Amide CnH2n+1NO H–CONH2 CH3–CONH2

12. Nitro alkane CnH2n+1NO2 O O

13. Amine CnH2n+3N CH3–NH2 CH3–CH2–NH2

6. NOMENCLATURE OF ORGANIC COMPOUNDS

S.No. Compound Common Name Source

1. CH4 Marsh gas (Fire damp) Marshy places

2. CH3OH Wood spirit (Carbinol) Destructive distillation of wood

3. CH3CH2OH Grain alcohol Grain

4. NH2–C–NH2 Urea (Carbamide) Urine

5. HCOOH Formic acid Formica (Red ants)

6. CH3COOH Acetic acid Acetum (Vinegar)

7. HOOC–COOH Oxalic acid Oxalis plant

8. CH3–CH–COOH Lactic acid Lactum (Milk)

9. CH3CH2CH2COOH Butyric acid Butter

10. HO–CH–COOH Tartaric acid Tamarind

11. HO–CH–COOH Malic acid Malum (Apple)

12. CH2–COOH Citric acid Citron (Lemon)

6.2 SOME FREQUENTLY USED COMMON NAMES (TO BE REMEMBER) :

S.No. Common Name Structure Formula

17. Mesityl oxide (Dimer of acetone)

18. Phorone (Trimer of acetone) CH3–C=CH–C–CH=C–CH3

19. Oxalic acid HOOC–COOH

20 Malonic acid HOOC–CH2–COOH

21. Succinic acid HOOC–(CH2)2–COOH

22. Gluteric acid HOOC–(CH2)3–COOH

23. Adipic acid HOOC–(CH2)4–COOH

24. Pimelic acid HOOC–(CH2)5–COOH

25. Maleic acid H–C–COOH

26. Fumeric acid H–C–COOH

27. Cyanic acid HO–CN

28. Isocyanic acid (Tautomer of cyanic acid) O=C=NH

29. Isourea (Tautomer of urea) H2N–C=NH

30. Chloroform (Anaesthatic agent) CHCl3

31. Chloropicrin (Nitro Chloroform) Cl3C–NO2

32. Chloretone CCl3

33. Pyrene (Fire - extinguisher) CCl4

S.No. Common Name Structure Formula

37. Isoprene CH2=C–CH=CH2

38. Chloroprene CH2=C–CH=CH2