Page 1
147
CHAPTER 12
Organic chemistry : Some Basic Principles and Techniques
Organic compounds are the hydrocarbons and their derivatives and organic
chemistry is that branch of chemistry that deals with the study of these compounds
Tetravalency of carbon
The atomic number of Carbon is 6 and its electronic configuration is 2,4 i.e. it has 4
valence electrons. Thus carbon is always tetracovalent, i.e. it forms 4 covalent
bonds with other atoms
C
Due to tetravalency of carbon it has a tetrahedron shape.
Catenation- The self linking property of carbon is known as catenation. This is the
main reason of existence of such large number of compounds
Classification of organic compounds
Organic compounds
Acyclic Cyclic
Homocyclic heterocyclic
Alicyclic aromatic
Benzenoid non benzenoid
Functional groups:A functional group may be defined as an atom or a group of
atoms present in a molecule which largely determines the chemical properties.
CLASS OF ORGANIC NAME OF FUNCTIONAL STRUCTURE
COMPOUNDS GROUP
Alkenes double bond =C=C=
Alkynes triple bond - C ? C -
Halogens halogen - X ( F,Cl,Br,I )
Alcohols hydroxyl -OH
Aldehydes aldehydic(formyl) -CHO
Carboxylic acids carboxyl -COOH
Acid amides amides -CONH
2
Primary amines amino - NH
2
Page 2
147
CHAPTER 12
Organic chemistry : Some Basic Principles and Techniques
Organic compounds are the hydrocarbons and their derivatives and organic
chemistry is that branch of chemistry that deals with the study of these compounds
Tetravalency of carbon
The atomic number of Carbon is 6 and its electronic configuration is 2,4 i.e. it has 4
valence electrons. Thus carbon is always tetracovalent, i.e. it forms 4 covalent
bonds with other atoms
C
Due to tetravalency of carbon it has a tetrahedron shape.
Catenation- The self linking property of carbon is known as catenation. This is the
main reason of existence of such large number of compounds
Classification of organic compounds
Organic compounds
Acyclic Cyclic
Homocyclic heterocyclic
Alicyclic aromatic
Benzenoid non benzenoid
Functional groups:A functional group may be defined as an atom or a group of
atoms present in a molecule which largely determines the chemical properties.
CLASS OF ORGANIC NAME OF FUNCTIONAL STRUCTURE
COMPOUNDS GROUP
Alkenes double bond =C=C=
Alkynes triple bond - C ? C -
Halogens halogen - X ( F,Cl,Br,I )
Alcohols hydroxyl -OH
Aldehydes aldehydic(formyl) -CHO
Carboxylic acids carboxyl -COOH
Acid amides amides -CONH
2
Primary amines amino - NH
2
148
HOMOLOGOUS SERIES
Homologous series is defined as a family or group of structurally similar organic
compounds all members of which contain the same functional group, show a
gradation in physical and similarity in chemical properties and any two adjacent
members of which differ by -CH
2
group. The individual members of this group are
called homologues and the phenomenon is called homology.
NOMENCLATURE OF ORGANIC COMPOUNDS
Organic chemistry deals with millions of compounds. In order to clearly identify
them, a systematic method of naming known as IUPAC system of nomenclature is
adopted. The names are such that the listener can deduce the structure from it. The
IUPAC name consists of three parts:
Prefix Word root Suffix
EX: 3 methlyoctane
NOMENCLATURE OF ALKANES
Straight chain alkanes:
The names of such compounds is based on their chain structure,and end with suffix
‘-ane’ and carry a prefix indicating the number of carbon atoms present in the chain.
Branched chain hydrocarbons:
1.) The longest carbon chain in the molecule is identified.
2.) The numbering is done in such a way that the branched carbon atoms get the
lowest possible value.
3.) The names of the alkyl groups attached as a branch are then prefixed to the
name of the parent alkane and its position is indicated by numbers.
4.) The lower number is given to the first in alphabetical order.
5.) The carbon atom of the branch that attaches to the root alkane is numbered 1.
Organic compounds having Functional Groups:
The longest chain of carbon atoms containing the functional groups is numbered in
such a way that the functional group attached to the carbon atom gets the lowest
possible number in the chain.
When there are more functional groups then a priority order is followed as:
-COOH, -SO
3
H, -COOR, COCl, -CONH
2
, -CN, -HC=O, =C=O, -OH, -NH
2
, =C=C=,
-C? C-.
ISOMERISM
Two or more compounds having the same molecular formula but different physical
and chemical properties are called isomers and this phenomenon is called isomerism.
Page 3
147
CHAPTER 12
Organic chemistry : Some Basic Principles and Techniques
Organic compounds are the hydrocarbons and their derivatives and organic
chemistry is that branch of chemistry that deals with the study of these compounds
Tetravalency of carbon
The atomic number of Carbon is 6 and its electronic configuration is 2,4 i.e. it has 4
valence electrons. Thus carbon is always tetracovalent, i.e. it forms 4 covalent
bonds with other atoms
C
Due to tetravalency of carbon it has a tetrahedron shape.
Catenation- The self linking property of carbon is known as catenation. This is the
main reason of existence of such large number of compounds
Classification of organic compounds
Organic compounds
Acyclic Cyclic
Homocyclic heterocyclic
Alicyclic aromatic
Benzenoid non benzenoid
Functional groups:A functional group may be defined as an atom or a group of
atoms present in a molecule which largely determines the chemical properties.
CLASS OF ORGANIC NAME OF FUNCTIONAL STRUCTURE
COMPOUNDS GROUP
Alkenes double bond =C=C=
Alkynes triple bond - C ? C -
Halogens halogen - X ( F,Cl,Br,I )
Alcohols hydroxyl -OH
Aldehydes aldehydic(formyl) -CHO
Carboxylic acids carboxyl -COOH
Acid amides amides -CONH
2
Primary amines amino - NH
2
148
HOMOLOGOUS SERIES
Homologous series is defined as a family or group of structurally similar organic
compounds all members of which contain the same functional group, show a
gradation in physical and similarity in chemical properties and any two adjacent
members of which differ by -CH
2
group. The individual members of this group are
called homologues and the phenomenon is called homology.
NOMENCLATURE OF ORGANIC COMPOUNDS
Organic chemistry deals with millions of compounds. In order to clearly identify
them, a systematic method of naming known as IUPAC system of nomenclature is
adopted. The names are such that the listener can deduce the structure from it. The
IUPAC name consists of three parts:
Prefix Word root Suffix
EX: 3 methlyoctane
NOMENCLATURE OF ALKANES
Straight chain alkanes:
The names of such compounds is based on their chain structure,and end with suffix
‘-ane’ and carry a prefix indicating the number of carbon atoms present in the chain.
Branched chain hydrocarbons:
1.) The longest carbon chain in the molecule is identified.
2.) The numbering is done in such a way that the branched carbon atoms get the
lowest possible value.
3.) The names of the alkyl groups attached as a branch are then prefixed to the
name of the parent alkane and its position is indicated by numbers.
4.) The lower number is given to the first in alphabetical order.
5.) The carbon atom of the branch that attaches to the root alkane is numbered 1.
Organic compounds having Functional Groups:
The longest chain of carbon atoms containing the functional groups is numbered in
such a way that the functional group attached to the carbon atom gets the lowest
possible number in the chain.
When there are more functional groups then a priority order is followed as:
-COOH, -SO
3
H, -COOR, COCl, -CONH
2
, -CN, -HC=O, =C=O, -OH, -NH
2
, =C=C=,
-C? C-.
ISOMERISM
Two or more compounds having the same molecular formula but different physical
and chemical properties are called isomers and this phenomenon is called isomerism.
149
Chain isomerism: When two or more compounds having same molecular formula
but different carbon skeletons are referred to as chain isomers.
Position Isomerism : Compounds which have the same structure of carbon chain but
differ in position of double or triple bonds or functional group are called position
isomers and this phenomenon is called Position Isomerism. e g
CH
3
-CH
2
-CH=CH
2
CH
3
-CH = CH – CH
3
Functional Isomerism :Compounds which have the same molecular formula but
different functional group are called functional isomers and this phenomenon is
called functional Isomerism. e g
CH
3
– CH
2
– OH CH
3
– O – CH
3
Metamerism:It is due to the presence of different alkyl groups on either side of
functional group in the molecule. Ex. C
4
H
10
O represents C
2
H
5
OC
2
H
5
and
CH
3
OC
3
H
7
.
FISSION OF COVALENT BOND
Heterolytic cleavage: In this cleavage the bond breaks in such a way that the shared
pair of electron remains with one of the fragments.
H
3
C – Br
+
CH
3
+ Br
-
Homolytic Cleavage: In this cleavage the shared pair of electron goes with each of
the bonded atom.
R – X R
.
+ X
.
Alkyl free radical
Nucleophiles : A reagent that brings an electron pair is called nucleophile ie nucleus
seeking e g -OH , -CN
Electrophiles: A reagent that takes away electron pair is called electrophile I e
electron seeking e g > C= O , R
3
C – X
Inductive Effect: The displacement of the electron along the chain of the carbon
atoms due to presence of an atom or group at the end of the chain.
Page 4
147
CHAPTER 12
Organic chemistry : Some Basic Principles and Techniques
Organic compounds are the hydrocarbons and their derivatives and organic
chemistry is that branch of chemistry that deals with the study of these compounds
Tetravalency of carbon
The atomic number of Carbon is 6 and its electronic configuration is 2,4 i.e. it has 4
valence electrons. Thus carbon is always tetracovalent, i.e. it forms 4 covalent
bonds with other atoms
C
Due to tetravalency of carbon it has a tetrahedron shape.
Catenation- The self linking property of carbon is known as catenation. This is the
main reason of existence of such large number of compounds
Classification of organic compounds
Organic compounds
Acyclic Cyclic
Homocyclic heterocyclic
Alicyclic aromatic
Benzenoid non benzenoid
Functional groups:A functional group may be defined as an atom or a group of
atoms present in a molecule which largely determines the chemical properties.
CLASS OF ORGANIC NAME OF FUNCTIONAL STRUCTURE
COMPOUNDS GROUP
Alkenes double bond =C=C=
Alkynes triple bond - C ? C -
Halogens halogen - X ( F,Cl,Br,I )
Alcohols hydroxyl -OH
Aldehydes aldehydic(formyl) -CHO
Carboxylic acids carboxyl -COOH
Acid amides amides -CONH
2
Primary amines amino - NH
2
148
HOMOLOGOUS SERIES
Homologous series is defined as a family or group of structurally similar organic
compounds all members of which contain the same functional group, show a
gradation in physical and similarity in chemical properties and any two adjacent
members of which differ by -CH
2
group. The individual members of this group are
called homologues and the phenomenon is called homology.
NOMENCLATURE OF ORGANIC COMPOUNDS
Organic chemistry deals with millions of compounds. In order to clearly identify
them, a systematic method of naming known as IUPAC system of nomenclature is
adopted. The names are such that the listener can deduce the structure from it. The
IUPAC name consists of three parts:
Prefix Word root Suffix
EX: 3 methlyoctane
NOMENCLATURE OF ALKANES
Straight chain alkanes:
The names of such compounds is based on their chain structure,and end with suffix
‘-ane’ and carry a prefix indicating the number of carbon atoms present in the chain.
Branched chain hydrocarbons:
1.) The longest carbon chain in the molecule is identified.
2.) The numbering is done in such a way that the branched carbon atoms get the
lowest possible value.
3.) The names of the alkyl groups attached as a branch are then prefixed to the
name of the parent alkane and its position is indicated by numbers.
4.) The lower number is given to the first in alphabetical order.
5.) The carbon atom of the branch that attaches to the root alkane is numbered 1.
Organic compounds having Functional Groups:
The longest chain of carbon atoms containing the functional groups is numbered in
such a way that the functional group attached to the carbon atom gets the lowest
possible number in the chain.
When there are more functional groups then a priority order is followed as:
-COOH, -SO
3
H, -COOR, COCl, -CONH
2
, -CN, -HC=O, =C=O, -OH, -NH
2
, =C=C=,
-C? C-.
ISOMERISM
Two or more compounds having the same molecular formula but different physical
and chemical properties are called isomers and this phenomenon is called isomerism.
149
Chain isomerism: When two or more compounds having same molecular formula
but different carbon skeletons are referred to as chain isomers.
Position Isomerism : Compounds which have the same structure of carbon chain but
differ in position of double or triple bonds or functional group are called position
isomers and this phenomenon is called Position Isomerism. e g
CH
3
-CH
2
-CH=CH
2
CH
3
-CH = CH – CH
3
Functional Isomerism :Compounds which have the same molecular formula but
different functional group are called functional isomers and this phenomenon is
called functional Isomerism. e g
CH
3
– CH
2
– OH CH
3
– O – CH
3
Metamerism:It is due to the presence of different alkyl groups on either side of
functional group in the molecule. Ex. C
4
H
10
O represents C
2
H
5
OC
2
H
5
and
CH
3
OC
3
H
7
.
FISSION OF COVALENT BOND
Heterolytic cleavage: In this cleavage the bond breaks in such a way that the shared
pair of electron remains with one of the fragments.
H
3
C – Br
+
CH
3
+ Br
-
Homolytic Cleavage: In this cleavage the shared pair of electron goes with each of
the bonded atom.
R – X R
.
+ X
.
Alkyl free radical
Nucleophiles : A reagent that brings an electron pair is called nucleophile ie nucleus
seeking e g -OH , -CN
Electrophiles: A reagent that takes away electron pair is called electrophile I e
electron seeking e g > C= O , R
3
C – X
Inductive Effect: The displacement of the electron along the chain of the carbon
atoms due to presence of an atom or group at the end of the chain.
150
?+++ ? ++ ?+
CH
3
- C H
2
CH
2
Cl
Resonance Effect : The polarity produced in the molecule by the interaction of two
pi bonds or between a pi bond and lone pair of electron present on an adjacent atom.
There are two types of resonance effect:
1) Positive resonance effect : In this effect the transfer of electrons is away from
an atom or substituent group attached to the conjugated system.
The atoms or groups which shows +R effect are halogens,-OH , -OR,-
NH
2
2) Negative resonance effect : In this effect the transfer of electrons is towards
the atom or substituent group attached to the conjugated system.
The atoms or groups which shows -R effect are –COOH , -CHO , -CN
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS :
Sublimation : This method is used to separate the sublimable compounds from non
sublimable compounds.
Crystallisation: This method is based on the difference in the solubilities of
compound and impurities in a suitable solvent. The impure compound is dissolved in
solvent at heated at higher temp .on cooling the hot and conc solution pure
compounds crystallizes out.
Distillation: This method is used to separate volatile liquids from non volatile liquids
and liquids having sufficient difference in their boiling points.
Fractional distillation: If the boiling points of two liquids is not much , they are
separated by this method.
Distillation under reduced pressure : This method is used to purify liquids having
high boiling points and decomposes at or below their boiling points.
Steam distillation : This method is used to separate substances which are steam
volatile and are immiscible with water.
Differential Extraction: When an organic compound is present in an aqueous
medium it is separated by shaking it with organic solvent in which it is more soluble
than in water. The aqueous solution is mixed with organic solvent in a separating
funnel and shaken for sometimes and then allowed to stand for some time .when
organic solvent and water form two separate layers the lower layer is run out by
opening the tap of funnel and organic layer is separated. the process is repeated
several times and pure organic compound is separated.
Chromatography :This technique is used to separate mixtures in to their
components ,purify the compounds and test the purity of compounds.It is classified
as
Page 5
147
CHAPTER 12
Organic chemistry : Some Basic Principles and Techniques
Organic compounds are the hydrocarbons and their derivatives and organic
chemistry is that branch of chemistry that deals with the study of these compounds
Tetravalency of carbon
The atomic number of Carbon is 6 and its electronic configuration is 2,4 i.e. it has 4
valence electrons. Thus carbon is always tetracovalent, i.e. it forms 4 covalent
bonds with other atoms
C
Due to tetravalency of carbon it has a tetrahedron shape.
Catenation- The self linking property of carbon is known as catenation. This is the
main reason of existence of such large number of compounds
Classification of organic compounds
Organic compounds
Acyclic Cyclic
Homocyclic heterocyclic
Alicyclic aromatic
Benzenoid non benzenoid
Functional groups:A functional group may be defined as an atom or a group of
atoms present in a molecule which largely determines the chemical properties.
CLASS OF ORGANIC NAME OF FUNCTIONAL STRUCTURE
COMPOUNDS GROUP
Alkenes double bond =C=C=
Alkynes triple bond - C ? C -
Halogens halogen - X ( F,Cl,Br,I )
Alcohols hydroxyl -OH
Aldehydes aldehydic(formyl) -CHO
Carboxylic acids carboxyl -COOH
Acid amides amides -CONH
2
Primary amines amino - NH
2
148
HOMOLOGOUS SERIES
Homologous series is defined as a family or group of structurally similar organic
compounds all members of which contain the same functional group, show a
gradation in physical and similarity in chemical properties and any two adjacent
members of which differ by -CH
2
group. The individual members of this group are
called homologues and the phenomenon is called homology.
NOMENCLATURE OF ORGANIC COMPOUNDS
Organic chemistry deals with millions of compounds. In order to clearly identify
them, a systematic method of naming known as IUPAC system of nomenclature is
adopted. The names are such that the listener can deduce the structure from it. The
IUPAC name consists of three parts:
Prefix Word root Suffix
EX: 3 methlyoctane
NOMENCLATURE OF ALKANES
Straight chain alkanes:
The names of such compounds is based on their chain structure,and end with suffix
‘-ane’ and carry a prefix indicating the number of carbon atoms present in the chain.
Branched chain hydrocarbons:
1.) The longest carbon chain in the molecule is identified.
2.) The numbering is done in such a way that the branched carbon atoms get the
lowest possible value.
3.) The names of the alkyl groups attached as a branch are then prefixed to the
name of the parent alkane and its position is indicated by numbers.
4.) The lower number is given to the first in alphabetical order.
5.) The carbon atom of the branch that attaches to the root alkane is numbered 1.
Organic compounds having Functional Groups:
The longest chain of carbon atoms containing the functional groups is numbered in
such a way that the functional group attached to the carbon atom gets the lowest
possible number in the chain.
When there are more functional groups then a priority order is followed as:
-COOH, -SO
3
H, -COOR, COCl, -CONH
2
, -CN, -HC=O, =C=O, -OH, -NH
2
, =C=C=,
-C? C-.
ISOMERISM
Two or more compounds having the same molecular formula but different physical
and chemical properties are called isomers and this phenomenon is called isomerism.
149
Chain isomerism: When two or more compounds having same molecular formula
but different carbon skeletons are referred to as chain isomers.
Position Isomerism : Compounds which have the same structure of carbon chain but
differ in position of double or triple bonds or functional group are called position
isomers and this phenomenon is called Position Isomerism. e g
CH
3
-CH
2
-CH=CH
2
CH
3
-CH = CH – CH
3
Functional Isomerism :Compounds which have the same molecular formula but
different functional group are called functional isomers and this phenomenon is
called functional Isomerism. e g
CH
3
– CH
2
– OH CH
3
– O – CH
3
Metamerism:It is due to the presence of different alkyl groups on either side of
functional group in the molecule. Ex. C
4
H
10
O represents C
2
H
5
OC
2
H
5
and
CH
3
OC
3
H
7
.
FISSION OF COVALENT BOND
Heterolytic cleavage: In this cleavage the bond breaks in such a way that the shared
pair of electron remains with one of the fragments.
H
3
C – Br
+
CH
3
+ Br
-
Homolytic Cleavage: In this cleavage the shared pair of electron goes with each of
the bonded atom.
R – X R
.
+ X
.
Alkyl free radical
Nucleophiles : A reagent that brings an electron pair is called nucleophile ie nucleus
seeking e g -OH , -CN
Electrophiles: A reagent that takes away electron pair is called electrophile I e
electron seeking e g > C= O , R
3
C – X
Inductive Effect: The displacement of the electron along the chain of the carbon
atoms due to presence of an atom or group at the end of the chain.
150
?+++ ? ++ ?+
CH
3
- C H
2
CH
2
Cl
Resonance Effect : The polarity produced in the molecule by the interaction of two
pi bonds or between a pi bond and lone pair of electron present on an adjacent atom.
There are two types of resonance effect:
1) Positive resonance effect : In this effect the transfer of electrons is away from
an atom or substituent group attached to the conjugated system.
The atoms or groups which shows +R effect are halogens,-OH , -OR,-
NH
2
2) Negative resonance effect : In this effect the transfer of electrons is towards
the atom or substituent group attached to the conjugated system.
The atoms or groups which shows -R effect are –COOH , -CHO , -CN
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS :
Sublimation : This method is used to separate the sublimable compounds from non
sublimable compounds.
Crystallisation: This method is based on the difference in the solubilities of
compound and impurities in a suitable solvent. The impure compound is dissolved in
solvent at heated at higher temp .on cooling the hot and conc solution pure
compounds crystallizes out.
Distillation: This method is used to separate volatile liquids from non volatile liquids
and liquids having sufficient difference in their boiling points.
Fractional distillation: If the boiling points of two liquids is not much , they are
separated by this method.
Distillation under reduced pressure : This method is used to purify liquids having
high boiling points and decomposes at or below their boiling points.
Steam distillation : This method is used to separate substances which are steam
volatile and are immiscible with water.
Differential Extraction: When an organic compound is present in an aqueous
medium it is separated by shaking it with organic solvent in which it is more soluble
than in water. The aqueous solution is mixed with organic solvent in a separating
funnel and shaken for sometimes and then allowed to stand for some time .when
organic solvent and water form two separate layers the lower layer is run out by
opening the tap of funnel and organic layer is separated. the process is repeated
several times and pure organic compound is separated.
Chromatography :This technique is used to separate mixtures in to their
components ,purify the compounds and test the purity of compounds.It is classified
as
151
Adsorption Chromatography : It is based on the fact that different compounds are
adsorbed on an adsorbent to different degrees. Silica jel or alumina is used as
adsorbents.
Partition Chromatography : It is based on the continuous differential portioning of
components of a mixture between stationary and mobile phase.
QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS
Detection of Carbon and Hydrogen: The Carbon and Hydrogen present in the
Organic compound is detected by heating the compound with Copper II oxide in a
hard glass tube when carbon present in the compound is oxidized to CO2 which can
be tested with lime Water and Hydrogenis converted to water which can be tested
with anhydrous copper sulphate which turns blue.
C + CuO 2Cu + CO
2
2 H +CuO Cu + H2O
CO
2
+Ca (OH )
2
CaCO
3
+ H
2
O
5H
2
O + CuSO
4
CuSO
4
.5H
2
O
DETECTION OF OTHER ELEMENTS
Sodium Fusion Extract: A small piece of dry Sodium metal is heated with a organic
compound in a fusion tube for 2 -3 minutes and the red hot tube is plunged in to
distilled water contained in a china dish. The contained of the china dish is boiled
,cooled and filtered. The filtrate is known as Sodium fusion extract.
Test for Nitrogen : The sodium fusion extract is boiled with iron II sulphate and
then acidified with Concsulphuric acid , the formation of Prussian blue colour
confirms the presence of nitrogen.
6CN
-
+ Fe
2+
[Fe(CN)
6
]
4-
3[Fe(CN)
6
]
4-
+ 4Fe
3+ xH
2
O
Fe
4
[Fe(CN)
6
]
3
.xH
2
O
Test for Sulphur: the sodium fusion extract is acidified with acetic acid and lead
acetate is added to it. A black precipitate of lead sulphide indicates the presence of
sulphur. S
2-
+ Pb
2+
PbS
Black
Test for halogens:The sodium fusion extract is acidified with nitric acid and then
treated with silver nitrate. A white precipitate, soluble in ammonium hydroxide
shows the presence of chlorine, a yellowish ppt. sparingly soluble in ammonium
hydroxide shows the presence of bromine, a yellowish ppt. insoluble in ammonium
hydroxide shows the presence of iodine.
X
-
+ Ag
+
AgX
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