Organic Chemistry

Organic Chemistry

It is the chemistry of specific carbon compounds except oxides, carbonates and carbides.

Hydrocarbons

Organic compounds composed of carbon and hydrogen only.

Examples: Methane (CH4), ethane (C2H6)

Unique Nature of Carbon

Tetravalency of Carbon
 Carbon forms four covalent bonds by mutually sharing its four electrons with other atoms.
 It is hence tetravalent or exhibits tetravalency.

Catenation
 It is the tendency of an element to form chains of identical atoms.
 Catenation is maximum in carbon because the value of the C–C bond energy is maximum.
 Carbon undergoes self-linking forming straight, branched and closed chains.

 Catenation and tetravalency also result in the formation of single, double and triple bonds.
Classification of Organic Compounds

Homologous Series

It is a group of organic compounds with a similar structure and similar chemical properties in which the
successive compounds differ by a CH2 group.

Characteristics of a homologous series

i. Each member of the series differs from the preceding one by the addition of a CH2 group and by 14
amu.
ii. All members of a homologous series share a general formula.
For example, the general formula for alkane is CnH2n+2 and that for alkene is CnH2n.
iii. The physical properties of the members show gradation in properties as molecular mass increases.
iv. The chemical properties also show gradient similarity.
For example, methane and ethane react with chlorine to form methyl chloride and ethyl chloride,
respectively.
CH4 + Cl2 → CH3Cl
C2H6 + Cl2 → C2H5Cl
v. All members of a homologous series can be prepared by the same general method of preparation.
For example, alcohols can be prepared from alkyl halides.

Significance of a Homologous Series

i. Helps in the systematic study of organic compounds.
ii. Predicts the properties and the nature of other elements of the series if the same is known of the first
few members.
Isomers

Compounds with the same molecular formula but different structural formula are known as isomers, and
the phenomenon is known as isomerism.
Examples: Butane and isobutane are two different compounds with the same molecular formula C 4H10.

Butane Isobutane

Causes of Isomerism
i. Difference in the mode of linking of atoms.
ii. Difference in the arrangement of atoms or groups in space.

Different Types of Structural Isomerism

i. Chain isomerism
Two or more compounds which have a similar molecular formula but different arrangement of
carbon atoms in straight or branched chains are referred to as chain isomers, and the
phenomenon is known as chain isomerism.

ii. Position isomerism

When two or more compounds with the same molecular formula differ in the position of the
substituent atom or functional group on the carbon atom, they are called position isomers, and the
phenomenon is known as position isomerism.
 iii. Functional isomerism
Two or more compounds with the same molecular formula but different functional groups are called
functional isomers, and the phenomenon is known as functional isomerism.

iv. Metamerism
It arises because of unequal distribution of alkyl groups on either side of the functional groups in
the molecules.

Nomenclature

It is the system of assigning names to organic compounds.

The Systems of Nomenclature Are

i. Trivial system
ii. IUPAC (International Union of Pure and Applied Chemistry) system

According to the IUPAC system, the name of an organic compound consists of three parts:
i. Root word
ii. Suffix
iii. Prefix

i. Root word
It depends on the number of carbon atoms present in the longest carbon chain selected.

Number of carbon atoms Root word

One carbon atom C1 Meth
Two carbon atoms C2 Eth
Three carbon atoms C3 Prop
Four carbon atoms C4 But
Five carbon atoms C5 Pent
Six carbon atoms C6 Hex
Seven carbon atoms C7 Hept
Eight carbon atoms C8 Oct
Nine carbon atoms C9 Non
Ten carbon atoms C10 Dec

ii. Suffix
The root word is followed by an appropriate suffix, which represents the nature of the bond in a
carbon–carbon atom.
Nature of bond Suffix General name General formula
Single bond (C–C) -ane Alkane CnH2n+2
Double bond (C=C) -ene Alkene CnH2n
Triple bond ( ) -yne Alkyne CnH2n−2
Group (R-) -yl Alkyl CnH2n+1

iii. Prefix
It denotes the substituent, alkyl or functional group and its position in the carbon chain.
Di-, tri- and tetra- are used for two, three and four groups of the same type, respectively.
Functional Group

It is an atom or a group of atoms which defines the structure (or the properties of a particular family) of
organic compounds.

Characteristics of a Functional Group

i. Compounds of the same functional group are identified using the same types of tests.
ii. The physical and chemical properties of the compounds of different functional groups are different.
iii. There exists a homologous series of compounds containing a particular type of functional group.

Functional General Organic Suffix Examples with common and IUPAC

group formulae compound name
Halide R–X Haloalkanes ane CH3Cl
–X Common name: Methyl chloride
(F, Cl, Br, I) IUPAC name: Chloromethane
Hydroxyl R–OH Alcohols ol C2H5OH
–OH Common name: Ethyl alcohol
IUPAC name: Ethanol
Aldehyde Aldehydes al CH3CHO
–CHO Common name: Acetaldehyde
IUPAC name: Ethanal
Carboxyl Carboxylic oic CH3CH2COOH
–COOH acids acid Common name: Propionic acid
IUPAC name: Propanoic acid
Ketones one CH3COC2H5
Common name: Diethyl ketone
Keto IUPAC name: Pentanone
Ethers R–O–R′ Ethers oxy CH3–O–C2H5
Common name: Ethyl methyl ether
IUPAC name: Methoxy ethane

Alkanes

 Alkanes are hydrocarbons in which all the linkages between the carbon atoms are single covalent
bonds.
 Compounds are known as saturated hydrocarbons because all the four valencies of carbon are fully
satisfied.
 General formula : CnH2n+2
 These hydrocarbons are relatively unreactive under ordinary conditions so they are also called
paraffins.
Isomerism in Alkanes
 Alkanes with more than three carbon atoms form isomers.
 The various isomers differ in the framework of the carbon chains.
Example:
Isomers of Pentane (C5H12)

n-pentane isopropane neo-pentane

Laboratory Preparation of Methane and Ethane

CH3COONa + NaOH Na2CO3 + CH4

C2H5COONa + NaOH Na2CO3 + C2H6

Methods of Preparation of Methane and Ethane

1. From iodomethane or bromoethane:

CH3I + 2[H] → CH4 + HI
C2H5I + 2[H] → C2H6 + HI

2. Methane is produced on addition of water to aluminium carbide at room temperature.

Al4C3 + 12H2O → 3CH4 + 4Al (OH)3

3. Ethane from alkyl halides:

2CH3I + 2Na CH3–CH3 + 2NaI
This reaction is known as the Wurtz reaction.

Chemical Properties
1. Substitution reaction
(i) Reaction with halogens

CH4 + Cl2 CH3Cl + HCl

CH3Cl + Cl2 → CH2Cl2 + HCl
CH2Cl2 + Cl2 → CHCl3 + HCl
CHCl3 + Cl2 → CCl4 + HCl
(Carbon tetrachloride)
 (ii) Reaction with oxygen
CH4 + 2O2 →CO2 + 2H2O
2C2H6 + 7O2 →4CO2 + 6H2O

Insufficient supply of air

2CH4 + 3O2 →2CO + 4H2O
2C2H6 + 5O2 →4CO + 6H2O

2. Cracking or Pyrolysis
2CH4 CH CH +3H2

CH3–CH3 CH2=CH2 + H2

3. Catalytic oxidation of alkanes

2CH4 + O2 2CH3OH

2C2H6 + O2 2C2H5OH
CH4 +O2 HCHO + H2O
C2H6 + O2 CH3CHO + H2O

4. Slow combustion

CH4 CH3OH HCHO HCOOH

Alkenes

 Alkenes are unsaturated aliphatic hydrocarbons containing a carbon–carbon double bond.

 They are also called olefins because of their tendency to form oily products.
 The general formula of alkenes is CnH2n.

Structure of Ethene

Electronic structure Structural formula (C2H4)

 Two carbon atoms linked by a double covalent bond.

 A double covalent bond is formed by sharing of two pairs of electrons between the two carbon atoms.
 Four C–H single covalent bonds and one C=C double covalent bond.
 It is a planar molecule and all bond angles (H–C–H and H–C=C) are of 120°.
Preparation of Ethene
i. Dehydration of ethyl alcohol

CH2 =CH2 + H2O

ii. Dehydrohalogenation of ethyl bromide

+ KOH CH2=CH2 + KBr + H2O

(alcoholic)

iii. Cracking of methane

CH3–CH3 CH2=CH2 + H2

Chemical properties
1. Addition Reactions
(i) Catalytic hydrogenation

CH2=CH2 + H2 C2H6

(ii) Halogenation

CH2=CH2 + Cl2 (1,2-dichlorethane)

(iii) Reaction with Halogen Acids

CH2=CH2 + HBr → (bromoethane)

(iv) Reaction with Sulphuric acid

CH2=CH2 + H. HSO4 → (ethyl hydrogen sulphate)

(v) Ozone

CH2=CH2 + O3 (ethylene ozonide)

 (vi) Oxidation

CH2=CH2 + H–O–H + [O] → (1,2-ethanediol)

Cold alkaline
KMnO4 solution
C2H4 + 3O2 → 2CO2 + 2H2O + Heat

(vii) Polymerisation

n CH2=CH2 (polyethylene)

Alkynes

 Alkynes are unsaturated aliphatic hydrocarbons containing a carbon–carbon triple bond in their
molecule.
 The general formula of alkynes is CnH2n−2.
 They are more reactive than alkenes because of the presence of a triple bond, often referred to as an
acetylenic linkage.

Structural formula of Ethyne

Electronic structure Structural formula (CH2=CH2)

Preparation of Ethyne
i. Laboratory preparation from calcium carbide

+ 2H–OH → + Ca(OH)2

ii. From 1,2-dibromoethane

+ 2KOH + 2KBr + 2H2O

iii. From methane

2CH4 + 3H2
Chemical Properties
1. Addition Reactions
a] Catalytic Hydrogenation

+ H2 CH2=CH2 + H2 C2H6

b] Halogenation

+ Cl2 + Cl2 →

c] Reaction with Halogen Acids

+ HBr → + HBr →

d] Ozone

+ O3 → (acetylene ozonide)

e] Oxidation of ethyne (Combustion)

2 + 5O2 → 4CO2 + 2H2O + Heat

Alcohols

 Alcohols are hydroxyl derivatives of alkanes obtained by replacement of one, two or three hydrogen
atoms of alkanes by the corresponding number of –OH groups.
 The hydroxyl group is the functional group of alcohols.
 The general molecular formula of alcohols is CnH2n+1 OH.

Preparation of Ethanol
(i) Laboratory preparation by hydrolysis of alkyl halides
C2H5Cl + NaOH (aq) C2H5OH + NaCl

(ii) Industrial Method

(a) Hydration of Ethene

C2H4 + H2SO4 C2H5HSO4

C2H5HSO4 + H2O →C2H5OH + H2SO4

(b) Fermentation of Carbohydrates

C12H22O11 + H2O C6H12O6 + C6H12O6

C6H12O6 2C2H5OH + 2CO2

Chemical properties
1. Combustion
C2H5OH + 3O2 → 2CO2 + 3H2O

2. Oxidation with K2Cr2O7

C2H5OH CH3CHO CH3COOH (acetic acid)

3. Reaction with Sodium

2C2H5OH + 2Na →2C2H5ONa + H2
4. Reaction with Acetic acid
C2H5OH + CH3COOH → CH3COOC2H5 + H2O

5. Reaction with Sulphuric acid

C2H5OH CH2=CH2 + H2O

2C2H5OH C2H5 –O – C2H5 + H2O

6. Reaction with PCl3

3C2H5OH + PCl3 → 3C2H5Cl + H3PO3
Carboxylic Acids

 Carboxylic acids are organic compounds containing a carboxylic group (–COOH) attached to an alkyl
group or to a hydrogen atom.
 Representation of carboxylic acids: R-COOH (R is either –H or alkyl)
 The functional group of carboxylic acids: –COOH (carboxylic)
 The acidic character in carboxylic acids is because of the presence of the replaceable hydrogen atom
in the carboxylic group.

Preparation of Acetic Acid

A] By oxidation of ethyl alcohol

C2H5OH + [O] CH3CHO + H2O

CH3CHO+ [O] CH3COOH

B] By hydrolysis of ethyl acetate

CH3COOC2H5 + H2O CH3COOH + C2H5OH

Chemical Properties
1. It is a weak acid and turns blue litmus red.

2. Reaction with Alkalis

CH3COOH + NaOH → CH3COONa + H2O
CH3COOH + NH4OH → CH3COONH4 + H2O

3. Reaction with Carbonates

2CH3COOH + Na2CO3 →2CH3COONa + H2O + CO2
CH3COOH + NaHCO3→CH3COONa + H2O + CO2

4. Reaction with Alcohols

CH3COOH + C2H5OH CH3COOC2H5 + H2O

5. Reaction with PCl3

CH3COOH + PCl5 → CH3COCl + POCl3 + HCl

6. Reduction
CH3COOH + 4[H] →C2H5OH + H2O