Module 7: Aliphatic Hydrocarbons

Older chemists classified hydrocarbons as either aliphatic or aromatic. The classification was done
based on their source and properties. As such, it was found out that Aliphatic hydrocarbons were
derived from chemical degradation of fats or oils whereas aromatic hydrocarbons contained
substances that were a result of chemical degradation of certain plant extracts. However, today we
classify hydrocarbons on the basis of structure and not merely on the origin.

Types of Hydrocarbons

• Saturated Hydrocarbons: In these compounds, carbon-carbon atoms and carbon-hydrogen atoms

are held together by single bonds. These single bonded compounds are the simplest
hydrocarbons. These types of hydrocarbons don’t have double or triple bonds. In terms
of hybridization, they have Sp3 hybridised carbon atom with no Sp2 or Sp hybridised carbon
atoms. They are together called alkanes which have a general formula CnH2n+2. For example,
CH4C3H6.

• Unsaturated Hydrocarbons: These compounds consist of a single, double or a triple bond between
carbon-carbon atoms. The double-bonded compounds are called alkenes and the triple bonded
compounds are called alkynes. The general formula for alkenes is CnH2n and for alkynes the
general formula is CnH2n-2.

• Cycloalkanes: These hydrocarbons possess one or multiple carbon rings. The hydrogen atom is
attached to the carbon ring.

• Aromatic Hydrocarbons: These are also called arenes. Arenes are compounds which consist of at
least one aromatic ring.

• Aliphatic Hydrocarbons: They are straight chain structures having no rings in them.

• Alicyclic Hydrocarbons: They are hydrocarbons having a ring structure in them. The carbons atoms
can be Sp, Sp2 or Sp3 hybridised.

Physical Properties

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Alkanes with 10 C-atoms or less are generally gases at room temperatures more than 10 C-atoms, the
molecules are gases or liquid. Alkanes generally have low boiling and melting points owing to their weak
Vanderwal’s interaction.

Boiling point depends on the following factors:

Molecular mass

Branching

Alkanes having high molecular mass and high boiling points. Eg: C2H6 has more boiling point than CH4

Alkanes having the same molecular mass but having a different number of branches, the one with less
branching has more boiling point this is because of the Vanderwal’s force weak on as area increases.

For example, CH3-CH2-CH2-CH3 has more boiling point. Alkanes are very feebly soluble in water but they
are soluble in non-polar solvents such as Benzene, CCl4, etc.

Reaction of Alkanes

Alkanes are referred to as paraffins, a name derived from the Latin parum affinis ( not enough affinity).
The name was given to alkanes to describe the low reactivity of alkanes or inertness towards common
reagents. However, alkanes do react with halogens and with oxygen under the proper conditions.

Combustion of Alkanes

The reaction of alkanes with oxygen to form carbon dioxide and water and to generate heat is probably
the most important reaction of alkanes in terms of practical use in the home and in industry. The
general overall reaction for the complete combustion of an alkane is given below.

CnH2n+2 + 3n+1/2O2 ----- > nCO2 + (n+1)H2O + heat

The quantity of heat evolved when one mole of a hydrocarbon undergoes complete combustion is called
the heat of combustion; it is simply dH of the reaction excluding the minus sign.

Halogenation of Alkanes

In the presence of light or heat, alkanes react with halogens to yield alkyl halides.

CH4 + X2 ------ uv light-→ CH3X + HX

The reactivity of the halogens follow the order F2>Cl2>Cr2>I2. In the laboratory, only Cl2 andBr2 are
used for halogenation for the reason that F2 is too reactive and uncontrollable while I2 is too unreactive
and so may not react at all.

Halogenation involves the substitution of a hydrogen atom in an alkane by a halogen. Let us see how
this substitution reaction takes place.

Mechanism of free-radical halogenation

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Reactions of Alkenes and Alkynes
Carbon–carbon double and triple bonds are the functional groups of alkenes and alkynes, respectively. The simplest
alkene is ethene (ethylene) which acts as a plant hormone controlling the maturation of flowers
and fruit; it is also an important source of industrial chemicals. Characteristic flavours and fragrances of plants and
trees are often due to terpenes, which are a class of naturally occurring compounds, very many of which are alkenes.
Compounds used by insects for communication are called pheromones and many of these are also alkenes. Alkynes
are rather rare in nature, but one (ichthyothereol) is the active constituent of the leaves of a family of flowering
plants (ichthyothere) found in South and Central America which are toxic to animals, especially to fi sh. Ethyne itself
is used industrially to produce a high-temperature flame in oxyacetylene welding.

Electrophilic Addition to Alkenes and Alkynes

The π electrons associated with multiple bonds are less tightly bound and more diffuse than σ electrons, so are more
susceptible to attack by an electrophile. In other words, simple alkenes are nucleophilic (although only weakly so compared
with most anions and molecules with lone pairs) and electrophilic addition to the double bond is their most general and
characteristic reaction. An electrophile fi rst forms a new σ bond to one of the sp 2 carbons of the alkene; this gives a
carbenium ion intermediate which is then captured by a nucleophile to complete the addition.

Mechanism of Electrophilic Addition

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Conjugate Addition
Buta-1,3-diene has conjugated double bonds, and undergoes a distinctive reaction with electrophilic reagents. For example, HCl
yields an addition product with a migrated double bond besides the expected product.

The reaction at lower temperatures, when the ratio of products is determined by the rates of their formation from the common
intermediate, is said to be kinetically controlled. In contrast, the reaction at higher temperatures when the ratio of the
products is determined by their relative stabilities is said to be thermodynamically controlled . In the addition reactions of
buta-1,3-diene, the 1,2-adduct is usually the kinetic product while the 1,4-adduct is the thermodynamic product.

Oxidative Cleavage of Alkenes and Alkynes

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Oxidation of Alkenes with KMnO4
Alkenes can easily be oxidized by potassium permanganate and other oxidizing agents. What products form depend on the
reaction conditions. At cold temperatures with low concentrations of oxidizing reagents, alkenes tend to form glycols.

This reaction is sometimes referred to as the Baeyer test. Because potassium permanganate, which is purple, is reduced to
manganese dioxide, which is a brown precipitate, any water‐soluble compound that produces this color change when added to
cold potassium permanganate must possess double or triple bonds. This reaction involves syn addition, leading to a cis‐glycol (a
vicinal dihydroxy compound). A cis‐glycol can also be produced by reacting the alkene with osmium tetroxide, OsO 4.

When more concentrated solutions of potassium permanganate and higher temperatures are employed, the glycol is further
oxidized, leading to the formation of a mixture of ketones and carboxylic acids.

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