ALKANES

Prepared by: Francis Carlo Lao

Alkanes are classified as aliphatic hydrocarbons having only C – C and
C – H 𝜎 bonds.

Because their carbon atoms can be joined together in chains or rings,

they can be categorized as acyclic or cyclic.
 Acyclic alkanes

Have a molecular formula 𝐶𝑛 𝐻2𝑛+2 (where n= an integer) and contain

only linear and branched chains of carbon atoms. They are also called
saturated hydrocarbons because they have the maximum number of
hydrogen atoms.
 Acyclic Alkanes Having One to Five C Atoms

All carbon atoms in an alkane are surrounded by four groups, making

them sp3 hybridized and tetrahedral, and all bond angles are 109.5°.
 Acyclic Alkanes Having One to Five C Atoms

The three-carbon alkane, 𝐶𝐻3 𝐶𝐻2 𝐶𝐻3 , called propane, has molecular
formula 𝐶3 𝐻8 .
 Acyclic Alkanes Having One to Five C Atoms

There are two different ways to arrange four carbons, giving two compounds
with molecular formula 𝐶4 𝐻10 , named butane and isobutane.
Acyclic Alkanes Having One to Five C Atoms

Butane and isobutane are isomers, two different

compounds with the same molecular formula. They
belong to one of the two major classes of isomers, called
constitutional or structural isomers.

Constitutional isomers differ in the way atoms are

connected to each other.
 Acyclic Alkanes Having One to Five C Atoms

Butane, which has four carbons in a row, is a straight-chain or normal

alkane (an n-alkane). Isobutane, on the other hand, is a branched-chain
alkane.
Acyclic Alkanes Having One to Five C Atoms

Alkanes which have more than four carbon atoms, the names of the
straight-chain isomers are systematic and derive from Greek roots:
pentane, for five carbon atoms, hexane for six and so on.
Constitutional isomers of five-carbon alkane
Carbon atoms in alkanes and other organic compounds are classified by
the number of other carbons bonded to them.

 A primary carbon (1° carbon) is bonded to one other C atom

 A secondary carbon (2° carbon) is bonded to two other C atoms
 A tertiary carbon (3° carbon) is bonded to three other C atoms
 A quaternary carbon (4° carbon) is bonded to four other C atoms
Hydrogen atoms are also classified as primary (1°), secondary (2°), or
tertiary (3°) depending on the type of carbon atom to which they are
bonded.

 A primary hydrogen (1° H) is on a C bonded to one other C atom

 A secondary carbon (2° H) is on a C bonded to two other C atoms
 A tertiary carbon (3° H) is on a C bonded to three other C atoms
 Acyclic Alkanes Having More than Five C Atoms

The maximum number of possible constitutional isomers increases

dramatically as the number of carbon atoms in the alkane increases.
NOMENCLATURE
The International Union of Pure and Applied Chemistry (IUPAC)
developed a systematic method of naming compounds. It is referred to as
the IUPAC system of nomenclature.
 Naming of Alkanes
The name of every organic molecule has 3 parts:
1.The parent name indicates the number of carbons in the longest continuous
chain.
2.The suffix indicates what functional group is present.
3.The prefix tells us the identity, location, and number of substituents attached
to the carbon chain.
Naming of Alkanes
Naming of Alkanes
Naming of Alkanes
 Naming Substituents

Carbon substituents bonded to a long carbon chain are called alkyl

groups.

 An alkyl group is formed by removing one hydrogen from an alkane

 To name an alkyl group, change the -ane ending of the parent alkane
to -yl
 Naming Substituents
Example:

𝑪𝑯𝟒 becomes methyl (𝐶𝐻3 −)

𝑪𝑯𝟑 𝑪𝑯𝟑 becomes ethyl (𝑪𝑯𝟑 𝑪𝑯𝟐 −)

 Any alkyl groups are denoted by R.

 Naming Substituents
Naming three- and four-carbon alkyl groups is more complicated
because the parent hydrocarbons have more than one type of hydrogen
atom.
 Naming Substituents

Since there are two different isomers of butane, each isomers have
two different kinds H atoms, thus, there are four possible alkyl groups
containing four carbon atoms.
Naming Substituents
 Naming an Acyclic Alkane

STEP 1. Find the Parent Carbon chain and add the suffix
 Naming an Acyclic Alkane
STEP 1. Find the Parent Carbon chain and add the suffix

If there are two chains of equal length, pick the chain with more
substituents.
 Naming an Acyclic Alkane
STEP 2. Number the Atoms in the carbon chain

Number the longest chain to give the first substituent the lower number
 Naming an Acyclic Alkane
STEP 2. Number the Atoms in the carbon chain

If the first substituent is the same distance from both ends, number the
chain to give the second substituent the lower number.
 Naming an Acyclic Alkane
STEP 2. Number the Atoms in the carbon chain
When numbering a carbon chain results in the same numbers from either end
of the chain, assign the lower number alphabetically to the first substituent.
 Naming an Acyclic Alkane
STEP 3. Name and number the substituents
Name the substituents as alkyl groups, and use the numbers from Step 2 to
designate their location.
 Naming an Acyclic Alkane
STEP 3. Name and number the substituents

 Every carbon belongs to either the longest chain or a substituent, but not
both.
 Each substituent needs its own number.
 Naming an Acyclic Alkane
STEP 3. Name and number the substituents

 If two or more identical substituents are bonded to the longest chain, use
prefixes to indicate how many: di- for two groups, tri- for three groups,
tetra- for four groups, and so forth. The preceding molecule has two methyl
substituents, and so its name contains the prefix di- before the word
methyl → dimethyl.
 Naming an Acyclic Alkane
STEP 4. Combine substituent names and numbers + parent + suffix

 Precede the name of the parent by the names of the substituents.

 Alphabetize the names of the substituents, ignoring all prefixes except iso,
as in isopropyl and isobutyl.

 Precede the name of each substituent by the number that indicates its
location. There must be one number for each substituent.
 Naming an Acyclic Alkane
STEP 4. Combine substituent names and numbers + parent + suffix

 Separate numbers by commas and separate numbers from letters by

hyphens. The name of an alkane is a single word, with no spaces after
hyphens or commas.
 Naming an Acyclic Alkane
STEP 4. Combine substituent names and numbers + parent + suffix
Naming an Acyclic Alkane

2,3-dimethylpentane
Naming an Acyclic Alkane

5-tert-butyl-3-methylnonane
 Physical
Properties
Alkanes contain only nonpolar C–C and C–H bonds, and as a result
they exhibit only weak van der Waals forces. This affects the
physical properties of alkanes.
 Boiling Point
Alkanes have low boiling point compared to more polar compounds of
comparable size
 Boiling Point
Boiling point increases as the number of carbons increases because of
increased surface area.
 Boiling Point
The boiling point of isomers decreases with branching because of
decreased surface area.
 Melting Point
Alkanes have low melting point compared to more polar compounds of
comparable size.
 Melting Point
Melting point increases as the number of carbons increases because of
increased surface area.
 Melting Point
Melting point increases with increased symmetry
 Solubility

Alkanes are soluble in organic solvents

Alkanes are insoluble in water

Sources of
Alkanes
 Natural Gas

Approximately 90%-95% methane, 5%-10% ethane; and a mixture of other

relatively low-boiling alkanes, namely, propane, butane, and 2-
methylpropane are obtained from natural gases.
 Petroleum

A complex mixture of compounds, most of which are hydrocarbons

containing 1–40 carbon atoms.

Refining is the process of distilling crude petroleum which separates it into

usable fractions that differ in boiling point.

Gasoline: C5H12–C12H26
Kerosene: C12H26–C16H34
Diesel fuel: C15H32–C18H38
Petroleum
Uses of Alkanes
Gasoline
Propellants in aerosol sprays
Fuels
Diesel and Aviation fuel
Lubricants
Preparation of
Alkanes
 Preparation of Alkanes from Unsaturated Hydrocarbons

Unsaturated hydrocarbons, such as alkenes and alkynes, react with H2

in the presence of finely divided catalysts such as platinum, palladium or
nickel to form alkanes. This process is called hydrogenation.
 Preparation of Alkanes from Alkyl Halides

Alkyl halides (except alkyl fluorides) on reduction with zinc and dilute
hydrochloric acid produce alkanes.
 Preparation of Alkanes from Alkyl Halides

Haloalkanes (Alkyl Halides) react with sodium in dry ether to form

symmetrical alkanes with double the number of carbon atoms present in
the alkyl halide. This reaction is known as Wurtz reaction.
 Preparation of Alkanes from Carboxylic Acids

Sodium salts of carboxylic acids (RCOONa) in heating with soda lime

(NaOH + CaO) form alkanes containing one carbon less than the salt. This
process is called decarboxylation.

Note: CaO is used to keep NaOH dry as NaOH tends to absorb moisture from air.