ALIPHATIC HYDROCARBONS

BY

ABDULLAHI MOYOSORE

DEPARTMENT OF CHEMISTRY

FEDERAL COLLEGE OF EDUCATION, KATSINA

Nations of the world have been endowed with natural resources of one
kind or the other. The activities of man by way of exploration have since over
the years led to the discovery of these hidden treasures of nature in
commercial quantities and have solved man’s needs in several ways.

Crude oil or petroleum in Nigeria is one of such natural resources that

are found in underground rocks. It is a dark viscous mixture containing both
light and heavy hydrocarbons, natural gas, dissolved salts, ions and other
volatile compounds. Upon its exploration and exploitation through
underground pipes, crude oil is transported to refineries and processed by
fractional distillation, cracking and reforming to yield hydrocarbons, which
have provided our energy needs, revenue generation, as export commodity,
solvents, adhesive, in transportation and useful as basic raw materials in
petrochemical industries in making plastics and industrial chemicals etc.

Interestingly, molecules of Aliphatic hydrocarbons exist in various

classes either as solids, liquids or in the gaseous state, possession of different
molecular weights and uses, existence in different ratios or proportions of
carbon to hydrogen per molecule, differences in structures and bonding types,
possession of different properties and reactivities depending on the number of
electrons being shared in the C to C bonding per molecule and different
methods of preparations. These essential features mentioned above have led
to the study of aliphatic hydrocarbons on the basis of three distinct types of
homologous series for easier understanding. Aliphatic hydrocarbons are
important class of organic compounds, hence should be studied as component
of organic chemistry.

Objectives

At the end of this chapter, the reader should be able to:

(1) Explain what organic compounds are.

(2) List the various examples of organic compounds based on their
homologous series.
(3) Explain what Aliphatic hydrocarbons are.
(4) Classify Aliphatic hydrocarbons based on their general formulars.
(5) Discuss bond formation in each class of Aliphatic hydrocarbon.
(6) List and explain types of chemical reactions which each class of
Aliphatic hydrocarbon undergo.
(7) Explain the various available laboratory methods of preparations of
Aliphatic hydrocarbons.

What is an organic compound?

Organic compounds are compounds in which carbon atoms are

covalently bonded to nonmetallic atoms of elements such as with hydrogen as
in hydrocarbons, with hydrogen and oxygen as in carboxylic acids, Alkanols,
Alkanals, Alkanones, Alkanoates, or when carbon is covalently bonded to
nitrogen as in amines. All these is made in fixed reaction stoichiometries
between carbon and these non-metal atoms of elements in order to form
unique classes of covalent molecules which possess distinct properties,
reactivity and uses.

Organic compounds have beneficial roles such as in sustaining lives of

living organisms as can be noticed in metabolism, respiration, energy supply
as may be required for cellular functions.

Aliphatic hydrocarbon and their classification

Aliphatic hydrocarbons are strictly speaking being regarded as members

of the hydrocarbons class of organic compounds. A hydrocarbon according to
Maitland (2000), are compounds that are entirely composed of carbon and
hydrogen. According to Ababio (2010), a hydrocarbon is defined as an organic
compound that contain carbon and hydrogen represented by the general
formular CxHy, x and y representing whole members.

Aliphatic hydrocarbon can therefore, from the above, be regarded as

molecule of hydrocarbon family that do exist structurally either as straight,
branched or cyclic and consist of small to medium to large number of carbon
atoms containing single, double or triple bonds. Aliphatic hydrocarbons can be
saturated with (single C – C bond), unsaturated with C = C double bond or C
≡ C triple bond. Their molecular weights vary as the number of carbon and

hydrogen atoms increases, which also affects their physical properties. They
can even exist as gaseous form, e.g methane (CH 4) and propane C3H8, liquids
e.g hexane C6H14, and octane C8H18 or as waxy solids like ecosane C20H42 and
triacontane C30H62. Saturated Aliphatic hydrocarbons include n-pentane C5H12
(H – C – C – C – C – C – H) cyclobutane, branched Aliphatic hydrocarbons
include
Isobutane, methylpropone; unsaturated straight or cyclic Aliphatic
hydrocarbon, include i-butene C4H8 ( , as example of the
straight and unsaturated type, while the cyclic ones include cyclohexene.

It can therefore be seen from the above discussions and examples that
aliphatic hydrocarbon do not contain any benzene ring in their molecules.

Aliphatic hydrocarbons can further be classified in the basis of the

general molecular formulars which defines the three homologous series
ALKANES (CnH2n+2), ALKENES (CnH2n) and ALKYNES (Cnk1n-2) where n= 1, 2,
3…..

Reactions of Aliphatic hydrocarbons

Aliphatic hydrocarbons especially the Alkanes are saturated and said to

be unreactive to a large extent due to this saturation. They however have
chemical properties to indicate they undergo certain reactions types if not
many, usually at fairly high temperatures and with the use of photolytic
initiators. Low molecular weight member of the aliphatic hydrocarbon
undergo stepwise substitution reactions with halogens. The reaction involves
first the initiation step involving the breaking of one of the C – H bond in H4 in
the presence of light, to form radical of carbon and hydrogen. This is then
followed by the cleaving or splitting of the bond between a halogen molecule
to yield halogen radical. The propagation step in the reaction involves the or
bond formation between the CH3 radical and Cl to yield CH3Cl, and H radical
with another cl to yield Hcl. The propagation step continues with further
cleaving of C – H bond in CH3cl initially formed. This now yield .CH2cl + .cl to
give CH2cl2 + and H. combining with .cl again gives Hcl, the pro step continues
until all the hydrogen atoms in CH4 have been removed and substituted with cl
at the termination step in which ccl4 + Hcl are being formed as substitution
products.

 Alkanes also undergo combustion reaction when burnt or exploded with

oxygen on the application of flame/electric spark to form carbondioxide
and water. The quantities (moles) of carbondioxide gas and water being
formed in this case, depends on the molecular mass of the Alkane used.

C5H12 + 8O2(g)  5C02 + 6H20; CH4 + 2O2  CO2 + 2H2 0.

 Alkanes undergo nitration reaction involving the use of Hno3 (Nitric

acid) whereby the C-H bond is broken and the hydrogen atom
substituted by an –N02 (nito group) at a temperature of (150 – 400 0c) to
form nitor Alkanes as products.

Similarly if the above reaction involves the use of H 2S04 acid instead of
HN03, the product are called Alkylsulphonic acid such as methylsulphonic acid
CH3S03H when CH4 is the alkane being used.

Bond formation in Aliphatic hydrocarbons

The formation of homologous series by each class of Aliphatic

hydrocarbon is for easy identification on the basis of the number of covalent
bond that is formed and exist between the carbon atoms the number of
covalent bonds being formed gives and the idea about the number of electrons
that are being contributed and shared between the carbon atoms during
bonding in an Aliphatic hydrocarbon molecule. Thus, in a single C – C bond,
each carbon atom contributes one electron out of four it has so that 2
electrons are being shared between any two carbon atoms as represented by
single C to C bonds in Alkane molecules. The remaining three electrons from
each of the participating caronatoms are being shared singly with any 3
H

adjacent hydrogen atoms to form covalent bond.

H H

In the case of the ALKENEs, the double bond is the reactive site. It is
normally situated between any two carbon atoms whereby each one of the
carbon contribute two out of its four electron, making it possible to share four
electrons in order to form double bond. . Similarly the triple bond
is another reactive site specifically in Alkynes. As with the Alkanes and the
Alknes, the triple bond is situated between any two carbon atoms whereby
each of the carbon atom contribute three out of four electrons it has, so that
six electrons are shared between any two carbon atoms for bonding whenever
triple bond is situated.

Cracking is actually an process for obtaining higher yield of low

molecular weight hydrocarbons petroleum industry to meet daily petrol
fraction requirement of our vehicles and transportation.

Reactivity of Alkenes

The reactive unsaturated Aliphatic hydrocarbons have chemical

properties in reactions, which normally occurs of their double/triple bond
sites, and are called Addition reactions.

In the case of the alkenes one of the two π bonds is expected to cleave
or break, releasing the H as leaving group forming an unstable C atom. The
incoming group called the nucleophile then attacks to form a new sigma bond
and then yield an addition product.

Thus with ethane

(1)
H H H H H H

C=C + C=C C -C +
H H Cl2  H H  H H

H H
Cl2
H C -C -H

cl cl

H H

H C -C -H

cl cl
1,2 – dichloroaethane.

(2)
H H H H H H

C=C + Br OH -C
C+ C=C +
H H H H H H

 Br
-O
H

H H

H C -C -H

Br OH

(3)
H
H H H
[o]
C=C H C C H

H H OH OH Ethane -1, 2 – dio 1

Kmno4/H2o (colorless)
(purple)
(for distinguishing unsaturated
Aliphatic hydrocarbons from
saturated ones)
 (4) Other types of addition reactions of alkenes are hydration,
hydrogenation, polymerization, ozonolysis.

In all, the reaction proved via the double bond as illustrated, to yield
addition products. In polymerization, several small units of alkene
(monomers) are polymerized to form polymers under specified temperature
and catalyst.
BF (C - C - C - C -) n
(CH2 = CH2)n
0
-100 c

Monomens polymes

Reactive of Alkynes

Reactivity of the Alkynes like those of the Alkenes also occur at the
reactive site where the triple bonds (one π bonds and one sigma bond) is
located.

This implies that all addition reactions involving a reaction between the
Alkyne Aliphatic hydrocarbon occurs in a stepwise manner through the
reactive site. The sigma bond first cleave/breaks, leaving the π bond which
also breaks/cleaves to give rise, finally, to a sigma bond. In each after the
cleaving, a group leave forming an unstable carbon atom to which then adds a
nucleophile to form new sigma bond of addition products.
Br
(1) H–C ≡ C–H + 2Br2 ⟶ H – C = C – 2H ⟶ H–C=C–H

Ethyne

Br Br

H–C ∓ C–H
 | |
Br Br

Br2 (Br – Br)

H–C–C–H
Br Br Br Br
(1,1,2,2, - tetra bromoethane)
+
(2) H–C ≡ C – H +2HI(g) ⟶ H – C ≡H-IC – H ⟶ H – C = C – H

H I

H+I

H–C ∓ C–H
H I
H
H–C–C–H
H I I
(1, 1, d-1- doethane)

Laboratory method of preparing Aliphatic hydrocarbons

In acyclic Aliphatic hydrocarbon can be prepared using any of the

following methods.

(A) Saturated Aliphatic hydrocarbons The ALKANES

1. Use of alkyhalides (R – X), were R= alky/group (CH3, C2H5, C3H7)
etc and X = halogen (cl, Br, I). this is called the wurtz reaction and
it involves treating the alkyhalide compound with sodium metal in
 an anhydrous ethereal solution. The reaction can be explained as
follows
(i) Sodium transfer are electron to the halogen to produce
sodium halide and an alkyl radical
(ii) The alkyl radical accepts on electron from another
sodium atom to form an alkyl anion.
(iii) Sodium becomes cationic.
(iv) An alkyl anion then displaces the halide and forms a new
carbon-carbon covalent bond.

Generally (R – x + 2Na(s) ⟶ R – R + Nax)

Example

CH3 – Br + 2Na + Br – CH3 ⟶ CH3 – CH3 + 2Na Br

Dry ether
(Bromomethane) (ethane)
Dry ether
C2 H5 Br + 2Na + Br – C2 H5 ⟶ C2 H5 – C2 H5 + 2Na Br
(Butane)

2. By heating sodium ethanoate with on alkali e.g soda lime. This

reaction is another route for producing saturated aliphatic
hydrocarbon upon heating the sodium ethanoate with sodium
hydroxide solution, in the presence of catalyst, (Cao), the –cooNa
group from the CH CooNa is replaced by H-atom of the NaoH.

The overall recaton equation is CH3 cooNa + NaoH ⟶ CH4 + Na2C03.

(methane)

To prepare others, -CH2 group is added thus CH3CH2 CooNa + NaoH

⟶ CH3 CH3 Na2 Co3
 (ethane)

CH3 CH2 CH2 CooNa + Naoh ⟶ CH3 CH2 CH3 Na2 Co3

(propane)

3. Kolbes method.

Sodium acitate (Sodium Ethonoate CH 3 CooNa are made to react with

water and then electrolyzed to yield saturated aliphatic hydrocarbon and
other by products such as Co2, H2 and NaoH.

The reaction simply involves the breaking up of water molecules into H +

and oH- at the cathode during electrolysis. H+ and H+ combine to form H2.

At the anode, the sodium acetate gets decomposed into acetate ion
CH3Coo- and sodium ion Na+. Two of the acetate ions then accept two electrons
to form two acetate free radicals which subsequently transforms into 2
molecule of C02 and. 2 free radical of methyl CH3 and CH3 which then combine
to form CH3 – CH3 ethane molecule.

4. Saturated Aliphatic hydrocarbons can also be prepared by

hydrogenation of unsaturated hydrocarbons in the presence of
finely divided catalysts like pt pd/m
C2H4 + H2 Pd/pt/m
⟶ C2H6
(ethane)
5. Wurtz reduction of method for pre saturated aliphatic
hydrocarbon involves the use of Alkyhalide and hydrogen atoms
on the presence of Zn as reducing agent which acts by delivering
H2 to the Alkyhalide molecule. The C – X bond breaks, and the X
 atom is replaced by a H-atom. The other H-atom then attachy itself
to the x atom being released in order to from H – X bond.

ALKENES

(1) Dehydronhalogenation of Haloalkances. A dehydrologenation of

reaction involve the remove of both the halogen atom hydrogen atom
from a C atomthey is adjacent to the one carrying the halogen atom of
a haloalkane molecule (R_X).
(2) Dehydration of alcohols using concentrated sulpharic acid H 2S04 or
phosphoric acid H3P04 and the application of heat.
(3) The dehydration reaction involve the protonation or attach of a
proton on the oxygen of the alcoholthus (R_OH_ R_ ). This is
followed by loss of water as in R0H2, thus @@@@@@@@@@@ to
from hustable corbocations, which them rearranges and loss of one
hydrogen atom to form Alkenes: thus
(4) By the reduction of Alkenes. This involve using Na/ki in the
conversing of = using catehdliqiNH3.
(5) Hydrogenation of Alkynes this reaction involve the reaction of H2
usually via the triple bond to give carres ponding Cis/trans Alkanes.