Samiha Nuzhat (ID 160123) and Sinthia Arefeen (160153)

Course – Organic Chemistry

Course Instructor – Professor Paulraj Mosae Selvakumar
Date of Submission – 7 November, 2019

A Report on Alkanes and Cyclic Aliphatic Hydrocarbons

Introduction

In general, organic chemistry is the study of carbon compounds. To explain a bit elaborately,
Anslyn & Dougherty (2006) define organic chemistry as the study of all the physical, chemical
properties of hydrocarbons along with other similar types of compounds having oxygen,
nitrogen, sulphur, halogens and other atoms present in it. Alkane is one of the most common and
most important homologous series. General Formula for Alkane is CnH2n+2 and for Cyclic
Aliphatic Hydrocarbon is CnH2n. Both of them have only sigma bonds and all the carbons in
these compounds are sp3 hybridized. They don’t contain any element other than Carbon and
Hydrogen. They are less reactive and can participate in only few types of reactions for which
they are known as ‘Paraffin’. This homologous series contains most of our significantly used
fuels. It has its importance in the biochemical mechanism of different animals. Even it is highly
used to produce different cosmetics, colors or other necessary products. Besides, alkane is also
important for the preparation of many other organic compounds. This is why understanding
Alkanes and their derivatives along with their special features is important.

Nomenclature

Based on the hydrocarbon chain, alkanes are named which is known as the IUPAC
nomenclature. IUPAC is the systematic way of naming compounds. According to the IUPAC,
linear, saturated hydrocarbon chains are named systematically with a Greek numerical prefix
denoting the number of carbons and the suffix "-ane" (Panico et al, 1993).
There are few IUPAC rules for naming Alkane:

a. Longest continuous carbon chain is the parent chain

b. Branches on the parent chain are named as “Alkyl” groups
c. The parent should be counted as a way that the first branch gets the lower carbon number
d. If an alkyl group appears multiple times, prefixes like di, tri, tetra etc need to use.
e. Each alkyl group must have a locant
 f. The name is written as one word with the parent name last. The names and locants for the
alkyl branches are put in alphabetic order. Separation of numbers from numbers will be
with commas and letters from numbers with hyphens.

Linear alkanes: Straight-chain alkanes are sometimes indicated by the prefix "n-" (for normal)
where a non-linear isomer exists. Linear alkanes are also named as linear paraffin or n-paraffin
Methane (CH4) – one carbon and 4 hydrogen
Ethane (C2H6) – two carbon and 6 hydrogen
Propane (C3H8) – three carbon and 8 hydrogen
Butane (C4H10) – four carbon and 10 hydrogen
Pentane (C5H12) – five carbon and 12 hydrogen
Hexane (C6H14) – six carbon and 14 hydrogen

Branched alkanes: Nomenclature of branched alkanes is a little different than that of linear
alkanes. Generally, simple branched alkanes have a common name using a prefix to distinguish
them from linear alkanes, for example n-pentane, isopentane, and neopentane.
According to IUPAC, naming of complicated branched alkanes are given below.

a. Identify the longest continuous chain of carbon atoms

b. Name this longest root chain using standard naming rules
c. Name each side chain by changing the suffix of the name of the alkane from "-ane" to
"yl"
d. Number the longest continuous chain in order to give the lowest possible numbers for the
side-chains
e. Number and name the side chains before the name of the root chain
f. If there are multiple side chains of the same type, use prefixes such as "di-" and "tri-" to
indicate it as such, and number each one.
g. Add side chain names in alphabetical (disregarding "di-" etc. prefixes) order in front of
the name of the root chain. (Reusch, 1999).

Hexanes C6H14 (IUPAC names)

CH3
CH3CH2CH2CH2CH2CH3 CH3CHCH2CH2CH3
(n-hexane) (isohexane)
n-hexane 2-methylpentane

CH3 CH3
CH3CH2CHCH2CH3 CH3CCH2CH3
(no common name) CH3
3-methylpentane (neohexane)
 2,2-dimethylbutane

CH3
CH3CHCHCH3
CH3
(no common name)
2,3-dimethylbutane

Cycloalkanes: Cyclic alkenes contain rings in their structures and technically distinct from the
alkanes. There are also few IUPAC rule to name these group of alkane.

a. A prefix “Cyclo” is added to distinguish them from other general alkanes

b. Cycloalkanes are named as per their acyclic counterparts with respect to the number of
carbon atoms in their backbones.
For example, cyclopentane (C5H10) is a cycloalkane with 5 carbon atoms just
like pentane (C5H12), but they are joined up in a five-membered ring.

Pentane Cyclopentane
 Sources and Basic Uses

Major sources of Alkane are Petroleum Preservers in specific geological sites. These petroleum
goes through fractional distillation and are separated based on their molecular weight. For
instance, Alkanes having 1 to 4 carbon numbers are found in natural. Heavier Alkanes are found
being mixed with different other organic compounds at different levels of underground.
Few of the basic uses of alkanes of different molecular weights are given below (Solomons &
Craig, 2011).

Synthesis

Alkanes can be synthesized in multiple ways. Some of the most popular ways of Alkane
synthesis is given below.
a. Hydrogenation of Alkenes and Alkynes
In presence of metal catalyst, alkene and alkyne produce alkane. Reaction occurring in
this process is given below (Solomons & Craig, 2011).
𝑃𝑡 𝑜𝑟 𝑁𝑖
CH2 = CH2 + H2 → CH3 – CH3
Ethene Ethane

𝑃𝑡 𝑜𝑟 𝑁𝑖
CH ≡ CH + H2 → CH3 – CH3
Ethyne Ethane

b. Decarboxylation Reaction
In presence of sodalime, sodium or potassium salts of fatty acids covert into alkanes.
Reaction occurring in this process is given below (Solomons & Craig, 2011).
𝐶𝑎𝑂, ∆
RCOONa + NaOH → R – H + Na2CO3

c. Wurtz Reaction
 Alkyl Halides produce Alkanes when they react with Sodium. Reaction occurring in this
process is given below (Solomons & Craig, 2011).
𝐷𝑟𝑦 𝐸𝑡ℎ𝑒𝑟
2R – X + 2Na → R – R + 2NaX

d. Reduction of Alkyl Halide

In presence of different reducing agents, alkyl halides convert into alkanes. Reaction
occurring in this process is given below (Solomons & Craig, 2011).
𝑍𝑛−𝐶𝑢/𝐴𝑙𝑐𝑜ℎ𝑜𝑙
R – X + 2[H] → R–H+H–X

e. Kolbe’s Electrolysis
Alkanes are produced when they are electrolyzed in presence of Oxygen. Even number of
carbon containing alkanes are produced in this reaction. Reaction occurring in this
process is given below (Solomons & Craig, 2011).
𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑠𝑖𝑠
2CH3COONa + 2H2O → CH3 – CH3 + 2NaOH + 2CO2 + H2

f. Corey House Synthesis

Corey house synthesis of alkanes can produce larger alkanes. In this case, R′X should be
either methyl or 1o alkyl halide. Reaction occurring in this process is given below (Brown
& Poon, 2014).
R – X + Li → R – Li + CuI → R2CuLi
R2CuLi + R′ – X → R – R′

g. Clemmensen Reduction
Carbonyl groups can produce alkanes in reduction reaction. Reaction occurring in this
process is given below (Brown & Poon, 2014).
𝑍𝑛 (𝐻𝑔),𝐻𝐶𝑙,𝑊𝑎𝑡𝑒𝑟
R – CO – R′ → R – CH2 - R′
𝑍𝑛 (𝐻𝑔),𝐻𝐶𝑙,𝑊𝑎𝑡𝑒𝑟
R – CHO → R – CH3

Cyclic Aliphatic Hydrocarbons can also be produced in some of the above mentioned reactions.
Besides, there are some special synthesis processes for cyclic aliphatic hydrocarbons. Some of
those are mentioned below.
a. Dihalogen Compounds
Cyclic aliphatic hydrocarbons can be produced from dihalogen compounds. Reaction
occurring in this process is given below (Brown & Poon, 2014).
CH2

𝐸𝑡ℎ𝑒𝑟
X – CH2 – CH2 – CH2 – X + 2Na → H2C CH2 + 2NaX

b. From Alkenes
 Cyclic aliphatic hydrocarbons can also be produced from alkenes in presence of
methylene iodide and Zn – Cu Couple. Reaction occurring in this process is given below
(Brown & Poon, 2014).
CH2

𝑍𝑛−𝐶𝑢 𝑐𝑜𝑢𝑝𝑙𝑒
CH2 = CH2 + CH2I2 → H2C CH2

c. Dieckmann Cylisation
Esters of dicarboxylic acids in presence of different reagents produce cyclic aliphatic
hydrocarbons in multiple steps. The net reaction occurring in this process is given below
(Brown & Poon, 2014).
R – COO – CH2 – CH2 – CH2 – COO – R′ → Cyclic Aliphatic Hydrocarbons (of
same Carbon number as reagent)

d. Hydrogenation of Aromatic Compounds

Aromatic compounds can be hydrogenated to produce cyclic aliphatic hydrocarbons.
Reaction occurring in this process is given below (Brown & Poon, 2014).
𝑁𝑖,200 𝑑𝑒𝑔𝑟𝑒𝑒 𝑐𝑒𝑛𝑡𝑖𝑔𝑟𝑎𝑑𝑒 𝑡𝑒𝑚𝑝.
+ H2 →
e. Clemmensen Reduction
Carbonyl groups can produce alkanes in reduction reaction. Reaction occurring in this
process is given below (Brown & Poon, 2014).
𝑍𝑛 (𝐻𝑔),𝐻𝐶𝑙,𝑊𝑎𝑡𝑒𝑟
R – CO – R′ → R – CH2 - R′
𝑍𝑛 (𝐻𝑔),𝐻𝐶𝑙,𝑊𝑎𝑡𝑒𝑟
R – CHO → R – CH3
Here, the alkyl group is actually cyclic. And the reagents are cyclic ketones and
aldehydes.
Isomerism
Alkanes can give rise to different kinds of isomerism. Conformers, chain isomerism, ring chain
isomerism etc. are few of the most common isomerism that Alkane can have.
a. Conformers – Conformers are isomers when the substitutions with the Carbons are in
different plains. For instance, the below mentioned structures (side view) of ethane are
conformers to each other.

Figure: Staggered and eclipsed forms of Ethane where

two planes are assumed on two carbons
 b. Chain Isomer – Chain Isomers are isomers having different carbon chains in two
compounds. For instance, Hexane and Dimethyl Pentane are chain isomers.
c. Stereo Isomer – Cyclo Aliphatic compounds show stereo or geometric isomerism. For
instance, cyclo hexane shows different types of formation in space, i. e. boat shape, chair
shape etc.

Figure: Chair and Boat Shape of Cyclohexane

Physical Properties

There are different physical properties that needs to be considered for organic compounds. Some
of those are color, odor, state in room temperature and so on. In room temperature, methane to
butane are gaseous. Pentane to heptadecane are liquid. Alkanes having more carbons than
heptadecane are solid in room temperature. Apart from these there are three major physical
properties that needs to be considered enough to understand the uses of organic compounds and
these are solubility, melting point, boiling point. These three properties have been discussed
below in terms of alkanes and cyclic aliphatic hydrocarbons.
Solubility: Solubility of Alkanes depends on which sort of solvent is being used. Besides, as
Alkanes and Cyclic Aliphatic Hydrocarbons are non-polar and sometimes weakly polar, they
don’t dissolve in any highly polar solvent. And lack of polarity is also responsible for having no
to very little intermolecular forces in between the Alkane molecules. These compounds are fully
water insoluble and slightly soluble in weakly polarized solvents. Besides, they are often soluble
in non-polarized solvents. Moreover, liquid alkanes and cycloalkanes are soluble into each other
(Solomons & Craig, 2011).
Melting Point and Boiling Point: Meling point is the temperature at which a material changes
from solid to liquid state or melts while boiling point is the temperature at which a material
changes from liquid to gaseous state or boils. The boiling point of unbranched alkanes and cyclo
alkanes regularly increases, as the carbon number increases. Boiling point is related with
intermolecular forces involved. The bigger the carbon chain of the Alkane is, the more is the
surface area of the molecule that leads to higher van der waals or intermolecular force. And in
that case the molecule needs more energy to boil and this is why the boiling point increases. And
branching of the Alkanes actually lowers the boiling point of Alkanes, as it reduces the surface
area by increasing the compactness of the alkane. Then it becomes easier to be free from smaller
amount of intermolecular forces created by smaller surface area. Thus, we need less energy or
less temperature to boil the molecule. Besides, in case of melting point, compactness and
symmetricity of the molecules is important. This is why usually branching in the hydrocarbons
increase the melting point of the molecule. Besides, a regular increase in the melting point is also
noticed with an increase in the carbon numbers. Moreover, as even number of carbons present in
the carbon chain make it more symmetric, it is noticed that in case of even number carbon atom
present in the molecule, there is a larger increase in the melting point. Thus, melting point and
boiling point, two major physical properties of the organic homologous series have similarities or
regular change in their characteristics (Solomons & Craig, 2011). Melting and boiling points of
few initial alkanes and cyclo aliphatic hydrocarbons are given below (McCain Jr., 2017)

Chemical Properties

Alkanes are known as ‘Parafins’. In Latin, Paraffin denotes ‘Lack of Affinity’. As alkanes have
lack of affinity of reactivity with other chemicals, they are also known as paraffins. But they yet
participate in several reactions. Some of the major reaction of alkanes are halogenation,
combustion and cracking. A brief description of these reactions are given below.
Halogenation
Alkanes participate in halogenation reaction in presence of heat or light and produce several
different chemicals of different yield. For instance, in presence of light and chlorine, methane
produce methyl chloride, methylene chloride, chloroform and carbon tetrachloride along with
Hydrochloric Acid. Iodine doesn’t react in this way. Chlorine is more reactive than Bromine in
this type of reaction, as Bromine is more selective in this reaction. And because of the high
reactivity of Fluorine in this regard, it is quite risky to conduct this experiment in improper safety
setting (Solomons & Craig, 2011). Moreover, the reactivity series of hydrocarbons is as below.
3o > 2o > 1o > CH4 (Solomons & Craig, 2011)
The general reaction is as below.
𝐻𝑒𝑎𝑡
R – H + X2 → R–X+H–X
Cyclic Aliphatic Hydrocarbons also participate in this reaction under specific conditions.
Combustion
Combustion denotes oxidation of chemicals. Combustion can be of two types; partial and full
combustion. Partial combustion occurs in lack of Oxygen and full combustion occurs in presence
of abundant Oxygen. Partial oxidation of Alkanes produce Carbon monoxide and full
combustion of Alkanes produce Carbon dioxide. Here, water is produced as a byproduct in this
process.
Partial Combustion: R – H + O2 → CO + H2O
Full Combustion: R – H + O2 → CO2 + H2O
In high temperature and pressure Cyclic Aliphatic Hydrocarbons also participate in such type of
reactions.
Pyrolysis
Pyrolysis is the process of breaking down long chained Alkanes producing smaller chained
Alkanes (Solomons & Craig, 2011). This process is also known as cracking. Cracking can be of
two types; catalytic cracking and thermal cracking. Catalytic cracking denotes breakdown of
long chain alkanes into smaller chain alkanes in presence of variety of catalysts. And such
cracking usually produces highly branched Alkanes. On the other hand, thermal cracking denotes
breakdown of long chain Alkanes in higher temperature. Thermal cracking usually produces
unbranched alkanes. The general reaction of cracking is given below.
400−600 𝑑𝑒𝑔𝑟𝑒𝑠𝑠 𝑐𝑒𝑛𝑡𝑖𝑔𝑟𝑎𝑑𝑒
Alkanes → Smaller Alkanes + Alkenes + H2
Cyclic Aliphatic Hydrocarbons don’t participate in such cracking.

Real life Application of Alkanes

Real life applications and uses of alkanes are uncountable. Alkanes are the main energy
providers.
a. In electricity production: Alkanes are highly used as the fuel to generate electricity.
b. Transportation and aviation fuel: Gasoline, diesel, Octane and other transformational
fuel is extracted from alkane. Alkanes from C9H20 to C16H34 are higher viscous liquid,
less and less suitable for use in gasoline. They form instead the major part
of diesel and aviation fuel. Diesel fuels are characterized by their cetane number. Cetane
being an old name for hexadecane.
c. Heating and cooking: Alkanes are famous for heating and cooking. The first four
alkanes (Methane, Ethane, Propane, and Butane) are used a lot for cooking, heating and
electricity production. Again, Methane and Ethane are the main constituents of natural
gas. In liquefied petroleum gas (LPG), Propane (C3H8) and Butane (C4H10) are used.
 Propane (C3H8) is also used as gas burner. On top of that, Butane (C4H10) is used in
disposable cigarette lighters.
d. Solvent for non-polar substances: Alkanes which has carbon number 5-8 are mainly
volatile liquids. Pentane (C5H12), Hexane (C6H14), Heptane (C7H16), Octane (C8H18) are
used as fuel sand as solvent for nonpolar substances.
e. Cleaning agents: Alkanes themselves are commonly used as cleaning agent for their
property of dissolving organic substances of low polarity, such as fats, oils, and waxes.
f. Lubricating oil and anti-corrosive agents: Alkanes with 17 to 35 carbon atoms form
the major components of lubricating oil. They also act as anti-corrosive agents, as their
hydrophobic nature protects the metal surface from contact with water.
g. Road surfacing: Alkanes containing higher carbon number (>35) are found in bitumen.
And solid tar can occur as residues from oil distillation, which is used in road surfacing
h. Plastic and synthetic materials productions: Alkane is the starting element to make all
kind of commercial synthetic materials. A good example of a polymer is polyethylene.
Ethylene (ethane) is the monomer and, when lots of these are connected end-to-end in a
chain by a chemical reaction that breaks the double bond, a polymer is formed.
Monomers are obtained by refining petroleum.
i. Medicine and health sector: Alkane is highly used in medicine and health sector
because of its dissolving characteristic. Sodium tetradecyl sulfate (alkane), as an anionic
surfactant used to treat varicose veins of the lower extremities. Also, Acamprosate, a
medication used to maintain alcohol abstinence in patients with alcohol dependence.
Sodium lauryl sulfate, another anionic surfactant used in cosmetics and pharmaceuticals
as a fat emulsifier, wetting agent, and detergent.
j. Agricultural chemicals: Alkanes are also used as harbisides. Chlorophenoxy herbicides
are used to control broadleaf weeds (dicotyledons) which are derivatives of
phenoxyalkane.

Conclusion
Alkanes play a very crucial role in our daily life as most of the energy comes from alkane.
Medicine, industrial synthetic material made of alkane. And we can’t think of life in earth
without Alkane, as an organic matter.
 References

Anslyn, E. V., & Dougherty, D. A. (2006). Modern physical organic chemistry. University
science books.
Brown, W. H. & Poon, T. (2014). Introduction to Organic Chemistry. John Wiley & Sons.
McCain Jr, W. D. (2017). Properties of Petroleum Fluids. PennWell Corporation.
Solomons, T. W. G. & Craig, B. F. (2011). Organic Chemistry, 9th edition.
Panico, R., Powell, W. H., & Richer, J. C. (1993). A guide to IUPAC nomenclature of organic
compounds (p. 102). Blackwell Scientific Publications, Oxford.
Reusch, W. (1999). Virtual textbook of organic chemistry. Michigan State University.