CHAPTER 2

ALKANES: STRUCTURE AND NOMENCLATURE

OF SIMPLE HYDROCARBONS
 HYDROCARBON
 Compound which composed by carbon & hydrogen
 2 major classes of hydrocarbon which are saturated and
unsaturated
 Saturated – alkanes - which all carbon-carbon bonds are
single bonds
 Unsaturated
alkenes – the molecules have at least one
carbon-carbon double bonds
alkynes – the molecules have at least one
carbon-carbon triple bonds
MOLECULAR & STRUCTURAL
FORMULA
 Molecular Formula – the exact number each
kind of atom in a compound
 Structural Formula – is a graphical
representation of the molecular structure
showing how the atoms are arranged. There
are three common representations:
condensed, Lewis type and line-angle
formulæ
 Structural isomerism – form of isomerism in
which molecules with the same
molecular formula have atoms bonded
together in different orders.
 Three types of structural isomers: skeletal,
positional, and functional isomers
 Skeletal isomer - carbon skeleton are
distinctly re-ordered to create different
structures. Example: pentane C5H12

n-pentane isopentane/
neopentane/
2-methylbutane 2,2-
methylpropane
REPRESENTATION OF STRUCTURAL
FORMULA
POSITIONAL ISOMERISM
 Positional Isomerism –a functional group
changes position on the chain.
 occurs when functional groups are in
different positions on the same carbon chain.
 Example:
FUNCTIONAL GROUP ISOMERISM

 functional group isomerism a functional

group splits up and becomes a different
group.
 Example: benzene and 1-hexene
 IUPAC NOMENCLATURE
Number of
Prefix Structure
Carbons
Continuous-chain hydrocarbon
1 Methane CH4
2 Ethane CH3CH3
3 Propane CH3CH2CH3
4 Butane CH3(CH2)2CH3
5 Pentane CH3(CH2)3CH3
6 Hexane CH3(CH2)4CH3
7 Heptane CH3(CH2)5CH3
8 Octane CH3(CH2)6CH3
9 Nonane CH3(CH2)7CH3
10 Decane CH3(CH2)8CH3
11 Undecane CH3(CH2)9CH3
12 Dodecane CH3(CH2)10CH3

Ring or cyclic, prefix cyclo is used to indicate the

ring.
NOMENCLATURE OF THE BRANCHED
ALKANES
According to IUPAC rules, there are steps in
naming the organic compounds.
3) Find the longest chain in the molecule. For a
cyclic compound, the ring is usually the base of
the name regardless of the longest continuous
chain.
4) Numbering the longest chain
 3) Name the attached shorter chains (alkyl group).
Give the location of each substituent by the
number of the main-chain carbon to which it is
attached.
CH3— methyl CH3(CH2)4CH2 —
hexyl
CH3CH2 — ethyl CH3(CH2)5CH2 —
heptyl
CH3CH2CH2 — propyl CH3(CH2)6CH2 —
octyl
CH3(CH2)2CH2 — butyl CH3(CH2)7CH2 —
nonyl
CH3CHCH 3 3(CH2)3CH2 CH
CH 3CHCH2CH3
— pentyl CH
CH33CH(CH 3)CH
(CH2)8CH —
2 2—
C(CH3)3 decyl
| | |
Isopropyl sec-butyl isobutyl
tert-butyl
3) When 2 or more subst. are present, list them in
alphabetical. When 2,3 or more same alkyl group
are present, use prefix di, tri, tetra and so on
(ignored in alphabetizing)
NOMENCLATURE FOR
HALOGENATED HYDROCARBONS
(ALKYL HALIDES)

Halogen :
 Fluorine (F) - fluoro
 Chlorine (Cl) - chloro
 Bromine (Br) – bromo
 Iodin (I) - iodo
CORFORMATIONAL ISOMERISM
 conformational isomerism is a form of stereoisomerism
involving the phenomenon of molecules with the same
structural formula existing as different conformational
isomers or conformers due to atoms rotating about a bond.
 Stereoisomerism - the molecules have the same molecular
formula and the same structural formula . However, the atoms
have a different three dimensional arrangement in space which
makes them non-superimposable
 Example: Ethane CH3CH3

Sawhorse Newman
diagram projection
 If the hydrogen on the adjacent carbons are lined up with
one another and as close together as possible results
eclipsed conformation. This conformation is less stable.
 If the hydrogen on the adjacent carbons are far away results
staggered conformation. This confirmation is more stable
for ethane molecule.
 These conformation can be represented by either Sawhorse
diagram or Newman projection.
 Example: Butane

2 methyl groups are as far as

possible – 180o

Sawhorse Newman
diagram projection
 In the anti conformation (when the dihedral angle=180°) the
potential energy is at its lowest, therefore the most stable.
This is due to the methyl groups being the farthest away
from each other in the molecule.

 When the dihedral angle=120° or 240°, (eclipsed

conformation) in butane, the methyl groups align
themselves with hydrogens on the same plane, resulting in
the butane having a higher potential energy than the
gauche conformations though still having a lower potential
energy than the eclipsed conformation (dihedral angle=0°
or 360°)

 When the dihedral angle=60° or 300°, (gauche

conformation) in butane, the methyl groups are farther apart
.

 When the dihedral angle=0° or 360°, (eclipsed

conformation) in butane, the two methyl groups are in close
proximity with the molecule, therefore the potential energy
is at its highest.
CYCLOALKANES-
CONFORMATIONAL AND
GEOMETRIC STRUCTURE
 Cycloalkanes: saturated ring hydrocarbons

 Each carbon atom in the ring has 4 bonded atoms, sp3

hybridized — shall have the angle of 109.5o
 But the internal angles for : cyclopropane= 60o,
cyclobutane= 90o — angle strain, thus make them
reactive. cyclopentane = 108o (slightly reactice).
 High cycloalkane, example:, cyclohexane -= 120o, ,
cycloheptane = 128o , the rings are large and have
sufficient flexibility to twist, bend and pucker out of the
plane until each carbon has stable tetrahedral angle.
The Bayer Strain Theory
CONFORMATIONAL ISOMERISM IN
CYCLOHEXANE
 Two conformational isomers in cyclohexane; boat
conformation and chair conformation
 Both conformations have sp3 hybridized for the carbon
atoms.
 The two conformations are not equally stable, chair
conformation is more stable.
Hydrogens:

 6 axial hydrogens
 6 equitorial hydrogens
CONFORMATIONAL ISOMERISM IN
SUBSTITUTED CYCLOHEXANES
 Example: methylcyclohexane
 If there are two groups attached (axial
position) to the ring,
 If there are two groups attached (axial-
equitorial) to the ring,
HYDROCARBON: RELATION OF
STRUCTURE AND PHYSICAL
PROPERTIES
 Solid, liquid and gaseous do not represent
differences in structure of the individual
molecules.
 They represent variations in the
ARRANGEMENT of the molecules
 Solid – arranged very compactly and are
relatively immobilized. Very maximum
attractive forces.
 Liquid – the molecules are mobile but the
interaction between molecules are still exist.
 Gas – molecular mobility is so great because
no interaction between the molecules,
theoretically independent of others.
A) MELTING POINT, BOILING POINT
AND MOLECULAR WEIGHT
 Increase with increasing in molecular weight.
- the plentiful of sites for intermolecular
attractions
solid liquid gasoeus
- the heavier the substance, more energy is
needed to break the intermolecules forces
 B) MELTING POINT, BOILING POINT AND
MOLECULAR STRUCTURE

•Boiling points for unbranched alkanes increase smoothly with the

increasing number of atom carbon and molecular weight. Why???
* larger molecules have larger surface area, resulting in increased
intermolecular Van de Walls attractions.
CH3 CH3
H2 H2 H2 H2 H2
H3C C C C C CH3 H3C C C CH3 H3C C CH3
H
Melting point (MP) : -160oC -130oC CH3 -17oC
Boiling point (BP) : 36oC 28oC 9.5oC

•BP decrease with chain branching in hydrocarbons. Why????

* branching makes a molecule more compact and decreases the
surface area
*Small surface – few intermolecular attraction.
•MP for highly branched are higher than longer straight chain
C) SOLUBILITY AND DENSITY
 Alkanes are nonpolar – dissolve in nonpolar
or weakly polar organic solvent
 Alkanes – hydrophobic – do not dissolve in
water
 Hydrophobic nature make alkanes good
lubricants and preservatives for metal –
can avoid metal corrosion.
 Alkanes have densities around 0.7g/mL
compare with 1.0g/mL for water. So, the
mixture of these two quickly separated into
two layers