Chapter 12
Saturated
Hydrocarbons
Chapter 12
Table of Contents
12.1 Organic and Inorganic Compounds
12.2 Bonding Characteristics of the Carbon Atom
12.3 Hydrocarbons and Hydrocarbon Derivatives
12.4 Alkanes: Acyclic Saturated Hydrocarbons
12.5 Structural Formulas
12.6 Alkane Isomerism
12.7 Conformations of Alkanes
12.8 IUPAC Nomenclature of Alkanes
12.9 Line-Angle Structural Formulas for Alkanes
12.10 Classification of Carbon Atoms
12.11 Branched-Chain Alkyl Groups
12.12 Cycloalkanes
12.13 IUPAC Nomenclature for Cycloalkanes
12.14 Isomerism in Cycloalkanes
12.15 Sources of Alkanes and Cycloalkanes
12.16 Physical Properties of Alkanes and Cycloalkanes
12.17 Chemical Properties of Alkanes and Cycloalkanes
12.18 Nomenclature and Properties of Halogenated Alkanes
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Section 12.1
Organic and Inorganic Compounds
Organic vs. Inorganic
• Organic chemistry: Study of hydrocarbons
(only carbon and hydrogen atoms) and their
various derivatives.
– Examples: natural gas, petroleum,
plastics, rubbers, paper, carbohydrates
(sugar, starch), proteins, enzymes, fatty
acids, food stuff, drugs, textiles, etc.
• Inorganic chemistry: Study of all substances
other than hydrocarbons and their
derivatives.
– Examples of inorganic compounds:
sulfuric acid, nitric acid, ores and
minerals, air, baking powder, caustic
soda, table salt, metal alloys (brass,
bronze), etc.
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Section 12.2
Bonding Characteristics of the Carbon Atom
• C-atom always makes total 4 Bonds
• The sharing of four valance electrons requires the formation of
four covalent bonds which are represented by four lines as shown
here.
C C
Bonded with other 4 Bonded with other 3
atoms atoms
C C
Bonded with other 2 Bonded with
atoms other 2 atoms Return to TOC
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Section 12.3
Hydrocarbons and Hydrocarbon Derivatives
• Hydrocarbon: Compound that contains only carbon and
hydrogen atoms.
• Hydrocarbon derivative: Compound that contains carbon
and hydrogen and one or more additional elements.
• Saturated hydrocarbon: Hydrocarbon with all carbon–
carbon bonds are single bonds.
• Unsaturated hydrocarbon: Hydrocarbon with one or
more carbon–carbon multiple bonds (double bonds,
triple bonds, or both).
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Section 12.3
Hydrocarbons and Hydrocarbon Derivatives
Summary of Classification Terms for Organic Compounds
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Section 12.4
Alkanes: Acyclic Saturated Hydrocarbons
• Alkanes: Open chain (straight or branched) binary
compounds of carbon and hydrogen.
• All bonds are single bonds.
• General formula: CnH2n+2 .
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Section 12.5
Structural Formulas
• Expanded Structural Formula: A two-dimensional structural
representation that depicts the bonding of all atoms in a
molecule.
• Condensed Structural Formula: Structural arrangements
of different groupings (a central atom connected with other
atoms) in a molecule.
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Section 12.5
Structural Formulas
• Skeletal Structural Formula: Structural arrangement of all
bonded carbon atoms without showing the attached
hydrogen atoms.
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Section 12.6
Alkane Isomerism
Structural (Constitutional) Isomerism
• Compounds having same molecular formula, but different
structural arrangements (different connectivity of atoms)
are called Isomers, and the phenomenon is known as
isomerism.
• Space-filing models for the three isomeric C5H12 alkanes:
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Section 12.6
Alkane Isomerism
Number of Isomers Possible for Alkanes of Various Carbon Chain
Lengths
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Section 12.7
Conformations of Alkanes
• Conformation: At a given instant, the specific three
dimensional spatial arrangement of atoms due to the
rotation of C-C single bond in the same molecule.
• Different conformational structures result from C-C single
bond rotation, but no breaking of bonds takes place.
• Different structural isomers result from different
connectivity of atoms, which requires breaking and making
of bonds in the same molecule.
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Section 12.8
IUPAC Nomenclature for Alkanes
• Systematic approach for naming alkanes was
introduced by the International Union of Pure and
Applied Chemistry (IUPAC), and the rules are being
updated periodically.
• The rules are applied to both types of alkanes:
– Straight chain (continuous) alkanes
– Branched chain (divided / substituted) alkanes
– Substituent: an atom or group of atoms attached to
a chain (or ring) of carbon atoms.
– Alkyl group: the group of atoms that would be
obtained by removing a hydrogen atom from an
alkane. Return to TOC
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Section 12.8
IUPAC Nomenclature for Alkanes
Rules for Naming Branched-Chain Alkanes
Rule 1: Identify the longest continuous carbon chain and name that
chain as the parent
Rule 2: Number the carbon atoms in the parent chain in such a way so
that to give the lowest possible number for a substituent (alkyl
group).
Rule 3: If only one substituent present, name and locate it by number;
then, prefix the number and name to that of the parent carbon
chain.
Rule 4: If two or more of the same kind of alkyl group are present in a
molecule, indicate the number with a Greek numerical prefix
(di-, tri-, tetra-, penta-, and so forth). In addition, a number
specifying the location of each identical group must be included.
These position numbers, separated by commas, precede the
numerical prefix. Numbers are separated from words by
hyphens. Return to TOC
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Section 12.8
IUPAC Nomenclature for Alkanes
Rules for Naming Branched-Chain Alkanes
Rule 5: When two kinds of alkyl groups are present on the
same carbon chain, number each group separately,
and list the names of the alkyl groups in
alphabetical order.
Rule 6: Follow IUPAC punctuation rules:
1. Separate numbers from each other by commas.
2. Separate numbers from letters by hyphens.
3. Do not add a hyphen or a space between the last-
named substituent and the name of the parent alkane.
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Section 12.8
IUPAC Nomenclature for Alkanes
Practice Exercise
Answer:
a. 3,6-Dimethyloctane
b. 3,4,4,5-Tetramethyloctane
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Section 12.9
Line-Angle Structural Formulas for Alkanes
• Line-angle (Bond-Angle) structural formula:
– A structural representation in which a line represents a carbon–
carbon bond.
– A carbon atom is understood to be present at every point where
two lines meet ( at the intersection).
– At the ends of each lines.
– Example:
Octane
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Section 12.9
Line-Angle Structural Formulas for Alkanes
• Structures of branched-chain alkanes designated using
line-angle structural formulas.
• Example: The five constitutional isomers of C6H14.
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Section 12.10
Classification of Carbon Atoms
• Based on the skeletal structure of the C-atom in a
hydrocarbon chain, each C-atom can be classified as
follows:
– Primary: If bonded with only one C- atom
– Secondary: If bonded with other 2 C- atoms
– Tertiary: If bonded with other 3 C-atoms
– Quaternary: If bonded with other 4 C- atoms
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Section 12.11
Branched-Chain Alkyl Groups
• Continuous chain alkyl groups: The simplest type of alkyl
group with continuous chain of carbon atoms.
• Branched-chain alkyl groups: Alkyl groups are added to
the continuous parent chain of carbon atoms (Alkenes
with branched-chain alkyl groups).
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Section 12.12
Cycloalkanes
• Cycloalkanes are alkanes that contain a ring of three or
more carbons.
• General Formula of Cycloalkane: CnH2n
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Section 12.13
IUPAC Nomenclature for Cycloalkanes
• Count the number of carbons in the ring, and name the parent
cyclic chain (just like an alkane).
• Add the prefix cyclo to the IUPAC name of the unbranched
alkane, e.g., Cyclopentane
• Name any alkyl groups on the ring in the usual way
• Numbering conventions used in locating substituents on the ring:
1. If there is just one ring substituent, it is not necessary to
locate it by number.
2. When two ring substituents are present, the carbon atoms in
the ring are numbered beginning with the substituent of
higher alphabetical priority and proceeding in the direction
(clockwise or counterclockwise) that gives the other
substituent the lower number.
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Section 12.13
IUPAC Nomenclature for Cycloalkanes
3. When three or more ring substituents are present, ring numbering
begins at the substituent that leads to the lowest set of location
numbers. When two or more equivalent numbering sets exist,
alphabetical priority among substituents determines the set used.
H3 C CH3
CH2 CH3
3-Ethyl-1,1-dimethylcyclohexane
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Section 12.13
IUPAC Nomenclature for Cycloalkanes
Practice Exercise
Answers:
a. Methylcyclopropane
b. 1-Ethyl-4-methylcyclohexane
c. 4-Ethyl-1,2 dimethylcyclopentane
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Section 12.14
Isomerism in Cycloalkanes
• Cycloalkanes also exhibit stereoisomerism.
– Stereoisomers have the same molecular and
structural formulas but different orientations of atoms
in space.
– Several forms of stereoisomerism exist.
• Di-substituted Cycloalkanes exhibit Cis-Trans isomerism.
– Cis–trans isomers have the same molecular and
structural formulas but different spatial orientations of
atoms due to the restricted rotation about bonds.
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Section 12.14
Isomerism in Cycloalkanes
• Cis- is a prefix that means “on the same side.” In cis-1,2-
dimethylcyclopentane, the two methyl groups are on the
same side of the ring.
• Trans- is a prefix that means “across from.” In trans-1,2-
dimethylcyclopentane, the two methyl groups are on
opposite sides of the ring.
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Section 12.15
Sources of Alkanes and Cycloalkanes
Natural Gas and Petroleum
• Natural Gas:
– 50 - 90% Methane
– 1 - 10% Ethane
– Up to 8% Higher Alkanes (mostly Propane and
Butanes)
• Petroleum (crude oil):
– Complex mixture of acyclic and cyclic hydrocarbons
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Section 12.15
Sources of Alkanes and Cycloalkanes
Petroleum Refining
• Refining: Isolation of
soil, sand, sulfur, etc.,
from the crude oil and
physical separation of
the hydrocarbons
mixture into several
fractions.
• Fractional Distillation:
Process of separating
different components
from a mixture based
on their boiling points.
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Section 12.16
Physical Properties of Alkanes and Cycloalkanes
Solubility and Density
• Solubility: Follows the rule ‘like dissolves like’
– Soluble in non-polar solvents e.g., in hexanes
– Insoluble in polar solvents e.g., water, alcohol
– Application: protective wax coating on fruits to prevent loss of
water as well as from fungi or bacterial strain etc.
• Density: Lighter than water
– Densities of alkanes and cycloalkanes range from
– 0.6 – 0.8 g/mL (water density at 4 degree C = 1.0 g/mL)
– Practical illustration: quick spreading of oil spills in water.
– Fire caused by floating oil can not be extinguished by water.
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Section 12.16
Physical Properties of Alkanes and Cycloalkanes
Boiling Points
• The boiling points
increase with an
increase in the number
of carbon atom in chain
length or ring size.
• Branching in carbon
chain lowers the boiling
point of an alkane.
• Cycloalkanes have
higher boiling points
than their noncyclic
counterparts with the
same number of c-
atoms
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Section 12.17
Chemical Properties of Alkanes and Cycloalkanes
Combustion
• Vigorous reaction with oxygen (usually from air)
• Accompanied by the evolution of heat and light
• Always an exothermic process
• The final products of any complete combustion of
hydrocarbons are:
– Carbon dioxide and Water (vapor)
– CH4 + 2O2 CO2 + 2H2O + Energy
– 2C6H14 + 19O2 12CO2 + 14H2O + Energy
– Incomplete / partial combustion results in a mixture of
carbon dioxide and carbon monoxide with water (g)
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Section 12.17
Chemical Properties of Alkanes and Cycloalkanes
Halogenation
• Direct reaction with halogens (chlorine, bromine, iodine)
• Substitution of one or more H-atoms of hydrocarbons by
halogen atoms (substitution reaction of alkanes)
H H H H
Heat or
H C C H + Br2 H C C Br + HBr
Light
H H H H
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Section 12.18
Nomenclature and Properties of Halogenated Alkanes
• Halogenated Alkanes: Derivatives alkanes in which one
or more hydrogen atoms are substituted by halogen
atoms.
• Halogenated cycloalkanes: Cycloalkane derivatives in
which one or more hydrogen atoms are substituted by
halogen atoms
• These derivatives are named as:
– Haloalkanes or Halocycloalkanes (IUPAC naming)
– Alkyl Halides or Cycloalkyl halides (common naming)
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Section 12.18
Nomenclature and Properties of Halogenated Alkanes
IUPAC Rules
• Follow the same rules for naming alkanes / cycloalkanes
• Lowest locant number is given to the top priority group.
• Alkyl and halogen substituents have the same ranking.
• If 2 or more different substituents are present, the
alphabetical order determines their priority.
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Section 12.18
Nomenclature and Properties of Halogenated Alkanes
Physical Properties
• Density: Many halogen derivatives are heavier than
water.
• Polarity: They are mostly polar compounds (if
unsymmetrical).
• Boiling Points: Generally higher than parent
hydrocarbons.
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