Chapter

Outline

Chapter 19
Organic Chemistry: Saturated
Hydrocarbons
Organic
chemistry is
important in
nanotechnology.
A carbon
nanotube forest
is shown here.
General, Organic, and Biochemistry, 10e
John Wiley & Sons, Inc
Hein and Pattison
 Chapter
Outline

Chapter Outline

19.1 Organic Chemistry: History and Scope

19.2 The Carbon Atom: Bonding and Shape
19.3 Organic Formulas and Molecular Models
19.4 Classifying Organic Compounds
19.5 Hydrocarbons
19.6 Saturated Hydrocarbons: Alkanes
19.7 Carbon Bonding in Alkanes

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Chapter Outline

19.8 Isomerism
19.9 Naming Organic Compounds
19.10 Introduction to the Reactions of Carbon
19.11 Reactions of Alkanes
19.12 Sources of Alkanes
19.13 Gasoline: A Major Petroleum Product
19.14 Cycloalkanes
Chapter 19 Summary

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 Chapter
Outline

Organic Chemistry: History and Scope

Organic chemistry is the study of compounds containing
carbon.

These compounds occur naturally but can be prepared in a

laboratory.

The early history of organic chemistry included an

erroneous theory. (i.e. that organic compounds exist
only in living organisms).

The German chemist Wöhler disproved this theory in

1828 with the laboratory synthesis of urea. 4
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What is organic chemistry?

Carbon can form a vast array of long chain and ring

containing compounds because carbon has the unique
ability to bond to itself.

Organic compounds include drugs, fuels, toiletries, plastics,

and fabrics. You can see why organic chemistry is such
an important field of study.
Lipstick is made of organic molecules. Cosmetics
and perfumes contain organic compounds.

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 Chapter
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The Carbon Atom: Bonding and Shape

Carbon can form saturated compounds (i.e. where all

carbon atoms have four single bonds) or unsaturated
compounds (i.e. at least one carbon has a double bond
(C=C) or a triple bond (C≡C)).

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 Chapter
Outline

The Carbon Atom: Bonding and Shape

These are the

molecular
shapes of
carbon
compounds
predicted by the
VSEPR
Bonding
Theory.

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 Chapter
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The Carbon Atom: Bonding and Shape

This figure shows the bonding shape that results when

carbon has four single bonds.

Figure 19.1 Tetrahedral structure of carbon: (a) a regular tetrahedron;

(b) a carbon atom with tetrahedral bonds; (c) a carbon atom within a
regular tetrahedron; (d) a methane molecule, CH4 8
 Chapter
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Your Turn!

Estimate the bond angles around 1C and 2C in the

following structure.

H H
1
C C H
H C H
2
H C
H H

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 Chapter
Outline

Organic Formulas and Molecular Models

Structural formulas or models are often used in organic

chemistry to illustrate molecules.

For example,

or in the case of a model.

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Figure 19.3 Types of formulas and models used to represent
organic molecules. Each diagram is a representation of a
propane molecule.

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 Chapter
Outline

Organic Formulas and Molecular Models

This is an example of how to change a condensed structural
formula into a line structure.

The table on the next slide summarize formulas and

models used in organic chemistry. 12
 Chapter
Outline
Formula or model Definition
Lewis structure Shows all bonds, all atoms, and all nonbonding
electrons
Structural formula Same as Lewis structure except nonbonding
electrons are not shown

Bonds are collapsed so relative positions

Condensed structural formula of atoms are group together

Only bonds and functional groups are shown and

Line structure each endpoint and bend represents a carbon atom

Atoms are shown as balls and bonds as sticks

Ball-and-stick model and the shape is shown at the central atom.

Bonds are omitted and the size of atoms are

Space-filling model emphasized.
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Classifying Organic Compounds

Functional groups are group of atoms (or one atom) that

have specific behavioral characteristics in organic
compounds.
Organic compounds are classified based on the functional
groups that they contain.

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 Chapter
Outline

Classifying Organic Compounds

The list of common

functional groups
found in organic
compounds are
shown here on
Table 19.1.

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 Chapter
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Classifying Organic Compounds

The list of important functional groups found in

biological compounds is shown here on Table 19.2.

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 Chapter
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Classifying Organic Compounds

Ethanol contains the alcohol functional group and dimethyl

ether contains the ether functional group. They have the
same molecular formula but the boiling point (b.p.) of
ethanol is 78C while the b.p. of dimethyl ether is -23C
because of the structural differences between the
molecules. 17
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Hydrocarbons
Hydrocarbons are organic compounds that contain only
carbon and hydrogen atoms. (e.g. propane, CH3CH2CH3
is a hydrocarbon but ethanol, CH3CH2OH is not).

Hydrocarbons are classified as either aliphatic (i.e those

hydrocarbons without benzene rings in the chemical
structure) or aromatic.(i.e those hydrocarbons with
benzene rings in the chemical structure) as shown in
Figure 19.4 on the next slide.

Hydrocarbons are also classified as saturated or unsaturated

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compounds.
 Chapter
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Figure 19.4 Classes of Hydrocarbons

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Hydrocarbons

The principal source of hydrocarbons is fossil fuels which

include natural gas, petroleum, and coal.

Fossil fuels are the primary source of heat and also a

primary source of organic chemicals.

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Saturated Hydrocarbons: Alkanes

Alkanes are saturated hydrocarbons that are either straight-

chain or branched-chain hydrocarbons.

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 Chapter
Outline

Saturated Hydrocarbons: Alkanes

Alkanes form a homologous series of straight-chain

molecules as seen in Table 19.3 on the next slide.
Members of a homologous series have similar structures
but different chemical formulas.

The general formula for all non-cyclic alkanes is shown

here.

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 Chapter
Outline

Saturated Hydrocarbons: Alkanes

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 Chapter
Outline

Your Turn!

Write the formula for an alkane that has nine carbon

atoms.

Write the condensed structural formula for the

straight-chain alkane that has nine carbon atoms.

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 Chapter
Outline

Carbon Bonding in Alkanes

Alkanes contain saturated carbon atoms that have four sigma

bonds.
Sigma bonds are linear bonds formed by a pair of electrons
in overlapping atomic orbitals.

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 Chapter
Outline

Carbon Bonding in Alkanes

Carbon has the ability to form four sigma bonds because of

its ability to hybridize its valence shell electron orbitals
(i.e the s and the 2p orbitals) as shown in Figure 19.5 on
the next slide.

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 Chapter
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Carbon Bonding in Alkanes

Figure 19.5 Rearrangement of carbon 2s and 2p orbitals to form four

equivalent sp3 hybrid orbitals.

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 Chapter
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Carbon Bonding in Alkanes

Figure 19.6 shows the tetrahedral nature of the sp3-

hybridized orbitals.
Figure 19.6 (a) A single sp3-hybridized orbital; (b) four sp3-
hybridized orbitals in a tetrahedral arrangement; (c) sp3 and s orbitals
overlapping to form four C-H sigma bonds in methane.

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 Chapter
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Isomerism

The properties of an organic substance are dependent on its

molecular structure. The majority of organic compounds
are made up of relatively few elements: carbon, hydrogen,
oxygen, nitrogen, and the halogens.
The valence bonds or points of attachment may be
represented in structural formulas by a corresponding
number of dashes attached to each atom.

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 Chapter
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Isomerism

Carbon can form four single bonds each, nitrogen can form
three single bonds, oxygen can only form two single
bonds, and hydrogen and the halogens can form one
single bond each.

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 Chapter
Outline

Isomerism

Because carbon can form four single bonds, alkanes with

four or more carbon atoms can form isomers.

Isomers are molecules that have the same molecular formula

but different structural formula.

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 Chapter
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Isomerism

For example, it is possible to write two structural formulas

corresponding to the molecular formula C4H10 (i.e., butane
and isobutane are isomers of each other). Notice the ball-
and-stick models of these molecules on the next slide.

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 Chapter
Outline

Figure 19.7 Ball-and-stick models illustrating the structural formulas

of several alkanes.

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 Chapter
Outline

Your Turn!

There are several isomers of heptane, C7H16. Draw

structural formulas and condensed structural
formulas for the two isomers that only have one
branching methyl group.

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 Chapter
Outline

Your Turn!

There are several isomers of heptane, C7H16. Draw

structural formulas and condensed structural
formulas for the two isomers that only have one
branching methyl group.
H CH3 H H H H

H C C C C C C H (CH3)2CHCH2CH2CH2CH3

H H H H H H

H H CH3 H H H
CH3CH2CHCH3CH2CH2CH3
H C C C C C C H
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H H H H H H
 Chapter
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Naming Organic Compounds

How do chemists name organic compounds?

Organic compounds are named using the IUPAC System

(International Union of Pure and Applied Chemistry).

The IUPAC System was developed at an international

science meeting in Geneva in 1892.

The IUPAC System is essentially a set of rules that allow

for a systematic and uniform method of naming
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compounds.
 Chapter
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Naming Alkyl Groups

Alkyl groups have one hydrogen less than the respective

alkane.

The general formula for alkyl groups is shown here and a

list of alkyl groups are shown in Table 19.4.

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 Chapter
Outline

Naming Alkyl Groups

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 Chapter
Outline

Naming Organic Compounds

Carbon atoms are often classified based on the number of

carbon atoms directly attached to them.

Primary (1) A carbon with one carbon attached

Secondary (2) A carbon with two carbons attached

Tertiary (3) A carbon with three carbons attached

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 Chapter
Outline

Naming Organic Compounds

Here is an example of a molecule with all three types of

carbon atoms.

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 Chapter
Outline

Your Turn!

Identify all the carbon atoms in the structure below as

1o, 2o or 3o.

H H CH3

H C C C OH

H H CH3

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 Chapter
Outline

IUPAC Rules for Naming Alkanes

1. Identify and then name the longest continuous chain

of carbon atoms. The longest chain in this molecule
contains six carbon atoms.

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 Chapter
Outline

IUPAC Rules for Naming Alkanes

2. Number the chain so any branch alkyl groups have the

lowest possible number. There is only one correct way
to number the carbon atoms in the longest chain.

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 Chapter
Outline

IUPAC Rules for Naming Alkanes

3. The methyl group is attached to the #3 carbon atom

not the #4 carbon atom. The IUPAC name for the
molecule is 3-methylhexane.

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 Chapter
Outline

IUPAC Rules for Naming Alkanes

4. Use prefixes (i.e. di, tri, tetra etc. ) if two or more of

the same alkyl group branches appear on the longest
chain. One methyl group is on the #2 carbon atom and
another methyl group is on the #3 carbon atom.

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 Chapter
Outline

IUPAC Rules for Naming Alkanes

5. When several different groups are attached to the same

parent compound, list the groups in alphabetical order
(e.g. chloro is listed before isopropyl and isopropyl is
listed before methyl).

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 Chapter
Outline

Your Turn!

Give the IUPAC name for the this alkane.

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 Chapter
Outline

Your Turn!

Write the structural formula for 5-ethyl-3-

methyloctane.

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 Chapter
Outline

Introduction to the Reactions of Carbon

The importance of organic chemistry is illustrated by the

variety of reactions that occur at the carbon atom which
include four major types.

• Oxidation-reduction
• Substitution
• Addition
• Elimination

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 Chapter
Outline

Introduction to the Reactions of Carbon

Oxidation involves a higher number of oxygen atoms

bonding to carbon. Carbon dioxide is more oxidized
than methane so this is an oxidation reaction.

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 Chapter
Outline

Introduction to the Reactions of Carbon

Reduction is the reverse of oxidation and involves a

higher number of hydrogen atoms bonding to carbon.
Methanol is more reduced than carbon dioxide so this
is a reduction.

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 Chapter
Outline

Introduction to the Reactions of Carbon

Substitution is the exchange of one atom for another at the

carbon atom.

In this reaction a bromine atom changes position with a

hydrogen atom in methane.

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 Chapter
Outline

Introduction to the Reactions of Carbon

Addition is a reaction where two reactants join to form a

single product.

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 Chapter
Outline

Introduction to the Reactions of Carbon

Elimination is the splitting of a single reactant into two

products.

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 Chapter
Outline

Your Turn!

Classify the following reaction as substitution,

elimination or addition.
H H
H H Cl
C H
H C C C H H C C + HCl
H H
H H H

55
 Chapter
Outline

Reactions of Alkanes

Reaction Class Name of Reaction

Oxidation Combustion
Reactions of
alkanes can be Substitution Halogenation
classified as
shown in Elimination Dehydrogenation
this table.

Decomposition Cracking

Rearrangement Isomerization 56
 Chapter
Outline

Reactions of Alkanes

Combustion (oxidation)
Alkanes are a valuable energy source due to their ability to
react with oxygen . Alkanes release a large amount of
energy as shown here.

Alkanes generally are considered to be unreactive and for

reactions other than combustion a catalyst or other
special reaction conditions are necessary.
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 Chapter
Outline

Reactions of Alkanes

Halogenation (substitution): Here a chlorine atom

is replacing a hydrogen atom on an ethane molecule.

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 Chapter
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Reactions of Alkanes

Dehydrogenation (elimination): Here two hydrogen

atoms are removed from a propane molecule to form
propene.

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 Chapter
Outline

Reactions of Alkanes

Cracking (decomposition): Here an alkane undergoes

decomposition to form a smaller alkane and an alkene.

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 Chapter
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Reactions of Alkanes

Isomerization (rearrangement): Here an unbranched

alkane (pentane) undergoes isomerization to form a
branched compound that is an isomer of pentane (2-
methylbutane).

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 Chapter
Outline
The chlorination of methane with excess chlorine can
produce each of the compounds shown in Table 19.5.

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 Chapter
Outline

Reactions of Alkanes

Alkyl halides are compounds that have an X (X = -F

(fluoro), -Cl (chloro), -Br (bromo), or - I (iodo) attached
to a carbon atom.

RX is the general formula for alkyl halides.

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 Chapter
Outline

Reactions of Alkanes

Examples of Alkyl Halides

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 Chapter
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Reactions of Alkanes

The mechanism of halogenation consists of three steps:

initiation, propagation, and termination as shown on the
next few slides.

A mechanism is the individual steps that lead to the product

from the reactant.

Overall Reaction

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 Chapter
Outline

Reactions of Alkanes

Step I Initiation: Formation of chlorine free radicals.

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 Chapter
Outline

Reactions of Alkanes

Step II Propagation: A chlorine free radical reacts with

the alkane to form hydrogen chloride and an alkyl free
radical. The alkyl free radical reacts with a molecule of
chlorine to form another chlorine free radical and an alkyl
halide.

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 Chapter
Outline

Reactions of Alkanes

Step III Termination: 1) The reaction of two chlorine free

radicals; 2) the reaction of a chlorine free radical and an
alkyl free radical to form an alky halide; 3) the reaction of
two alkyl free radicals to form a larger alkane.

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 Chapter
Outline

Free Radical Stability and Reactivity

Experimental results show that tertiary (3o) free radicals

are the most stable and the most easily formed
radicals in chemical reactions.

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 Chapter
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Free Radical Stability and Reactivity

Secondary (2o) free-radicals are next in stability and

primary (1o) free radicals are the least stable.

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 Chapter
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Free Radical Stability and Reactivity

Therefore the major product formed in the chlorination

of propane corresponds to the secondary free radical,
i.e. 2-chloropropane. The minor product corresponds
to the primary free radical.

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 Chapter
Outline

Your Turn!

Write an equation for each step in the free-radical

mechanism forming 2-chlorobutane.

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 Chapter
Outline

Your Turn!

Write an equation for each step in the free-radical

mechanism forming 2-chlorobutane.
Initiation
UV
Cl Cl 2 Cl
light

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 Chapter
Outline

Your Turn!

Write an equation for each step in the free-radical

mechanism forming 2-chlorobutane.
Propagation

Cl + CH3CH2CH2CH3 HCl + CH3CHCH2CH3

Cl

CH3CHCH2CH3 + Cl Cl CH3CHCH2CH3 + Cl

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 Chapter
Outline

Your Turn!

Write an equation for each step in the free-radical

mechanism forming 2-chlorobutane.
Termination

2 Cl Cl Cl
Cl

Cl + CH3CHCH2CH3 CH3CHCH2CH3

CH3CHCH2CH3
CH3CHCH2CH3 + CH3CHCH2CH3
CH3CHCH2CH3
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 Chapter
Outline

Sources of Alkanes

• Alkanes are produced from natural gas and

petroleum.

• Natural gas and petroleum are formed by the decay

of plants and animals

• Natural gas and petroleum are non-renewable

sources of energy.

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 Chapter
Outline

Gasoline: A Major Petroleum Product

Gasoline is a mixture of
hydrocarbons. Without
additives it causes
knocking which is a
detonation of the air-fuel
mixture in an engine.
Figure 19.8 Uses of petroleum

The octane rating of gasoline is the knocking performance

based on the percent isooctane in an isooctane/heptane
mixture. (higher octane ratings = less knocking)
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 Chapter
Outline

Gasoline: A Major Petroleum Product

Manufacturers of gasoline have switched from tetraethyl

lead to more environmentally friendly additives like
MTBE (methyl-tert-butyl ether) and ethanol.

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 Chapter
Outline

Gasoline: A Major Petroleum Product

These additives boost octane ratings like lead additives but

are better for the environment. However studies have
shown that MTBE can pollute ground water and is also
being replaced.

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 Chapter
Outline

Cycloalkanes

Cycloalkanes are cyclic alkanes with the general formula

CnH2n.

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 Chapter
Outline

Cycloalkanes

The physical properties and the chemical reactivity of

cycloalkanes are similar to their open-chain counterparts
(the alkanes) with two exceptions. Cyclopropane and
cyclobutane are more reactive.

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 Chapter
Outline

Cycloalkanes

Cyclopropane and cyclobutane have higher reactivity

because their bonds are strained. The basis for the strain is
the deviation of their bond angles from the normal
tetrahedral carbon bond angle of 109.5.

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 Chapter
Outline

Cycloalkanes

These molecules cannot change shape to significantly change

their bond angles like cycloalkanes that have larger ring
sizes.

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 Chapter
Outline

Cycloalkanes

The result of the bond strain in cyclopropane is that it reacts

readily with molecules like bromine as shown here.

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 Chapter
Outline
Figure 19.10 Ball-and-stick models of cyclopropane, hexane, and
cyclohexane. In cyclopropane, all the carbon atoms are in one
plane (bond angles = 60° instead of 109.5° ).

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 Chapter
Outline
The cyclohexane molecule is puckered (as shown in the
chair conformation) with bond angles about 109.5° as
found in hexane.

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 Chapter
Outline

Cycloalkanes

Cyclohexane can exist in either the chair or boat

conformation.

A conformation is the three-dimensional spatial arrangement

of the atoms in a molecule.

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 Chapter
Outline

Cycloalkanes

Figure 19.11 Conformations of cyclohexane: (a) chair conformation;

(b) boat conformation. Axial hydrogens are shown in blue in the chair
conformation.
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 Chapter
Outline

Cycloalkanes

When naming monosubstituted cycloalkanes:

1. Name the substituent
2. Name the parent cyclohexane

Both of these structures are the same molecule and have

the same name (methylcyclohexane).
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methyl + cyclohexane = methylcyclohexane
 Chapter
Outline

Cycloalkanes

When naming polysubstituted cycloalkanes.

1. Number the ring (clockwise or counterclockwise)

to give the substituted groups the lowest possible
numbers.
2. Name the groups and their locations.
3. Name the parent cyclohexane.

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 Chapter
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Cycloalkanes

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 Chapter
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Your Turn!

Write structural formulas for 1-bromo-2-

methylcyclopentane and 1,1-dichloro-3-
ethylcyclohexane.

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Chapter 19 Summary

 Organic chemistry is the chemistry of carbon

compounds.

 Alkanes are hydrocarbons that are either saturated (no

double or triple bonds) or unsaturated (one or more
multiple bonds ).

 Organic compounds are classified by functional groups

which is the smaller part of the molecule that determines
the chemical profile of the molecule.
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 Chapter
Outline

Chapter 19 Summary

 Organic molecules can be represented by ball-and stick

models, space-filling models, Lewis structures, line
structures, and condensed structural formulas.

 Saturated carbon atoms are sp3 hybridized which form

can four sigma bonds.

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 Chapter
Outline

Chapter 19 Summary

 Reactions of organic molecules are classified as

oxidation-reduction, substitution, elimination, and
addition.

 Alkanes undergo combustion but need special reaction

conditions to undergo halogenation, dehydrogenation,
cracking, and isomerization.

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 Chapter
Outline

Chapter 19 Summary

 Cycloalkanes (CnH2n ) exist in conformations with

hydrogen on each carbon in axial or equatorial position

 Cyclopropane and cyclobutane are unusually reactive

because of strained bonds.

 The most stable form of cyclohexane is the chair

conformation.

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