Chapter Outline

Organic Chemistry: 19.1 Organic Chemistry: 19.4 Classifying Organic Compounds

Saturated Hydrocarbons History and Scope
19.5 Hydrocarbons
19.2 The Carbon Atom:
Chapter 19 Bonding and Shape

19.3 Molecular Models

Hein * Best * Pattison * Arena

Colleen Kelley
Chemistry Department
Version 1.0 1
Pima Community College
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© John Wiley and Sons, Inc.

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• Carbon, in combination with hydrogen,

!"#$%&'()*%+,-&(./0-%,-*&12 oxygen, nitrogen, and sulfur, forms the basis
for millions of organic compounds.
19.6 Saturated 19.11 Reactions of Alkanes
Hydrocarbons: Alkanes 19.12 Sources of Alkanes • Organic molecules form the products used
19.7 Carbon Bonding in 19.13 Gasoline
Alkanes
in:
19.14 Cycloalkanes
19.8 Isomerism 1. Cosmetics and perfumes
19. 9 Naming Organic 2. Pharmaceutical products
Compounds
3. Soaps and detergents
19.10 Introduction to the
Reactions of Carbon 4. Paints, varnishes, dyes
5. Many more!
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• The carbon atom is central to all organic

compounds.
• A carbon atom usually forms four covalent
bonds.
The Carbon Atom: – Single bonds
• Ex: H3C-CH3 in ethane
– Double bonds
Bonding and Shape • Ex: H2C=CH2 in ethene
– Triple bonds
• Ex: HCºCH in ethyne (acetylene)

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 • An organic compound is classified as The Shapes of Carbon-
saturated if it contains only single bonds. Containing Compounds
– Ex: H3C-CH3 in ethane • Valence Shell Electron Pair Repulsion
theory (VSEPR)
• An organic compound is classified as
unsaturated if the molecules possess one or – VSEPR theory states that electron pairs
more multiple carbon-carbon bonds. repel each other because they have like
charges.
– Ex: H2C=CH2 in ethene
– The electron pairs will try to spread out
– Ex: HCºCH in ethyne (acetylene)
as far as possible around an atom.
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7 8

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

tetrahedron; (b) a carbon atom with tetrahedral bonds; (c) a Figure 19.2 (a) Lewis structure for C2H4. (b)
Shape of a molecule with a carbon-carbon double
carbon atom within a regular tetrahedron; (d) a methane
bond. The hydrogens and carbon form the vertices
molecule, CH4
of a triangle. The bond angles are 120°.
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9 10

In a triple bond, the carbon has only two Molecular Models

regions for shared electrons. To be
placed as far apart as possible, a linear • Models are often used in organic
arrangement is required. chemistry to illustrate molecules.
180°

H:C:::C:H H C C H

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11 12

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 Figure 19.4 Models of ethane: (a) Lewis
structure; (b) bond-line drawing; (c) ball-
and-stick model; (d) spacefilling model

Figure 19.3 Molecular models of methane:

(a) ball-and-stick model; (b) spacefilling
model 13 14

13 14

Structural Formulas
• In a structural formula, the
arrangement of atoms within the Classes of Organic
molecule is clearly shown.
• These structural formulas are often
Compounds
shortened into condensed structural
formulas.
– e.g. CH3CH2CH3 & CH3-CH2-CH3
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15 16

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 19 20

19 20

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21 22

Functional Groups
• Organic compounds with similar
structures are grouped into classes as
Classifying Organic shown in Table 19.1.
• The members of each class of compounds
Compounds contain a characteristic atom or group of
atoms called a functional group.

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 Functional Groups
• A functional group:
– is part of a larger molecule.
– is composed of an atom or group of
atoms that have characteristic chemical
behavior.
Hydrocarbons
– Chemically, a given functional group
behaves in nearly the same way in every
molecule it’s part of.
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25 26

Hydrocarbons
Hydrocarbons
• Hydrocarbons are classified into
• Hydrocarbons are compounds that are two major categories, aliphatic and
composed entirely of carbon and aromatic.
hydrogen atoms bonded to each other
– aliphatic (do not contain benzene ring)
by covalent bonds.
• alkanes, alkenes, alkynes, cycloalkanes
• Fossil fuels – natural gas, petroleum,
and coal – are the principal sources of – aromatic (contain a benzene ring)
hydrocarbons.
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27 28

Figure 19.5
Classes of
Hydrocarbons

Saturated
Hydrocarbons:
Alkanes
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29 30

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 The alkanes, also known as paraffins or saturated
hydrocarbons, are straight- or branched-chain Homologous Series
hydrocarbons with only single covalent bonds
between the carbon atoms.
• When each member of a series differs
CH3CH2CH2CH2CH3 from the next member by a CH2 group,
straight-carbon chain the series is called a homologous
series.
• The members of a homologous series
(CH3)2CHCH2CH2CH3 are similar in structure, but have a
regular difference in formula.
branched chain of carbon atoms 31 32

31 32

Homologous Series

CnH2n + 2

general formula for open-chain

alkanes

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33 34

Name Molecular Formula Condensed Structural Formula BP (°C) MP (°C)

Carbon Bonding in
Alkanes

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35 36

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 Figure 19.7 The tetrahedral nature of sp3 orbitals:
(a) a single sp3-hybridized orbital;
(b) four sp3-hybridized orbitals in a tetrahedral
arrangement; (c) sp3 and s orbitals overlapping to form
C-H bonds in methane.

Figure 19.6 Schematic hybridization of 2s22px12pz0

orbitals of carbon to form four sp3 electron orbitals.

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37 38

Sigma (s) Bond

• A C-C and C-H single bond result from the
overlap of sp3 orbitals.
• This type of bond is called a sigma (s)
bond.
• A sigma bond exists if the electron cloud
Isomerism
formed by the pair of bonding electrons lies
on a straight line drawn between the nuclei
of the bonded atoms.
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39 40

The valence bonds or points of attachment • Alkane molecules are non-polar.

may be represented in structural formulas – Carbon-carbon bonds are non-polar, since
by a corresponding number of dashes they are between like atoms.
attached to each atom:
– Carbon-hydrogen bonds are only slightly
polar.
C N O H Cl – The bonds in an alkane are symmetrically
directed toward the corners of a
S F Br tetrahedron.

I
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 Writing the Correct Structural Formula
for Propane, C3H8
In virtue of their low polarity, alkane An alkane contains only single bonds.
molecules have relatively low boiling H H H
points compared with other organic
compounds of similar molar mass. H C C C H

H H H

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43 44

It is possible to write two structural formulas

corresponding to the molecular formula C4H10: Isomerism
H • The phenomenon of two or more
H H H H H H compounds having the same molecular
H C H formula but different structural
H C C C C H
arrangements of their atoms is called
H C C C H
H H H H
isomerism.
butane or n-butane H H H • The various individual compounds are
bp = -0.5 C isobutane
called isomers.
mp = -138.3 C bp = -11.7 C – e.g. There are two isomers of C4H10.
mp = -159.5 C
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45 46

Figure 19.8 Ball-and-stick models illustrating Figure 19.8 Ball-and-stick models illustrating
structural formulas of methane, ethane and structural formulas of butane and isobutane.
propane.

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 Isomers are compounds that
have the same molecular Example for Drawing
formula, but different structural
formulas.
Isomers

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49 50

There are three isomers of pentane, C4H12. Write Isomers of Pentane, C5H12 (continued)
structural formulas and condensed structural formulas
• Forthe next isomer, start by writing a four-carbon chain and
for these isomers.
attach the fifth carbon atom to either of the middle carbon
1. Write the carbon skeleton of the compound containing the atoms – do not use the end ones. Add 12 hydrogens to
longest continuous carbon chain. complete the structure.
C-C-C-C-C H
H
H
H H C H
2. Complete the structure by attaching hydrogen atoms CH3
around each carbon. H C C C C H CH3CH2CHCH3 CH3CH2CH(CH3)2

H H H H H H H H H

H C C C C C H CH3CH2CH2CH2CH3 •This is the only four-chain compound that can be

written.
H H H H H
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51 52

Isomers of Pentane, C5H12 (continued)

For the third isomer, start with a three-carbon
chain, attach the other carbon atoms to the
central carbon atom, and complete the structure
by adding 12 hydrogen atoms:
H
H
H C
H
H CH3 No more isomers of
Naming Organic Compounds
C5H12 can be written.
H C C C H CH3CCH3
H C H
CH3
H H
H
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 IUPAC System for Naming
Alkyl Groups
Organic Compounds
• Alkyl groups have the general formula CnH2n+1
• The method recommended by the (one less hydrogen than the corresponding
International Union of Pure and alkane).
Applied Chemistry is systematic, • The name of the group is formed from the name of
the corresponding alkane by simply dropping –ane
generally unambiguous, and and substituting a –yl ending.
internationally accepted. CH4 = methane -CH3 = methyl
• Some trivial or common names are still • The letter R is often used in formulas to mean any
used. of the many possible alkyl groups.
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55 56

Table 19.3 Table 19.3

Names and
Formulas of
Selected
Alkyl Groups

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57 58

IUPAC Rules for Naming Alkanes

Primary (1°), Secondary (2°), and 1. Select the longest continuous chain of carbon
Tertiary (3°) Carbon Atoms atoms as the parent compound, and consider all
alkyl groups attached to it as branch chains that
primary have replaced hydrogen atoms of the parent
hydrocarbon. The name of the alkane consists of
CH3 the name of the parent compound prefixed by the
primary names of the branch-chain alkyl groups attached
primary H2 to it. CH3

CH C H2
CH C CH3
H3C C CH3 H3C C C
tertiary H2 H2 H2
secondary The longest continuous chain is 6 carbons; the
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parent hydrocarbon is hexane. 60

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 IUPAC Rules for Naming Alkanes IUPAC Rules for Naming Alkanes
2. Number the carbon atoms in the parent carbon 4. When the same alkyl-group branch chain occurs
chain from one end to the other, starting at the end more than once, indicate this by a prefix (di-, tri-,
closest to the first carbon atom that has a branch tetra-, etc.) written in front of the alkyl group
chain. name (e.g. dimethyl indicates two methyl groups).
3. Name each branch-chain alkyl group and The numbers indicating the positions of these
designate its position on the parent carbon by a alkyl groups are separated by a comma, followed
number. by a hyphen, and placed in front of the name.
2-methyl CH3

CH3 H2
1 C 3 C 5 CH3
H2 H3C 2 CH 4 C 6
CH 3 C 5 CH3 H2
1 2 CH3
H3C C 4 C 6
H2 H2 CH3
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2-methylhexane 2,2,3-trimethylhexane

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IUPAC Rules for Naming Alkanes

5. When several different alkyl groups are attached Name the following alkane:
to the parent compound, list them in alphabetical
order (e.g. ethyl before methyl as in CH3
3-ethyl-4-methyloctane). CH H2 H2 H2
3 C CH C C
H2 H2 H3C CH CH C CH3
H2
1 C 3 CH 5 C 7 CH2
CH2 CH3
H3C 2 CH 4 C 6 C 8 H2C
H2 H2
CH3
CH2
H3C 63 64

63 64

5-methyl

Write the formula for 3-ethylpentane

4-ethyl
CH3
H2 H2 H2 H2 H2
C
4 CH
5
6 C
7
8 C
9
10 1 C 3 C 5
H3C CH CH C
H2
CH3
H3C
2 CH 4 CH3
3 CH2 CH3
H2C 2
CH2
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CH 6-methyl
H3C
4-ethyl-5,6-dimethyldecane 65 66

65 66

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 Write the formula for 2,2,4-trimethylpentane

CH3 CH3

Introduction to the
1 C CH
H3C 2 3
C 4
5
CH3 Reactions of Carbon
H2
CH3

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Oxidation
One of the most important
When carbon atoms are oxidized, they often
carbon reactions is form additional bonds to oxygen.
H
oxidation reduction.
H C H + 2 O2 O C O + 2H2O

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Reduction Other Reactions of Carbon

When carbon atoms are reduced,

they often form additional bonds to 1. Substitution reactions
hydrogen.
H 2. Elimination reactions
O C O + 3 H2 H C OH + H2O
3.Addition reactions
H

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 Substitution Reaction Elimination Reaction
If, in a reaction, one atom in a molecule • An elimination reaction is a reaction in
is exchanged by another atom or group of which a single reactant is split into two
atoms, a substitution reaction has taken products, and one of the products is
place. eliminated.
H H • Elimination reactions form multiple bonds.
H H H H
H C H + Br2 H C Br + HBr
H C C Br C C + HBr
H H
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Addition Reaction
• Two reactants adding together to form a
single product is called an addition
reaction.
• An addition reaction can be thought of as
the reverse of an elimination. Reactions of Alkanes
H H H H

C C + HBr H C C Br

H H H H 75 76

75 76

Combustion of Alkanes Aside from their combustibility,

alkanes are relatively sluggish and
Alkanes, as well as other hydrocarbons, undergo
limited in reactivity.
combustion with oxygen with the evolution of large
amounts of heat energy.
CH4(g) + 2O2 (g) ® CO2(g) + 2H2O(g) + 802.5 kJ With proper activation, such as with
high temperature or catalysts,
When CO2 is formed, the alkane has undergone alkanes can be made to react in a
complete oxidation. variety of ways.
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 Some Important Noncombustion
Some Important Noncombustion
Reactions of Alkanes
Reactions of Alkanes
• Halogenation • Halogenation (a substitution reaction)
– a substitution reaction
• Dehydrogenation
•A halogen is substituted for a
– an elimination reaction hydrogen atom.
• Cracking
– breaking up large molecules to form smaller ones
• Isomerization
CH3CH3 + Cl2 ® CH3CH2Cl + HCl
– rearrangement of molecular structures
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79 80

Alkyl Halides
• The formula RX indicates a halogen
atom attached to an alkyl group and
represents the class of compounds
known as alkyl halides.
• Ex:
– CH3CH2CH2Cl 1-chloropropane
– CH3CH2CH2CHBr2 1,1-dibromobutane

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Some Important Noncombustion Some Important Noncombustion

Reactions of Alkanes Reactions of Alkanes
• Dehydrogenation (an elimination reaction)
–Hydrogen is lost from an organic • Cracking
compound.
C16H34 ® C8H18 + C8H16
CH3CH2CH3 ® CH3CH=CH2 + H2

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 Some Important Noncombustion
Reactions of Alkanes
• Isomerization

CH3CH2CH2CH2CH3
catalyst,
pressure,
heat CH3CH2CHCH3
Sources of Alkanes
CH3

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85 86

Sources of Alkanes
• The two main sources of alkanes are
natural gas and petroleum.
– Natural gas is formed by the anaerobic
decay of plants and animals.
Gasoline: A Major
– Petroleum, also called crude oil, consists
of a mixture of hydrocarbons and is Petroleum Product
formed by the decomposition of plants
and animals over millions of years.

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87 88

Figure 19.9 Uses of petroleum

Cycloalkanes

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 Cycloalkanes

• Cycloalkanes have the formula

CnH2n.
• Their names are formed by
adding the prefix cyclo to the
name of the alkane with the
same number of carbon atoms.
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91 92

Figure 19.11 Ball-and-stick

models illustrating cyclopropane,
hexane, and cyclohexane. In
Cycloalkanes cyclopropane, all the carbon
atoms are in one plane (bond
angles = 60°). The cyclohexane
molecule is puckered (as shown
• With the exception that follows for in the chair conformation) with
cyclopropane and cyclobutane, bond angles at 109.5°.

cycloalkanes are generally similar to open-

chain alkanes in both physical properties
and chemical reactivity.
• Cycloalkanes are saturated hydrocarbons;
they contain only single bonds between
carbon atoms.
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Conformations of Cyclohexane
Reactivity of Cyclopropane and
Cyclobutane • The conformation of a molecule is its
three-dimensional shape in space.
• There is a greater reactivity in cyclopropane
and cyclobutane because the carbon-carbon
bond angles in these substances deviate
substantially from the tetrahedral angle.
• Their carbon-carbon bonds are strained and
therefore weakened.
Figure 19.12 Conformations of cyclohexane: (a)
chair conformation; (b) boat conformation. Axial
hydrogens are shown in blue in the chair
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conformation.
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 Naming Cycloalkanes
• Substituted cycloalkanes are named by Naming Cycloalkanes
identifying and numbering the location
of the substituent(s) on the carbon ring, • When a cycloalkane has two or more
followed by the name of the parent substituted groups, the ring is
alkane. numbered (clockwise or
CH3
counterclockwise) to give the location
of the substituted groups the smallest
numbers.

methylcyclohexane 97 98

97 98

Naming Cycloalkanes
CH3
CH3 H3C CH3

1,1-dimethylcyclohexane 1,3-dimethylcyclohexane
CH3 CH3

CH3 H3C
1,2-dimethylcyclohexane 1,4-dimethylcyclohexane
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