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Chapter 10
An Introduction to Organic
Chemistry:
The Saturated Hydrocarbons

Denniston
Topping
Caret
5th Edition
10.1 The Chemistry of Carbon 10.1 The Chemistry of Carbon
Why are there so many organic compounds?
1. Carbon forms stable, covalent bonds with other
carbon atoms
• Consider three allotropic forms of elemental carbon
– Graphite in planar layers
– Diamond is a three-dimensional network
– Buckminsterfullerene is 60 C in a roughly spherical shape
• The stable carbon to carbon bonds accounts for the
high melting and boiling points of these allotropes
10.1 The Chemistry of Carbon Why are there so many
organic compounds?
2. Carbon atoms form stable bonds with
other elements, such as:
– Oxygen (alcohols, aldehydes, ketones,
carboxylic acids, esters and ethers)
– Nitrogen
– Sulfur
– Halogen (Group VIIA)
• Presence of these other elements confers
many new physical and chemical
properties on an organic compound
10.1 The Chemistry of Carbon Why are there so many
organic compounds?
3. Carbon atoms form H2C CH2
double or triple bonds
with: H2C O
– Other carbon atoms
(double & triple) H2C NH
– Oxygen (double only)
– Nitrogen (double & triple)
double bonds
• These combinations act HC CH
to produce a variety of
organic molecules with HC N
very different properties triple bonds
 Why are there so many
organic compounds?
10.1 The Chemistry of
4. The number of ways carbon atoms can be
arranged with these other atoms is nearly
limitless
Carbon

– Linear chains
– Branched chains H2
– C
Ring structures H2C CH2
CH3CH2CH2CH3 H2C CH2
• Two organic compounds may even have the same
number and kinds of atoms but completely
different structures and thus, different properties
– These are called isomers
10.1 The Chemistry of Isomers

• Many carbon compounds exist in the

form of isomers
Carbon

• Isomers are compounds with the same

molecular formula but different structures
• An isomer example: both are C4H10
but have different structures
– Butane
– Methylpropane
10.1 The Chemistry of Isomers
All have the same molecular formula: C 4H8

CH3CH2CH CH2 A
Carbon

CH3CH CH CH3 B
CH2 CH2
C
CH2 CH2
 Important Differences Between
Organic and Inorganic Compounds
10.1 The Chemistry of

• Bond type
–Organics have covalent bonds
Carbon

• Electron sharing
–Inorganics usually have ionic bonds
• Electron transfer
• Structure
–Organics
• Molecules
• Nonelectrolytes
–Inorganics
• Three-dimensional crystal structures
• Often water-soluble, dissociating into ions
 Important Differences Between
Organic and Inorganic Compounds
10.1 The Chemistry of

• Melting Point & Boiling Point

–Organics have covalent bonds
Carbon

• Intermolecular forces broken fairly easily

–Inorganics usually have ionic bonds
• Ionic bonds require more energy to break
• Water Solubility
–Organics
• Nonpolar, water insoluble
–Inorganics
• Water-soluble, readily dissociate
 Comparison of Major Properties of
10.1 The Chemistry of
Carbon Organic and Inorganic Compounds
10.1 The Chemistry of Families of Organic Compounds
• Most general classification divides
organic compound into:
– Hydrocarbons
– Substituted hydrocarbons
Carbon

• Hydrocarbons contain only carbon

and hydrogen
• They are nonpolar molecules
– Not soluble in water
– Are soluble in typical nonpolar organic
solvents
• Toluene
• Pentane
 Families of Organic Compounds
10.1 The Chemistry of

• Hydrocarbons are constructed of chains

or rings of carbon atoms with sufficient
Carbon

hydrogen atoms to fulfill carbon’s need

for four bonds
• Substituted hydrocarbon is one in which
one or more hydrogen atoms is replaced
by another atom or group of atoms
– Solubility alters with individual substituent
 Division of the Family
10.1 The Chemistry of
of Hydrocarbons
Carbon
10.1 The Chemistry of Hydrocarbon Saturation
• Alkanes are compounds that contain only
carbon-carbon and carbon-hydrogen single
bonds
– A saturated hydrocarbon has no double or
Carbon

triple bonds
• Alkenes and alkynes are unsaturated
because they contain at least one carbon to
carbon double or triple bond
10.1 The Chemistry of Cyclic Structure of Hydrocarbons
• Some hydrocarbons are cyclic
– Form a closed ring
– Aromatic hydrocarbons contain a benzene
ring or related structure
Carbon
 Common Functional Groups
• Substituted hydrocarbon is one in which one
10.1 The Chemistry of
or more hydrogen atoms is replaced by
another atom or group of atoms
• A functional group is defined as an atom or a
Carbon

group of atoms arranged in a particular way

that effectively determines the chemical and
physical properties of an organic compound.
• A homologous series is a series of
compounds that have the same functional
group, and each member differs from the next
member by a – CH2 – unit in their formulae.
10.1 The Chemistry of
Carbon
Common Functional Groups
 10.2 Alkanes
• Alkanes are saturated hydrocarbons
– Contain only carbon and hydrogen bonded together
– Bonds are carbon-hydrogen and carbon-carbon
single bonds
• The general formula for chain alkanes is
CnH2n+2
– In this formula n = the number of carbon atoms in
the molecule
– E.g. If and alkane has 10 C then it will have a total
of 22 H with molecular formula C10H22
 Formulas Used in Organic Chemistry
• Four types of formulas used in organic chemistry
– Molecular formula, structural formula, condensed formula
and line formula
10.2 Alkanes

• Molecular formula - tells the kind and number of each

type of atom in a molecule, no bonding pattern

• Structural formula - shows each atom and bond in a

molecule
 Formulas Used in Organic Chemistry
• Condensed formula - shows all the atoms in a
molecule in sequential order indicating which atoms
are bonded to which
10.2 Alkanes
 Formulas Used in Organic Chemistry
• Line formula - assume a carbon atom at any location
where lines intersect
– Assume a carbon at the end of any line
10.2 Alkanes

– Each carbon in the structure is bonded to the correct number

of hydrogen atoms
Formulas Used in Organic Chemistry
Formulas Used in Organic Chemistry
Formulas Used in Organic Chemistry
 The Tetrahedral Carbon Atom
10.2 Alkanes

(a) Lewis dot structure

(b) The tetrahedral shape around the carbon atom
according to the VSEPR and molecular geometry
(c) The tetrahedral carbon drawn with dashes and
wedges
(d) The stick drawing of the tetrahedral carbon atom
(e) Ball and stick model of methane
 Drawing Methane and Ethane
H H H
in plane
H
H C C
H
10.2 Alkanes

109.5 o
behind plane H
H in front of plane H H
Staggered form of ethane
 Comparison of Ethane and
Butane Structures
10.2 Alkanes
Names and Formulas of the First Ten
Straight-Chain Alkanes
 Structural Isomers
• Constitutional/Structural Isomers differ in how
atoms are connected
10.2 Alkanes

– Two isomers of butane have different physical

properties
– The carbon atoms are connected in different
patterns
CH3
CH3 CH2 CH2 CH3 CH3 CH CH3
Butane Isobutane
Bp –0.4 oC Bp –12 oC
Mp –139 oC Mp –145 oC
 Comparison of Physical Properties of
Five Isomers of Hexane
• Compare the basic linear structure of hexane
– All other isomers have one or more carbon atoms
10.2 Alkanes

branching from the main chain

– Branched-chain forms of the molecule have a much
smaller surface area
• Intermolecular forces are weaker
• Boiling and melting points are lower than straight chains
Comparison of Physical Properties of
Five Isomers of Hexane
 Physical Properties of
Organic Molecules
1. Nonpolar
10.2 Alkanes

2. Not water soluble

3. Soluble in nonpolar organic solvents
4. Low melting points
5. Low boiling points
6. Generally less dense (lighter) than water
7. As length (molecular weight) increases, melting
and boiling points increase as does the density
 Properties of Alkanes
200

150
10.2 Alkanes

100

50
Temperature

0
Melting Point
0 1 2 3 4 5 6 7 8 9 10
Boiling Point
-50

-100

-150

-200

-250
Number of Carbons in Chain
 Properties of Alkanes
• Most of the alkanes are hydrophobic:
water hating
10.2 Alkanes

• Straight chain alkanes comprise a homologous

series: compounds of the same functional
class that differ by a –CH2- group
• Nonpolar alkanes are:
– Insoluble in water (a highly polar solvent)
– Less dense than water and float on it
• As length (molecular weight) increases,
melting and boiling points increase as does
the density.
 Alkyl Groups
H H
H C H H C or CH3
10.2 Alkanes

H H
• An alkyl group is an alkane with one hydrogen
atom removed
• It is named by replacing the -ane of the alkane
name with -yl
• Methane becomes a methyl group
 Alkyl Groups

• All six hydrogens on ethane are equivalent

10.2 Alkanes

• Removing one H generates the ethyl group

• All 3 structures shown at right are the same

HH CH3 CH2
HCCH CH2 CH3
HH C2H5
 Names and Formulas of the First
Five Alkyl Groups
10.2 Alkanes
 Alkyl Group Classification
• Alkyl groups are classified according to the
number of carbons attached to the carbon
10.2 Alkanes

atom that joins the alkyl group to a molecule

• All continuous chain alkyl groups are 1º
• Isopropyl and sec-butyl are 2º groups
 Iso- Alkyl Groups
• Propane: removal of a hydrogen generates
two different propyl groups depending on
10.2 Alkanes

whether an end or center H is removed

CH3 CH2 CH3

CH3CH2CH2 CH3CH CH3

n-propyl isopropyl
 Sec- Alkyl Groups
• n-butane gives two butyl groups depending
on whether an end (1º) or interior (2º) H is
10.2 Alkanes

removed
CH3 CH2 CH2 CH3

CH3 CH2 CH2 CH2 CH3 CH CH2 CH3

n-butyl sec-butyl
 More Alkyl Group Classification
• Isobutane gives two butyl groups
depending on whether a 1o or 3o H is
10.2 Alkanes

removed
CH3
CH3
CH CH 3
1 C
o o
3 C
CH3 CH3
CH3 CH CH2 CH3 C CH3
isobutyl t-butyl
 Structures and Names of Some
Branched-Chain Alkyl Groups
10.2 Alkanes
 Nomenclature
• The IUPAC (International Union of
Pure and Applied Chemistry) is
10.2 Alkanes

responsible for chemical names

• Before learning the IUPAC rules for
naming alkanes, the names and
structures of ten alkyl groups must be
learned
• These alkyl groups are historical names
accepted by the IUPAC and integrated
into modern nomenclature
 Carbon Chain Length and Prefixes
10.2 Alkanes
 IUPAC Names for Alkanes

1. The base or parent name for an alkane is

10.2 Alkanes

determined by the longest chain of

carbon atoms in the formula
– The longest chain may bend and twist, it is
seldom horizontal
– Any carbon groups not part of the base chain
are called branches or substituents
– These carbon groups are also called alkyl
groups
 IUPAC Names for Alkanes

• Rule 1 applied
10.2 Alkanes

– Find the longest chain in each molecule

• A=7 – heptane B=8 - octane

A CH3
CH2CH2CH CH2CH3
B CH3
CH2
CH3CH2CH2 CH2
CH3
CH3CH2CH CH2CH CH3
 IUPAC Names for Alkanes

2. Number the carbon atoms in the

10.2 Alkanes

longest chain starting from the end

with the first branch
– If both branches are equally from the
ends, continue until a point of
difference occurs
 IUPAC Names for Alkanes
Number the carbon atoms correctly
10.2 Alkanes

• Left: first branch is on carbon 3

• Right: first branch is on carbon 3 (From
top) not carbon 4 (if number from right)
CH1
3 6 7 8
CH3 2
CH CH2CH2CH3
2
4
5 CH2CH2CH CH2CH3 CH3CH CH2CH CH2CH3
3 2 1 3 4 5
6 CH2 this branch would be on C-4
if you started at correct C-8
7 CH3
 IUPAC Names for Alkanes
3. Write each of the branches/substituents in
alphabetical order before the base/stem
10.2 Alkanes

name (longest chain)

– Halogens usually come first
– Indicate the position of the branch on the main
chain by prefixing its name with the carbon
number to which it is attached
– Separate numbers and letters with a hyphen
– Separate two or more numbers with commas
 IUPAC Names for Alkanes
Write each of the branches/substituents
• Left: 3-methyl
10.2 Alkanes

– 3-methylheptane
• Right: 3-methyl and 5-ethyl
– Alphabetical order 5-ethyl-3methyloctane

1 CH3
6 7 8
CH3 2 CH2 CH2CH2CH3
4
5 CH2CH2CH CH2CH3 CH3CH CH2CH CH2CH3
3 2 1 3 4 5
6 CH2
7 CH3
 IUPAC Names for Alkanes

CH3
10.2 Alkanes

CH2 CH3
CH3 CH2 CH CH2 CH CH3
Name : 4-ethyl-2-methylhexane
 IUPAC Names for Alkanes
• Hyphenated and number prefixes are
not considered when alphabetizing
groups
10.2 Alkanes

– Name the compound below

– 5-sec-butyl-4-isopropylnonane

CH3
CH3 CH CH2 CH3
CH CH CH CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH3
 IUPAC Names for Alkanes
• When a branch/substituent occurs more
than once
10.2 Alkanes

– Prefix the name with

• di
• tri
• tetra
– Then list the number of the carbon branch for
that substituent to the name with a separate
number for each occurrence
• Separate numbers with commas
• e.g., 3,4-dimethyl or 4,4,6-triethyl
 IUPAC Names for Alkanes
Name
CH3 CH2CH3
10.2 Alkanes

CH3CH CH CH2CH CH2CH3

CH3

5-ethyl-2,3-dimethylheptane
ethyl>dimethyl
 Practice: IUPAC Name

Name
10.2 Alkanes

CH
1
3 CH 3CH CH 3
CH
2
2
CH2
CH3C3 CH
4 CH
5 C6 CH CH
2 2 2 3
CH3 CH
7
2CH
8
2CH
9
2CH
10
3
6-ethyl-6-isobutyl-3,3-dimethyldecane
Practice: IUPAC Name
Practice: IUPAC Name
 10.3 Cycloalkanes

• Cycloalkanes have two less hydrogens than

the corresponding chain alkane (CnH2n)
– Hexane=C6H14; cyclohexane=C6H12
• To name cycloalkanes, prefix cyclo- to the
name of the corresponding alkane
– Place substituents in alphabetical order before
the base name as for alkanes
– For multiple substituents, use the lowest
possible set of numbers; a single substituent
requires no number
 Cycloalkane Structures
10.3 Cycloalkanes

Cyclopropane

Cyclobutane

Cyclohexane

Type of Formula: Structural Condensed Line

10.3 Cycloalkanes Naming a Substituted Cycloalkane

Name the two cycloalkanes shown below

• Parent chain 6 carbon ring 5 carbon ring
cyclohexane cyclopentane
• Substituent 1 chlorine atom a methyl group
chloro methyl
• Name Chlorocyclohexane Methylcyclopentane
 cis-trans Isomers in Cycloalkanes
• Atoms of an alkane can rotate freely around the carbon-
carbon single bond having an unlimited number of
10.3 Cycloalkanes

arrangements
• Rotation around the bonds in a cyclic structure is limited by
the fact that all carbons in the ring are interlocked
– Formation of cis-trans isomers or geometric isomers, is a
consequence of the lack of free rotation
– Cis-trans isomers or geometric isomers are a type of
stereoisomers.
• Stereoisomers are molecules that have the same structural
formulas and bonding patterns, but different arrangements
of atoms in space
– cis-trans isomers of cycloalkanes are stereoisomers whose
substituents differ in spatial arrangement
10.3 Cycloalkanes cis-trans Isomers in Cycloalkanes
• Two groups may be on the same side (cis) of the imagined
plane of the cycloring or they may be on the opposite side
(trans)
• Geometric isomers do not readily interconvert, only by
breaking carbon-carbon bonds can they interconvert
Practice: IUPAC Name
Practice: IUPAC Name
 10.4 Conformations of Alkanes
• Conformations differ only in rotation about carbon-
carbon single bonds
• Two conformations of ethane and butane are shown
– The first (staggered form) is more stable because it allows
hydrogens to be farther apart and thus, the atoms are less
crowded
Alkanes and Cycloalkanes
Two Conformations of Cyclohexane
10.4 Conformations of

Chair form (more stable) Boat form

A A H H
E H H H H
E A E
A E
E E H H H
A H
A
H H
E=equitorial A=axial
 10.5 Reactions of Alkanes

• Alkanes, cycloalkanes, and other

hydrocarbons can be:
– Oxidized (by burning) in the presence of excess
molecular oxygen, in a process called
combustion
– Reacted with a halogen (usually chlorine or
bromine) in a halogenation reaction
10.5 Reactions of Alkanes Alkane Reactions
The majority of the reaction of alkanes are
combustion reactions
– Complete CH4 + 2O2 CO2 + 2H2O
Complete combustion produces
– Carbon dioxide and water

– Incomplete 2CH4 + 3O2 2CO + 4H2O

• Incomplete combustion produces
– Carbon monoxide and water
– Carbon monoxide is a poison that binds
irreversibly to red blood cells
10.5 Reactions of Alkanes Halogenation
Halogenation is a type of substitution reaction, a
reaction that results in a replacement or substitution
of one group for another
– Products of this reaction are:
• Alkyl halide or haloalkane
• Hydrogen halide
– This reaction is important in converting unreactive
alkanes into many starting materials for other products
– Halogenation of alkanes ONLY occurs in the presence
of heat and/or light (UV)

H Br
H + Br2 heat or H
light
+HBr
10.5 Reactions of Alkanes
Halogenation
Practice: Reaction of Alkanes
Practice: Reaction of Alkanes
 Petroleum Processing
Fraction Boiling Pt Range ºC Carbon size Typical uses

Natural Gas ­164­30 C1­C4 Heating, cooking

Gasoline 30­200 C5­C12 Motor fuel

Kerosene 175­275 C12­C16 Fuel for stoves, 
diesel and jet engines

Heating oil Up to 375 C15­C18 Furnace oil

Lubricating  350 and up C16­C20 Lubrication, mineral 

oil oil
Greases Semisolid C18­up Lubrication, 
petroleum jelly
Paraffin  Melts at 52­57 C20­up Candles, toiletries
(wax)
Pitch / tar Residue in boiler High Roofing, asphalt 
paving