Anda di halaman 1dari 62

Alkanes and

Cycloalkanes

Key Questions

2.1 How Do We Write Structural Formulas of Alkanes?


2.2 What Are Constitutional Isomers?
2.3 How Do We Name Alkanes?
2.4 Where Do We Obtain Alkanes?
2.5 What Are Cycloalkanes?
2.6 What Are the Shapes of Alkanes and Cycloalkanes?
2.7 What Is Cis-Trans Isomerism in Cycloalkanes?
2.8 What Are the Physical Properties of Alkanes?
2.9 What Are the Characteristic Reactions of Alkanes?
2.10 What Are Some Important Haloalkanes?

2.1 How Do We Write Structural


Formulas of Alkanes?
Alkane
A saturated hydrocarbon whose carbon atoms
are arranged in a chain
Hydrocarbon
A compound that contains only carbon and
hydrogen atoms

Saturated hydrocarbon
A hydrocarbon that contains only carboncarbon
single bonds
Unsaturated hydrocarbon
A hydrocarbon that contains one or more carbon
carbon double bonds, triple bonds, or benzene
rings

Aliphatic hydrocarbon
An alkane

Line-angle formula
An abbreviated way to draw structural formulas
in which each vertex and line terminus
represents a carbon atom and each line
represents a bond.

Butane, CH3CH2CH2CH3,
is the fuel in this lighter.
Butane molecules are
present in both the liquid
and gaseous states in the
lighter.
CH3(CH2)2CH3

The structural formula of


pentane contains three
CH2 (methylene) groups
in the middle of the
chain. We can group
them together and write
the structural formula
CH3(CH2)2CH3.

Example 2.1 Drawing Line-Angle


Formulas
Table 2.1 gives the condensed structural formula for
hexane. Draw a line-angle formula for this alkane, and
number the carbons on the chain beginning at one
end and proceeding to the other end.

2.2 What Are Constitutional Isomers?


Constitutional isomers
Compounds with the same molecular formula
but a different connectivity of their atoms.
- By different structural formulas we mean
that they differ in the kinds of bonds (single,
double, or triple) and/or in the connectivity of
their atoms.

For the molecular formulas CH4, C2H6, and


C3H8, only one connectivity of their atoms is
possible, so there are no constitutional
isomers for these molecular formulas.
For the molecular formula C4H10, however,
two structural formulas are possible:

Example 2.2 Constitutional Isomerism


Do the structural formulas in each of the following sets
represent the same compound or constitutional isomers?
(Hint: You will find it helpful to redraw each molecule as a
line-angle formula, which will make it easier for you to see
similarities and differences in molecular structure.)

Solution
(a) Each structural formula has an unbranched
chain of six carbons; they are identical and
represent the same compound.

(b) Each structural formula has the same molecular


formula, C7H16. In addition, each has a chain of five
carbons with two CH3 branches. Although the branches
are identical, they are at different locations on the
chains. Therefore, these structural formulas represent
constitutional isomers.

Problem 2.2
Do the line-angle formulas in each of the
following sets represent the same compound or
constitutional isomers?

Example 2.3 Constitutional Isomerism


Draw line-angle formulas for the five
constitutional isomers with the molecular
formula C6H14.

Problem 2.3
Draw structural formulas for the three
constitutional isomers with the molecular
formula C5H12.

2.3 How Do We Name Alkanes?


A. The IUPAC System
International Union of Pure and Applied
Chemistry (IUPAC)
The IUPAC name for an alkane with an unbranched
chain of carbon atoms consists of two parts:
(1) a prefix that shows the number of carbon atoms
in the chain and
(2) the suffix -ane, which shows that the compound
is a saturated hydrocarbon.

Alkyl group
A group derived by removing a hydrogen from
an alkane; given the symbol RR A symbol used to represent an alkyl group

The rules of the IUPAC system for naming


alkanes are as follows:
1. The name for an alkane with an unbranched
chain of carbon atoms consists of a prefix
showing the number of carbon atoms in the
parent chain and the suffix -ane.
2. For branched-chain alkanes, take the longest
chain of carbon atoms as the parent chain
and its name becomes the root name.

3. Give each substituent on the parent chain a


name and a number. The number shows the
carbon atom of the parent chain to which the
substituent is bonded. Use a hyphen to
connect the number to the name.

4. If there is one substituent, number the parent


chain from the end that gives the substituent
the lower number.

5. If the same substituent occurs more than


once, number the parent chain from the end
that gives the lower number to the
substituent encountered first. Indicate the
number of times the substituent occurs by a
prefix di-, tri-, tetra-, penta-, hexa-, and so on.
Use a comma to separate position numbers.

6. If there are two or more different substituents,


list them in alphabetical order and number the
chain from the end that gives the lower number
to the substituent encountered first. If there are
different substituents in equivalent positions on
opposite ends of the parent chain, give the
substituent of lower alphabetical order the lower
number.

7. Do not include the prefixes di-, tri-, tetra-, and


so on or the hyphenated prefixes sec- and
tert- in alphabetizing. Alphabetize the names
of substituents first, and then insert these
prefixes. In the following example, the
alphabetizing parts are ethyl and methyl, not
ethyl and dimethyl.

Example 2.4 IUPAC Names of Alkanes


Write the molecular formula and IUPAC name
for each alkane.

Solution

Problem 2.4
Write the molecular formula and IUPAC name
for each alkane.

B. Common Names
All alkanes with the molecular formula C4H10 are
called butanes, all those with the molecular
formula C5H12 are called pentanes, and all those
with the molecular formula C6H14 are called
hexanes.
For alkanes beyond propane, iso indicates that
one end of an otherwise unbranched chain
terminates in a (CH3)2CH- group

2.4 Where Do We Obtain Alkanes?


The two major sources of
alkanes are natural gas and
petroleum.
Natural
gas
consists of approximately 90 to
95% methane, 5 to 10%
ethane, and a mixture of other
relatively
low-boiling
alkaneschiefly
propane,
butane, and 2-methylpropane.
Petroleum is a thick, viscous liquid
mixture of thousands of compounds,
most of them hydrocarbons, formed
from the decomposition of marine
plants and animals.

2.5 What Are Cycloalkanes?


Cycloalkane
A saturated hydrocarbon that contains carbon atoms
bonded to form a ring

To name a cycloalkane, prefix the name of the


corresponding open-chain alkane with cyclo-, and
name each substituent on the ring.

Example 2.5 IUPAC Names of


Cycloalkanes
Write the molecular formula and IUPAC name
for each cycloalkane.

isopropylcyclopentane
1-tert-butyl-4-methylcyclohexane

A. Alkane
Conformation
Any three-dimensional arrangement of atoms in a molecule that
results from rotation about a single bond.

B. Cycloalkanes
Cyclopentane
Cyclohexane

Cyclohexane. The most stable conformation is


a chair conformation.

Equatorial position A position


on a chair conformation of a
cyclohexane ring that extends from
the ring roughly perpendicular to the
imaginary axis of the ring

Axial position A position on a chair


conformation of a cyclohexane ring that
extends from the ring parallel to the
imaginary axis of the ring

Example 2.6 Chair Conformations of


Cyclohexanes
Following is a chair conformation of
methylcyclohexane showing a methyl group and
one hydrogen. Indicate by a label whether each is
equatorial or axial.
Solution
The methyl group is axial, and the hydrogen
is equatorial.
Problem 2.6
Following is a chair conformation of
cyclohexane with carbon atoms numbered 1
through 6. Draw methyl groups that are
equatorial on carbons 1, 2, and 4.

Chemists have discovered that a six-membered


ring is more stable when the maximum number
of substituent groups are equatorial. Perhaps the
simplest way to confirm this relationship is to
examine molecular models.
Thus the more stable conformation of a
substituted cyclohexane ring has the substituent
group(s) as equatorial.

2.7 What Is Cis-Trans Isomerism


in Cycloalkanes?
Cis-trans isomers
- Isomers that have the same connectivity of their
atoms but a different arrangement of their atoms
in space due to the presence of either a ring or a
carboncarbon double bond
- have also been called geometric isomers.

A stereocenter is a tetrahedral atom, most


commonly carbon, at which exchange of two
groups produces a stereoisomer. Both carbons 1
and 2 of 1,2-dimethylcyclopentane, for example,
are stereocenters; in this molecule, exchange of H
and CH3 groups at either stereocenter converts a
trans isomer to a cis isomer, or vice versa.

Configuration refers to the arrangement of atoms


about a stereocenter. We say, for example, that
exchange of groups at either stereocenter in the
cis configuration gives the isomer with the trans
configuration.

Stereoisomers
Isomers that have the same connectivity of their atoms
but a different orientation of their atoms in space

Example 2.7 Cis-Trans Isomerism in


Cycloalkanes
Which of the following cycloalkanes show cis-trans isomerism? For each that
does, draw both isomers.
(a) Methylcyclopentane
(b) 1,1-Dimethylcyclopentane
(c) 1,3-Dimethylcyclobutane

Problem 2.7
Which of the following cycloalkanes show cis-trans isomerism? For each
that
does, draw both isomers.
(a) 1,3-Dimethylcyclopentane
(b) Ethylcyclopentane
(c) 1,3-Dimethylcyclohexane

Alkanes
What Are the Physical Properties of Alkanes?
A. Melting and Boiling Points
The boiling points of alkanes are lower than
those of almost any other type of compound
with the same molecular weight. In general,
both boiling and melting points of alkanes
increase with increasing molecular weight

Physical Properties of Some Unbranched Alkanes

Alkanes containing 1 to 4 carbons are gases at room temp.


Alkanes containing 5 to 17 carbons are colorless liquids.
High-molecular-weight alkanes (those containing 18 or more
carbons) are white, waxy solids.

The wax found in apple


skins, for example, is
an unbranched alkane
with the molecular
formula C27H56.

Paraffin wax, a mixture of highmolecular-weight alkanes, is used


for wax candles, in lubricants, and
to seal home-canned jams, jellies,
and other preserves.
Petrolatum, so named because it is
derived from petroleum refining, is a
liquid mixture of high-molecularweight alkanes. It is sold as mineral oil
and Vaseline, and is used as an
ointment base in pharmaceuticals and
cosmetics, and as a lubricant and rust
preventive.

As branching increases, the alkane molecule becomes more


compact and its surface area decreases. As surface area
decreases, London dispersion forces act over a smaller
surface area. Hence the attraction between molecules
decreases and boiling point decreases.

B. Solubility: A Case of
Like Dissolves Like

Alkanes are nonpolar compounds, they are not


soluble in water, which dissolves only ionic and
polar compounds.
Alkanes, however, are soluble in each other, an
example of like dissolves like. Alkanes are also
soluble in other nonpolar organic compounds,
such as toluene and diethyl ether.

C. Density
The average density of the
liquid alkanes is about 0.7
g/mL; that of highermolecular-weight alkanes
is about 0.8 g/mL.
All liquid and solid alkanes are less dense than
water (1.000 g/mL) and, because they are
insoluble in water, they float on water.

Example 2.8 Physical Properties of


Alkanes
Arrange the alkanes in each set in order of
increasing boiling point.
(a) Butane, decane, and hexane

(b) 2-Methylheptane, octane, and 2,2,4-trimethylpentane

Problem 2.8
Arrange the alkanes in each set in order of
increasing boiling point.
(a) 2-Methylbutane, pentane, and 2,2dimethylpropane
(b) 3,3-Dimethylheptane, nonane, and 2,2,4trimethylhexane

2.9 What Are the Characteristic


Reactions of Alkanes?
The most important chemical property of
alkanes and cycloalkanes is their inertness.

A. Reaction with Oxygen: Combustion

B. Reaction with Halogens: Halogenation

A. Reaction with Oxygen: Combustion


Oxidation of hydrocarbons, including alkanes and
cycloalkanes, is the basis for their use as energy
sources for heat [natural gas, liquefied petroleum gas
(LPG), and fuel oil] and power (gasoline, diesel, and
aviation fuel).

B. Reaction with Halogens:


Halogenation

Example 2.9 Halogenation of Alkanes


Write a balanced equation for the reaction of
ethane with chlorine to form chloroethane,
C2H5Cl.

Problem 2.9
Reaction of propane with chlorine gives two products, each
with the molecular formula C3H7Cl. Draw structural
formulas for these two compounds, and give each an IUPAC
name and a common name.

2.10 What Are Some Important


Haloalkanes?
A. Chlorofluorocarbons
Of all the haloalkanes, the chlorofluorocarbons (CFCs)
manufactured under the trade name Freons are the
most widely known. CFCs are nontoxic, nonflammable,
odorless, and noncorrosive. Among the CFCs most
widely
used
for
this
purpose
were
trichlorofluoromethane
(CCl3F,
Freon-11)
and
dichlorodifluoromethane (CCl2F2, Freon-12). The CFCs
also found wide use as industrial cleaning solvents to
prepare surfaces for coatings, to remove cutting oils
and waxes from millings, and to remove protective
coatings. In addition, they were employed as
propellants for aerosol sprays.

B. Solvents
Several low-molecular-weight haloalkanes are
excellent solvents in which to carry out organic
reactions and to use as cleaners and degreasers.
Carbon tetrachloride (carbon tet) was the first
of these compounds to find wide application, but
its use for this purpose has since been
discontinued because it is now known that
carbon tet is both toxic and a carcinogen. Today,
the most widely used haloalkane solvent is
dichloromethane, CH2Cl2.