ALKANES: ACYCLIC SATURATED HYDROCARBONS

An alkane is a saturated hydrocarbon in which the carbon atom arrangement is acyclic. Thus an

alkane is a hydrocarbon that contains only carbon–carbon single bonds (saturated) and has no

rings of carbon atoms (acyclic).

The molecular formulas of all alkanes fit the general formula CnH2n+2 , where n is the number of

carbon atoms present. The number of hydrogen atoms present in an alkane is always twice the

number of carbon atoms plus two more, as in C4H10 , C5 H12 , and C8 H18 .The three simplest alkanes

are methane (CH4 ), ethane (C2 H6 ), and propane (C3H8 ). Three different methods for showing

the three-dimensional structures of these simplest of all alkanes are given below. They are dash-

wedge-line structures, ball-and-stick models, and space-filling models. Note how each carbon

atom in each of the models participates in four bonds . Note also that the geometrical

arrangement of atoms about each carbon atom is tetrahedral, an arrangement consistent with

the principles of VSEPR theory . The tetrahedral arrangement of the atoms bonded to alkane

carbon atoms is fundamental to understanding the structural aspects of organic chemistry.

STRUCTURAL FORMULA

The structures of alkanes, as well as other types of organic compounds, are generally
represented in two dimensions rather than three because of the difficulty in drawing the latter.
These two-dimensional structural representations make no attempt to portray accurately the
bond angles or molecular geometry of molecules. Their purpose is to convey information about
which atoms in a molecule are bonded to which other atoms. Two-dimensional structural
representations for organic molecules are called structural formulas. A structural formula is a two-
dimensional structural representation that shows how the various atoms in a molecule are bonded
to each other. Structural formulas are of two types: expanded structural formulas and condensed
structural formulas.

An expanded structural formula is a structural formula that shows all atoms in a molecule
and all bonds connecting the atoms. When written out, expanded structural formulas generally
occupy a lot of space, and condensed structural formulas represent a shorthand method for
conveying the same information. A condensed structural formula is a structural formula that uses
groupings of atoms, in which central atoms and the atoms connected to them are written as a
group, to convey molecular structural information. The expanded and condensed structural
formulas for methane, ethane, and propane follow.

The condensed structural formula for propane, CH3 —CH2 —CH3 , is interpreted in the following
manner: The first carbon atom is bonded to three hydrogen atoms, and its fourth bond is to the
middle carbon atom. The middle carbon atom, besides its bond to the first carbon atom, is also
bonded to two hydrogen atoms and to the last carbon atom. The last carbon atom has bonds to
three hydrogen atoms in addition to its bond to the middle carbon atom. As is always the case,
each carbon atom has four bonds. The condensed structural formulas of hydrocarbons in which
a long chain of carbon atoms is present are often condensed even more. The formula
CH3 —CH2 —CH2 —CH2 —CH2 —CH2 —CH2 —CH3
can be further abbreviated as
CH3 —(CH2 )6 —CH3
where parentheses and a subscript are used to denote the number of —CH2 — groups in the
chain.
It is important to note that expanded structural formulas show all bonds within a molecule and
that condensed structural formulas show only certain bonds—the bonds between carbon atoms.
In situations where the focus is solely on the arrangement of carbon atoms in an alkane, skeletal
structural formulas that omit the hydrogen atoms are often used. A skeletal structural formula is a
structural formula that shows the arrangement and bonding of carbon atoms present in an
organic molecule but does not show the hydrogen atoms attached to the carbon atoms.

ALKANE
ISOMERISM

The word isomer comes from the Greek isos, which means “the same,” and meros, which means
“parts.” Isomers have the same parts put together in different ways. The molecular formulas CH4 ,
C2 H6 , and C3 H 8 represent the alkanes methane, ethane, and propane, respectively. Next in the
alkane molecular formula sequence (CnH2n+2 ) is C4H10 , which would be expected to be the
molecular formula of the four-carbon alkane. A new phenomenon arises, however, when an
alkane has four or more carbon atoms. There is more than one structural formula that is consistent
with the molecular formula. Consequently, more than one compound exists with that molecular
formula. This situation brings us to the topic of isomerism. Isomers are compounds that have the
same molecular formula (that is, the same numbers and kinds of atoms) but that differ in the way
the atoms are arranged. Isomers, even though they have the same molecular formula, are always
different compounds with different properties.
There are two four-carbon alkane isomers, the compounds butane and isobutane. Both
have the molecular formula C4H10 .

A continuous-chain alkane is an alkane in which all carbon atoms are connected in a continuous
nonbranching chain. The other C4 H 10 isomer, isobutane, has a chain of three carbon atoms with
the fourth carbon attached as a branch on the middle carbon of the three-carbon chain. It is an
example of a branched-chain alkane. A branched-chain alkane is an alkane in which one or
more branches (of carbon atoms) are attached to a continuous chain of carbon atoms.
Constitutional isomers are also frequently called structural isomers. The general characteristics of
such isomers, independent of which name is used, are the same molecular formula and different
structural formulas. There are three isomers for alkanes with five carbon atoms (C5H12):

IUPAC NOMENCLATURE FOR ALKANES

When relatively few organic compounds were known, chemists arbitrarily named them using what
today are called common names. These common names gave no information about the
structures of the compounds they described. However, as more organic compounds became
known, this nonsystematic approach to naming compounds became unwieldy. Today, formal
systematic rules exist for generating names for organic compounds. These rules, which were
formulated and are updated periodically by the International Union of Pure and Applied
Chemistry (IUPAC), are known as IUPAC rules.
The advantage of the IUPAC naming system is that it assigns each compound a name that not
only identifies it but also enables one to draw its structural formula. Note that all of these names
end in -ane, the characteristic ending for all alkane names. Note also that beginning with the five-
carbon alkane, Greek numerical prefixes are used to denote the actual number of carbon atoms
in the continuous chain.

To name branched-chain alkanes, we must be able to name the branch or branches that are
attached to the main carbon chain. These branches are formally called substituents. A substituent
is an atom or group of atoms attached to a chain (or ring) of carbon atoms. Note that substituent
is a general term that applies to carbon-chain attachments in all organic molecules, not just
alkanes. For branched-chain alkanes, the substituents are specifically called alkyl groups. An alkyl
group is the group of atoms that would be obtained by removing a hydrogen atom from an
alkane. The two most commonly encountered alkyl groups are the two simplest: the one carbon
and two-carbon alkyl groups.

The extra-long bond in these formulas denotes the point of attachment to the carbon chain. Note
that alkyl groups do not lead a stable, independent existence; that is, they are not molecules.
They are always found attached to another entity (usually a carbon chain).Alkyl groups are
named by taking the stem of the name of the alkane that contains the same number of carbon
atoms and adding the ending -yl.

IUPAC rules for naming branched-chain alkanes.

a. Identify the longest continuous carbon chain (the parent chain), which may or may not
be shown in a straight line, and name the chain.
b. Number the carbon atoms in the parent chain from the end of the chain nearest a
substituent (alkyl group). There always are two ways to number the chain (either from left
to right or from right to left). This rule gives the first-encountered alkyl group the lowest
possible number.
 c. If only one alkyl group is present, name and locate it (by number), and prefix the number
and name to that of the parent carbon chain.
d. 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.
e. 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.
f. Follow IUPAC punctuation rules, which include the following: (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 that follows.

A line-angle structural formula is a structural representation in which a line represents a

carbon–carbon bond and a carbon atom is understood to be present at every point where two

lines meet and at the ends of lines. Note that the zigzag (sawtooth) pattern used in line-angle

structural formulas has a relationship to the three-dimensional shape of the molecules that are

represented. The line-angle structural formula for an unbranched chain of eight carbon atoms

would be Ball-and-stick-models and line-angle structural formulas for the alkanes propane,

butane, and pentane are as follows:

CYCLOALKANES

A cycloalkane is a saturated hydrocarbon in which carbon atoms connected to one

another in a cyclic (ring) arrangement are present. The simplest cycloalkane is cyclopropane,

which contains a cyclic arrangement of three carbon atoms. The general formula for
cycloalkanes is Cn H2n . Thus a given cycloalkane contains two fewer hydrogen atoms than an

alkane with the same number of hydrogen atoms (CnH2n+2 ). Butane (C4 H10 ) and cyclobutane (C4

H8 ) are not isomers; isomers must have the same molecular formula. Line-angle structural formulas

are generally used to represent cycloalkane structures. The line-angle structural formula for

cyclopropane is a triangle, that for cyclobutane a square, that for cyclopentane a pentagon,

and that for cyclohexane a hexagon.

IUPAC NOMENCLATURE FOR CYCLOALKANES

IUPAC naming procedures for cycloalkanes are similar to those for alkanes. The ring

portion of a cycloalkane molecule serves as the name base, and the prefix cyclo- is used to

indicate the presence of the ring. Alkyl substituents are named in the same manner as in

alkanes. Numbering conventions used in locating substituents on the ring include the following:

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.

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.

PHYSICAL PROPERTIES OF ALKANES AND CYCLOALKANES

1. Alkanes and cycloalkanes are insoluble in water. Water molecules are polar, and

alkane and cycloalkane molecules are nonpolar. Molecules of unlike polarity have

limited solubility in one another. The water insolubility of alkanes makes them good

preservatives for metals. They prevent water from reaching the metal surface and

causing corrosion. They also have biological functions as protective coatings.

2. Alkanes and cycloalkanes have densities lower than that of water. Alkane and

cycloalkane densities fall in the range 0.6 g/mL to 0.8 g/mL, compared with water’s

density of 1.0 g/mL. When alkanes and cycloalkanes are mixed with water, two layers

form (because of insolubility), with the hydrocarbon layer on top (because of its lower

density). This density difference between alkanes/cycloalkanes and water explains

why oil spills in aqueous environments spread so quickly. The floating oil follows the

movement of the water.

3. The boiling points of continuous-chain alkanes and cycloalkanes increase with an

increase in carbon chain length or ring size. For continuous-chain alkanes, the boiling

point increases roughly 30OC for every carbon atom added to the chain.