Structure and Nomenclature of

Hydrocarbons
The Saturated
What Is an Organic
Hydrocarbons, or The Cycloalkanes
Compound?
Alkanes
The Unsaturated
Rotation Around The Nomenclature of
Hydrocarbons: Alkenes and
C C Bonds Alkanes
Alkynes

What is an Organic Compound?

When you drive up to the pump at some gas stations you are faced with a variety of
choices.

You can buy "leaded" gas or different forms of "unleaded" gas that have different octane
numbers. As you filled the tank, you might wonder, "What is 'leaded' gas, and why do
they add lead to gas?" Or, "What would I get for my money if I bought premium gas,
with a higher octane number?"

You then stop to buy drugs for a sore back that has been bothering you since you helped a
friend move into a new apartment. Once again, you are faced with choices (see the figure
below). You could buy aspirin, which has been used for almost a hundred years. Or
Tylenol, which contains acetaminophen. Or a more modern pain-killer, such as
ibuprofen. While you are deciding which drug to buy, you might wonder, "What is the
difference between these drugs?," and even, "How do they work?"
You then drive to campus, where you sit in a "plastic" chair to eat a sandwich that has
been wrapped in "plastic," without worrying about why one of these plastics is flexibile
while the other is rigid. While you're eating, a friend stops by and starts to tease you
about the effect of your diet on the level of cholesterol in your blood, which brings up the
questions, "What is cholesterol?" and "Why do so many people worry about it?"

Answers to each of these questions fall within the realm of a field known as organic
chemistry. For more than 200 years, chemists have divided materials into two categories.
Those isolated from plants and animals were classified as organic, while those that trace
back to minerals were inorganic. At one time, chemists believed that organic compounds
were fundamentally different from those that were inorganic because organic compounds
contained a vital force that was only found in living systems.

The first step in the decline of the vital force theory occurred in 1828, when Friederich
Wohler synthesized urea from inorganic starting materials. Wohler was trying to make
ammonium cyanate (NH4OCN) from silver cyanate (AgOCN) and ammonium chloride
(NH4Cl). What he expected is described by the following equation.

AgOCN(aq) + NH4Cl(aq) AgCl(s) + NH4OCN(aq)

The product he isolated from this reaction had none of the properties of cyanate
compounds. It was a white, crystalline material that was identical to urea, H2NCONH2,
which could be isolated from urine.
Neither Wohler nor his contemporaries claimed that his results disproved the vital force
theory. But his results set in motion a series of experiments that led to the synthesis of a
variety of organic compounds from inorganic starting materials. This inevitably led to the
disappearance of "vital force" from the list of theories that had any relevance to
chemistry, although it did not lead to the death of the theory, which still had proponents
more than 90 years later.

If the difference between organic and inorganic compounds isn't the presence of some
mysterious vital force required for their synthesis, what is the basis for distinguishing
between these classes of compounds? Most compounds extracted from living organisms
contain carbon. It is therefore tempting to identify organic chemistry as the chemistry of
carbon. But this definition would include compounds such as calcium carbonate (CaCO3),
as well as the elemental forms of carbon diamond and graphite that are clearly
inorganic. We will therefore define organic chemistry as the chemistry of compounds
that contain both carbon and hydrogen.

Even though organic chemistry focuses on compounds that contain carbon and hydrogen,
more than 95% of the compounds that have isolated from natural sources or synthesized
in the laboratory are organic. The special role of carbon in the chemistry of the elements
is the result of a combination of factors, including the number of valence electrons on a
neutral carbon atom, the electronegativity of carbon, and the atomic radius of carbon
atoms (see the table below).

The Physical Properties of Carbon

Electronic configuration 1s2 2s2 2p2

Electronegativity 2.55
Covalent radius 0.077 nm

Carbon has four valence electrons 2s2 2p2 and it must either gain four electrons or
lose four electrons to reach a rare-gas configuration. The electronegativity of carbon is
too small for carbon to gain electrons from most elements to form C4- ions, and too large
for carbon to lose electrons to form C4+ ions. Carbon therefore forms covalent bonds with
a large number of other elements, including the hydrogen, nitrogen, oxygen, phosphorus,
and sulfur found in living systems.
Because they are relatively small, carbon atoms can come close enough together to form
strong C=C double bonds or even C C triple bonds. Carbon also forms strong double
and triple bonds to nitrogen and oxygen. It can even form double bonds to elements such
as phosphorus or sulfur that do not form double bonds to themselves.

Several years ago, the unmanned Viking spacecraft carried out experiments designed to
search for evidence of life on Mars. These experiments were based on the assumption
that living systems contain carbon, and the absence of any evidence for carbon-based life
on that planet was presumed to mean that no life existed. Several factors make carbon
essential to life.

• The ease with which carbon atoms form bonds to other carbon atoms.
• The strength of C C single bonds and the covalent bonds carbon forms to other
nonmetals, such as N, O, P, and S.
• The ability of carbon to form multiple bonds to other nonmetals, including C, N,
O, P, and S atoms.

These factors provide an almost infinite variety of potential structures for organic
compounds, such as vitamin C shown in the figure below.

No other element can provide the variety of combinations and permutations necessary for
life to exist.

The Saturated Hydrocarbons, or Alkanes

Compounds that contain only carbon and hydrogen are known as hydrocarbons. Those
that contain as many hydrogen atoms as possible are said to be saturated. The saturated
hydrocarbons are also known as alkanes.

The simplest alkane is methane: CH4. The Lewis structure of methane can be generated
by combining the four electrons in the valence shell of a neutral carbon atom with four
hydrogen atoms to form a compound in which the carbon atom shares a total of eight
valence electrons with the four hydrogen atoms.

Methane is an example of a general rule that carbon is tetravalent; it forms a total of four
bonds in almost all of its compounds. To minimize the repulsion between pairs of
electrons in the four C H bonds, the geometry around the carbon atom is tetrahedral, as
shown in the figure below.

Practice Problem 1:

Use the fact that carbon is usually tetravalent to predict the formula of ethane, the alkane
that contains two carbon atoms.

Click here to check your answer to Practice Problem 1

The alkane that contains three carbon atoms is known as propane, which has the formula
C3H8 and the following skeleton structure.

The four-carbon alkane is butane, with the formula C4H10.

The names, formulas, and physical properties for a variety of alkanes with the generic
formula CnH2n+2 are given in the table below. The boiling points of the alkanes gradually
increase with the molecular weight of these compounds. At room temperature, the lighter
alkanes are gases; the midweight alkanes are liquids; and the heavier alkanes are solids,
or tars.

The Saturated Hydrocarbons, or Alkanes

Molecular Melting Boiling State

Name Formula Point (oC) Point (oC) at 25oC
methane CH4 -182.5 -164 gas
ethane C2H6 -183.3 -88.6 gas
propane C3H8 -189.7 -42.1 gas
butane C4H10 -138.4 -0.5 gas
pentane C5H12 -129.7 36.1 liquid
hexane C6H14 -95 68.9 liquid
heptane C7H16 -90.6 98.4 liquid
octane C8H18 -56.8 124.7 liquid
nonane C9H20 -51 150.8 liquid
decane C10H22 -29.7 174.1 liquid
undecane C11H24 -24.6 195.9 liquid
dodecane C12H26 -9.6 216.3 liquid
eicosane C20H42 36.8 343 solid
triacontane C30H62 65.8 449.7 solid

The alkanes in the table above are all straight-chain hydrocarbons, in which the carbon
atoms form a chain that runs from one end of the molecule to the other. The generic
formula for these compounds can be understood by assuming that they contain chains of
CH2 groups with an additional hydrogen atom capping either end of the chain. Thus, for
every n carbon atoms there must be 2n + 2 hydrogen atoms: CnH2n+2.

Because two points define a line, the carbon skeleton of the ethane molecule is linear, as
shown in the figure below.

Because the bond angle in a tetrahedron is 109.5, alkanes molecules that contain three or
four carbon atoms can no longer be thought of as "linear," as shown in the figure below.
 Propane Butane

In addition to the straight-chain examples considered so far, alkanes also form branched
structures. The smallest hydrocarbon in which a branch can occur has four carbon atoms.
This compound has the same formula as butane (C4H10), but a different structure.
Compounds with the same formula and different structures are known as isomers (from
the Greek isos, "equal," and meros, "parts"). When it was first discovered, the branched
isomer with the formula C4H10 was therefore given the name isobutane.

Isobutane

The best way to understand the difference between the structures of butane and isobutane
is to compare the ball-and-stick models of these compounds shown in the figure below.

Butane Isobutane

Butane and isobutane are called constitutional isomers because they literally differ in
their constitution. One contains two CH3 groups and two CH2 groups; the other contains
three CH3 groups and one CH group.

There are three constitutional isomers of pentane, C5H12. The first is "normal" pentane, or
n-pentane.

A branched isomer is also possible, which was originally named isopentane. When a
more highly branched isomer was discovered, it was named neopentane (the new isomer
of pentane).
Ball-and-stick models of the three isomers of pentane are shown in the figure below.

n-Pentane Isopentane

Neopentane

Practice Problem 2:

The following structures all have the same molecular formula: C6H14. Which of these
structures represent the same molecule?
Click here to check your answer to Practice Problem 2

Practice Problem 3:

Determine the number of constitutional isomers of hexane, C6H14.

Click here to check your answer to Practice Problem 3

There are two constitutional isomers with the formula C4H10, three isomers of C5H12, and
five isomers of C6H14. The number of isomers of a compound increases rapidly with
additional carbon atoms. There are over 4 billion isomers for C30H62, for example.

The Cycloalkanes

If the carbon chain that forms the backbone of a straight-chain hydrocarbon is long
enough, we can envision the two ends coming together to form a cycloalkane. One
hydrogen atom has to be removed from each end of the hydrocarbon chain to form the C
C bond that closes the ring. Cycloalkanes therefore have two less hydrogen atoms
than the parent alkane and a generic formula of CnH2n.

The smallest alkane that can form a ring is cyclopropane, C3H6, in which the three carbon
atoms lie in the same plane. The angle between adjacent C C bonds is only 60, which
is very much smaller than the 109.5 angle in a tetrahedron, as shown in the figure below.
Cyclopropane is therefore susceptible to chemical reactions that can open up the three-
membered ring.

Any attempt to force the four carbons that form a cyclobutane ring into a plane of atoms
would produce the structure shown in the figure below, in which the angle between
adjacent C C bonds would be 90.

One of the four carbon atoms in the cyclobutane ring is therefore displaced from the
plane of the other three to form a "puckered" structure that is vaguely reminiscent of the
wings of a butterfly.

The angle between adjacent C C bonds in a planar cyclopentane molecule would be

108, which is close to the ideal angle around a tetrahedral carbon atom. Cyclopentane is
not a planar molecule, as shown in the figure below, because displacing two of the carbon
atoms from the plane of the other three produces a puckered structure that relieves some
of the repulsion between the hydrogen atoms on adjacent carbon atoms in the ring.

By the time we get to the six-membered ring in cyclohexane, a puckered structure can be
formed by displacing a pair of carbon atoms at either end of the ring from the plane of the
other four members of the ring. One of these carbon atoms is tilted up, out of the ring,
whereas the other is tilted down to form the "chair" structure shown in the figure below.
 Rotation Around C C Bonds

As one looks at the structure of the ethane molecule, it is easy to fall into the trap of
thinking about this molecule as if it was static. Nothing could be further from the truth.
At room temperature, the average velocity of an ethane molecule is about 500 m/s
more than twice the speed of a Boeing 747. While it moves through space, the molecule
is tumbling around its center of gravity like an airplane out of control. At the same time,
the C H and C C bonds are vibrating like a spring at rates as fast as 9 x 1013 s-1.

There is another way in which the ethane molecule can move. The CH3 groups at either
end of the molecule can rotate with respect to each around the C C bond. When this
happens, the molecule passes through an infinite number of conformations that have
slightly different energies. The highest energy conformation corresponds to a structure in
which the hydrogen atoms are "eclipsed." If we view the molecule along the C C bond,
the hydrogen atoms on one CH3 group would obscure those on the other, as shown in the
figure below.

The lowest energy conformation is a structure in which the hydrogen atoms are
"staggered," as shown in the figure below.
The difference between the eclipsed and staggered conformations of ethane are best
illustrated by viewing these molecules along the C C bond, as shown in the figure
below.

Eclipsed Staggered

The difference between the energies of these conformations is relatively small, only
about 12 kJ/mol. But it is large enough that rotation around the C C bond is not
smooth. Although the frequency of this rotation is on the order of 1010 revolutions per
second, the ethane molecule spends a slightly larger percentage of the time in the
staggered conformation.

The different conformations of a molecule are often described in terms of Newman

projections. These line drawings show the six substituents on the C C bond as if the
structure of the molecule was projected onto a piece of paper by shining a bright light
along the C C bond in a ball-and-stick model of the molecule. Newman projections for
the different staggered conformations of butane are shown in the figure below.

Because of the ease of rotation around C C bonds, there are several conformations of
some of the cycloalkanes described in the previous section. Cyclohexane, for example,
forms both the "chair" and "boat" conformations shown in the figure below.
 Chair Boat

The difference between the energies of the chair conformation, in which the hydrogen
atoms are staggered, and the boat conformation, in which they are eclipsed, is about 30
kJ/mol. As a result, even though the rate at which these two conformations interchange is
about 1 x 105 s-1, we can assume that most cyclohexane molecules at any moment in time
are in the chair conformation.

The Nomenclature of Alkanes

Common names such as pentane, isopentane, and neopentane are sufficient to

differentiate between the three isomers with the formula C5H12. They become less useful,
however, as the size of the hydrocarbon chain increases.

The International Union of Pure and Applied Chemistry (IUPAC) has developed a
systematic approach to naming alkanes and cycloalkanes based on the following steps.

• Find the longest continuous chain of carbon atoms in the skeleton structure. Name
the compound as a derivative of the alkane with this number of carbon atoms. The
following compound, for example, is a derivative of pentane because the longest
chain contains five carbon atoms.
 • Name the substituents on the chain. Substituents derived from alkanes are named
by replacing the -ane ending with -yl. This compound contains a methyl (CH3-)
substituent.

• Number the chain starting at the end nearest the first substituent and specify the
carbon atoms on which the substituents are located. Use the lowest possible
numbers. This compound, for example, is 2-methylpentane, not 4-methylpentane.

• Use the prefixes di-, tri-, and tetra- to describe substituents that are found two,
three, or four times on the same chain of carbon atoms.
• Arrange the names of the substituents in alphabetical order.

Practice Problem 4:

Name the following compound.

Practice Problem 5:

Name the following compound.

 The Unsaturated Hydrocarbons: Alkenes and Alkynes

Carbon not only forms the strong C C single bonds found in alkanes, it also forms
strong C=C double bonds. Compounds that contain C=C double bonds were once known
as olefins (literally, "to make an oil") because they were hard to crystallize. (They tend to
remain oily liquids when cooled.) These compounds are now called alkenes. The
simplest alkene has the formula C2H4 and the following Lewis structure.

The relationship between alkanes and alkenes can be understood by thinking about the
following hypothetical reaction. We start by breaking the bond in an H2 molecule so that
one of the electrons ends up on each of hydrogen atoms. We do the same thing to one of
the bonds between the carbon atoms in an alkene. We then allow the unpaired electron on
each hydrogen atom to interact with the unpaired electron on a carbon atom to form a
new C H bond.

Thus, in theory, we can transform an alkene into the parent alkane by adding an H2
molecule across a C=C double bond. In practice, this reaction only occurs at high
pressures in the presence of a suitable catalyst, such as piece of nickel metal.
Because an alkene can be thought of as a derivative of an alkane from which an H2
molecule has been removed, the generic formula for an alkene with one C=C double
bond is CnH2n.

Alkenes are examples of unsaturated hydrocarbons because they have fewer hydrogen
atoms than the corresponding alkanes. They were once named by adding the suffix -ene
to the name of the substituent that carried the same number of carbon atoms.

The IUPAC nomenclature for alkenes names these compounds as derivatives of the
parent alkanes. The presence of the C=C double bond is indicated by changing the -ane
ending on the name of the parent alkane to -ene.

The location of the C=C double bond in the skeleton structure of the compound is
indicated by specifying the number of the carbon atom at which the C=C bond starts.

The names of substituents are then added as prefixes to the name of the alkene.

Compounds that contain C C triple bonds are called alkynes. These compounds have
four less hydrogen atoms than the parent alkanes, so the generic formula for an alkyne
with a single C C triple bond is CnH2n-2. The simplest alkyne has the formula C2H2 and
is known by the common name acetylene.

The IUPAC nomenclature for alkynes names these compounds as derivatives of the
parent alkane, with the ending -yne replacing -ane.
In addition to compounds that contain one double bond (alkenes) or one triple bond
(alkynes), we can also envision compounds with two double bonds (dienes), three double
bonds (trienes), or a combination of double and triple bonds.

Organic Chemistry: Structure and Nomenclature of Hydrocarbons

Structure and Nomenclature of Hydrocarbons | Isomers | The

Reactions of Alkanes, Alkenes, and Alkynes | Hydrocarbons |
Petroleum and Coal | Chirality and Optical Activity

Periodic Table | Periodic Table | Glossary | Cool Applets

Gen Chem Topic Review | General Chemistry Help Homepage |

Search: The general chemistry web site.