Hydrocarbon

Hydrocarbon, any of a class of organic chemical compounds composed only of the elements carbon (C)
and hydrogen (H). The carbon atoms join together to form the framework of the compound, and the
hydrogen atoms attach to them in many different configurations. Hydrocarbons are the principal
constituents of petroleum and natural gas. They serve as fuels and lubricants as well as raw materials for
the production of plastics, fibres, rubbers, solvents, explosives, and industrial chemicals.

Many hydrocarbons occur in nature. In addition to making up fossil fuels, they are present in trees and
plants, as, for example, in the form of pigments called carotenes that occur in carrots and green leaves.
More than 98 percent of natural crude rubber is a hydrocarbon polymer, a chainlike molecule consisting
of many units linked together. The structures and chemistry of individual hydrocarbons depend in large
part on the types of chemical bonds that link together the atoms of their constituent molecules.

Nineteenth-century chemists classified hydrocarbons as either aliphatic or aromatic on the basis of their
sources and properties. Aliphatic (from Greek aleiphar, “fat”) described hydrocarbons derived by
chemical degradation of fats or oils. Aromatic hydrocarbons constituted a group of related substances
obtained by chemical degradation of certain pleasant-smelling plant extracts. The terms aliphatic and
aromatic are retained in modern terminology, but the compounds they describe are distinguished on
the basis of structure rather than origin.

Aliphatic hydrocarbons are divided into three main groups according to the types of bonds they contain:
alkanes, alkenes, and alkynes. Alkanes have only single bonds, alkenes contain a carbon-carbon double
bond, and alkynes contain a carbon-carbon triple bond. Aromatic hydrocarbons are those that are
significantly more stable than their Lewis structures would suggest; i.e., they possess “special stability.”
They are classified as either arenes, which contain a benzene ring as a structural unit, or nonbenzenoid
aromatic hydrocarbons, which possess special stability but lack a benzene ring as a structural unit.

Structures of representative hydrocarbons (an aliphatic hydrocarbon and an aromatic hydrocarbon).

chemical compound

This classification of hydrocarbons serves as an aid in associating structural features with properties but
does not require that a particular substance be assigned to a single class. Indeed, it is common for a
molecule to incorporate structural units characteristic of two or more hydrocarbon families. A molecule
that contains both a carbon-carbon triple bond and a benzene ring, for example, would exhibit some
properties that are characteristic of alkynes and others that are characteristic of arenes.

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Alkanes are described as saturated hydrocarbons, while alkenes, alkynes, and aromatic hydrocarbons
are said to be unsaturated.

Aliphatic hydrocarbons

Alkanes

Alkanes, hydrocarbons in which all the bonds are single, have molecular formulas that satisfy the
general expression CnH2n + 2 (where n is an integer). Carbon is sp3 hybridized (three electron pairs are
involved in bonding, forming a tetrahedral complex), and each C—C and C—H bond is a sigma (σ) bond
(see chemical bonding). In order of increasing number of carbon atoms, methane (CH4), ethane (C2H6),
and propane (C3H8) are the first three members of the series.

Hydrocarbon; Isomerism. Structural formulas for methane (CH4), ethane (C2H6) and propane (C3H8).

Methane, ethane, and propane are the only alkanes uniquely defined by their molecular formula. For
C4H10 two different alkanes satisfy the rules of chemical bonding (namely, that carbon has four bonds
and hydrogen has one in neutral molecules). One compound, called n-butane, where the prefix n-
represents normal, has its four carbon atoms bonded in a continuous chain. The other, called isobutane,
has a branched chain.

Hydrocarbon, Isomerism. Structural formulas for n-butane (CH3CH2CH2CH3) and isobutane (CH3)3CH

Different compounds that have the same molecular formula are called isomers. Isomers that differ in the
order in which the atoms are connected are said to have different constitutions and are referred to as
constitutional isomers. (An older name is structural isomers.) The compounds n-butane and isobutane
are constitutional isomers and are the only ones possible for the formula C4H10. Because isomers are
different compounds, they can have different physical and chemical properties. For example, n-butane
has a higher boiling point (−0.5 °C [31.1 °F]) than isobutane (−11.7 °C [10.9 °F]).
There is no simple arithmetic relationship between the number of carbon atoms in a formula and the
number of isomers. Graph theory has been used to calculate the number of constitutionally isomeric
alkanes possible for values of n in CnH2n + 2 from 1 through 400. The number of constitutional isomers
increases sharply as the number of carbon atoms increases. There is probably no upper limit to the
number of carbon atoms possible in hydrocarbons. The alkane CH3(CH2)388CH3, in which 390 carbon
atoms are bonded in a continuous chain, has been synthesized as an example of a so-called superlong
alkane. Several thousand carbon atoms are joined together in molecules of hydrocarbon polymers such
as polyethylene, polypropylene, and polystyrene.

Number of possible alkane isomers

molecular formula number of constitutional isomers

C3H8 1

C4H10 2

C5H12 3

C6H14 5

C7H16 9

C8H18 18

C9H20 35

C10H22 75

C15H32 4,347

C20H42 366,319

C30H62 4,111,846,763

Nomenclature

The need to give each compound a unique name requires a richer variety of terms than is available with
descriptive prefixes such as n- and iso-. The naming of organic compounds is facilitated through the use
of formal systems of nomenclature. Nomenclature in organic chemistry is of two types: common and
systematic. Common names originate in many different ways but share the feature that there is no
necessary connection between name and structure. The name that corresponds to a specific structure
must simply be memorized, much like learning the name of a person. Systematic names, on the other
hand, are keyed directly to molecular structure according to a generally agreed upon set of rules. The
most widely used standards for organic nomenclature evolved from suggestions made by a group of
chemists assembled for that purpose in Geneva in 1892 and have been revised on a regular basis by the
International Union of Pure and Applied Chemistry (IUPAC). The IUPAC rules govern all classes of organic
compounds but are ultimately based on alkane names. Compounds in other families are viewed as
derived from alkanes by appending functional groups to, or otherwise modifying, the carbon skeleton.
The IUPAC rules assign names to unbranched alkanes according to the number of their carbon atoms.
Methane, ethane, and propane are retained for CH4, CH3CH3, and CH3CH2CH3, respectively. The n-
prefix is not used for unbranched alkanes in systematic IUPAC nomenclature; therefore, CH3CH2CH2CH3
is defined as butane, not n-butane. Beginning with five-carbon chains, the names of unbranched alkanes
consist of a Latin or Greek stem corresponding to the number of carbons in the chain followed by the
suffix -ane. A group of compounds such as the unbranched alkanes that differ from one another by
successive introduction of CH2 groups constitute a homologous series.

IUPAC names of unbranched alkanes

alkane formula name alkane formula name

CH4 methane CH3(CH2)6CH3 octane

CH3CH3 ethane CH3(CH2)7CH3 nonane

CH3CH2CH3 propane CH3(CH2)8CH3 decane

CH3CH2CH2CH3 butane CH3(CH2)13CH3 pentadecane

CH3(CH2)3CH3 pentane CH3(CH2)18CH3 icosane

CH3(CH2)4CH3 hexane CH3(CH2)28CH3 triacontane

CH3(CH2)5CH3 heptane CH3(CH2)98CH3 hectane

Alkanes with branched chains are named on the basis of the name of the longest chain of carbon atoms
in the molecule, called the parent. The alkane shown has seven carbons in its longest chain and is
therefore named as a derivative of heptane, the unbranched alkane that contains seven carbon atoms.
The position of the CH3 (methyl) substituent on the seven-carbon chain is specified by a number (3-),
called a locant, obtained by successively numbering the carbons in the parent chain starting at the end
nearer the branch. The compound is therefore called 3-methylheptane.

Hydrocarbon. formula for the compound 3-methylheptane.

When there are two or more identical substituents, replicating prefixes (di-, tri-, tetra-, etc.) are used,
along with a separate locant for each substituent. Different substituents, such as ethyl (―CH2CH3) and
methyl (―CH3) groups, are cited in alphabetical order. Replicating prefixes are ignored when
alphabetizing. In alkanes, numbering begins at the end nearest the substituent that appears first on the
chain so that the carbon to which it is attached has as low a number as possible.

Hydrocarbon. Formula for the compound 4-ethyl-2,4-dimethyloctane.

Methyl and ethyl are examples of alkyl groups. An alkyl group is derived from an alkane by deleting one
of its hydrogens, thereby leaving a potential point of attachment. Methyl is the only alkyl group
derivable from methane and ethyl the only one from ethane. There are two C3H7 and four C4H9 alkyl
groups. The IUPAC rules for naming alkanes and alkyl groups cover even very complex structures and are
regularly updated. They are unambiguous in the sense that, although a single compound may have more
than one correct IUPAC name, there is no possibility that two different compounds will have the same
name.

Three-dimensional structures

chemical structure of methane

chemical structure of methane

Tetrahedral geometry of methane: (A) stick-and-ball model and (B) diagram showing bond angles and
distances. (Plain bonds represent bonds in the plane of the image; wedge and dashed bonds represent
those directed toward and away from the viewer, respectively.)

Most organic molecules, including all alkanes, are not planar but are instead characterized by three-
dimensional structures. Methane, for example, has the shape of a regular tetrahedron with carbon at
the centre and a hydrogen atom at each corner. Each H―C―H angle in methane is 109.5°, and each
C―H bond distance is 1.09 angstroms (Å; 1Å = 1 × 10−10 metre). Higher alkanes such as butane have
bonds that are tetrahedrally disposed on each carbon except that the resulting C―C―C and H―C―H
angles are slightly larger and smaller, respectively, than the ideal value of 109.5° characteristic of a
perfectly symmetrical tetrahedron. Carbon-carbon bond distances in alkanes are normally close to 1.53
angstroms.

eclipsed conformation of ethane

eclipsed conformation of ethane

Eclipsed conformation is the least stable of all ethane conformations because the repulsive forces
between electron pairs in the C―H bonds of adjacent carbons are maximized.

staggered conformation of ethane

staggered conformation of ethane

Staggered conformation is the most stable of all ethane conformations because the repulsive forces
between electron pairs in the C―H bonds of adjacent carbons are minimized.

An important aspect of the three-dimensional shape of alkanes and other organic molecules is their
conformations, the nonidentical arrangements of atoms that are generated by rotation about single
bonds. Of the infinite number of conformations possible for ethane—which are related by tiny
increments of rotation of one CH3 group with respect to the other—the eclipsed conformation is the
least stable, and the staggered conformation is the most stable. The eclipsed conformation is said to
suffer torsional strain because of repulsive forces between electron pairs in the C―H bonds of adjacent
carbons. These repulsive forces are minimized in the staggered conformation since all C―H bonds are as
far from one another as possible. Although rotation about the C―C bond of ethane is exceedingly rapid
(millions of times per second at room temperature), at any instant most of the molecules exist in the
staggered conformation.

For butane, two different staggered conformations, called anti and gauche, are possible. Methyl is a
larger substituent than hydrogen, and the greater separation between methyl groups in the anti
conformation makes it slightly more stable than the gauche.

Hydrocarbon. The two different staggered conformations (anti and gauche) for butane.

The three-dimensional structures of higher alkanes are governed by the tetrahedral disposition of the
four bonds to each carbon atom, by the preference for staggered conformations, and by the greater
stability of anti C―C―C―C arrangements over gauche.

Cycloalkanes

Countless organic compounds are known in which a sequence of carbon atoms, rather than being
connected in a chain, closes to form a ring. Saturated hydrocarbons that contain one ring are referred to
as cycloalkanes. With a general formula of CnH2n (n is an integer greater than 2), they have two fewer
hydrogen atoms than an alkane with the same number of carbon atoms. Cyclopropane (C3H6) is the
smallest cycloalkane, whereas cyclohexane (C6H12) is the most studied, best understood, and most
important. It is customary to represent cycloalkane rings as polygons, with the understanding that each
corner corresponds to a carbon atom to which is attached the requisite number of hydrogen atoms to
bring its total number of bonds to four.

Hydrocarbon, Isomerism. Structural formulas showing cycloalkane rings as polygons (each corner
corresponds to a carbon atom). Cyclopropane and Cyclohexane.

In naming cycloalkanes, alkyl groups attached to the ring are indicated explicitly and listed in
alphabetical order, and the ring is numbered so as to give the lowest locant to the first-appearing
substituent. If two different directions yield equivalent locants, the direction is chosen that gives the
lower number to the substituent appearing first in the name.

Hydrocarbon. Structural formulas for 1,1,3-trimethylcyclopentane and 1-ethyl-3-methylcycloheptane.

The three carbon atoms of cyclopropane define the corners of an equilateral triangle, a geometry that
requires the C―C―C angles to be 60°. This 60° angle is much smaller than the normal tetrahedral bond
angle of 109.5° and imposes considerable strain (called angle strain) on cyclopropane. Cyclopropane is
further destabilized by the torsional strain that results from having three eclipsed C―H bonds above the
plane of the ring and three below.

Cyclopropane is the only cycloalkane that is planar. Cyclobutane (C4H8) and higher cycloalkanes adopt
nonplanar conformations in order to minimize the eclipsing of bonds on adjacent atoms. The angle
strain in cyclobutane is less than in cyclopropane, whereas cyclopentane and higher cycloalkanes are
virtually free of angle strain. With the exception of cyclopropane, all cycloalkanes undergo rapid internal
motion involving interconversion of nonplanar “puckered” conformations.

Hydrocarbon. Structural formulas for cyclopropane, cyclobutane, and cyclopentane.

Many of the most important principles of conformational analysis have been developed by examining
cyclohexane. Three conformations of cyclohexane, designated as chair, boat, and skew (or twist), are
essentially free of angle strain. Of these three the chair is the most stable, mainly because it has a
staggered arrangement of all its bonds. The boat and skew conformations lack perfect staggering of
bonds and are destabilized by torsional strain. The boat conformation is further destabilized by the
mutual crowding of hydrogen atoms at carbons one and four. The shape of the boat brings its two
“flagpole” hydrogen atoms to within 1.80 angstroms of each other, far closer than the 2.20-angstrom
distance at which repulsive forces between hydrogen atoms become significant. At room temperature,
999 of every 1,000 cyclohexane molecules exist in the chair form (the other being skew).

Hydrocarbon, Isomerism. Three conformations of cyclohexane, designated as chair, boat, and skew (or
twist).

There are two orientations of carbon-hydrogen bonds in the chair conformation of cyclohexane. Six
bonds are parallel to a vertical axis passing through the centre of the ring and are called axial (a) bonds.
The directions of these six axial bonds alternate up and down from one carbon to the next around the
ring; thus, the axial hydrogens at carbons one, three, and five lie on one side of the ring and those at
carbons two, four, and six on the other. The remaining six bonds are referred to as equatorial (e)
because they lie in a region corresponding to the approximate “equator” of the molecule. The shortest
distances between nonbonded atoms are those involving axial hydrogens on the same side of the
molecule.
A rapid process of chair-chair interconversion (called ring-flipping) interconverts the six axial and six
equatorial hydrogen atoms in cyclohexane. Chair-chair interconversion is a complicated process brought
about by successive conformational changes within the molecule. It is different from simple whole-
molecule motions, such as spinning and tumbling, and because it is a conformational change only, it
does not require any bonds to be broken.

Hydrocarbon, Isomerism. Chair-chair interconversion (called ring-flipping) interconverts the six axial and
six equatorial hydrogen atoms in cyclohexane.

Chair-chair interconversion is especially important in substituted derivatives of cyclohexane. Any

substituent is more stable when it occupies an equatorial rather than an axial site on the ring, since
equatorial substituents are less crowded than axial ones. In methylcyclohexane, the chair conformation
in which the large methyl group is equatorial is the most stable and, therefore, the most populated of all
possible conformations. At any instant, almost all the methylcyclohexane molecules in a given sample
exist in chair conformations, and about 95 percent of these have the methyl group in an equatorial
orientation.

Hydrocarbon, Isomerism: chair-chair interconversion in methylcyclohexane.

The highly branched tert-butyl group (CH3)3C― (tert-butyl) is even more spatially demanding than the
methyl group, and more than 99.99 percent of tert-butylcyclohexane molecules adopt chair
conformations in which the (CH3)3C― group is equatorial.

Conformational analysis of six-membered rings, especially the greater stability of chair conformations
with equatorial substituents, not only is important in the area of hydrocarbons but also is essential to an
understanding of the properties of biologically important molecules, especially steroids and
carbohydrates. Odd Hassel of Norway and Derek H.R. Barton of England shared the Nobel Prize for
Chemistry in 1969 for their important discoveries in this area. Hassel’s studies dealt with structure, while
Barton showed how conformational effects influence chemical reactivity.

The most stable structures of cycloalkanes and compounds based on them have been determined by a
number of experimental techniques, including X-ray diffraction and electron diffraction analyses and
infrared, nuclear magnetic resonance, and microwave spectroscopies. These experimental techniques
have been joined by advances in computational methods such as molecular mechanics, whereby the
total strain energies of various conformations are calculated and compared (see also chemical bonding:
Computational approaches to molecular structure). The structure with the lowest total energy is the
most stable and corresponds to the best combination of bond distances, bond angles, and
conformation. One benefit of such calculations is that unstable conformations, which are difficult to
study experimentally, can be examined. The quality of molecular mechanics calculations is such that it is
claimed that many structural features of hydrocarbons can be computed more accurately than they can
be measured.

The conformations of rings with 7–12 carbons have been special targets for study by molecular
mechanics. Unlike cyclohexane, in which one conformation (the chair) is much more stable than any
other, cycloalkanes with 7–12 carbons are generally populated by several conformations of similar
energy. Rings with more than 12 carbons are sufficiently flexible to adopt conformations that are
essentially strain-free.

Polycyclic hydrocarbons are hydrocarbons that contain more than one ring. They are classified as
bicyclic, tricyclic, tetracyclic, and so forth, according to the number of formal bond disconnections
necessary to produce a noncyclic carbon chain. Examples include trans-decalin and adamantane—both
of which are present in small amounts in petroleum—and cubane, a compound synthesized for the
purpose of studying the effects of strain on chemical reactivity.

Hydrocarbon. Polycyclic hydrocarbons, trans-decalin, adamantane, and cubane.

Stereoisomerism

Certain substituted derivatives of cycloalkanes exhibit a type of isomerism called stereoisomerism in

which two substances have the same molecular formula and the same constitution but differ in the
arrangement of their atoms in space. Methyl groups in 1,2-dimethylcyclopropane, for example, may be
on the same (cis) or opposite (trans) sides of the plane defined by the ring. The resulting two substances
are different compounds, each having its own properties such as boiling point (abbreviated bp here):

Hydrocarbon, Isomerism. Stereoisomerism: comparing compounds cis-1,2-dimethylcyclopropane and

trans-1,2-dimethylcyclopropane

Cis-trans isomers belong to a class of stereoisomers known as diastereomers and are often referred to
as geometric isomers, although this is an obsolete term. Cis-trans stereoisomers normally cannot be
interconverted at room temperature, because to do so requires the breaking and reforming of chemical
bonds.

Physical properties
Alkanes and cycloalkanes are nonpolar substances. Attractive forces between alkane molecules are
dictated by London forces (or dispersion forces, arising from electron fluctuations in molecules; see
chemical bonding: Intermolecular forces) and are weak. Thus, alkanes have relatively low boiling points
compared with polar molecules of comparable molecular weight. The boiling points of alkanes increase
with increasing number of carbons. This is because the intermolecular attractive forces, although
individually weak, become cumulatively more significant as the number of atoms and electrons in the
molecule increases.

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Physical properties of unbranched alkanes

name formulaboiling point (°C) melting point (°C)

methane CH4 −164 −182.5

ethane CH3CH3 −88.6 −183.3

propane CH3CH2CH3 −42 −189.7

butane CH3(CH2)2CH3 −0.5 −138.35

pentane CH3(CH2)3CH3 +36.1 −129.7

hexane CH3(CH2)4CH3 +68.9 −95.0

heptane CH3(CH2)5CH3 +98.4 −90.6

octane CH3(CH2)6CH3 +125.6 −56.8

nonane CH3(CH2)7CH3 +150.8 −51.0

decane CH3(CH2)8CH3 +174.1 −29.7

pentadecane CH3(CH2)13CH3 +270 +10

octadecane CH3(CH2)16CH3 +316.1 +28.2

icosane CH3(CH2)18CH3 +343 +36.8

triacontane CH3(CH2)28CH3 +449.7 +65.8

tetracontane CH3(CH2)38CH3 — +81

pentacontane CH3(CH2)48CH3 — +92

For a given number of carbon atoms, an unbranched alkane has a higher boiling point than any of its
branched-chain isomers. This effect is evident upon comparing the boiling points (bp) of selected C8H18
isomers. An unbranched alkane has a more extended shape, thereby increasing the number of
intermolecular attractive forces that must be broken in order to go from the liquid state to the gaseous
state. On the other hand, the relatively compact ellipsoidal shape of 2,2,3,3-tetramethylbutane permits
it to pack into a crystal lattice more effectively than octane and so raises its melting point (mp).

Hydrocarbon. Structural formula for unbranced alkanes, octane, 2-methylheptane, 2,2,3,3-

tetramethylbutane.

In general, solid alkanes do not often have high melting points. Unbranched alkanes tend toward a
maximum in that the melting point of CH3(CH2)98CH3 (115 °C [239 °F]) is not much different from that
of CH3(CH2)148CH3 (123 °C [253 °F]).

The viscosity of liquid alkanes increases with the number of carbons. Increased intermolecular attractive
forces, as well as an increase in the extent to which nearby molecules become entangled when they
have an extended shape, cause unbranched alkanes to be more viscous than their branched-chain
isomers.

The densities of liquid hydrocarbons are all less than that of water, which is quite polar and possesses
strong intermolecular attractive forces. All hydrocarbons are insoluble in water and, being less dense
than water, float on its surface. Hydrocarbons are, however, usually soluble in one another as well as in
organic solvents such as diethyl ether (CH3CH2OCH2CH3).

Sources and occurrence

The most abundant sources of alkanes are natural gas and petroleum deposits, formed over a period of
millions of years by the decay of organic matter in the absence of oxygen. Natural gas contains 60–80
percent methane, 5–9 percent ethane, 3–18 percent propane, and 2–14 percent higher hydrocarbons.
Petroleum is a complex liquid mixture of hundreds of substances—including 150 or more hydrocarbons,
approximately half of which are saturated.

Approximately two billion tons of methane are produced annually by the bacteria that live in termites
and in the digestive systems of plant-eating animals. Smaller quantities of alkanes also can be found in a
variety of natural materials. The so-called aggregation pheromone whereby Blaberus craniifer
cockroaches attract others of the same species is a 1:1 mixture of the volatile but relatively high-boiling
liquid alkanes undecane, CH3(CH2)9CH3, and tetradecane, CH3(CH2)12CH3. Hentriacontane,
CH3(CH2)29CH3, is a solid alkane present to the extent of 8–9 percent in beeswax, where its stability
and impermeability to water contribute to the role it plays as a structural component.
With the exception of the alkanes that are readily available from petroleum, alkanes are synthesized in
the laboratory and in industry by the hydrogenation of alkenes. Only a few methods are available in
which a carbon-carbon bond-forming operation gives an alkane directly, and these tend to be suitable
only for syntheses carried out on a small scale.