The Saturated Hydrocarbons: Alkanes and Cycloalkanes

Organic chemistry is the study of carbon containing compounds. The Swedish chemist Jon Jakob Berzelius coined
the term organic in 1807 by. In 1828 a 27-year-old German physician, Friedrich Wohler, synthesized the organic
molecule urea, (NH2)2C=O, from inorganic starting materials (potassium sulfate, K 2SO4 and ammonium cyanate,
NH4NCO).
There are three allotropic forms of elemental carbon: graphite, diamond, and buckministerfullerene. Allotropes are
forms of an element that have the same physical state but different properties. (e.g., oxygen has two allotropic forms
O2 and O3.)
Why are there so many carbon containing compounds?
1. Carbon can form stable, covalent bonds with other carbon atoms (catenate).
2. Carbon can form stable bonds with other elements.
3. Carbon can form double and triple bonds with other carbon atoms or other elements.
4. Carbon can bond with itself either as straight chains or cyclic compounds with branching possible in either
case.
Two different organic compounds can also have the same number of carbon atoms. These are called
isomers. Isomers are molecules that have the same molecular formulas but different structures and thus different
physical and chemical characteristics. An example of isomerism is butane and 2-methylpropane. Both have the
same molecular formula, C4H10, but differing physical and chemical properties.

Contrasts Between Organic and Inorganic Molecules

Carbon bonds are almost always covalent. Covalent compounds are often referred to as molecules.
Most bonds between a metal and a nonmetal are ionic. Many inorganic compounds are ionic compounds.
Ionic bonds:
1. result from the transfer of atoms and not sharing.
2. are electrostatic.
3. result with formation of large lattice crystals of cations and anions.
4. often dissolve in water to give electrolytic solutions (i.e., they conduct electricity).
Classification of Organic Compounds
All organic compounds be generally classified as hydrocarbons (molecules containing only hydrogen and carbon) or
substituted hydrocarbons (molecules having one or more hydrogen atoms replaced by another atom or group of
atoms).
Hydrocarbons can be further subdivided into Aliphatic (Greek aleiphat "fat") and Aromatic.

Aliphatic can be divided into alkanes, alkenes, and alkynes.

Alkanes are saturated hydrocarbons. Saturated means that the hydrocarbon has only single bonds and that the
hydrocarbon contains the maximum number of hydrogen atoms for each carbon atom. Unsaturated hydrocarbons
contain multiple bonding and contain less than the maximum number of hydrogens per carbon.
Ethane, C2H6, is an alkane and is an example of a saturated hydrocarbon.

Ethene, C2H4, is an alkene and is an example of unsaturated hydrocarbon.

Ethyne, C2H2, is an alkyne and is also an example of unsaturated hydrocarbon.

Aromatic compounds are unsaturated hydrocarbons and contain a benzene ring.

A substituted hydrocarbon results when one or more hydrogens is replaced by some other atom or groups of atoms,
known as a functional group. A functional group is an atom on group of atoms arranged in a particular way that is
primarily responsible for the chemical and physical properties of that molecule. These particular combination and
arrangement of atoms, when attached to a hydrocarbon, give the resulting molecule its unique physical and chemical
properties. That is to say that the functional group is responsible for the particular set of reactions that all
compounds with this group have.
Functional Group

Name

Family of Organic Example

Compounds
carbon-carbon double bond Alkene
1Butene

carbon-carbon triple bond

Alkyne

1-Butyne

Benzene ring

Aromatic

Toluene

Halogen atom (-X)

Alkyl halide

Chloromethane
CH3Cl

Hydroxyl group (-OH)

Alcohol

Ethanol
CH3CH2OH

Alkoxy group (-OR)

Ether

Dimethyl ether
CH3-O-CH3

Carbonyl group

Aldehyde or
ketone

Carboxyl group

Carboxylic acids

Acyl group

Carboxylic acid
derivatives

Amino group

Amines

Ethanal

Acetic acid
Methyl

acetate
Methyl amine

Alkanes
Alkanes are saturated hydrocarbons. This means that contain only carbon and hydrogen atoms bonded by single
bonds only.
The general formula for an alkane is CnH2n+2. In this formula, n, is the number of carbon atoms in the molecule.
The molecular formula is the actual ratio of atoms to one another in a molecule.
A structural formula represents a structure and emphasizes the bond connection between atoms.
A condensed formula is a simplification of the structural formula.
A line formula is a simplified representation of a structural formula in which many of the C-H bonds are not
shown.
In a line formula, the carbons are understood to exist at the vertices of each of the angles and the number of
hydrogens necessary are also understood, though not written.

Alkane

Molecular
Formula

Structural
Formula

Condensed
Formula

Line
Formula

Propane

C3H8

CH3CH2CH3

Butane

C4H10

CH3CH2CH2CH3

Names and Formulas of the First Ten Straight-Chain Alkanes & Alkyl Groups
Name
Methane
Ethane
Propane
Butane
Pentane

Molecular
Formula
CH4
C2H6
C3H8
C4H10
C5H12

Hexane
Heptane
Octane
Nonane
Decane

C6H14
C7H16
C8H18
C9H20
C10H22

Condensed Formula
CH4
CH3-CH3
CH3-CH2-CH3
CH3-CH2-CH2-CH3
CH3CH2CH2CH2CH3
or
CH3-(CH2)3-CH3
CH3-(CH2)4-CH3
CH3-(CH2)5-CH3
CH3-(CH2)6-CH3
CH3-(CH2)7-CH3
CH3-(CH2)8-CH3

R-

Alkyl
group
methyl
ethyl
propyl
butyl
pentyl

CH3CH3-CH2CH3-CH2-CH2CH3CH2CH2CH2CH3-(CH2)3-CH2-

hexyl
heptyl
octyl
nonyl
decyl

CH3-(CH2)4-CH2CH3-(CH2)5-CH2CH3-(CH2)6-CH2CH3-(CH2)7-CH2CH3-(CH2)8-CH2-

Hydrocarbon carbon bonding characteristics:

Carbon always forms 4 bonds with no lone pair electrons on the carbon atom. (One exception of this is carbon
monoxide.)
Single bonded carbon atoms have bond angles of 109.5 o. Alkanes are composed of carbon atoms that have
tetrahedral geometry. Any compound with carbon having four single bonds will have a tetrahedral shape about any
of the single bonded carbon atoms, with the bonded atoms at the vertices of a tetrahedron.
Hydrocarbon physical characteristics:
Hydrocarbons are nonpolar. They are immiscible with water.
They have relatively low melting points and boiling points. The first four alkanes (methane butane) are all gases at
room temperature.
Hydrocarbons are generally less dense than water.
Compounds that differ only in the number of -CH2- groups inserted in the carbon chain form a family group called a
homologous series.
Members of this family are called homologs.
Members of a homologous series are very similar in their chemical reactivity.
As more carbons are added and the size of the molecule increases, they exhibit gradually changing physical
properties.

As number of carbon atoms increases (increase in molecular weight) the melting points and boiling points.
Except for the very small alkanes, the boiling point rises 20 to 30 degrees for each carbon that is added to the chain.
The first four alkanes (i.e. with fewer than 5 carbons) are gases at room temp.
Alkyl groups
When a hydrogen is removed from a hydrocarbon, the resulting fragment is called an alkyl group. The name of the
alkyl group is derived from the alkane by removing the ane and replacing with yl. An alkyl group can be
represented by "R" in chemical structures.
Alkane
Methane
Ethane
Propane
Butane
Pentane

Condensed Lewis
Structure
CH4
CH3-CH3
CH3-CH2-CH3
CH3-CH2-CH2-CH3
CH3CH2CH2CH2CH3

Alkyl
group
methyl
ethyl
propyl
butyl
pentyl

RCH3CH3CH2CH3CH2CH2CH3CH2CH2CH2CH3CH2CH2CH2CH2-

Carbon atoms are classified by the number of other carbon atoms bonded to it.
A primary carbon (1o) is bonded to one carbon.
A secondary carbon (2o) is bonded to two carbons.
A tertiary carbon (3o) is bonded to three carbons.
A quaternary carbon (4o) is bonded to four carbons.
Alkyl groups are classified according to the number of carbons attached to the carbon that joins the alkyl group to
the molecule.

primary
alkyl group

secondary
alkyl group

tertiary
alkyl group

Hydrogen atoms are classified according to the type of carbon to which they are attached and are given equivalent
names.
Primary = connected to a primary carbon.
Secondary = connected to a secondary carbon.
Tertiary = connected to a tertiary carbon.
Remove a primary hydrogen from propane and the resulting alkyl group is the normal propyl group or n-propyl
group.
n-propyl CH3CH2CH2Remove a secondary hydrogen from propane and the resulting alkyl group is a isopropyl group.
isopropyl (CH3)2CH-

The alkyl groups the butanes, C4H10, are n-butyl, sec-butyl, iso-butyl, and tert-butyl.
Nomenclature of Alkanes
A chemical name has three parts in the IUPAC system: Prefix, Parent, Suffix.
Prefix gives the location.
Parent or stem tells how many carbons.
Suffix identifies the functional group.
I.U.P.A.C. Nomenclature of Alkanes
1. Determine the parent compound find the longest continuous chain of carbon atoms. If two different chains of
equal length are present, choose the one with the larger number of branch points.
2. Name and number the atoms. The stem name is derived from the parent hydrocarbon.
3. Number the parent chain to give the lowest number to the carbon bonded to the first group encountered on the
parent chain.
4. If the same substituent occurs more than once, the number of each carbon of the parent alkane to which it is
attached is given, and the number of substituent groups involved is indicated by prefix such as di-, tri, tetra-, and so
on.
5. Name the compound, beginning with the side chains in alphabetical order and ending with the name of the parent
compound. Follow these rules:
a. Always use commas between numbers.
b. Always use hyphens between numbers and words.
c. Do not leave spaces in the name.
d. When alphabetizing substituent groups, ignore the prefixes, di-, tri-, and so on.
e. Use the lowest possible numbers.
Constitutional isomers
Isomers are compounds with identical molecular formulas but which differ in the atomic arrangements. These
compounds differ in shape and properties and are actually different compounds. Constitutional isomers are
molecules having the same molecular formula but different arrangement of atoms (e.g., n-butane and 2methylpropane). Geometric isomers are molecules which have the same molecular formula but differing spatial
arrangement of atoms due to absence of free rotation.
There are 2 butane, C4H10, isomers.
There are 3 pentane, C5H12, isomers.
There are 4 hexane, C6H14, isomers.
There are 9 heptane, C7H16, isomers.
There are 18 octane, C8H18, isomers.
There are 35 nonane, C9H20, isomers.
There are 75 decane, C10H22, isomers.
Cycloalkanes
The cycloalkanes have the general formula of CnH2n.

Cyclopropane
C3H6

Cyclobutane
C4H8

Cyclopentane
C5H10

Cyclohexane
C6H12

Cycloheptane
C7H14

I.U.P.A.C. Nomenclature of Cycloalkanes

1. Count the number of carbon atoms in the ring and the number in the largest substituent. If the number of carbon
atoms in the ring is equal to or greater than the number in the largest substituent, the compound in named as an
alkyl-substituted cycloalkane. If the number of carbon atoms in the largest substituent is greater than the number in
the ring, the compound is named as a cycloalkyl-substituted alkane.
2. For alkyl-substituted cycloalkanes, start at a point of attachment and number the substituents on the ring so as to
arrive at the lowest sum.
a. Number substituents alphabetically.
b. Halogen are treated exactly like alkyl groups.
3. Use hyphen after cis or trans.
Cis-Trans Isomerism in Cycloalkanes
Rotation around the bonds in a cyclic structure is limited. The formation of cis-trans isomers or geometric isomers,
is a consequence of the absence of the free rotation. Geometric isomers are a type of stereoisomer. The term "cis" is
derived from Latin and means "on the same side." The term "trans" is also derived from Latin and means "across
from."

Conformations of Alkanes and Cycloalkanes

Because there is free rotation around a carbon-carbon single bond, even a very simple alkane like ethane, can exist
in an unlimited number of forms. Cycloalkanes (except cyclopropane) also exist in different
conformations. Cyclohexane exist in a "chair conformation" (the most energetically favorable) or a "boat
conformation." The hydrogen atoms which lie above or below the ring are said to be axial. Those that lie roughly
in the plane of the ring are called equatorial. When the chair form "flips", the six equatorial hydrogens become
axial and vice versa for the six axial.

The axial hydrogens are actually quite crowded. If one of them is replaced by a larger group, even one as small as a
methyl group, the chair form in which the larger substituent is equatorial is strongly favored. This minimizes the
crowding, resulting in a more stable structure.
The boat conformation is less stable than the chair because the hydrogen atoms are not perfectly staggered.
Reactions of Alkanes and Cycloalkanes
Combustion
Hydrocarbons react with an excess of oxygen to yield carbon dioxide and water.
CH4 + 2 O2 --> CO2 + 2 H2O + Heat
2 C2H6 + 7 O2 --> 4 CO2 + 6 H2O + Heat
If alkanes are burned with insufficient oxygen then carbon monoxide is formed instead of carbon dioxide.
2 CH4 + 3 O2 --> 2 CO + 4 H2O + Heat (?)
2 C2H6 + 5 O2 --> 4 CO + 6 H2O
Halogenation
Halogenation is a substitution reaction. Substitution reactions involve replacement of an atom with another atom or
group of atoms. In halogenation, hydrogens in the hydrocarbon are substituted with a halogen (Cl or Br). The
product of a halogenation is an alkyl halide (RX) and hydrogen halide.
light or heat (200-400oC)
R-H + X2 -------------------------> R-X + HCl
X2 represents either Cl2 or Br2. [Iodine, I2, does not work.]
Tertiary hydrogens (3o ) are replaced more rapidly than secondary ( 2 o) which react faster than primary (1o ).
If the halogenation reaction is allowed to continue, the alkyl halide can react with halogen atoms and more than one
product can be formed, resulting in a mixture of products.
CH4 + Br2 --> CH3Br + HBr
CH3Br + Br2 --> CH2Br2 + HBr
CH2Br2 + Br2 --> CHBr3 + HBr
CHBr3 + Br2 --> CBr4 + HBr

n-propane + Cl2/light ---> 1-chloropropane + 2-chloropropane

45%
55%
n-butane + Cl2/light ---> 1-chlorobutane + 2-chlorobutane
28%
72%
isobutane + Cl2/light ---> 1-chloro-2-methylpropane + 2-chloro-2-methylpropane
64%
Chlorination gives mixtures in which no isomer greatly predominates; in bromination, by contrast, one isomer may
predominate to such an extent as to be almost the only product, making up 97-99% of the total mixture.
Bromination of the same alkanes above results with the more substituted carbon being the site of bromination with
only trace amounts of the other possibilities.