Alkanes

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Alkanes are organic compounds that consist entirely of single-bonded carbon and hydrogen
atoms and lack any other functional groups. Alkanes have the general
formula CnH2n+2CnH2n+2 and can be subdivided into the following three groups: the linear
straight-chain alkanes, branched alkanes, and cycloalkanes. Alkanes are also saturated
hydrocarbons. Alkanes are the simplest and least reactive hydrocarbon species containing only
carbons and hydrogens. They are commercially very important, being the principal constituent of
gasoline and lubricating oils and are extensively employed in organic chemistry; though the role
of pure alkanes (such as hexanes) is delegated mostly to solvents. The distinguishing feature of
an alkane, making it distinct from other compounds that also exclusively contain carbon and
hydrogen, is its lack of unsaturation. That is to say, it contains no double or triple bonds, which
are highly reactive in organic chemistry. Though not totally devoid of reactivity, their lack of
reactivity under most laboratory conditions makes them a relatively uninteresting, though very
important component of organic chemistry. As you will learn about later, the energy confined
within the carbon-carbon bond and the carbon-hydrogen bond is quite high and their rapid
oxidation produces a large amount of heat, typically in the form of fire.

Nomenclature of Alkanes
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The names of all alkanes end with -ane. Whether or not the carbons are linked together end-to-
end in a ring (called cyclic alkanes or cycloalkanes) or whether they contain side chains and
branches, the name of every carbon-hydrogen chain that lacks any double bonds or functional
groups will end with the suffix -ane.
Alkanes with unbranched carbon chains are simply named by the number of carbons in the chain.
The first four members of the series (in terms of number of carbon atoms) are named as follows:
1. CH4 = methane = one hydrogen-saturated carbon
2. C2H6 = ethane = two hydrogen-saturated carbons
3. C3H8 = propane = three hydrogen-saturated carbons
4. C4H10 = butane = four hydrogen-saturated carbons
Alkanes with five or more carbon atoms are named by adding the suffix -ane to the appropriate
numerical multiplier, except the terminal -a is removed from the basic numerical term. Hence,
C5H12 is called pentane, C6H14 is called hexane, C7H16 is called heptane and so forth.
Straight-chain alkanes are sometimes indicated by the prefix n- (for normal) to distinguish them
from branched-chain alkanes having the same number of carbon atoms. Although this is not
strictly necessary, the usage is still common in cases where there is an important difference in
properties between the straight-chain and branched-chain isomers: e.g. n-hexane is a neurotoxin
while its branched-chain isomers are not.
IUPAC NOMENCLATURE

The IUPAC nomenclature is a system on which most organic chemists have agreed to provide
guidelines to allow them to learn from each others' works. Nomenclature, in other words,
provides a foundation of language for organic chemistry.

Number of Hydrogen to Carbons

This equation describes the relationship between the number of hydrogen and carbon
atoms in alkanes:
H = 2C + 2
where "C" and "H" are used to represent the number of carbon and hydrogen atoms
present in one molecule. If C = 2, then H = 6.
Many textbooks put this in the following format:
CnH2n+2
where "Cn" and "H2n+2" represent the number of carbon and hydrogen atoms present in
one molecule. If Cn = 3, then H2n+2 = 2(3) + 2 = 8. (For this formula look to the "n" for the
number, the "C" and the "H" letters themselves do not change.)
Progressively longer hydrocarbon chains can be made and are named systematically,
depending on the number of carbons in the longest chain.

The following table contains the systematic names for the first twenty straight
chain alkanes. It will be important to familiarize yourself with these names because they
will be the basis for naming many other organic molecules throughout your course of
study.
Drawing Hydrocarbons
Recall that when carbon makes four bonds, it adopts the tetrahedral geometry. In the
tetrahedral geometry, only two bonds can occupy a plane simultaneously. The other two
bonds point in back or in front of this plane. In order to represent the tetrahedral
geometry in two dimensions, solid wedges are used to represent bonds pointing out of
the plane of the drawing toward the viewer, and dashed wedges are used to represent
bonds pointing out of the plane of the drawing away from the viewer. Consider the
following representation of the molecule methane:

Figure 1: Two dimensional representation of methane

In the above drawing, the two hydrogens connected by solid lines, as well as the carbon
in the center of the molecule, exist in a plane (specifically, the plane of the computer
monitor / piece of paper, etc.). The hydrogen connected by a solid wedge points out of
this plane toward the viewer, and the hydrogen connected by the dashed wedge points
behind this plane and away from the viewer.
In drawing hydrocarbons, it can be time-consuming to write out each atom and bond
individually. In organic chemistry, hydrocarbons can be represented in a shorthand
notation called a skeletal structure. In a skeletal structure, only the bonds between
carbon atoms are represented. Individual carbon and hydrogen atoms are not drawn,
and bonds to hydrogen are not drawn. In the case that the molecule contains just single
bonds (sp3 bonds), these bonds are drawn in a "zig-zag" fashion. This is because in the
tetrahedral geometry all bonds point as far away from each other as possible, and the
structure is not linear. Consider the following representations of the molecule propane:

Figure 2: Full structure of propane and skeletal structure of propane

Only the bonds between carbons have been drawn, and these have been drawn in a
"zig-zag" manner. Note that there is no representation of hydrogens in a skeletal
structure. Since, in the absence of double or triple bonds, carbon makes four bonds
total, the presence of hydrogens is implicit. Whenever an insufficient number of bonds
to a carbon atom are specified in the structure, it is assumed that the rest of the bonds
are made to hydrogens. For example, if the carbon atom makes only one explicit bond,
there are three hydrogens implicitly attached to it. If it makes two explicit bonds, there
are two hydrogens implicitly attached, etc. Note also that two lines are sufficient to
represent three carbon atoms. It is the bonds only that are being drawn out, and it is
understood that there are carbon atoms (with three hydrogens attached!) at the terminal
ends of the structure.
 Alkyl Groups
Alkanes can be described by the general formula CnH2n+2. An alkyl group is formed by
removing one hydrogen from the alkane chain and is described by the formula C nH2n+1.
The removal of this hydrogen results in a stem change from -ane to -yl. Take a look at
the following examples.

The same concept can be applied to any of the straight chain alkane names provided in
the table above.

Name Molecular Formula Condensed Structural Formula

Methane CH4 CH4

Ethane C2H6 CH3CH3

Propane C3H8 CH3CH2CH3

Butane C4H10 CH3(CH2)2CH3

Pentane C5H12 CH3(CH2)3CH3

Hexane C6H14 CH3(CH2)4CH3

Heptane C7H16 CH3(CH2)5CH3

 Name Molecular Formula Condensed Structural Formula

Octane C8H18 CH3(CH2)6CH3

Nonane C9H20 CH3(CH2)7CH3

Decane C10H22 CH3(CH2)8CH3

Undecane C11H24 CH3(CH2)9CH3

Dodecane C12H26 CH3(CH2)10CH3

Tridecane C13H28 CH3(CH2)11CH3

Tetradecane C14H30 CH3(CH2)12CH3

Pentadecane C15H32 CH3(CH2)13CH3

Hexadecane C16H34 CH3(CH2)14CH3

Heptadecane C17H36 CH3(CH2)15CH3

Octadecane C18H38 CH3(CH2)16CH3

Nonadecane C19H40 CH3(CH2)17CH3

Name Molecular Formula Condensed Structural Formula

Eicosane C20H42 CH3(CH2)18CH3

Using Common Names with Branched

Alkanes
Certain branched alkanes have common names that are still widely used today. These
common names make use of prefixes, such as iso-, sec-, tert-, and neo-. The
prefix iso-, which stands for isomer, is commonly given to 2-methyl alkanes. In other
words, if there is methyl group located on the second carbon of a carbon chain, we can
use the prefix iso-. The prefix will be placed in front of the alkane name that indicates
the total number of carbons. Examples:
 isopentane which is the same as 2-methylbutane
 isobutane which is the same as 2-methylpropane
To assign the prefixes sec-, which stands for secondary, and tert-, for tertiary, it is
important that we first learn how to classify carbon molecules. If a carbon is attached to
only one other carbon, it is called a primary carbon. If a carbon is attached to two other
carbons, it is called a seconday carbon. A tertiary carbon is attached to three other
carbons and last, a quaternary carbon is attached to four other carbons. Examples:
 4-sec-butylheptane (30g)
 4-tert-butyl-5-isopropylhexane (30d); if using this example, may want to move sec/tert
after iso disc
The prefix neo- refers to a substituent whose second-to-last carbon of the chain is
trisubstituted (has three methyl groups attached to it). A neo-pentyl has five carbons
total. Examples:
 neopentane
 neoheptane

Alkoxy Groups
Alkoxides consist of an organic group bonded to a negatively charged oxygen atom. In
the general form, alkoxides are written as RO-, where R represents the organic
substituent. Similar to the alkyl groups above, the concept of naming alkoxides can be
applied to any of the straight chain alkanes provided in the table above.
Three Principles of Naming
1. Choose the longest, most substituted carbon chain containing a functional group.
2. A carbon bonded to a functional group must have the lowest possible carbon number. If
there are no functional groups, then any substitute present must have the lowest
possible number.
3. Take the alphabetical order into consideration; that is, after applying the first two rules
given above, make sure that your substitutes and/or functional groups are written in
alphabetical order.
EXAMPLE 1

What is the name of the following molecule?

SOLUTION
Rule #1: Choose the longest, most substituted carbon chain containing a functional
group. This example does not contain any functional groups, so we only need to be
concerned with choosing the longest, most substituted carbon chain. The longest
carbon chain has been highlighted in red and consists of eight carbons.

Rule #2: Carbons bonded to a functional group must have the lowest possible carbon
number. If there are no functional groups, then any substitute present must have the
lowest possible number. Because this example does not contain any functional groups,
we only need to be concerned with the two substitutes present, that is, the two methyl
groups. If we begin numbering the chain from the left, the methyls would be assigned
the numbers 4 and 7, respectively. If we begin numbering the chain from the right, the
methyls would be assigned the numbers 2 and 5. Therefore, to satisfy the second rule,
numbering begins on the right side of the carbon chain as shown below. This gives the
methyl groups the lowest possible numbering.

Rule 3: In this example, there is no need to utilize the third rule. Because the two
substitutes are identical, neither takes alphabetical precedence with respect to
numbering the carbons. This concept will become clearer in the following examples.
EXAMPLE 2

What is the name of the following molecule?

SOLUTION
Rule #1: Choose the longest, most substituted carbon chain containing a functional
group. This example contains two functional groups, bromine and chlorine. The longest
carbon chain has been highlighted in red and consists of seven carbons.

Rule #2: Carbons bonded to a functional group must have the lowest possible carbon
number. If there are no functional groups, then any substitute present must have the
lowest possible number. In this example, numbering the chain from the left or the right
would satisfy this rule. If we number the chain from the left, bromine and chlorine would
be assigned the second and sixth carbon positions, respectively. If we number the chain
from the right, chlorine would be assigned the second position and bromine would be
assigned the sixth position. In other words, whether we choose to number from the left
or right, the functional groups occupy the second and sixth positions in the chain. To
select the correct numbering scheme, we need to utilize the third rule.

Rule #3: After applying the first two rules, take the alphabetical order into consideration.
Alphabetically, bromine comes before chlorine. Therefore, bromine is assigned the
second carbon position, and chlorine is assigned the sixth carbon position.

EXAMPLE 3

What is the name of the follow molecule?

SOLUTION
Rule #1: Choose the longest, most substituted carbon chain containing a functional
group. This example contains two functional groups, bromine and chlorine, and one
substitute, the methyl group. The longest carbon chain has been highlighted in red and
consists of seven carbons.

Rule #2: Carbons bonded to a functional group must have the lowest possible carbon
number. After taking functional groups into consideration, any substitutes present must
have the lowest possible carbon number. This particular example illustrates the point of
difference principle. If we number the chain from the left, bromine, the methyl group
and chlorine would occupy the second, fifth and sixth positions, respectively. This
concept is illustrated in the second drawing below. If we number the chain from the
right, chlorine, the methyl group and bromine would occupy the second, third and sixth
positions, respectively, which is illustrated in the first drawing below. The position of the
methyl, therefore, becomes a point of difference. In the first drawing, the
methyl occupies the third position. In the second drawing, the methyl occupies the fifth
position. To satisfy the second rule, we want to choose the numbering scheme that
provides the lowest possible numbering of this substitute. Therefore, the first of the two
carbon chains shown below is correct.

Therefore, the first numbering scheme is the appropriate one to use.

Once you have determined the correct numbering of the carbons, it is often useful to
make a list, including the functional groups, substitutes, and the name of the parent
chain.
Rule #3: After applying the first two rules, take the alphabetical order into consideration.
Alphabetically, bromine comes before chlorine. Therefore, bromine is assigned the
second carbon position, and chlorine is assigned the sixth carbon position.
Parent chain: heptane 2-Chloro 3-Methyl 6-Bromo
6-bromo-2-chloro-3-methylheptane

Problems
What is the name of the follow molecules?
 Chemical Properties of Alkanes
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Alkanes are not very reactive when compared with other chemical species. This is
because the backbone carbon atoms in alkanes have attained their octet of electrons
through forming four covalent bonds (the maximum allowed number of bonds under the
octet rule; which is why carbon's valence number is 4). These four bonds formed by
carbon in alkanes are sigma bonds, which are more stable than other types of bond
because of the greater overlap of carbon's atomic orbitals with neighboring atoms'
atomic orbitals. To make alkanes react, the input of additional energy is needed; either
through heat or radiation.
Gasoline is a mixture of the alkanes and unlike many chemicals, can be stored for long
periods and transported without problem. It is only when ignited that it has enough
energy to continue reacting. This property makes it difficult for alkanes to be converted
into other types of organic molecules. (There are only a few ways to do this). Alkanes
are also less dense than water, as one can observe, oil, an alkane, floats on water.
Alkanes are non-polar solvents. Since only C and H atoms are present, alkanes are
nonpolar. Alkanes are immiscible in water but freely miscible in other non-polar
solvents. Alkanes consisting of weak dipole dipole bonds can not break the strong
hydrogen bond between water molecules hence it is not miscible in water. The same
character is also shown by alkenes. Because alkanes contain only carbon and
hydrogen, combustion produces compounds that contain only carbon, hydrogen, and/or
oxygen. Like other hydrocarbons, combustion under most circumstances produces
mainly carbon dioxide and water. However, alkanes require more heat to combust and
do not release as much heat when they combust as other classes of hydrocarbons.
Therefore, combustion of alkanes produces higher concentrations of organic
compounds containing oxygen, such as aldehydes and ketones, when combusting at
the same temperature as other hydrocarbons.
The general formula for alkanes is CNH2N+2; the simplest possible alkane is therefore
methane, CH4. The next simplest is ethane, C2H6; the series continues indefinitely. Each
carbon atom in an alkane has sp³ hybridization.
Alkanes are also known as paraffins, or collectively as the paraffin series. These terms
are also used for alkanes whose carbon atoms form a single, unbranched chain.
Branched-chain alkanes are called isoparaffins.
Methane through Butane are very flammable gases at standard temperature and
pressure (STP). Pentane is an extremely flammable liquid boiling at 36 °C and boiling
points and melting points steadily increase from there; octadecane is the first alkane
which is solid at room temperature. Longer alkanes are waxy solids; candle wax
generally has between C20 and C25 chains. As chain length increases ultimately we
reach polyethylene, which consists of carbon chains of indefinite length, which is
generally a hard white solid.

Reactions
Alkanes react only very poorly with ionic or other polar substances. The pKa values of
all alkanes are above 50, and so they are practically inert to acids and bases. This
inertness is the source of the term paraffins (Latin para + affinis, with the meaning here
 of "lacking affinity"). In crude oil the alkane molecules have remained chemically
unchanged for millions of years.
However redox reactions of alkanes, in particular with oxygen and the halogens, are
possible as the carbon atoms are in a strongly reduced condition; in the case of
methane, the lowest possible oxidation state for carbon (−4) is reached. Reaction with
oxygen leads to combustion without any smoke; with halogens, substitution. In addition,
alkanes have been shown to interact with, and bind to, certain transition metal
complexes.
Free radicals, molecules with unpaired electrons, play a large role in most reactions of
alkanes, such as cracking and reformation where long-chain alkanes are converted into
shorter-chain alkanes and straight-chain alkanes into branched-chain isomers.
In highly branched alkanes and cycloalkanes, the bond angles may differ significantly
from the optimal value (109.5°) in order to allow the different groups sufficient space.
This causes a tension in the molecule, known as steric hinderance, and can
substantially increase the reactivity. The same is preferred for alkenes too.

Physical Properties of Alkanes

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
 Contributed by Jim Clark
 Former Head of Chemistry and Head of Science at Truro School in Cornwall
Alkanes are not very reactive and have little biological activity; all alkanes are colorless and
odorless.
Boiling Points
The boiling points shown are for the "straight chain" isomers of which there is more than one.
The first four alkanes are gases at room temperature, and solids do not begin to appear until
about C17H36C17H36, but this is imprecise because different isomers typically have different
melting and boiling points. By the time you get 17 carbons into an alkane, there are unbelievable
numbers of isomers!

Cycloalkanes have boiling points that are approximately 20 K higher than the corresponding
straight chain alkane.
There is not a significant electronegativity difference between carbon and hydrogen, thus, there
is not any significant bond polarity. The molecules themselves also have very little polarity. A
totally symmetrical molecule like methane is completely non-polar, meaning that the only
attractions between one molecule and its neighbors will be Van der Waals dispersion forces.
These forces will be very small for a molecule like methane but will increase as the molecules
get bigger. Therefore, the boiling points of the alkanes increase with molecular size.
Where you have isomers, the more branched the chain, the lower the boiling point tends to be.
Van der Waals dispersion forces are smaller for shorter molecules and only operate over very
short distances between one molecule and its neighbors. It is more difficult for short, fat
molecules (with lots of branching) to lie as close together as long, thin molecules.

EXAMPLE 11: STRUCTURE DEPENDENT BOILING POINTS

For example, the boiling points of the three isomers of C5H12C5H12 are:
 pentane: 309.2 K
 2-methylbutane: 301.0 K
 2,2-dimethylpropane: 282.6 K
The slightly higher boiling points for the cycloalkanes are presumably because the
molecules can get closer together because the ring structure makes them tidier and less
"wriggly"!

Solubility
Alkanes (both alkanes and cycloalkanes) are virtually insoluble in water, but dissolve in
organic solvents. However, liquid alkanes are good solvents for many other non-ionic
organic compounds.

Solubility in Water
When a molecular substance dissolves in water, the following must occur:
 break the intermolecular forces within the substance. In the case of the alkanes, these
are the Van der Waals dispersion forces.
 break the intermolecular forces in the water so that the substance can fit between the
water molecules. In water, the primary intermolecular attractions are hydrogen bonds.
Breaking either of these attractions requires energy, although the amount of energy to
break the Van der Waals dispersion forces in something like methane is relatively
negligible; this is not true of the hydrogen bonds in water.
As something of a simplification, a substance will dissolve if there is enough energy
released when new bonds are made between the substance and the water
to compensate for what is used in breaking the original attractions. The only new
attractions between the alkane and the water molecules are Van der Waals forces.
These forces do not release a sufficient amount of energy to compensate for the energy
required to break the hydrogen bonds in water.; the alkane does not dissolve.
The energy only description of solvation is an oversimplification because entropic
effects are also important when things dissolve.

Solubility in organic solvents

In most organic solvents, the primary forces of attraction between the solvent molecules
are Van der Waals - either dispersion forces or dipole-dipole attractions. Therefore,
when an alkane dissolves in an organic solvent, the Van der Waals forces are broken
and are replaced by new Van der Waals forces. The two processes more or less cancel
each other out energetically; thus, there is no barrier to solubility.
 Synthesis of Alkanes

Corey-House Reaction
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Corey-House Reaction is also called as 'coupling of alkyl halides with organo metallic
compounds'. It is a better method than Wurtz reaction. An alkyl halides and a lithium dialkyl
copper are reacted to give a higher hydrocarbon
R′−X+R2CuLi→R−R′+R−Cu+LiX(1)(1)R′−X+R2CuLi→R−R′+R−Cu+LiX
(R and R' may be same or different)

Wurtz reaction
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Wurtz reaction is coupling of haloalkanes using sodium metal in solvent like dry ether
2R−X+2Na→R−R+2Na+X−(1)(1)2R−X+2Na→R−R+2Na+X−
The reaction consists of a halogen-metal exchange involving the free radical species R• (in a
similar fashion to the formation of a Grignard reagent and then the carbon-carbon bond
formation in a nucleophilic substitution reaction.)
One electron from the metal is transferred to the halogen to produce a metal halide and an alkyl
radical.
R−X+M→R⋅+M+X−(2)(2)R−X+M→R⋅+M+X−
The alkyl radical then accepts an electron from another metal atom to form an alkyl anion and
the metal becomes cationic. This intermediate has been isolated in a several cases.
R⋅+M→R−M+(3)(3)R⋅+M→R−M+
The nucleophilic carbon of the alkyl anion then displaces the halide in an SN2 reaction, forming a
new carbon-carbon covalent bond.
R−M++R−X→R−R+M+X−(4)