ALKENES

The common family of hydrocarbons found in crude oil is alkenes. In this family there is at
least one carbon–carbon double bond. This double bond makes a big difference to the chemistry
of the compounds of the family. Alkenes are also called olefins (oil-forming) because the lower
members of alkenes form oily products when they are treated with chlorine or bromine.

Alkenes and particularly ethene are tremendously important in the chemical industry. They are
not found in crude oil in very large quantities but are produced by the cracking of the alkanes.
The alkenes like all hydrocarbons, burn in air to form carbon dioxide and water. In oxygen
ethene reacts explosively so it is not much good as a fuel. The alkenes are also too useful in the
chemical industry for the manufacture of plastics and many other chemicals to be used as fuels.
Alkenes are the second group of hydrocarbons and differ from alkanes in that they have
a double bond. The presence of a double bond brings up some important structural and
functional changes. Let’s first mention that the C=C double bonds reduce the number of
hydrogens per carbons and the general formula changes to C2H2n vs the C2H2n+n of the
alkanes. This corresponds to one degree of unsaturation – hydrogen deficiency index (HDI).
 NAMING ALKENES
IUPAC Rules for Alkene Nomenclature
1. The ene suffix (ending) indicates an alkene or cycloalkene.
2. The longest chain chosen for the root name must include both carbon atoms of the
double bond.
3. The root chain must be numbered from the end nearest a double bond carbon atom. If
the double bond is in the center of the chain, the nearest substituent rule is used to
determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double bond is
used as the double bond locator.
5. If more than one double bond is present the compound is named as a diene, triene or
equivalent prefix indicating the number of double bonds, and each double bond is
assigned a locator number.
6. Substituent groups containing double bonds are:
 H2C=CH– Vinyl group
 H2C=CH–CH2– Allyl group

The Basic Rules for Naming Alkenes

1) Find the longest carbon chain that contains both carbons of the double bond.

2) Start numbering from the end of the parent chain which gives the lowest possible number to
the double bond. If the double bond is equidistant from both ends of the parent chain, number
from the end which gives the substituents the lowest possible number. The double bond in
cycloalkenes do not need to number because it is understood that they are in the one position.
3) Place the location number of the double bond directly before the parent name. The location
number indicates the position of the first carbon of the double bond. Add substituents and their
position to the alkene as prefixes. Remember substituents are written in alphabetical order.
The presence of multiple double bonds is indicated by using the appropriate suffix such as -
diene, -triene, ect. Each of the multiple bonds receives a location number. Also, only -ne is
removed from the parent alkane chain name leaving an "a" in the name.
Overall, the name of an alkene should look like:
(Location number of substituent)-(Name of substituent)-(Location number of double bond)-(Name of parent chain) + ene

Note:
Newer IUPAC Nomenclature
In 1993 IUPAC updated their naming recommendation to place the location number of
the double bond before the -ene suffix of alkene names. The provides names such as hex-2-ene
rather than 2-hexene. The newer system is slowly being accepted so it may occasionally be
encountered.
The root name is the same, however, the suffix changes from “ane” to “ene”:

CLASSIFICATION OF ALKENES
Alkyl groups bonded to the sp2 hybridised carbon atoms of alkenes affect the stability of the
double bond. The chemical reactivity of alkenes also is often affected by the number of alkyl
groups bonded to the sp2 hybridised carbon atoms. Thus, it is useful to classify alkenes by the
number of alkyl groups attached to the C=C structural unit. This feature is called the degree of
substitution.
An alkene that has a single alkyl group attached to the sp2 hybridised carbon atom of the double
bond is monosubstituted. An alkene whose double bond is at the end of the chain of carbon
atoms is also sometimes called a terminal alkene. Alkenes that have two, three and four alkyl
groups bonded to the carbon atoms of the double bond are disubstituted, trisubstituted and
tetrasubstituted respectively.

monosubstituted RCH=CH2

disubstituted RCH=CHR or R2C=CH

trisubstituted R2C=CHR

tetrasubstituted R2C=CR2
 METHODS OF PREPARATION OF ALKENES
Alkenes belong to the family of hydrocarbons. They contain at least one double bond between
two adjacent carbon atoms. The general chemical formula of an alkene is CnH2n. Alkenes can
be prepared via various methods. A few methods of preparation of alkenes have been detailed
in this article.
From alkynes: Alkynes can be used for the preparation of alkenes. Alkyne to alkene
conversion is carried out by the reduction of alkynes with hydrogen in the presence of
palladised charcoal. The charcoal used is moderately deactivated with the help of quinoline or
sulphur compounds. This reaction results in the formation of alkenes. Palladised charcoal
which is halfway deactivated is called as Lindlar’s catalyst. The alkenes obtained from the
above reaction have cis geometry. In order to form trans alkenes, alkynes are made to undergo
reduction with sodium in liquid ammonia.

From alkyl halides: Alkenes are obtained by heating alkyl halides with alcoholic potash.
Alcoholic potash is obtained by dissolving potassium hydroxide in alcohol. In this reaction,
dehydrohalogenation takes place i.e. a single molecule of halogen acid is removed. The rate of
reaction depends upon the alkyl group and the nature of the halogen group attached.

From vicinal halides: Vicinal dihalides can be defined as the dihalides in which two adjacent
carbon atoms are attached to two halogens. When such dihalides react with zinc metal, they
lose halogen molecules which result in the formation of alkenes. Such a reaction of preparation
of alkenes from Vicinal dihalides is known as dehalogenation.
From alcohols: Alcohols react with concentrated sulphuric acid which results in the formation
of alkenes due to the elimination of a water molecule. As water molecule is removed in this
reaction, it is called as acidic dehydration of alcohol and the dehydrating agent is concentrated
sulphuric acid.

PHYSICAL PROPERTIES OF ALKENES

1. Physical state
These double-bonded compounds are colourless and odourless in nature.
However, ethene is an exception because it is a colourless gas with a faintly sweet odour.
The first three members of the alkene group are gaseous in nature, the next fourteen
members are liquids and the remaining alkenes are solids at room temperature and they burn
in air with a luminous smoky flame.
2. Density – Alkenes are lighter than water.
3. Solubility
The alkenes are insoluble in water due to their nonpolar characteristics.
But are completely soluble in nonpolar solvents such as benzene, ligroin, etc.
4. Boiling point
The boiling points of the compounds increase as the number of carbon atoms in the
compound increases.
When alkenes are compared with alkanes, it is found that the boiling points of both are
almost similar, as if the compounds are made up of the same carbon skeleton.
The boiling point of straight-chain alkenes is more than branched-chain alkenes just as in
alkanes.
5. Melting point
The melting points of these double-bonded compounds depend upon the positioning of the
molecules.
The melting point of alkenes is similar to that of alkanes.
However, cis-isomer molecules have a lower melting point than trans- isomers as the
molecules are packed in a U-bending shape.
6. Polarity
Alkenes are weakly polar just like alkanes but are slightly more reactive than alkanes due
to the presence of double bonds.
The π electrons which make up the double bonds can easily be removed or added as they
are weakly held.
Hence, the dipole moments exhibited by alkenes are more than alkanes.
The polarity depends upon the functional group attached to the compounds and the chemical
structures

Note:
Alkenes can have different states of matter from a gas to a solid depending mainly on their
molecular mass:

Like for any other class of compounds, the boiling point of alkenes typically increases with
stronger intermolecular interactions which can be London forces or dipole-dipole interactions
when halogens are present in the molecule. The melting point, on the other hand, depends also
on the symmetry of the molecule. More symmetrical molecules pack better in the solid phase
and therefore have higher melting points. Trans alkenes usually have a higher melting point
than cis alkenes.
An interesting example is the comparison of melting and boiling points
of cis– and trans alkenes.
Despite being nonpolar, the trans isomer of 1,2-dichloroethane has a higher melting
point (−50 oC) than the cis isomer (−80 oC) because of higher symmetry which allows for
compact packing in the solid phase.
In contrast, the cis isomer is a polar molecule with a higher boiling point (60 oC vs 48 oC )
because of the net molecular dipole moment and intermolecular dipole-dipole interactions.

Why alkenes are insoluble in water?

Due to their non-polar properties, alkenes are lighter than water and insoluble in water. Alkenes
can only be dissolved in nonpolar solvents.
Why does cis have lower melting point than trans?
Trans isomers pack better than cis isomers. Cis isomers pack poorly, which means that the
intermolecular forces aren’t as effective as they should be and thus less amount of energy is
required to melt the cis molecule. Hence, cis molecules have lower melting point.

CHEMICAL REACTIONS OF ALKENES

Alkenes are unsaturated compounds, which makes them highly reactive. Most of
these chemical reactions occur at the Carbon-Carbon double bonds. This makes alkenes far
more reactive than alkanes. Alkenes undergo three types of main reactions, which are as follows
Addition Reactions
Addition of Hydrogen: In the presence of nickel or platinum alkenes will react to add to its
molecular chain one diatomic molecule of hydrogen (dihydrogen). And in this process, they
become alkanes due to the rearrangement of atoms.
Addition of Halogens: Halogens will react with alkenes to form vicinal dihalides. From the
halogens, iodine will not react with alkenes. But Bromine reacts with alkenes and will attach
at the unsaturated site. In fact, the reaction is used to as proof of unsaturation.

Addition of Hydrogen halides: These reactions follow a certain rule, the Markovnikov rule.
This rule states that the negative portion of the reactant (the molecule which gets added to the
chain) will attach itself to the carbon with the least number of hydrogen atoms attached. So
when a hydrogen halide will react with an alkene, the hydrogen will attach at the double bond
to the atom with more hydrogen atoms attached. The halide ion, on the other hand, will attach
to that carbon atom that has the lesser hydrogen atoms attached.

Addition of Water: According to the Markovnikov rule, water will react with an alkene to
form alcohols. This happens in the presence of sulphuric acid.

Oxidation Reactions
Combustion Reaction: The combustion of alkenes is very exothermic, it will give out huge
amounts of thermal energy. A practical example of this reaction is seen in welding of metals. It
is known as oxy-ethylene welding.
 CH2=CH2 + 3O2 → 2CO2 + 2H2O
Oxidation by Potassium Permanganate: When alkenes are reacted with cold
dilute KMnO4 also known as Baeyer’s reagent, it forms vicinal glycols. It will also decolourize
the pink colour of KMnO4. So, it is used for testing unsaturation in compounds.

Uses of Alkenes
The list of uses of various alkenes like ethene, propene etc., is given below.
 Manufacture of plastics like polythene for making buckets, bowls, bags etc.
 Manufacture of polystyrene used in making car battery cases and parts of the
refrigerator.
 Making ethane-1,2-diol used as anti-freezing for motor car radiators.
 Manufacture of ethanol and synthetic fibre terylene.
 Making an anti-knock for car engines.
 Manufacture of plastic, polypropene for making ropes and packaging material.
 Manufacture of propanol used in making acetone.
 Manufacture of acrylic fibres.
Note:
What are alkenes used for?
In manufacturing, alkenes find many different applications. They are used in the synthesis of
alcohols, plastics, lacquers, detergents, and fuels as starting materials. For the chemical
industry, the most important alkenes are ethene, propene, and 1,3-butadiene.
Where is alkene found?
Alkenes are the raw materials for plastics such as polyethene, PVC, polypropylene, and
polystyrene, among others. The chemistry of alkenes is present in unsaturated fats, beta-
carotene, and light through vision
Do alkenes have higher boiling points?
The further an additional intermolecular mass, the higher the boiling point. With the rise in the
size of the molecules, intermolecular forces of alkenes get stronger. For each case, the alkene
has a boiling point which is lower than the corresponding alkane by a small number of degrees
The Structure of Alkenes
The two carbons of a C=C double bond are sp2-hybridized.
Remember, the sp2 hybridization occurs when the s orbital is mixed with two p orbitals and
therefore, three orbitals are mixed, and the outcome is three hybrid orbitals which are
called sp2 hybrid orbitals.

The two sp2 hybridized carbon atoms then make a sigma (σ) bond by a linear overlap and one π
bond by a side-by-side overlap of the two 2p orbitals on each carbon.
Ethylene can be used as an example to illustrate the structure and geometry of a typical double
bond:

As a short summary for the key parameters about double bonds, remember that:
 All the atoms on the double bond are in one plane.
 The angle between the atoms is 120o.
 The angle between the plane and p orbitals is 90o.
Restricted Rotation
You may remember from alkanes and cycloalkanes that they were able to adopt different
conformations via the free rotation about sigma bonds. For example, this flexibility allows
for the ring flip, and in general, all the struggle with Newman projections that you may have
gone through is due to the free rotation about C-C single bonds.
Now, unlike the single bonds, the C=C double bond is locked as there is no rotation about
the bond without breaking it.

Because of this we have the cis and trans isomerism of alkenes. In short, if the two identical
groups (alkyl or hydrogen) on both carbon atoms of the double bond are on the same side of
the double bond, then it is cis and if they are on opposite sides of the double bond, then we
have a trans isomer:
The cis and trans alkenes are stereoisomers and because they are not mirror images, they
are diastereomers:

If there are no two identical groups, then the E and Z notation is used which is a more universal
approach for classifying the configuration of alkenes. Yes, cis/trans and E/Z notations
describe the configuration of and not conformation of alkenes since, remember, there is no
rotation about a C=C double bond.
Stability of Alkenes
There are two factors to consider when deciding the more stable alkene. One is
the sterics which is expressed when comparing cis and trans isomers – trans alkenes are
more stable because of a less steric hindrance:

Sterics is the fancy word for the space available to atoms/groups. High steric strain means less
space, bulky groups, and therefore, less stability. In cis alkenes, the two (larger) alkyl groups
are on the same side of the double bond fighting for space and yet cannot switch to a trans
arrangement.
The second factor is the number of alkyl groups bonded to the double bond; the more alkyl
groups, the more stable the double bond.
Another wording for this is the classification of alkenes as monosubstituted, disubstituted,
trisubstituted and tetrasubstituted. In other words, the stability of alkenes increases with the
substitution:

An alkene with two substitutes on one sp2 carbon has about the same stability as the
corresponding trans alkene:
Now, the question is why having more alkyl groups connected to the C=C bond makes it
more stable?
One way, suitable for a typical undergraduate class, to look at it is the electronegativity of
the sp2 and sp3-hybridized carbon atoms. Remember about the “s character” which is referred
to the % of the s orbital initially involved in the hybridization process. In the sp3 hybridization,
there is a total of four orbitals – one s and three p, and out of these only one is (was)
an s. Therefore, the s character of an sp3 orbital is ¼ = 25%. The sp2 orbitals, on the other
hand, have a 33% s character:

Higher s character means a more electronegative atom because s orbitals are smaller and
more electronegative than p orbitals. This has to do with the fact that in a smaller orbital, the
attraction force is stronger, and the electrons are closer to the nucleus.
Now, the sp2 hybridized carbon atoms in the C=C double bond, being more electronegative,
readily accept the electron density from sp3 hybridized carbon atoms of the alkyl group(s).
So, the more electron-donating alkyl groups on the C=C carbon atoms, the more stable the
alkene. Therefore, we have this pattern of stability: Tetrasubstituted > Trisubstituted >
Disubstituted > Monosubstituted.
To summarize, remember that:
 Trans alkenes are more stable than cis
 The more alkyls on the sp2 carbon(s), the more stable the alkene

Bond Stability:

 Bond strengths play an important part in determining the overall stability of a molecule
 C-C bond between a sp3 carbon and a sp2 carbon is slightly stronger than a C-C bond
between two sp3 carbons. Increasing the number alkyl substituents of a double bond
also increases the number of sp3-sp2 C-C bonds making the alkene more stable. This is
idea can be clearly seen when comparing the isomers1-butene and 2-butene.

The molecule1-butene is monosubstituted and contains a sp3-sp3 C-C and a sp3-sp2 C-C
bond. The disubstituted, 2-butene, contains 2 sp3-sp2 C-C bonds which contributes to its greater
stability.

Note:
Stabilities of alkenes: Alkenes have a pi bond acting as nucleophiles, which is formed by
electrons in the alkene joining a hydrogen atom in H2. The carbon with a negative formal charge
is the one that did not receive hydrogen after the pi bond breaks. This intermediate is called
carbocation. As two electrons remained in the H-H sigma bond, the (unreacted) hydrogen now
forms a hydride anion. A bond is formed with the positively charged carbon by the electrons of
the negatively charged hydride ion. Exothermic results from this reaction. Without a catalyst,
the reaction is slow.