Alkenes show four types of isomerism, which are described below.

• Chain isomerism

• Position isomerism

• Geometrical isomerism

• Functional isomerism.

Types of isomerisms
Chain isomerism
This is due to the difference in the structure of the carbon chain. For example, butene-1 and 2-methylpropene are
chain isomers.

Position isomerism
Position isomerism is the differences that arise in the position of the double bond in the same chain of alkenes.
Butene-1 is a position isomer of butene-2

because these differ only in the position of the double bond.

CH3-CH2-CH=CH2 CH3-CH=CH-CH3butene-1 butene-2

Geometrical isomerism
Two carbon atoms joined by a single bond are capable of free rotation about themselves. When two carbon atoms
are joined by a double bond, they cannot rotate freely and the relative positions of the various groups attached to
these carbon atoms get fixed. This gives rise to geometric isomers. Such compounds, which possess the same
structural formula but differ in the spatial arrangement of the groups about a double bond are called geometrical
isomers. The phenomenon is known as the geometrical isomerism or (also known) as cis - trans isomerism.

• In cis-form, the like groups lie on the same side.

• In trans-form, the like groups lie on the opposite sides.

cis-2-butene trans-2-butene(boiling point 3.7°C) (boiling point +1°C)

Functional isomerism
Alkenes and cycloalkanes have the same molecular formula (CnH2n). Since cycloalkanes do not behave as
unsaturated hydrocarbons, alkenes and cycloalkanes are termed functional isomers. For instance, propene is
isomeric with cyclopropane (or trimethylene).

CH3-CH=CH2propene

In alkenes, the functional group is the double bond, while in cycloalkanes the closed ring represents the functional
group.

Alkene stability
When we interconvert cis-2-butene with trans-2-butene and allow them to reach equilibrium, it is observed that they
are not of equal stability. At equilibrium, the ratio of isomers is 76% trans to 24% cis.

Trans (76%) Cis (24%)

Using the relationship between equilibrium constants and free-energy differences, one can calculate the stability
factor of these molecules. It is noticed that trans-2-butene is more stable than cis -2-butene by 0.66 kcal/mol. Cis
alkenes are less stable than their trans isomers because of steric (spatial) strain between the two bulky substituents
on the same side of the double bond similar to the eclipsed conformations of butane.
No steric strain in trans-2-butene Steric strain in cis-2-butene

Catalytic hydrogenation method is followed in order to obtain information about the relative stabilities of alkenes. In
this method, hydrogen adds to carbon-carbon double bonds to yield the corresponding saturated alkanes in the
presence of catalysts such as palladium or platinum.

trans-2-Butene cis-2-butene

In the hydrogenation of cis- and trans-2-butene, both alkenes react with hydrogen to give the same product, butane.

Since cis-2-butene is less stable than trans-2-butene by 0.66 kcal/mol, the energy diagram shows the cis alkene at a
higher energy level. After reaction, however, both cis and trans isomers are at the same energy level (butane).
Therefore G° for the cis isomer is larger than G° for the trans isomer. More energy is evolved in the hydrogenation of
the cis isomer than of the trans isomer. This difference in isomer stability is due to differences in bond strengths (H°).
If one were to measure the two heats of reaction and find their difference, one could have an independent means of
determining the relative stabilities of cis and trans isomers without having to measure an equilibrium position. A large
number of such heats of hydrogenation (H°hydrog) have been measured. For cis-2-butene, H°hydrog = 28.6 kcal/mol; for
the trans isomer, H°hydrog = 27.6 kcal/mol.

Note: that these H° values are negative since heat is evolved, but that the minus sign is dropped to make
comparisons easier.

Trans isomer Cis isomer

H°hydrog = 27.6 kcal/mol H°hydrog = 28.6 kcal/mol

Fig:15.3 - Energy diagrams for the hydrogenation of Cis- trans isomers.

Alkenes
Structure and reactivity
Although the energy difference in the heats of hydrogenation for the 2-butene isomers (1.0 kcal/mol) is in agreement
with the energy difference calculated from equilibrium data (0.66 kcal/mol), the two numbers are not exactly the
same. This is because the first is simply experimental error; heats of hydrogenation require considerable expertise
and specialized equipment to measure them accurately when we are looking at a small difference between two large
numbers. The second reason is that heats of reaction and equilibrium constants do not measure exactly the same
quantity. Heats of reaction measure enthalpy changes, H°, whereas equilibrium constants measure overall free-
energy changes, G° (G° = H° - TDS°). A slight difference is expected when comparing the two measurements.

From the heats of hydrogenation data, it has been found that alkenes become more stable with increasing
substitution. For example, ethylene has

H°hydrog = 32.8 kcal/mol, but when one alkyl substituent is introduced, an alkene becomes approximately 2.5
kcal/mol more stable than ethylene

(H°hydrog = 30.3).

Further, increasing the degree of substitution leads to further stability, and as a general rule alkenes follow this
stability order:Tetrasubstituted>Trisubstituted>Disubstituted>Monosubstituted

The reasons for this observed stability could be due to a stabilizing effect of hyperconjugation, which is an orbital
overlap between the carbon-carbon pi bond and a properly oriented carbon-hydrogen sigma bond on a neighboring
substituent. More the substituents present more the opportunities exist for hyperconjugation and more stable is the
alkene.
Hyperconjugation

Also the bonds between the sp2 carbon and the sp3 carbon are somewhat stronger than bonds between two sp3
carbons. Thus, in comparing the two isomers, 1-butene and 2-butene, the monosubstituted isomer has one sp3- sp3
bond and one sp3 - sp2 bond, and the disubstituted isomer has two

sp3 - sp2 bonds. Highly substituted alkenes always have a higher ratio of sp 3 - sp2 bonds to sp3 - sp3 bonds and are
therefore more stable than less substituted alkenes.