13.3.3 Isomerism

Alkenes show both structural isomerism and geometrical isomerism.

Structural isomerism : As in alkanes, ethene (C2H4) and propene (C3H6) can have only one structure but alkenes higher than propene have different structures. Alkenes possessing C4H8 as molecular formula can be written in the following three ways:

Structures I and III, and II and III are the examples of chain isomerism whereas structures I and II are position isomers.

Geometrical isomerism: Doubly bonded carbon atoms have to satisfy the remaining two valences by joining with two atoms or groups. If the two atoms or groups attached to each carbon atom are different, they can be represented by YX C = C XY like structure. YX C = C XY can be represented in space in the following two ways :

In (a), the two identical atoms i.e., both the X or both the Y lie on the same side of the double bond but in (b) the two X or two Y lie across the double bond or on the opposite sides of the double bond.

This results in different geometry of (a) and (b) i.e. disposition of atoms or groups in space in the two arrangements is different. Therefore, they are stereoisomers. They would have the same geometry if atoms or groups around C=C bond can be rotated but rotation around C=C bond is not free.

It is restricted. For understanding this concept, take two pieces of strong cardboards and join them with the help of two nails. Hold one cardboard in your one hand and try to rotate the other. Can you really rotate the other cardboard ? The answer is no.

The rotation is restricted. This illustrates that the restricted rotation of atoms or groups around the doubly bonded carbon atoms gives rise to different geometries of such compounds. The stereoisomers of this type are called geometrical isomers.

The isomer of the type (a), in which two identical atoms or groups lie on the same side of the double bond is called cis isomer and the other isomer of the type (b), in which identical atoms or groups lie on the opposite sides of the double bond is called trans isomer .

Thus cis and trans isomers have the same structure but have different configuration (arrangement of atoms or groups in space). Due to different arrangement of atoms or groups in space, these isomers differ in their properties like melting point, boiling point, dipole moment, solubility etc.

Geometrical or cis-trans isomers of but-2-ene are represented below :

Cis form of alkene is found to be more polar than the trans form. For example, dipole moment of cis-but-2-ene is 0.33 Debye, whereas, dipole moment of the trans form is almost zero or it can be said that trans-but-2-ene is non-polar.

This can be understood by drawing geometries of the two forms as given below from which it is clear that in the trans-but-2-ene, the two methyl groups are in opposite directions, Therefore, dipole moments of C-CH3 bonds cancel, thus making the trans form non-polar.

In the case of solids, it is observed that the trans isomer has higher melting point than the cis form. Geometrical or cis-trans isomerism is also shown by alkenes of the types XYC = CXZ and XYC = CZW

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