What is Isomerism?

Isomerism is the phenomenon in which more than one compounds have the same chemical formula but
different chemical structures There are two primary types of isomerism, which can be further categorized
into different subtypes. These primary types are Structural Isomerism and Stereoisomerism.

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Optical isomerism in lactic acid

In lactic acid molecule there is an asymmetric chiral carbon atom with four different groups
which lead to two spatial configurations (d-lactic acid l-lactic acid) which are super
imposable mirror images of each other.
The structures of two enantiomers of lactic acid are as follows:
When a plane polarized light is passed through a lactic acid solution the plane of polarized
light gas rotated through a certain angle. This property of rotating the plane of polarized
light towards right (clockwise) or towards (left)(anticlockwise) is called optical activity.
d-lactic acid rotates the plane of polarized light towards right whereas l-lactic acid rotates the
plane of polarized light towards left, which can be detected by polarimeter. In above
structure (I) is representing the (+) isomeric form or dextro rotatory form of lactic acid, while
structure (II) is representing (−) isomeric form or laevo rotatory for of lactic acid.

Optical isomerism in tartaric acid

The two asymmetric carbon atoms in tartaric acid.

Its molecule can be represented by space models of two tetrahedral joined corner to
corner but for the sake of convenience we will use the planed formulas. The end groups
being identical, in all four arrangements are possible according as one or both H groups
and OH groups are on the left or on the right.

Out of these, formula IV when rotated through 180o in the plane of the paper becomes
identical with formula III. Therefore, for tartaric acid we can have only three different
arrangements, viz. I, II and III.

Now, if the force which rotates the plane of polarised light be directed from H to OH,

1. structure I will rotate the plane of polarised light to the right and will represent (+)-
tartaric acid;
2. structure II will rotate the plane of polarised light to the left and will represent (-)-tartaric
acid; and
3. structure III will represent optically inactive tartaric acid, since the rotatory power of the
upper half of the molecules is balanced by that of the lower half.

It may also be noted that formulas I and II are mirror images of each other and hence
represent (+)- and (–)-isomers. Formula III, however, has a plane of symmetry (dotted
line) and hence represents and inactive isomer of tartaric acid.

In actual practice, four tartaric acids are known :

 1. (+)-Tartaric acid ;
2. (–)-Tartaric acid ;
3. Inactive or i-tartaric acid; this is also known as meso-tartaric acid or m-tartaric acid ;
4. (±) Tartaric acid ; this form of tartaric acid being a mixture of equal amounts of (+)-
and (–)-isomers

What is an Enantiomer?

Enantiomers are a pair of molecules that exist in two forms that are mirror images of one another but
cannot be superimposed one upon the other. A pair of enantiomers is distinguished by the direction in
which when dissolved in solution they rotate polarized light, either dextro (d or +) or levo (l or -)
rotatory

Characteristics of Enantiomers

• Enantiomers generally have identical physical properties such as melting point, boiling point,
infrared absorptions and NMR spectra.
• It is important to realize however, that whilst the melting point etc of one enantiomer will be
identical to that of the other enantiomer, the melting point of a mixture of the two
enantiomers may be different.
• This is because the intermolecular interactions between opposite enantiomers that are
between the R and S enantiomers may be -different to those between like enantiomers that
are between two molecules both of R or both of S stereochemistry.
• The one class of physical techniques that can distinguish between the two enantiomers of a
compound are chiroptical techniques, the most common of which is optical rotation.
• The chiroptical properties of a molecule are determined not just by the bond lengths and
angles but also by the sign and magnitude of the torsional angles, the sign of the torsional
angles being the one difference between enantiomers.

What are Diastereomers?

Diastereomers are defined as compounds which have the same molecular formula and sequence of
bonded elements but which are nonsuperimposable, non-mirror images.
Let us consider the formula of 2,3-dichloropentane which contains two chiral centres. Now compare
the two forms of 2,3-dichloropentane given

Characteristics of Diastereomers
▪ Diastereomers have different physical properties such as melting points, boiling points,
densities, solubilities, refractive indices, dielectric constants and specific rotations. Enantiomers
have similar physical properties except the opposite sign of specific rotation.
▪ Diastereomers other than geometrical isomers may or maynot be optically active.
▪ Diastereomers show similar, but not identical chemical properties. The rates of reactions of the
two diastereomers with a given reagent provided tha reagent is not rapidly active.
▪ On account of differences in their physical properties, diastereomers can be separated from one
another through techniques like fractional crystallization, fractional distillation, chromatography
etc. The difference from enantiomers which can’t be separated by these techniques.

Meso Compounds
Meso compounds are achiral compounds that has multiple chiral centers. It is superimposed on its mirror
image and is optically inactive despite its stereocenters.

In general, a meso compound should contain two or more identical substituted stereocenters. Also, it has
an internal symmetry plane that divides the compound in half. These two halves reflect each other by the
internal mirror. The stereochemistry of stereocenters should "cancel out". What it means here is that
when we have an internal plane that splits the compound into two symmetrical sides, the stereochemistry
of both left and right side should be opposite to each other, and therefore, result in optically inactive.
Cyclic compounds may also be meso.

If A is a meso compound, it should have two or more stereocenters, an internal plane, and the
stereochemistry should be R and S.

R cancels S out in a meso compound with two stereocenters

Racemic Mixtures

A racemic mixture is a 50:50 mixture of two enantiomers. Because they are

mirror images, each enantiomer rotates plane-polarized light in an equal but
opposite direction and is optically inactive.

Each enantiomer rotates the plane of polarization of plane-polarized light

through a characteristic angle, but, because the rotatory effect of each
component exactly cancels that of the other, the racemic mixture is optically
inactive.

The process by which an optically active substance is transformed into the

corresponding racemic modification is known as racemization; the converse
process, by which a racemic modification is separated into the two
enantiomers, is known as resolution

Conformational Isomers
If we observe the ball and stick model of ethane and rotate one carbon atom keeping another carbon
atom stationary about the C-C axis. We will observe that the rotations will result in an infinite number
of spatial arrangements of hydrogen atoms attached to one carbon atom with respect to the hydrogen
atoms attached to the other carbon atom. These different arrangements are better known
as conformational isomers or conformers.
Predominantly, these can be broadly classified into two different cases:

1. Eclipse conformation
Conformation in which hydrogen atoms are attached to two carbons stay nearest to each other as
possible is known as eclipsed

2. Staggered conformation
Confirmation in which hydrogen atoms attached to two carbons are as far as possible with respect to
each other is known as staggered The staggered conformation is thus relatively more stable in
comparison to eclipse conformation as there are minimum repulsive forces, minimum energy due to
many separations between the electron clouds of C-H bonds.

Representation of Eclipsed and Staggered Conformation:

Sawhorse projections:
In this kind of projection, the bond between carbon atoms is shown as a long straight line. The lower
end of the line designates the front carbon atom whereas the upper end designates the rear carbon
atom. Since each carbon atom in ethane is attached to three hydrogen atoms; each carbon atom has
three lines attached designating C-H bonds inclined at an angle of 120° to each other.

Newman projections:
In this projection, out of the two carbon atoms present in ethane one which is nearer is shown as a
dot whereas the rear carbon atom is represented as a circle. The three hydrogen atoms attached to
each carbon atom are represented with the help of three lines either bulging out of the circle or
diverging from the dotted lines. These lines are inclined to each other at an angle of 120° to each
other.

What are Conformational Isomers ?

Conformational isomers (or conformers or rotational isomers or rotamers)
are stereoisomers produced by rotation (twisting) about σ bonds, and are often
rapidly interconverting at room temperature.
There are two types of configurational isomers: diastereisomers and enantiomers