Structure 3

Classification of Matter
HL
3.2 Functional groups:
Isomerism
ESSENTIAL IDEA
Stereoisomerism involves isomers
which have different arrangements
of atoms in space but do not differ in
connectivity or bond multiplicity (i.e.
whether single, double or triple)
between the isomers themselves.
NATURE OF SCIENCE (4.1)
Transdisciplinary—the three-dimensional shape of an
organic molecule is the foundation pillar of its
structure and often its properties. Much of the human
body is chiral.
INTERNATIONAL-MINDEDNESS

Have drugs and medicines in some

countries been sold and
administered as racemates instead
of as the desired enantiomer with
the associated therapeutic activity?
Can you think of any drugs or
medicines which may serve as good
case studies for this?
 THEORY OF KNOWLEDGE
The existence of optical isomers provide indirect
evidence for a tetrahedrally bonded carbon atom.
Which ways of knowing allow us to connect indirect
evidence to our theories?
Stereoisomerism can be investigated by physical and
computer models. What is the role of such models in
other areas of knowledge?
One of the challenges for the scientist and the artist
is to represent the three dimensional world in two
dimensions. What are the similarities and differences
in the two approaches? What is the role of the
different ways of knowing in the two approaches?
 Key Idea
Stereoisomers are subdivided into two
classes—conformational isomers,
which interconvert by rotation about a
σ bond and configurational isomers
that interconvert only by breaking and
reforming a bond.
STEREOISOMERISM
▪ Remember that structural isomers have
the same molecular formula but different
arrangements of atoms.
▪ Stereoisomers have molecules attached
together in the same order but differ in
their three dimensional arrangements.
▪ Two types:
▪ Conformational
▪ Configurational
Conformational Isomerism

▪ These are isomers that spontaneously

interconvert by rotating around sigma
bonds.
▪ These are very difficult to isolate.
 Key Idea
Cis-trans isomers can occur in alkenes
or cycloalkanes (or heteroanalogues)
and differ in the positions of atoms (or
groups) relative to a reference plane.
Configurational Isomerism

▪ Configurational isomers occur when

there are carbon atoms that have
restricted rotation when there is a
double bond or cyclic structure.
▪ They can only be interconverted by
breaking covalent bonds.
▪ Two types:
▪ Cis-tran isomerism and E/Z
Isomerism
▪ Optical Isomerism
 APPLICATION/SKILLS
Be able explain stereoisomerism
in non-cyclic alkenes and C3
and C4 cycloalkanes.
Cis-tran isomerism
▪ If there are two different groups attached
to the carbons with restricted rotation,
then there are two different
three-dimensional arrangements that can
occur.
▪ The cis isomer has the groups on the
same side as the double bond or the
point of restriction.
▪ The trans isomer has the groups on the
opposite side of the double bond or point
of restriction.
▪ The words cis and trans are then prefixes
in the name.
H 3C CH3
C=C cis-but-2-ene
H H

H CH3
C=C trans-but-2-ene
H 3C H
▪ You may not use the condensed formula
when demonstrating stereoisomerism.
▪ You must draw out the structures.
CYCLIC MOLECULES
▪ Cycloalkanes contain a ring of carbon
atoms in which the bond angles are
strained from the tetrahedral angles in
the parent alkane.
▪ In cyclopropane (C3), the carbon atoms
form a triangle with bond angles of 60
degrees.
▪ In cyclobutane (C4), the carbon atoms
form a puckered square with angles near
90 degrees.
▪ The rings prevent the rotation around the
carbon atoms so when there are two
different groups attached to two carbons in
the ring, they can exist as cis and trans
forms.
▪ The groups do not have to be on adjacent
carbons.
▪ It is their position relative to the plane of
the ring that defines the cis-trans isomer.
Practice
PHYSICAL PROPERTIES

▪ Physical properties of cis-tran isomers

depend upon:
▪ The polarity of the molecules
▪ The shape or symmetry of the molecules
▪ Boiling point is mostly affected by the polarity
and the strength of the intermolecular forces.
CHEMICAL PROPERTIES

▪ The chemical properties of cis-tran

isomers are usually very similar.
 APPLICATION/SKILLS
Be able to describe and explain
optical isomerism in simple
organic molecules.
UNDERSTANDING/KEY IDEA
20.3.D
A chiral carbon is a carbon
joined to four different atoms or
groups.
OPTICAL ISOMERS

▪ A carbon atom attached to four different

atoms or groups is said to be asymmetric
or chiral.
▪ The four groups arranged tetrahedrally
around the carbon atom can be arranged
in two different three dimensional
configurations which are mirror images of
each other.
▪ This is known as optical isomerism.
 Key Idea
An optically active compound can
rotate the plane of polarized light as
it passes through a solution of the
compound. Optical isomers are
enantiomers.
 Key Idea
Enantiomers are
non-superimposeable mirror
images of each other.
Diastereomers are not mirror
images of each other.
ENANTIOMERS

▪ Chiral molecules have no plane of

symmetry.
▪ Enantiomers are two optical isomers of
chiral molecules which are
non-superimposable which means they
do not line up when put together.
▪ Mixtures containing the same amount of
the two enantiomers are known as
racemic mixtures.
DIASTEREOMERS

▪ Diastereomers have opposite

configurations at some but not all chiral
centers and are not mirror images of
each other.
▪ Diastereomers have different chemical
and physical properties.
 APPLICATION/SKILLS
Be able to distinguish between
optical isomers using a
polarimeter.
▪ Optical isomers show a difference in a
specific interaction with light.
▪ If light is passed through a polarizer, only
the light waves oscillating in a single
plane pass through, while light waves in
all other planes are blocked out.
▪ This is known as plane-polarized light.
▪ A similar effect is achieved in polarized
sunglasses.
▪ When a beam of plane-polarized light
passes through a solution of optical
isomers, they rotate the plane of
polarization.
▪ The amount and direction of rotation can
be measured with a polarimeter.
▪ Separate solutions of enantiomers at the
same concentration rotate
plane-polarized light in equal amounts
but opposite directions.
▪ Rotating plane-polarized light to the left is
said to be (-).
▪ Rotating plane-polarized light to the right
is said to be (+).
POLARIMETER
▪ The solution of isomers is placed in a
tube through which plane-polarized light
is passed.
▪ Rotation of the polarization plane occurs
and the light then passes through a
second polarizer known as the analyzer
which has been rotated until the light
passes through it.
▪ This analyzer measures the extent and
direction of rotation.
A – Light source produces light vibrating in all directions
B – Polarizing filter only allows light through that vibrates
in one direction
C – Plane polarize light passes through sample
D – If sample is optically active, the plane polarized light
is rotated in one direction
E – Analyzer – measures the amount of rotation
 APPLICATION/SKILLS
Be able to compare the physical
and chemical properties of
enantiomers.
 Key Idea
A racemic mixture (or racemate)
is a mixture of two enantiomers
in equal amounts and is
optically inactive.
PROPERTIES OF OPTICAL
ISOMERS
▪ Optical isomers, the enantiomers, have
identical physical and chemical
properties with two important exceptions:
▪ Optical activity
▪ Reactivity with other chiral molecules
▪ The two enantiomers of a chiral
compound rotate plane-polarized light in
equal and opposite directions.
▪ A racemic mixture does not rotate light so
it is said to be optically inactive.
REACTIVITY WITH OTHER
CHIRAL MOLECULES
▪ Resolution is the process by which two
enantiomers are separated from a
racemic mixture.
▪ When a racemic mixture is reacted with a
single enantiomer of another chiral
compound, the two components of the
mixture, the (+) and (-) enantiomers react to
produce different products.
▪ These products have different chemical and
physical properties which can be separated
easily.
 Citations

International Baccalaureate Organization. Chemistry Guide,

First assessment 2016. Updated 2015.
Brown, Catrin, and Mike Ford. Higher Level Chemistry. 2nd ed.
N.p.: Pearson Baccalaureate, 2014. Print.
ISBN 978 1 447 95975 5
eBook 978 1 447 95976 2

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from this textbook.

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