B.

Tech First Year Course

Course Title- Chemistry-I (Concepts in Chemistry for Engineering)
Course Code- BTCH101-18
Scheme & Credit – L-3, T-1, P-0, C-4

-Dr. Sanjeeb Sutradhar

 Stereochemistry (L-4)

Representations of 3 dimensional structures, structural isomers and stereoisomers,

configuration and symmetry and chirality, enantiomers. diastereomers, optical activity,
absolute configurations and conformational analysis. Isomerism in transitional metal
compounds.

References
 Isomers
Isomerism: Compounds which have the some molecular formula but differ from each other
in physical or chemical properties are called isomer and the phenomenon is called
isomerism.
e.g. C2H6O (ether or alcohol)
Two types of isomerism
Structural Isomerism Stereoisomerism
(Same molecular formula but different (Same molecular formula but atoms occupy
Structural formulae) different positions in space)
Chain isomerism Geometrical isomerism
Position isomerism Optical isomerism
Functional group isomerism Conformational isomerism
Metamerism
Tautomerism
 Structural (Constitutional) Isomerism
Chain isomerism: Two or more compounds have similar molecular formula but different
carbon skeletons, these are referred to as chain isomers and the phenomenon is termed as
chain isomerism. e.g. C5H12

Position isomerism: Two or more compounds differ in the position of substituent atom or
functional group on the carbon skeleton, they are called position isomers and this
phenomenon is termed as position isomerism. e.g. C3H8O

OH OH
NO2
and

NO2
 Structural (Constitutional) Isomerism
Functional group isomerism: Two or more compounds having the same molecular
formula but different functional groups are called functional isomers and the
phenomenon is termed as functional group isomerism. e.g. C2H6O (ether or alcohol)

CH3CH2OH & CH3-O-CH3

Metamerism: It arises due to different alkyl chains on either side of the functional group
in the molecule. e.g. C4H10O

Tautomerism: It arises due to 1,3-migration of a proton from C-atom to another (O or N)

atom with the rearrangement of single or double bond called tautomerism and the
phenomenon is called tautomerism. e.g. keto-enol tautomerism
 Stereoisomerism (3-D Chemistry)
Stereoisomerism: Caused by the different arrangement of atoms or groups in space the
phenomenon is called stereoisomerism.

Configuration: Particular arrangement of atoms in space that is characteristic of a given

molecule

Configurations are not the same as conformations

Difference
Conformations are inter-convertible by rotation about single bond(s) whereas bonds
must be broken to change one configuration into another.

Stereoisomerism: Three types

Geometrical isomerism (cis-trans isomer, E-Z isomer, syn-anti isomer)
Optical Isomerism (Enantiomers and Diastereomers)
Conformation isomerism
 Stereoisomerism (3-D Chemistry)
Geometrical isomerism: It occurs due to restricted rotation about double bond (p-bond)
or about single bonds in cyclic compounds.
Three types:
cis-trans isomer: Isomer with the groups on the same side is called the cis isomer, while
the isomer with the groups located on opposite sides is called the trans isomer.
Trans isomers of compounds are usually more stable than cis isomers.
 Stereoisomerism (3-D Chemistry)
E-Z isomer: It was difficult to identify the compounds if there is four different groups
around the double bond.

Z configuration (Z -zusammen, German for “together”): If the high-priority groups are

on the same side of the double bond

E configuration (E-entgegen, German for “opposite”): If the high-priority groups are on

opposite sides of the double bond

To determine priority, Cahn-Ingold-Prelog priority rule is applied

Rule-I: high atomic number high priority
 Stereoisomerism (3-D Chemistry)
Rule-II: If the two substituents bonded to an carbon start with the same atom, move to
the next attached group

Rule-III: If an atom is doubly bonded to another atom, the priority system treats it as if
it were singly bonded to two of those atoms. If an atom is triply bonded to another atom,
the priority system treats it as if it were singly bonded to three of those atoms.
 Stereoisomerism (3-D Chemistry)
Rule-IV: In the case of isotopes (atoms with the same atomic number, but different mass
numbers), the mass number is used to determine the relative priorities.

Syn-anti isomers: When C=N is formed between the reaction of aldehyde and NH2-G then
 Syn: H on C-atom and lone pair on N-atom are on the same side
 Anti: H on C-atom and lone pair on N-atom are on opposite side
Identify the Isomers
 Stereoisomerism (3-D Chemistry)
Optical isomerism: Isomers (optical active compounds) has the ability to rotate the plane
polarized light is called optical isomers and the phenomenon is called optical isomerism
(optical activity).

Optical active compounds: Compounds/molecules should be chiral molecules.

Chiral molecules: Molecules/compounds should contain at least one chiral center.

Chiral centre/stereogenic center/asymmetric carbon: Center of a molecule where four

different groups (or atoms) are attached to carbon
 Optical isomerism

Dextrorotatory (+): An optically active compound that rotates plane polarized light in a
clockwise direction. (+) or (d) do not confuse with D
Levorotatory (-): An optically active compound that rotates plane polarized light in a
counterclockwise direction. (-) or (l) do not confuse with L
 Optical isomerism
Specific rotation: The angle of rotation of plane polarized light by a 1 g/cm3
sample in a 1 dm tube. 
[]t =
l x c
 - angle of rotation measured in degrees
t - temperature
 - wavelength of light (sodium light = 589 nm)
l - length of sample cell (dm)
c - concentration in grams of substance contained in 1 mL of solution (g/mL)
?
Q. When one of the enantiomers of 2-butanol is placed in a polarimeter, the observed
rotation is 4.05° counterclockwise. The solution was made by diluting 6 g of 2-butanol to
a total of 40 mL, and the solution was placed into a 200-mm polarimeter tube for the
measurement. Determine the specific rotation for this enantiomer of 2-butanol.
 Relationship between Chirality and Symmetry
Cahn-Ingold-Prelog defined based on handedness
Chiral structures: Structure has no plane of symmetry and non-superimposable on its
mirror image

Achiral structures: Structure has plane of symmetry and superimposable on its mirror
image
 Mesocompound
Mesocompound (achiral): A mesocompound is one which is superimposable on its
mirror image through its plane of symmetry even though it contains stereogenic centers.

CH3 CH3
H Cl Cl H
H Cl Cl H
CH3 CH3

How many stereoisomers exist for this compound?

How many stereogenic centers does each molecule have?

 Optical isomerism
Optical isomerism can be further divided into two categories
Enantiomeris and Diastereomerism
Enantiomerism: Stereoisomer whose molecules are non-superimposible but mirror images
of each other is called enantiomer and the phenomenon is called enantiomerism.

CO2H CO2H
H3C H H CH3
NH2 H2N

Diastereomerism: Stereoisomer whose molecules are neither non-superimposible nor

mirror images of each other is called diastereomer and the phenomenon is called
diastereomerism.

H 3C CH3 H 3C H
C C C C
H H H CH3
 Conformational Isomerism (Representations of 3-D Structures)
R) and (S) Configuration:
Step-I: Assign Priority
 Atoms with higher atomic numbers receive higher priorities.
I > Br > Cl > S > F > O > N > 13C > 12C > 2H > 1H

 In case of ties, use the next atoms along the chain of each group as tiebreakers.

 Treat double and triple bonds as if each were a bond to a separate atom.
 Conformational Isomerism (Representations of 3-D Structures)
R (Rectus-Right) and S (Sinister-left) Configuration:
Step-II:
 Working in 3-D, rotate the molecule so that the lowest priority group is in back.
 Draw an arrow from highest (1) to second highest (2) to lowest (3) priority group.
 Clockwise = (R), Counterclockwise = (S) .

Counterclockwise
(S)
 Examples
3 CH3
1 CH2CH3
OH
rotate
C C
2
3 2 4
H CH3CH2CH=CH H
CH3CH2CH2 CH2CH3 CH3CH2CH2
H OH CH2CH2CH2CH3
4 1
 Relative configurations by D and L Notation
Introduced by E. Fischer (1885) and
Use Glyceraldehyde as standard
 simplest carbohydrate-an aldotriose its configuration could be easily related to
those of the other important carbohydrates
 Contains very reactive functional groups it could be converted into many other
types of compounds

D - OH group attached to chiral carbon is towards right

L - OH group attached to chiral carbon is towards left
Examples
Isomerism in Transitional Metal Compounds
 Structural Isomerism of Transitional Metal Compounds
 Hydrate isomerism  Ionization isomerism

 Co-ordination isomerism  Linkage isomerism

 Stereoisomers of Transitional Metal Compounds

Geometrical isomers can occur for octahedral and square planar but not tetrahedral
complexes