Physical Chemistry

of Polymers
Course Teacher – Dr. Suranjana Mandal
 Unit-I : Structure of Polymer Chain

  

 Introduction to chain conformation, configurations, conformation

of ethane and butane, factors influencing stereoregularity,
conformation of polymer chain.  
                                                                                   
Learning outcomes -

 Relate polymer characteristics to their

chemical structure and molecular
architecture. (Remembering)

 Recall the effect of orientation of

polymer chain on the properties of
polymers. (Remembering)
 Stereochemistry - Definition

The branch of chemistry which deals with three

dimensional structure of molecule and their
effect on physical and chemical properties is
known as stereochemistry.
 Conformation
Conformations are different spatial
arrangements of a molecule that are generated
by rotation about single bonds.
 Conformation
 When atoms in organic molecules connect via single
bonds, we can have a free rotation around those single
bonds.
 That gives a different 3D forms of the same molecule.
 Those forms are called as conformations of the
molecules. 
 Any one specific conformation is called a conformational
isomer, or conformer.
Conformation  Conformation refers to order
that arises from the rotation of
molecules about the single bonds

 thermal fluctuation of the bond

length (3%) and bond angle (3-5°)
are small at room temperature

 rotations around the bonds are

well possible
 Spot Question:

Take 2 minutes and

Write three points about Conformation.

 Polymer conformation

Polymer conformation refers to 

“the spatial configuration of the constitutive atoms
or atomic groups for a given, fixed connectivity”
For most polymers, the ability to adopt different
conformations arises from the rotational degree of
freedom around the single chemical bonds
connecting the backbone atoms.

1 2
-----CH2 ---- CH --------CH2-----------CH---------

Cl Cl
Sawhorse representation of a molecule

A carpenter's sawhorse.
 Sawhorse representation

 The saw-horse formula is a diagram used to depict a

specific conformation of a molecule.
 Sawhorse projection, allows better visualization of the 3D
geometry between adjacent carbon atoms in a molecule.
 This type of projection is customarily used to show
interactions between groups on adjacent carbon atoms in a
molecule.
 The sawhorse projection is named after its similar
appearance to a carpenter's sawhorse.
Sawhorse Representation
 Reflection Quiz:

 Draw the Sawhorse Projection of Ethane

CH3 CH3 (condensed formula)

Front Carbon H H

H C C H

H H
(structural formula)
 Sawhorse Projections of Ethane

Figure Acknowledgement:
https://www.organicchemistrytutor.com/lessons/newman-projections/
 Homework on 19th October,2022

 Draw the Sawhorse Projection of

Propane:
2
CH3 CH2
1
1 stands for front C atom
2 stands for back C atom
H H CH3
See from here

H 2
C C
1
H
H CH3
 Newman Representation
 In this representation one views the carbon-carbon bond
directly end-on and represents the two carbon atoms by a
circle.
 Lines going to the center of the circle represent
substituents on the front carbon, and lines going to the
edge of the circle represent substituents on the rear carbon.
 It is useful in alkane stereochemistry,
 It visualizes the conformation from front to back,
 The front carbon atom is represented by a dot and the
back carbon as a circle.
 The front carbon atom is called proximal, while the back
atom is called distal.
 Newman Representation
Proximal C atom

Distal C atom

Figure Acknowledgement: https://www.clutchprep.com/organic-chemistry/drawing-

newman-projections
Reflection Quiz:

 Draw the Newman Projection of

Ethane

1
CH3 2
CH3

1 stands for front C atom

2 stands for back C atom
 Newman Projections of Ethane

Staggered
Lowest energy

Eclipsed,
Higher energy

Figure Acknowledgement:
https://en.m.wikipedia.org/wiki/File:Newman_projection_ethane.png
Reflection Quiz:

1. Watch the Video Sawhorse to Newman Projection by Fun Man

Fung, Ph.D, https://youtu.be/fEFZn5kpTpg
2. Watch the Video
Newman Projection to Bond Line Notation Trick by by 
Leah4sci , https://youtu.be/D5NZERv_EDQ

 Now draw the Sawhorse and Newman projection for :

1 stands for front C atom

 1,1 dichloroethane 2 stands for back C atom
1
CH 2
CH3
Cl2
Flexibility mechanism
  Ethane is the simplest hydrocarbon that
can have distinct conformations.
 staggered conformation and the
eclipsed conformation, deserve special
CONFORMATIONAL attention.
ANALYSIS OF  The C-H bonds in the staggered
ETHANE conformation are arranged so that each
one bisects the angle made by a pair of
C-H bonds on the adjacent carbon.
 In the eclipsed conformation each C-H
bond is aligned with a C-H bond on the
adjacent carbon. The staggered and
eclipsed conformations interconverted
by rotation around the carbon-carbon
bond. Different conformations of the
same molecule are sometimes called
conformers or rotamers.
 Staggered
conformation
of ethane
Eclipsed
conformatio
n of ethane
Some commonly used representations Some commonly used representations
of the staggered conformation of the eclipsed conformation
of ethane. of ethane.
  The structural feature that above
CONFORMATIO figures illustrate is the spatial
NAL ANALYSIS relationship between atoms on
OF ETHANE adjacent carbon atoms.
 Each H-C-C-H unit in ethane is
characterized by a torsion angle or
dihedral angle, which is the angle
between the H-C-C plane and the C-
C-H plane.
 The torsion angle is easily seen in a
Newman projection of ethane as the
angle between C-H bonds of
adjacent carbons.
 Torsion Angle

Eclipsed bonds are characterized by a torsion angle of 0°. When the torsion
angle is approximately 60°, we say that the spatial relationship is gauche; and
when it is 180° we say that it is anti.
Staggered conformations have only gauche or anti relationships between
bonds on adjacent atoms.
Types of Strain
Torsional Strain Energy

 Force that opposes rotation due to the repulsion of bonding

electrons

 We do not observe perfectly free rotation

 There is a barrier to rotation, and some
 conformers are more stable than others
 Small energy barrier easily overcome at RT
Each eclipsed H-H costs 4 kJ/mol of Torsional Energy
Homework
 CONFORMATIONAL ANALYSIS OF BUTANE

 we consider conformations related by rotation about the bond between the

middle two carbons (CH3 CH2-----CH2 CH3).
 Unlike ethane, in which the staggered conformations are equivalent, two
different staggered conformations occur in butane, shown in figure below.
 The methyl groups are gauche to each other in one, anti in the other. Both
conformations are staggered, so are free of torsional strain, but two of the
methyl hydrogens of the gauche conformation lie within 210 pm of each other.
 This distance is less than the sum of their van der Waals radii (240 pm), and
there is a repulsive force between them. The destabilization of a molecule that
results when two of its atoms are too close to each other is called van der
Waals strain, or steric hindrance and contributes to the total steric strain.
 In the case of butane, van der Waals strain makes the gauche conformation
approximately 3.2 kJ/mol (0.8 kcal/mol) less stable than the anti
 Figure in slide no 34 illustrates the potential energy relationships among the
various conformations of butane. The staggered conformations are more stable
than the eclipsed.
 At any instant, almost all the molecules exist in staggered conformations, and
more are present in the anti conformation than in the gauche.
 The point of maximum potential energy lies some 25 kJ/mol (6.1 kcal/mol)
above the anti conformation. The total strain in this structure is approximately
equally divided between the torsional strain associated with three pairs of
eclipsed bonds (12 kJ/mol; 2.9 kcal/mol) and the van der Waals strain between
the methyl groups.
 Arithmetically, the total strain energy (Es) of an alkane or cycloalkane can be
considered as

where
 E bond stretching is the strain that results when C-C and C-H bond distances are
distorted from their ideal values of 153 pm and 111 pm, respectively.
 E angle bending is the strain that results from the expansion or contraction of bond
angles from the normal values of 109.5° for sp3 hybridized carbon.
 E torsional is the strain that results from deviation of torsion angles from their
stable staggered relationship.
 E Van der Waals is the strain that results from “nonbonded interactions.”
Cyclohexane
Home Assignment I
(To be submitted by 15th November, 2022)

 Of the three conformations of propane shown, which one is the most stable?
Which one is the least stable? Why? - 5 marks

• Sight down the C-2±C-3 bond, and draw Newman projection formulae
for the
(a) Most stable conformation of 2,2-dimethylbutane
(b) Two most stable conformations of 2-methylbutane
(c) Two most stable conformations of 2,3-dimethylbutane
 End to End Distance, r

Adapted from Fig.

14.6, Callister 7e.
Configuration
• describes the spatial position of atoms within the
molecule:
• The geometrical arrangement in polymers arising
from the order of atoms determined by chemical
bonds.
• The regularity and symmetry of the side-groups
can affect strongly the properties of polymers.
Side groups are atoms or molecules with free
bonds, called free-radicals, like H, O, methyl, etc.
• The configuration of a polymer cannot be altered
unless chemical bonds are broken and reformed.
• asymmetric C-atom ⇔ all substituents are different
 Configurational isomers - separable isomers that do not readily interconvert
chiral centers - absolute stereochemistry
sp3 carbons (or nitrogens, or ...)
chiral-handed (left or right)

enantiomers (enantio = opposite)

non-identical (non-superimposable) mirror image
R = recto (right-handed)
S = sinestro (left-handed)
 Configurational isomers - separable isomers that do not readily interconvert.
Most would require "breaking" and "making" of bonds.
 a. cis-trans (olefins)
 b. chiral centers - absolute stereochemistry
 Molecular Structures

 Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.

 Polymers – Molecular Shape
45
Configurations – to change must break bonds

H H H H H R
C C C C or C C
 H Stereoisomerism
R
H R H H

A A

C C
E E
B D D B
mirror
plane
46
cis/trans Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain
 Assignment II

 What is the difference between configuration and conformation

(use examples)? 
      Which configurational isomers are important for polymers?
Which ones are likely to      form crystalline structures?
Extra Reading on Conformation
and Configuration…..
 http://slideplayer.com/slide/4395311/ (Conformation of
Polymers)
 http://slideplayer.com/slide/8459490/
 https://www.youtube.com/watch?v=yWwxFmyZNfg
 https://youtu.be/E52oU-pwDxY Conformations of ethane
 http://www.open.edu/openlearn/science-maths-technology/scienc
e/chemistry/introduction-polymers/content-section-2.3.3#fig002-
004

 Gutta Percha and Natural rubber

(Refer Goodman1974thermopropertiesGP.pdf)
Tacticity:
 The orderliness of the succession of
configurationally repeating units in the main
chain of a polymer molecule (important for
crystallization).
 if the radicals are linked in the same order, the
configuration is called isotatic
 in a stereoisomer in a syndiotactic
configuration, the radical groups are at
alternative sides in the chain
 in the atactic configuration, the radical groups
are positioned at random
 Tacticity
51

Tacticity – stereoregularity of chain

H H H H H H H H
isotactic – all R groups
C C C C C C C C
on same side of chain
H R H R H R H R

H H H R H H H R
syndiotactic – R groups
C C C C C C C C
alternate sides
H R H H H R H H

H H H H H R H H
atactic – R groups
C C C C C C C C
random
H R H R H H H R
Stereochemistry of repeating units

Chiral centers

Chemically identical but they rotated plane-polarized

light in opposite directions.
Tacticity in polymers

Polymerization of monosubstituted ethylene

Pseudochiral center
isotactic

syndiotactic

atactic
2.4.3 Substitutional isomerism

Synthesis of diene type polymers

1,2
1,4
3,4
addition polymerization
isoprene
 Extra Reading
 http://www.open.edu/openlearn/science-maths-technology/science/chemistry/int
roduction-polymers/content-section-2.3.4

Polymers: Free and Gaussian chains

 https://www.youtube.com/watch?v=7USylDCgquI

Conformation of Butane
 https://chem.libretexts.org/Courses/University_of_Illinois_Springfield/UIS%3A
_CHE_267_-_Organic_Chemistry_I_(Morsch)/Chapters/Chapter_04%3A_Alka
nes/3.09%3A_Conformations_of_Butane
 Acknowledgement
 Moss, GP (1996-01-01). "Basic terminology of stereochemistry (IUPAC
Recommendations 1996)". Pure and Applied Chemistry. 68 (12): 2193–2222. 
doi:10.1351/pac199668122193. ISSN 1365-3075
 https://www.clutchprep.com/organic-chemistry/drawing-newman-projections
 50th Anniversary Perspective: Polymer Conformation—A Pedagogical Review,
Zhen-Gang Wang, Macromolecules 2017, 50, 23, 9073–9114
 https://www.stereoelectronics.org/webSC/SC101.html
 https://www.organicchemistrytutor.com/lessons/newman-projections/
 https://www.uou.ac.in/lecturenotes/science/MSCCH-17/CHEMISTRY%20LN%2
01%20STERIOCHEMISTRY.pdf
Thank You