School of Chemistry and Biochemistry, TIET, Patiala Applied Chemistry (UCB009)

Solutions of assignment (Chemistry of Polymers)

1. What is polymerization and degree of polymerization? How polymers are classified?

Ans: The chemical reaction in which high molecular mass molecules are formed from
monomers is known as polymerization or the fundamental process by which low molecular
weight compounds are converted into high molecular weight compounds.
The degree of polymerization (DP) refers to the number of repeat units in the chain, and gives
a measure of molecular weight.
Polymers can be classified as;
A. Classification on the basis of source:
i. Natural polymers – Polymers which are found in nature in plants and animals e.g. Starch,
cellulose, proteins, natural rubber etc.
ii. Synthetic polymers- These are man-made polymers like polyethylene, polypropylene,
polyvinylchloride, nylon etc.
B. Classification on the basis of structure:
i. Linear polymers – Monomeric units in these polymers are joined in form of long straight
chains e.g. nylons, polyester etc. They have high M.P, density and tensile strength due to
close packing of chains.
ii. Branched polymers - have a chain structure that consists of one main chain of molecules
with smaller molecular chains branching from it.

iii. Cross linked Polymers- In cross-linked polymers, adjacent linear chains of polymer are
joined one to another at various positions by covalent bonds e.g. Vulcanized natural rubber,
where sulfur joins the chains of natural rubber, Bakelite etc. Due to cross links, they are hard
and rigid.
 Other Ways to Classify Polymers
Classification Based on Polymerization
i. Addition Polymerization: Example, polyethylene, Teflon, Polyvinyl chloride (PVC)
ii. Condensation Polymerization: Example, Nylon -6, 6, perylene, polyesters.

Classification Based on Monomers

i. Homomer: In this type, a single type of monomer unit is present. For example, Polyethene
ii. Heteropolymer or co-polymer: It consists of different type of monomer units. For
example, nylon -6, 6
Classification Based on Molecular Forces
i. Elastomers: These are rubber-like solids weak interaction forces are present. For example,
Rubber.
ii. Fibres: Strong, tough, high tensile strength and strong forces of interaction are present. For
example, nylon -6, 6.
iii. Thermoplastics: These have intermediate forces of attraction. For example, polyvinyl
chloride.
iv. Thermosetting polymers: These polymers greatly improve the material’s mechanical
properties. It provides enhanced chemical and heat resistance. For example, phenolics,
epoxies, and silicones.
2. Differentiate the following with examples:
i. Addition and condensation polymerisation
Addition polymerisation Condensation polymerisation
1. The method involves the repeated addition 1. The method involves series ofcondensation
of monomers to produce long chains without reactions, generally involving two monomers
elimination of any by-products with the elimination small molecules like
H2O, NH3 or HCl
2. Monomers must have a double or triple 2. Monomers must have two similar or
bond different functional groups
3. The molecular weight of the resultant 3. The molecular weight of the resultant
polymers is a multiple of monomer’s polymer is not a multiple of monomer’s
molecular weight molecular weight
4. Lewis acids or bases, radical initiators are 4. No such catalysts are required
catalysts in addition polymerization
5. High molecular mass polymers are formed 5. Polymer molecular mass rises steadily
at once throughout the reaction
6. Example-polyethylene, Teflon, Polyvinyl 6. Example-Nylon -6, 6, perylene, polyesters.
chloride (PVC)

ii. Homopolymer and copolymer

Homopolymer Copolymer
 1. Homopolymers are produced by using a 1. Copolymers are formed by polymerisation
single type of monomer or single species of of mixture of two or more monomers/two or
repeating units more types of repeating units.
2. Homopolymers are formed through 2. Copolymers are formed through
addition polymerisation condensation polymerisation
3. They often have a simple structure 3. They usually have complex structure
4. Example-polyethylene, Teflon, Polyvinyl 4. Example-polyethylene-vinyl acetate
chloride (PVC) (PEVA), nitrile rubber, and acrylonitrile
butadiene styrene (ABS)

iii. Thermoplastic and thermosetting polymer

Thermoplastic polymer Thermosetting polymer

1. They soften on heating readily and once 1. They do not soften on heating, hence once
moulded they can be resoftened and reused moulded, they set permanently
2. They are softer and less strong; the 2. They are strong and hard, there are cross
polymeric chains are held together by weak linkages and covalent bond formation
vander Waals forces between the adjacent polymeric chains
3. They are generally formed by addition 3. These are formed by condensation
polymerisation reaction polymerisation reaction
4. As they soften again and again, they can be 4. They cannot be recycled, reused or
recycled, reused and reclaimed from waste. reclaimed from waste.
6. Example-polyethylene, Teflon, Polyvinyl 6. Example-Bakelite, melamine
chloride (PVC) formaldehyde.

3. Why polymers are expressed in terms of average molecular weights? For a polymeric
sample, discuss the number average and weight average type of molecular mass.
Ans: In the process of polymerisation, the chain termination is a random process, all the
polymeric chains formed are of different lengths, hence it becomes difficult to express the
molecular weight of the polymer. Therefore, the molecular weight can be expressed as average
of the molecular weights contributed by individual molecules in the sample. In other words,
polymers are mixtures of molecules of different molecular masses (polydisperse and
heterogeneous).
The molecular weight of a polymer is expressed in two ways:
i. Number average molecular weight Mn. - If N1, N2, N3, … are the numbers of molecules with
molecular masses M1, M2, M3, …, respectively, then the number average molecular weight is:
 Mn = [N1M1 + N2M2 + N3M3 + ----- ] = S N iM i/ S Ni
N1 + N2 + N3 + ----

Where N1, N2, N3 -number of molecules, M1, M2, M3 – Mol. wts

Total mass of the polymer sample / Total number of molecules present in the sample
ii. Weight average molecular weight Mw - If m1, m2, m3 ,... are the weights of species with
molecular masses M1 , M2 , M3 , …, respectively, then the weight average molecular weight is:
Mw = m1M1 + m2M3 + m3M3+---------
m1+ m2 + m3 + -----------

Mw = ∑mi Mi
∑ mi
But

Hence,
Mw = [N1M 2 + N M 2 + N M 2 + -----]
1 2 2 3 3 = S N M 2/ S N M
i i i i
N1M1 + N2M2 + N3M3 +--

where ni = number of molecules of mass Mi

4. Weight average molecular weight is higher than number average molecular weight in
polymers. Explain. What is polydispersity index?
Ans: Compared to Mn, Mw takes into account the molecular weight of a chain in determining
contributions to the molecular weight average. The more massive the chain, the more the chain
contributes to Mw. “Mn” the number average molecular weight, is evaluated from the mole
fraction distribution of different sized molecules in a sample while Mw, the weight average
molecular weight, is calculated from the weight fraction distribution of different sized
molecules. Since larger molecules in a sample weigh more than smaller molecules, the weight
average (Mw) has higher values, and is always greater than Mn. Moreover, the weight average
is proportional to the square of the molecular weight.

Polydispersity Index (PDI): The polydispersity index or heterogeneity index is a measure of

the distribution of molecular mass in a given polymer sample. The PDI calculated is the weight
average molecular weight divided by the number average molecular weight. It indicates the
distribution of individual molecular masses in a batch of polymers. The PDI has a value equal
to or greater than 1, but as the polymer chains approach uniform chain length or as the weight
 dispersion of molecules in a sample narrows, Mw approaches Mn, and in the unlikely case that
all the polymer molecules have identical weights (a pure mono-disperse sample), the ratio
Mw/ Mn (i.e PDI) becomes unity.

5. In a polymer sample, 30% molecules have a molecular mass 20000, 40% have molecular
mass 30000 and rest have 60000. Calculate mass average and number average molecular
masses.

Mn = [N1M1 + N2M2 + N3M3 + ----- ]

= S N i M i / S Ni
N1 + N2 + N3 + ----
Ans:

(30 × 20,000) + (40 × 30,000) + (30 × 60,000)

=
30 + 40 + 30
= 36000
Mw = [N1M 2 + N M 2 + N M 2 +----- ]
1 2 2 3 3 = S N M 2/ S N M
i i i i
N1M1 + N2M2 + N3M3 +--

30(20,000)2 + 30(20,000)2 + 30(20,000)2

=
(30 × 20,000) + (40 × 30,000) + (30 × 60,000)

= 43333

6. In a polymer there are 150 molecules of molecular weight 100, 200 molecules of molecular
weight 1000 and 300 molecules of molecular weight 10000. Find the number and weight
average molecular mass of the polymer and PDI.

Mn = [N1M1 + N2M2 + N3M3 + ----- ]

= S NiMi/ S Ni
N1 + N2 + N3 + ----
Ans:

(150 × 100) + (200 × 1000) + (300 × 10000)

=
150 + 200 + 300
= 4946.15
Mw = [N 1M 12 + N 2M 22 + N 3M 32 + ----- ]
= S N i M i 2 / S Ni M i
N 1M 1 + N 2M 2 + N 3M 3 +--

150(100)2 + 200(1000)2 + 300(10,000)2

=
(150 × 100) + (200 × 1000) + (300 × 10,000)

= 9393.93

PDI =
 9393.93
=
4946.15
= 1.89
7. Calculate the degree of polymerization of vinyl chloride if the number average weight of
polymer is 1.31× 105 g/mol.
Ans: Mn̅ = D.P (molar mass of monomer)
1.31× 105 g/mol = D.P (62.5 g/mol), hence D.P = 2096

8. When 52 g of styrene was polymerized, average degree of polymerization was found to be

1.5× 105. Calculate the number of styrene molecules in the original sample and number
of molecules of polystyrene produced.
Ans: (i) No. of molecules of styrene in 52g = 52 × (6.023 ×1023/ 104.15) = 12.07 ×1023 molecules
(ii) No. of molecules of polystyrene formed
No. of styrene molecules
=
Degree of polymerisation
12.07 × 1023
=
1.5 × 105
= 8.04 ×1018 molecules
9. What is tacticity? Draw and differentiate syndiotactic and isotactic forms of polyvinyl
chloride.
Ans: Tacticity is defined as the way pendant groups (side groups/functional groups) are arranged
along the backbone chain of polymer. This refers to different atomic configurations for the same
composition. Based on the orientation of the side groups polymers can be classified as isotactic,
syndiotactic or atactic polymers:
Isotactic polymers: When the orientation of the side groups on alternate asymmetric carbon
atoms is the same, the polymer is termed as a syndiotactic polymer.
Syndiotactic polymers: When the orientation of the side groups on alternate asymmetric
carbon atoms is the same, the polymer is termed as a syndiotactic polymer.
.
10. What are inorganic polymers? How are their properties different from organic polymers?
Ans: The polymers in which backbone of the carbon (as in organic polymers) is replaced by
silicon, phosphorous or any other inorganic atom are called Inorganic Polymers.

In contrast to organic polymers, inorganic polymers exhibit following properties:

• Nonflammability
• Low temperature flexibility
• Electrical conductivity
11. What are biodegradable polymers? Give two examples each of natural and synthetic
biodegradable polymers
Ans: The polymers that can be degraded into small segments after their intended purpose by
bacterial decomposition process to result in natural byproducts such as gases (CO2, N2), water,
biomass and inorganic salts are called “Biodegradable polymers”.
i. Natural - Starch, Cellulose, Proteins, DNA, Polyhydroxyalkanoates (PHA)
ii. Synthetic - Nylon-2-nylon-6, PHBV, Polylactic acid
12. Which functional groups are generally present in the biodegradable polymers? With the
help of suitable examples, explain how the synthetic polymers are also being degraded by
biocatalysts (enzymes)?
Ans: Biodegradable polymers tend to consist of ester, amide or ether functional groups.
Synthetic polymers can be biodegraded only if they possess same chemical linkage as that
present in natural polymers.

Nylon-2-nylon-6 has a peptide linkage that can be hydrolysed by same enzymes that degrade a
protein in nature while PHBV has an ester linkage that can be hydrolysed by living organisms
and the products of hydrolysis are further metabolized by soil microbes.

13. What are conducting polymers? Give examples. Write their applications
Ans: Some polymers, under certain conditions, have electrical conductivities comparable to that
of metallic conductors due to delocalized π electrons. Such polymers are called conducting
polymers. Examples of conducting polymers are given as below:

Polyphenylene

Polythiophene

S S

Polyphenylvinylene

Applications of conducting polymers

• Replacement of Metal Conductor: Conducting polymers have replaced conventional metallic
conductors due to their light weight and comparable conductivities in electronic devices.
• Chemical Sensors: Conducting polymers, such as polypyrrole, polyaniline, polythiophene and
their derivatives, have application as gas sensors.
• Printed Circuit Boards (PCBs): Conducting Polymer coated polymer sheets for PCBs are
inexpensive and have better adhesive properties compared to metallic conductors coated with
epoxy resins.
• Rechargeable Batteries: The capability of repeated oxidation and reduction of CPs make them
eligible for rechargeable batteries as compared to conventional Ni-Cd Cells.
• Numerous other applications such as Light Emitting Diodes (LEDs), in Display Device

14. Why doping is required in conducting polymers? Explain the mechanism of conduction
in n-doped polymers
Ans: The conductivity in conducting polymers is due to presence of conjugated system in the
backbone or delocalized π electrons but conjugated bonds do not render polymeric materials to
be highly conductive. Therefore, to enhance their conductivity a dopant needs to be added that
either generates a free electron or a hole, as in case of semiconductors.
Mechanism of Conduction in n-Doped Polym

Polyme

Na

Na

Na

Na

n-Doping: An electron-rich species (Lewis bases) like napthyl radical anion is added in the
conjugated system to induce reduction and thus generate a radical anion. Thus, a radical anion or
an electron is generated that when moves through the doped conjugated system causes electrical
conduction.