Molecular Weight of Polymers

Presented by Dedicated to
Raisul Awal Mahmood Dr. Chanchal Kumar Roy
ID: 1018032701 Assistant Professor
Bangladesh University of
Engineering & Technology (BUET)
 Table of content
1. Introduction
2. Molecular weight of a polymer
3. Types of molecular weight of a polymer
4. Number average molecular weight
5. Weight average molecular weight
6. Z-average Molecular weight
7. 𝒁𝒁 + 𝟏𝟏-average Molecular Weight
8. Molecular Weight Distribution Curve
9. Polydispersity Index, PDI
10. Influence of molecular weight on physical properties
Introduction
 Polymers consist of repeat unit
(monomers) chemically bonded into
long chain.
 To understand the physical properties of
a polymer such as mechanical strength,
solubility and brittleness, we need to
know the length of polymer chain.
 The molecular weight can not be
determined in a single value. Rather, the
polymer exists as a distribution of chain
lengths and molecular weights.
 The molecular weight of a polymer must
be determined as some average
molecular weight.
Molecular-weight of a polymer
 The molecular weight of a polymer is
defined as sum of the atomic weight of
each of the monomers present in a
polymer.
 Chain length is expressed in terms of
molecular weight of the polymer length.
Polymer sample

 It is a way of describing how long the N molecules

polymer chains are.

 Each monomer has a molecular weight

(also called the formula weight). Adding
the monomers together to make
polymers increases the molecular 𝑴𝑴𝟏𝟏 𝑵𝑵𝟏𝟏 𝑴𝑴𝟒𝟒 𝑵𝑵𝟒𝟒
weight
𝑴𝑴𝟑𝟑 𝑵𝑵𝟑𝟑
𝑴𝑴𝟐𝟐 𝑵𝑵𝟐𝟐
 The longer the chains, the higher the
Schematic diagram of molecular weight of polymers
molecular weight.
Types Molecular-weight of a polymer

Types Molecular-weight of a polymer

Number- Weight-average Viscosity- Z-average 𝒁𝒁 + 𝟏𝟏-average

average molecular average molecular molecular
molecular weight, molecular weight, weight,
weight, 𝑴𝑴𝒘𝒘 weight, 𝑴𝑴𝒛𝒛 𝑴𝑴𝒛𝒛+𝟏𝟏
𝑴𝑴𝒏𝒏 𝑴𝑴𝒗𝒗
Number-average molecular weight, 𝑴𝑴𝒏𝒏
The Number Average Molecular Weight,
𝑴𝑴𝒏𝒏 is the total weight of the polymer
molecules divided by the total number of 𝑴𝑴𝒏𝒏
polymer molecules.

∑ 𝑵𝑵𝒊𝒊 𝑴𝑴𝒊𝒊
𝑴𝑴𝒏𝒏 =

No. of chains
∑ 𝑵𝑵𝒊𝒊

𝑴𝑴𝒊𝒊 = The molecular weight of the chain.

𝑵𝑵𝒊𝒊 = The total number of chains of that Chain length
molecular weight.
Number-average molecular weight, 𝑴𝑴𝒏𝒏

Generalization of the concept

Total number of molecules (𝑁𝑁) = 𝑵𝑵𝟏𝟏 + 𝑵𝑵𝟐𝟐 + 𝑵𝑵𝟑𝟑 + … … … = � 𝑵𝑵𝒊𝒊

𝑁𝑁𝑖𝑖
Number fraction of each molecule is =
∑ 𝑵𝑵𝒊𝒊

𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖
No. average weight of each entity is =
∑ 𝑵𝑵𝒊𝒊

𝑁𝑁1 𝑀𝑀1 𝑁𝑁2 𝑀𝑀2 𝑁𝑁3 𝑀𝑀3 ∑ 𝑵𝑵𝒊𝒊 𝑀𝑀𝑖𝑖

Number average weight is each entity is = + + +⋯= = 𝑴𝑴𝒏𝒏
∑ 𝑵𝑵𝒊𝒊 ∑ 𝑵𝑵𝒊𝒊 ∑ 𝑵𝑵𝒊𝒊 ∑ 𝑵𝑵𝒊𝒊
Weight-average molecular weight, 𝑴𝑴𝒘𝒘
The weight average molecular weight, 𝑴𝑴𝒘𝒘 is
defined by

∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 2
𝑴𝑴𝒘𝒘 =
∑ 𝑵𝑵𝒊𝒊 𝑴𝑴𝒊𝒊 𝑴𝑴𝒘𝒘

𝑴𝑴𝒊𝒊 = The molecular weight of the chain.

𝑵𝑵𝒊𝒊 = The total number of chains of that

Weight fraction
molecular weight.

𝑴𝑴𝒘𝒘 takes into account that the larger

molecules contain a much higher amount of Molecular weight
the molecular mass of the polymer. 𝑴𝑴𝒘𝒘 is
almost always higher than the Number
Average Molecular Weight, 𝑴𝑴𝒏𝒏
Weight-average molecular weight, 𝑴𝑴𝒘𝒘
Generalization of the concept

Total number of molecules (N) = 𝑵𝑵𝟏𝟏 + 𝑵𝑵𝟐𝟐 + 𝑵𝑵𝟑𝟑 + … … … = � 𝑵𝑵𝒊𝒊

Total weight of polymer = � 𝑵𝑵𝒊𝒊 𝑴𝑴𝒊𝒊 = 𝑾𝑾

𝑁𝑁1 𝑀𝑀1 𝑁𝑁1 𝑀𝑀1

Weight fraction of each molecule is = =
𝑾𝑾 ∑ 𝑁𝑁1 𝑀𝑀1

𝑁𝑁1 𝑀𝑀1 𝑀𝑀1 𝑁𝑁1 𝑀𝑀1 2

Weight average of each entity is = =
∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 ∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖

𝑁𝑁1 𝑀𝑀1 2 𝑁𝑁2 𝑀𝑀2 2 𝑁𝑁3 𝑀𝑀3 2 𝑁𝑁4 𝑀𝑀4 2

Weight average molecular weight, 𝑴𝑴𝒘𝒘 = + + +⋯=
∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 ∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 ∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 ∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖
Viscosity-average Molecular weight, 𝑴𝑴𝒗𝒗

The viscosity average molecular weight, 𝑴𝑴𝒗𝒗

is defined by

Weight fraction
1
1+𝑎𝑎 2 𝑴𝑴𝒗𝒗
∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖
𝑴𝑴𝒗𝒗 =
∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖

𝑴𝑴𝒊𝒊 = The molecular weight of the chain.

𝑵𝑵𝒊𝒊 = The total number of molecules of that
molecular weight.
𝒂𝒂 = constant which depend on the Molecular weight
polymer-solvent in the viscosity experiments
Viscosity-average Molecular weight, 𝑴𝑴𝒗𝒗
𝑴𝑴𝒏𝒏 = 𝑴𝑴𝒗𝒗 𝒂𝒂 = 𝟏𝟏
 When 𝒂𝒂 = 𝟏𝟏,

Weight fraction
𝑴𝑴𝒘𝒘

𝑴𝑴𝒗𝒗 = weight average molecular weight, 𝑴𝑴𝒘𝒘

Molecular weight

𝑴𝑴𝒏𝒏
 When 𝒂𝒂 ≠ 𝟏𝟏, 𝑴𝑴𝒗𝒗
𝒂𝒂 ≠ 𝟏𝟏

Weight fraction
𝑴𝑴𝒘𝒘
𝑴𝑴𝒗𝒗 is between the weight-average molecular
weight, 𝑴𝑴𝒘𝒘 and the number-average
molecular weight, 𝑴𝑴𝒏𝒏 .
Molecular weight
Z-average Molecular weight, 𝑴𝑴𝒛𝒛
The Z-average molecular weight, 𝑴𝑴𝒛𝒛 is
defined by

∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 3
𝑴𝑴𝒛𝒛 =
∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 2

Weight fraction
𝑴𝑴𝒛𝒛
𝑴𝑴𝒊𝒊 = The molecular weight of the chain.
𝑵𝑵𝒊𝒊 = The total number of chains of that
molecular weight.

𝑴𝑴𝒛𝒛 is measured in some sedimentation

Molecular weight
equilibrium experiments. 𝑴𝑴𝒛𝒛 emphasizes
large particles and it defines the equation.
𝒁𝒁 + 𝟏𝟏-average Molecular Weight, 𝑴𝑴𝒛𝒛+𝟏𝟏
The Z+1-average molecular weight, 𝑴𝑴𝒛𝒛+𝟏𝟏 is
defined by

∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 𝑛𝑛+1 𝒏𝒏 ≥ 𝟑𝟑

𝑴𝑴𝒛𝒛+𝟏𝟏 =
∑ 𝑁𝑁𝑖𝑖 𝑀𝑀𝑖𝑖 𝑛𝑛

Weight fraction
𝑴𝑴𝒊𝒊 = The molecular weight of the chain. 𝑴𝑴𝒛𝒛+𝟏𝟏
𝑵𝑵𝒊𝒊 = The total number of chains of that
molecular weight.

The 𝑴𝑴𝒛𝒛+𝟏𝟏 is also known as higher averages

which are increasingly more sensitive to high Molecular weight

molecular weight polymers.

Molecular Weight Distribution Curve
 For monodisperse polymer
(polymers with chains of only
𝑴𝑴𝒏𝒏 one mass),
𝑴𝑴𝒗𝒗 𝑴𝑴𝒏𝒏 = 𝑴𝑴𝒗𝒗 = 𝑴𝑴𝒘𝒘 = 𝑴𝑴𝒛𝒛
 For polydisperse polymer
𝑴𝑴𝒘𝒘
(polymers has many different
Weight fraction

sized chains),
𝑴𝑴𝒛𝒛
𝑴𝑴𝒏𝒏 ≤ 𝑴𝑴𝒗𝒗 ≤ 𝑴𝑴𝒘𝒘 ≤ 𝑴𝑴𝒛𝒛
𝑴𝑴𝒛𝒛+𝟏𝟏

Molecular weight
Polydispersity Index, PDI
The polydispersity index is used as a measure of Synthetic polymers (narrow polymers used
the broadness of a molecular weight 𝑀𝑀𝑤𝑤
for calibrations) have = 1.02 𝑡𝑡𝑡𝑡 1.10
𝑀𝑀𝑛𝑛
distribution of a polymer and is defined as
𝑴𝑴𝒘𝒘
Polydispersity index, PDI =
𝑴𝑴𝒏𝒏 Synthetic polymers
The larger the polydispersity index, the broader
the molecular weight.

A monodisperse polymer where all the chain Step polymerization reactions typically
lengths are equal (such as a protein) has an yield values of
𝑀𝑀𝑤𝑤
= 1.5 𝑡𝑡𝑡𝑡 2.0
𝑴𝑴𝒘𝒘 𝑀𝑀𝑛𝑛
= 𝟏𝟏.
𝑴𝑴𝒏𝒏

Monodisperse
polymer Step polymerization
Influence of molecular weight on physical properties

Molecular Weight Polymer Properties

Number-average molecular weight

Brittleness, stress-strain
(𝑴𝑴𝒏𝒏 )

Weight-average molecular weight Tensile strength, impact strength, and

(𝑴𝑴𝒘𝒘 ) hardness
Viscosity-average molecular weight Solution viscosity, extrudability, molding
(𝑴𝑴𝒗𝒗 )

Z -average molecular weight Flex life, melt viscosity, deflection and

(𝑴𝑴𝒛𝒛 ) rigidity
Determination of molecular weight
Number Average
Molecular Weight
1. End Group Analysis
2. Colligative properties
a) Cryoscopy – Depression
in freezing point
b) Ebulliometry – Elevation
in boiling point
c) Osmometry –
i) Vapor phase
ii) Membrane osmometry
3. GPC
Molecular Weight Determination
Weight Average Viscosity Average
Molecular Weight Molecular Weight
1. Ultracentrifugation 1. Dilute solution
(a) Sedimentation viscosity measurement
velocity method (a) Relative viscosity
(b) Sedimentation (b) Specific viscosity
equilibrium method (c) Reduced viscosity
2. Light Scattering (d) Inherent viscosity
3. GPC (e) Intrinsic viscosity
Z-Average
Molecular Weight
1. Ultracentrifugation
(a) Sedimentation
velocity method
(b) Sedimentation
equilibrium method
2. Light Scattering
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