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Polymer Reaction Engineering: Molecular Weight and Its Distribution

The document discusses molecular weight and its distribution in polymers. It defines number average molecular weight (Mn) as the total weight of polymer divided by the total number of molecules. Weight average molecular weight (Mw) is based on light scattering and is greater for larger molecules. Viscosity average molecular weight (Mv) is measured using solution viscosity. Polydispersity index (PI) is the ratio of Mw to Mn and indicates the breadth of the molecular weight distribution. The properties of polymers depend on their molecular weight and distribution.

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Abhijit Nath
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54 views18 pages

Polymer Reaction Engineering: Molecular Weight and Its Distribution

The document discusses molecular weight and its distribution in polymers. It defines number average molecular weight (Mn) as the total weight of polymer divided by the total number of molecules. Weight average molecular weight (Mw) is based on light scattering and is greater for larger molecules. Viscosity average molecular weight (Mv) is measured using solution viscosity. Polydispersity index (PI) is the ratio of Mw to Mn and indicates the breadth of the molecular weight distribution. The properties of polymers depend on their molecular weight and distribution.

Uploaded by

Abhijit Nath
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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POLYMER REACTION ENGINEERING

Molecular weight and its distribution

Prof. Shishir Sinha


Department of Chemical Engineering

1
Molecular weight and its distributions
❑ Molecular weight
It has prime importance in polymer synthesis and applications. As the
mechanical, chemical and thermal properties of the polymer depend upon
molecular weight.
▪ Some of the properties increase with molecular weight to a maximum
value and then decrease on further an increase in the molecular weight.
▪ The problem with higher molecular weight polymer is the processibility
as the viscosity become high and melt flow difficult.
▪ .

2
Molecular weight and its distributions
▪ The synthesize of higher molecular weight polymer is not necessary, but
polymer with high, specified, and improvised molecular weight is
required in many applications.
❑ P1+P1→ P2
❑ P2 + P1 → P3

3
Molecular weight and its distributions
▪ Generally, polymers are the mixer of molecules of different molecular
weight. Therefore average molecular weight and exact distribution of
different molecular weight is usually required to characterized the
polymers.
▪ There are needs of control on the average molecular weight and
molecular weight distribution for desire physical properties in the
polymers.

4
Molecular weight and its distributions
➢ The average molecular weight is biased towards the larger and small-
sized molecules.
➢ Various methods are used to determine the average molecular weight
of the polymers, like colligative properties, light scattering , viscosity
measurements etc.

5
Molecular weight and its distributions
➢ Number average molecular weight ( M N )
▪ The number average molecular weight is defined as the total weight
of polymer divided by the total number of molecules.
▪ It is experimental methods which count the number of molecules in
the polymer. In this method, measuring the colligated properties of
the solution is measuring of 𝑀𝑁
Which is represented by the equation;

6
Molecular weight and its distributions
The most common methods for measuring the number average molecular
weight are vapor pressure osmometry (used to measure Mol. wt. below
10,000 to 15,000) and membrane osmometry (above 20,000 to 30,000 and
below 50,000).
Generally it is experimentally determined by:
➢ Vapor Pressure Osmometry
▪ It works by taking advantage of the decrease in
vapor pressure that occurs when solutes are
added to pure solvent.

8
Molecular weight and its distributions
This technique can be used for polymers with a molecular weight of up
to 20,000 though accuracy is best for those below 10,000
➢ Membrane Osmometry
▪ The membrane osmometry is a technique for the determination of
molecular masses of polymers by means of osmosis. It carries out in
membrane osmometer. Which consists of two chambers:
▪ One chamber contains pure solvent and other
one with solution that contains a solution in
which the solute is a polymer with an unknown
Mn.
9
Molecular weight and its distributions
• By measurement of osmotic pressure across the semi permeable
membrane gives information about Mn

➢ Weight average molecular weight ( 𝑴𝒘 )


▪ It is based upon the light scattering by the polymer solution, and it is
greater for larger sized molecules and smaller for small-sized molecules.
▪ This method is most accurate for higher molecular
weight polymers. There is no upper limit for light
scattering method to measure the molecular weight
but the lower limit is 5,000 to 10,000.

10
Molecular weight and its distributions
Weight average molecular weight (𝑀𝑤 )can be described as the product of
weight fraction (fx)of molecules whose weight is Mxi.e.

11
Molecular weight and its distributions
➢ Viscosity average molecular weight (𝑴𝑽 )
Theviscosity is useful for measuring the molecular weight of the
polymers. For larger molecules, the viscosity is larger and smaller for
smaller molecules.
The solution viscosity measures the viscosity average molecular weight.
This can be written as;
[Note]

12
Molecular weight and its distributions
❑ Poly-Dispersity Index (PI)
▪ Polydispersity index (PDI) is used as a measure of broadness of
molecular weight distribution.
▪ It is the ratio of weight average molecular weight to number average
molecular weight. It can be written as;
[Note]

▪ It is usually one (for monodispersed polymer)


or greater than one (actual polymer).

14
Molecular weight and its distributions
❑ Poly-Dispersity Index (PI)
▪ The characterization of the polymer with the
number average molecular weight alone without
considering the poly-dispersity may mislead. The
polymer properties are more dependent on larger
molecule size than the smaller ones.
▪ Poly-dispersity index depends upon the breadth of
the distribution curve (a graph in-between weight
fraction and molecular weight) as shown in the
following figure.
16
References
▪ G.Odian, Principles of Polymerization, Fourth Edition, John Wiley & Sons, Inc.,
(2004), ISBN:9780471478751 |DOI:10.1002/047147875X
▪ J.M. Asua, Polymer Reaction Engineering, Blackwell Publishing, (2007), ISBN: 978-1-
4051-4442-1.
▪ M. Szwarc, Marcel Van Beylen (auth.) - Ionic Polymerization and Living Polymers,
Springer Netherlands, (1993).
▪ Stephen L. Rosen. Fundamental principles of polymeric materials, An SPE textbook,
John Wiley & Sons (1937), ISBN:0-471-08704-1.
▪ V. R. Gowariker, N. V. Viswanathan, J. Sreedhar. Polymer Science, New age
international (P) limited, publishers (1986), ISBN-08-522-6307-4.
▪ Joel R. Fried. Polymer Science and Technology:, Prentice-Hall, Inc., (1995), ISBN-81-
203-1458-1.

17
Thank You

18

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