Example of MW

determination of Polymers
Molecular weight
Large macromolecules synthesized from molecules
Not all polymer chains grow to the same length
Average molecular weight is determined by measuring
viscosity and osmotic pressure
The chain is divided into size ranges
No. of moles (or fraction) of each size range is
determined

Chapter 14: Polymer Structures 2

Molecular weight continue

Number average molecular weight, M =xiMi

n
Where
Mi=Mean molecular weight within a size range

xi=Fraction of number of chains within the corresponding

(same) size range

Chapter 14: Polymer Structures 3

Molecular weight continue
Weight Average Molecular weight, =wiMi
Mw
Where,
Mi=Mean molecular weight within a size range

wi=weight fraction of molecules within the same size

range

Chapter 14: Polymer Structures 4

Molecular weight continue
Notice the shift

Source: William Callister 7th edition, chapter 14, page 498, figure 14.3
Chapter 14: Polymer Structures 5
Molecular weight continue

Source: William Callister 7th edition, chapter 14, page 498, figure 14.4
Chapter 14: Polymer Structures 6
Molecular weight continue
Degree of polymerization (n):
n= Average no of mer units in a chain
nn=Number average degree of polymerization

nw=Weight average degree of polymerization

Mn m Mer molecular weight

nn
m
Mw
nw
m
Chapter 14: Polymer Structures 7
Molecular weight continue
For a copolymer (i.e., two or more mer units),

m f j m j

Where,
fj= chain fraction of mer

mj=molecular weight of mer

Chapter 14: Polymer Structures 8

Problem 14.1:
Computations of Average Molecular Weights and Degree
of Polymerization
Assume that the molecular weight distributions shown in
Figure 14.3 are for poly(vinyl chloride). For this material,
compute:
(a) the number-average molecular weight,
(b) the degree of polymerization, and
(c) the weight-average molecular weight.
Chapter 14: Polymer Structures 9
Problem 14.1: continue

xiMi=21,150
Where, xi: Fraction of total no. of chain within the corresponding size change
M n : Number average molecular weight

Chapter 14: Polymer Structures 10

 Problem 14.1: continue

xiMi=23,200
Where, Mw : weight average molecular weight

Chapter 14: Polymer Structures 11

Problem 14.1: continue

PVC: C2H3Cl

C H Cl
Atomic weight (g/mol) 12.01 1.01 35.45

m 2(12.01) 3(1.01) 35.45

m 62.50g/mol

Chapter 14: Polymer Structures 12

Problem 14.1: continue

Number average degree of polymerization,

M n 21 , 150
nn 338
m 62.50

Chapter 14: Polymer Structures 13