POLYMER ARUP NAG

Molecular Mass of Polymer:

During the formation of polymer, different macromolecules have different degree of

polymerization i.e they have different chain length. Thus the molecular masses of the
individual macromolecules in a particular sample of polymer are different. Hence an average
value of molecular mass is taken. There are two types of average molecular masses of polymer
– (i) Number Average Molecular Mass (Mn)

(ii) Mass Average Molecular Mass (Mw)

Number Average Molecular Mass: When the total mass of all the molecule of a sample is
dividedby total number of molecule, the result obtained is called Number Average
Molecular Mass. e.g., Suppose in a particular sample

N1 Molecules have molecular mass M1

N2 Molecules have molecular mass M2

N3 Molecules have molecular mass M3

: : : : : : : :

Then Total mass of all the N1 molecule = N1 M1

Total mass of all the N2 molecule = N2 M2

Total mass of all the N3 molecule = N3 M3 and so on

 Total mass of all the molecules = N1M1+ N2M2 + N3M3 + … and so on

=  NiMi

 Total number of all the molecule = N1+N2+N3+… =  Ni

 NiMi
 Number average molecular mass (Mn) =
 𝑁𝑖
NOTE: Mn is generally determined by osmotic pressure measurement.

Mass Average molecular mass (Mw): When the total mass of groups of molecule having
different molecular masses are multiplied with their respective molecular masses, the
products are added and the sum is divided by total mass of all the molecule. The result
obtained is called Mass Average Molecular Mass. Suppose –

N1 Molecules have molecular mass M1

N2 Molecules have molecular mass M2

N3 Molecules have molecular mass M3

: : : : : : : :

Total mass of N1 molecule = N1 M1

Total mass of N2 molecule = N2 M2

Total mass of N3 molecule = N3 M3

The products with their respective molecular mass will be –

(N1 M1) x M1 , (N2 M2) x M2 , (N3 M3) x M3

= N1 M12 , N2 M22 , N3 M32

 The sum of the products = N1 M12 + N2 M22 + N3 M32 + . . .

=  NiMi2
Total mass of att the molecules = N1M1+ N2M2 + N3M3 + …

=  NiMi

 N𝑖M𝑖 2
 Mass Average Molecular Mass (Mw) =
 N𝑖M𝑖
Poly Dispersity Index (PDI): In general we have two different types of polymeric substance–

(i) Polymer whose molecules have same or narrow ranges of molecular masses, such
polymer is said to be mono disperse.
(ii) Polymer whose molecules have wide range of molecular masses, such polymers are
called poly disperse.
Poly Dispersity Index is the ratio of mass average molecular mass (Mw) to
the number average molecular mass (Mn)

M𝑤
PDI =
M𝑛
For natural polymer, PDI = 1 which means that they are mono disperse.
For synthetic polymer, PDI > 1 which means that they are polydisperse.

