Statistical Theory

Molecular Mass Distributions

Step Growth Polymerization

Dr. Saima Shabbir, MS&E

 Statistical Theory
Carothers theory: simple statistics can predict
whole picture.
Principle of equal reactivity

Dr. Saima Shabbir, MS&E

 Statistical Theory
Key assumption FLORY
The reactivity of a functional group is
independent of the length of the chain to
which it is attached

This group reacts

as readily as
This group
 Was Flory Right?

The rate constant

levels off and becomes
independent of
molecular size when N
> 2.

Redrawn from the data of Flory, P. J., Principles

of Polymer Chemistry, Cornell University
Press, 1953, p. 71
 Step Growth Polymerization
A-B + A-B A-BA-B Type - I
A-A + B-B A-AB-B Type - II

Dr. Saima Shabbir, MS&E

 Statistics of Molecular Mass
Distributions
Step 1: predict px
Step 2: predict nx
Step 3: predict wx
Step 4: Evaluate Xn and Xw
Step 5: PDI

Dr. Saima Shabbir, MS&E

 Molecular Mass Distributions

Step 1: predict px

Dr. Saima Shabbir, MS&E

 Molecular Mass Distributions
To obtain this distribution, we determine the
probability that a molecule selected at
random after extent of reaction (p) is an x-mer
(i.e. has x units in its chain)
px = Nx / N
The probability of an x mers (px) is equal to the
number of x mers (Nx) divided by the total
number of mers (N).

Dr. Saima Shabbir, MS&E

 Molecular Mass Distributions

Step 2: predict nx

Dr. Saima Shabbir, MS&E

 Number Fraction Distribution
Function, nx
The probability that this B has reacted is p.

The probability that the B on the chain end

has not reacted is (1-p).
For the whole chain there will be (x-1) B units
that have reacted and 1 unit (on the chain
end) that has not reacted
Dr. Saima Shabbir, MS&E
 Number Fraction Distribution
Function, nx
Probability of finding (x-1) linkages is px-1
The probability that of all of these independent
events have occurred is equal to the product of
their individual probabilities
Thus, the probability of finding the x-mer:
px = px-1 (1 - p)
px is also the mole fraction (nx = Nx/N) of x-mers
in the reaction.
nx = px-1 (1 - p) This distribution is called the most probable
distribution.
Dr. Saima Shabbir, MS&E
 Number Fraction Distribution
Function, nx
There are always more
monomers present than
any other species at all
stages of the reaction
nx decreases as the
length of the chain
grows
The number distribution
emphasizes low
molecular weights

Dr. Saima Shabbir, MS&E

 Molecular Mass Distributions

Step 3: predict wx

Dr. Saima Shabbir, MS&E

 Weight Fraction Distribution Function,
wx
Number average DP:
Xn = No / N = 1 / 1 p
Rearrange N = No (1 - p)
From Nx/N = px-1 (1 - p)
Rearrange Nx= N px-1 (1 - p)
Put value of N above
Nx= No px-1 (1 - p)2

Dr. Saima Shabbir, MS&E

 Weight Fraction Distribution Function,
wx
By weight, the fraction of monomers can be
very small
wx = total mass of molecules of x monomer units long
total mass of all molecules
wx = Nx(xMo) / NoMo
Since Nx= No px-1 (1 - p)2
wx = No px-1 (1 - p)2 x / No
wx = px-1 (1 - p)2 x

Dr. Saima Shabbir, MS&E

 Weight Fraction Distribution Function,
wx
Presence of a
maximum
The maximum shifts
to higher x with an
increase in p.
The peak broadens
as p increases

Dr. Saima Shabbir, MS&E

 Molecular Mass Distributions

Step 4: Evaluate Xn and Xw

Dr. Saima Shabbir, MS&E

 Number Average degree of
Polymerization, Xn
We have already shown:
Xn = 1 / 1 p
We can obtain the same result by noting that:
Xn = x nx
Xn = x px1 (1 p)
Mathematically for p<1:
x px1 = 1 / (1 - p)2
Thus Xn = 1 / 1 p
This is the same as Carothers theory
Dr. Saima Shabbir, MS&E
 Weight Average degree of
Polymerization, Xw
Same exercise for the weight average degree of
polymerization:
Xw = x wx
Since wx = px-1 (1 - p)2 x
So Xw = px-1 (1 - p)2 x2
Knowing that: x2 px1 = 1 + p / (1 - p)3
Thus Xw = (1 - p)2 1 + p / (1 - p)3
Xw = 1 + p / 1 - p
Dr. Saima Shabbir, MS&E
 Molecular Mass Distributions

Step 5: PDI

Dr. Saima Shabbir, MS&E

 Molecular Mass Distributions
To evaluate PDI:
Mw/Mn = Xw / Xn
Since Xn = 1 / 1 p
And Xw = 1 + p / 1 - p
Xw / Xn = 1 + p
As p 1:
Xw / Xn = 2

Dr. Saima Shabbir, MS&E