Scribd
Upload
53 views16 pages

Last Time:: Molecular Weight Distribution

The document discusses molecular weight distribution and different methods for modeling it, including: - The most probable distribution, which only depends on one parameter and assumes xw/xn is near 2. - The Schulz distribution, which is a more general form that allows xw/xn to vary. - The Wesslau distribution, which models the differential weight distribution. - Examples are given of calculating parameters like xw and xn from given molecular weight distribution models.

Uploaded by

bilal sheikh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
53 views16 pages

Last Time:: Molecular Weight Distribution

The document discusses molecular weight distribution and different methods for modeling it, including: - The most probable distribution, which only depends on one parameter and assumes xw/xn is near 2. - The Schulz distribution, which is a more general form that allows xw/xn to vary. - The Wesslau distribution, which models the differential weight distribution. - Examples are given of calculating parameters like xw and xn from given molecular weight distribution models.

Uploaded by

bilal sheikh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 16

Lecture 5

Last time:
Molecular Weight Distribution

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Another Example in Rodreguiz

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)
Example
Data from previous example
Table 6.2 Analysis of distribution from Figure 6.1.
Relative number
Degree of Number of Mole of monomer Weight
polymerization moles fraction units in x-mer fraction
x Nx Nx/Σ Nx Wx/M0 wx=Wx/ΣWx xwx

1 25 0.50 0.50 0.25 0.25


2 15 0.30 0.60 0.30 0.60
3 2 0.04 0.12 0.06 0.18
4 4 0.08 0.32 0.16 0.64
5 2 0.04 0.20 0.10 0.50
6 1 0.02 0.12 0.06 0.36
7 1 0.02 0.14 0.07 0.49
50 1.00 2.00 1.00 3.02

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Now
xn = Number Av Degree of Polymerization
= Number of monomer units in system
Mole fraction

= (wx/Mo) / (Nx/∑Nx)
= 2.0/1.0

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


xw = Weight Av Degree of Polymerization
= Total Weight of system
Total Weight fraction

= ∑xwx/∑wx
= 3.02/1.0

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Averages & Properties
Monomer (x=1)
o highest mole fraction

o but not the highest relative weight (Wx).


o Usefulness of averages depend on property examined.
o Reactivity of a urethane prepolymer may depend
entirely on xn. Viscosity of a polymer melt often varies
more directly with xw.

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


o Emperical MWD Models
o MWD important for
o flow of melts and solutions
o aging and weathering
o adhesion
o flocculation.
o Most probable distribution limitation
o Only one parameter p
o xw/xn should be near 2 else invalid
o Reasonable mathematical model required
 Then find x, xw, xn etc
Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)
o Schulz distribution
o More general form of the most probable distribution:

o
o where xw/xn=(a+1)/a
o Γ(a+1) is gamma function of a+1
o When a=1 and x is large, -- same as the most probable distribution,
o Qualitatively, the curves will resemble “most-probable”
o except that the overall breadth will reflect the influence of the polydispersity
index.
o Differential Distribution
o wx=dW/dx
o higher ranges of xn,
o approximation Σwx=∫wxdx is applicable
o Often W(x) against x on log gives a straight line.

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


o Wesslau distribution
o In terms of wx, this becomes the :

o where β2=ln(xw/xn)2 and x0=xn exp(β2/4).

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Example
The molecular-weight distribution for a certain polymer can
be described as

where x=1, 2, and 3 only and wx is the weight fraction of


polymer with degree of polymerization x. What is the value
of k? What is xw? What is xn?

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Solution
K from

so

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)
Example
Cummulative Weight Fractions
With high molecular weights (x>100) -- treat distributions
as being continuous.
Assume that the cumulative weight fraction W(x)of a
polymer with degree of polymerization less than x is given
by

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


The differential weight distribution wx then is

(6.27)
The degree of polymerization is obtained by integration and normalization.

Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)


Print to PDF without this message by purchasing novaPDF (http://www.novapdf.com/)

You might also like