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MOLECULAR WEIGHT
WHY IS IT IMPORTANT ?
MELT
VISCOSITY
TENSILE
STRENGTH
MOL.WT.
MOL.WT.
16
30
CH3 CH3
Gases
58
"Semi-solid"
44
Solid
114
450
Increasing
Molecular Weight
Molecular weight M simply:
(# C atoms x 12) + (# H atoms x 1)
And an
Average Molecular Weight (M )
The average degree of polymerization times the molecular
weight of the structural unit, M0
MOLECULAR WEIGHT
12
Mn 108, 500
Mw 118, 200
10
Moles
8
6
4
2
0
0
100000
200000
300000
Molecular Weight
Number Average
Mn =
N x Mx
Nx
Weight Average
Nx Mx
=
N x Mx
2
Mw
_
Mn
_
Mn
_
Mn
_
Mw
_
_
Mw , Mz
SOLUTION VISCOSITY
_
_
~
Mv
Mw
GPC
Complete
distribution
OSMOTIC PRESSURE
Concentrated
solution
Dilute
solution
A SECTION OF ROOT
A SCHEMATIC OF A LABORATORY
SCALE OSMOMETER
Pure
Solvent
Piston
Polymer
Solution
Pressure
=
Membrane Cap
[A]
[B]
[C]
1.01
Ideal gas
1.00
N2
0.99
PV
NRT
0.98
CH4
0.97
0.96
C2H4
0.95
0
6
P (atm)
PV
nRT
VIRIAL EQUATION
2
10
HENCE
=
c
__
c
M
RT
M
Osmotic
OsmoticPressure
Pressure
= RT
c
M
= RT + Bc + Cc 2 + Dc3 + -----c
Mn
Ideal Solution
Not So Ideal
Solution
2.0
1.5
1.6
x 10
c
-5
0.4
-2
cm2 sec
1.0
1.2
0.224
-3
c x 10 0.8
cm
0.75
0.5
0.3
0.2
0.0
0
6
3
10
0.4
-3
c x 10 g cm
0.21
0.0
0
6
2
10
12
-3
c x 10 g cm
We obtain
s - 0s
2
= ln s + 1 - 1 p + p
RT
Mn
2
= - RT ln s + p 1 - 1 + p
Vs
Mn
ln s = ln ( 1 - p )
= RT
Vs
p
Mn
p p
- ------= - p 2
3
+ p
2
1 - + p + -----2
3
LIGHT SCATTERING
Looks fiendishly difficult because
Of all the equations
Crucial point:
We will end up with a virial equation,
Just as in our treatment of osmotic
Pressure
K (1 + cos 2) c
1
1 + 22c + --=
R
Mw
Experimentally
measured parameters
Virial expansion
1+ S sin
( 2 ) )
(10.61)
Dependence on
angle of observation
THE EXPERIMENT
Incident
beam
Sample
cell
Transmitted
beam
Detector
E0
time
P
z
x
Incident beam polarized
in the zx plane
y
.
.
i' =
( )
N
V
# scatterers
per unit volume
.
.
( )
I0 8
( 2 )
1 + cos2
r2
Polarizability
Characteristics of
the incident beam
Geometry of
observation
(10.46)