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MOLECULAR WEIGHT

"Drop the idea of large molecules.


Organic molecules with a molecular
weight higher than 5000 do not exist."
Advice given to Hermann Staudinger*

MOLECULAR WEIGHT
WHY IS IT IMPORTANT ?

MELT
VISCOSITY

TENSILE
STRENGTH

MOL.WT.

MOL.WT.

Molecular Weight - Some Initial Observations


How does the molecular weight of a high polymer differ
from that of a low-molecular-weight substance ?

But for most polymers there is a


Distribution of Chain Lengths
CH4

16
30

CH3 CH3

Gases

CH3 CH2 CH3

58

CH3 CH2 CH2 CH3


Liquid

CH3 (CH2)6 CH3

CH3 (CH2)30 CH3

"Semi-solid"

CH3 (CH2)30000 CH3

44

Solid

114

450

We must therefore define an


Average Degree of Polymerization ( DP )
420030

Increasing
Molecular Weight
Molecular weight M simply:
(# C atoms x 12) + (# H atoms x 1)

The average number of structural units in the polymer chain

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

METHODS FOR THE DETERMINATION


OF MOLECULAR WEIGHT
A
B
S
O
L
U
T
E
R
E
L
A
T
I
V
E

END GROUP ANALYSIS


OSMOTIC PRESSURE
OTHER COLLIGATIVE
PROPERTY MEASUREMENTS
LIGHT SCATTERING
ULTRA - CENTRIFUGATION

_
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]

THE IDEA OF VIRIAL EQUATIONS


THE IDEAL GAS LAW
PV = nRT

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

= 1 + B'P + C'P + D'P + - - -

10

RELATIONSHIP TO MOLECULAR WEIGHT


PV = nRT
P V
_ = RT
n
moles
n_ = #________
w __
1
= __
V
volume
M V

HENCE

=
c

__
c
M

RT
M

NOW CONSIDER AN IDEAL SOLUTION

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

Graph of /c versus c for polystyrene in toluene.

0.21
0.0
0

6
2

10

12

-3

c x 10 g cm

Graph of /c versus c for polyisobutylene in chlorobenzene.

DERIVATION OF A VIRIAL EQUATION


FROM THE FLORY - HUGGINS EQUATION
Osmotic pressure can
Be related to the
Chemical potential

Expanding the ln term

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

THE ORIGIN OF LIGHT SCATTERING


Z

E0

time

LIGHT AS AN OSCILLATING ELECTRIC FIELD

P
z

x
Incident beam polarized
in the zx plane
y

Classical description The electric field of


The incident light induces
Oscillations of the
Electrons in the molecule,
So that the molecule now
Emits light in all directions

SCATTERING FROM A GAS


FOR SCATTERING FROM A BUNCH
OF RANDOMLY LOCATED OSCILLATORS
.

.
.

i' =

( )
N
V

# scatterers
per unit volume

.
.

( )
I0 8

( 2 )

1 + cos2
r2

Polarizability

Characteristics of
the incident beam

Geometry of
observation

(10.46)

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