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 ?

TENSILE MELT
STRENGTH
VISCOSITY

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
CH3 CH3 30
Gases
CH3 CH2 CH3 44
CH3 CH2 CH2 CH3 58

CH3 (CH2)6 CH3 Liquid

114

"Semi-solid"
CH3 (CH2)30 CH3 450
We must therefore define an
Average Degree of Polymerization ( DP )
Solid The average number of structural units in the polymer chain
CH3 (CH2)30000 CH3 420030
Increasing And an
Molecular Weight
Average Molecular Weight (M )
The average degree of polymerization times the molecular
Molecular weight M simply: weight of the structural unit, M0
(# C atoms x 12) + (# H atoms x 1)
MOLECULAR WEIGHT
12
Mn ≅ 108, 500
Mw ≅ 118, 200
10

8
Moles

0
0 100000 200000 300000
Molecular Weight

Number Average Weight Average

∑ N x Mx ∑ Nx Mx
2

Mn = Mw =
∑ Nx ∑ N x Mx
METHODS FOR THE DETERMINATION
OF MOLECULAR WEIGHT

_
END GROUP ANALYSIS Mn
A _
B OSMOTIC PRESSURE Mn
S
O _
OTHER COLLIGATIVE Mn
L PROPERTY MEASUREMENTS
U _
T LIGHT SCATTERING Mw
E _ _
ULTRA - CENTRIFUGATION Mw , Mz
R
E
_ _
L SOLUTION VISCOSITY Mv ~ Mw
A
T GPC Complete
I distribution
V
E
OSMOTIC PRESSURE

Concentrated
solution
Dilute
solution

A SECTION OF ROOT
A SCHEMATIC OF A LABORATORY
SCALE OSMOMETER

Pressure
=π
Pure Polymer Piston
Solvent Solution
h

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 2 4 6 8 10
P (atm)

VIRIAL EQUATION
PV 2 3
= 1 + B'P + C'P + D'P + - - -
nRT
RELATIONSHIP TO MOLECULAR WEIGHT

PV = nRT

P V
_ = RT
n

n_ = #________
moles
= __
w __
1 = __
c
V volume M V M

Π RT
HENCE =
c M

NOW CONSIDER AN IDEAL SOLUTION

Osmotic
OsmoticPressure
Pressure
π = RT
Ideal Solution c M
Not So Ideal π = RT + Bc + Cc 2 + Dc3 + ------
c
Solution Mn

2.0

1.5 1.6
π x 10 -5
0.4
c
-2
cm2 sec
1.0
1.2 0.3

0.224
0.5 0.75 π -3
0.2
c x 10 0.8 0 1 2 3
cm

0.0
0 2 4 6 8 10 0.4
3 -3
c x 10 g cm

0.21
Graph of π/c versus c for polystyrene in toluene.
0.0
0 2 4 6 8 10 12
2 -3
c x 10 g cm

Graph of π/c versus c for polyisobutylene in chlorobenzene.

 DERIVATION OF A VIRIAL EQUATION
FROM THE FLORY - HUGGINS EQUATION

( )
Osmotic pressure can µ s - µ 0s 2
= ln Φs + 1 - 1 Φ p + Φp χ
Be related to the RT Mn
Chemical potential 2
(
π = - RT ln Φ s + Φp 1 - 1 + Φp χ
Vs Mn )
2 3
Φp Φ p
Expanding the ln term ln Φ s = ln ( 1 - Φp ) = - Φp - - - -------
2 3

( )
Φp 1 - χ + Φp + ------
We obtain π = RT + Φp
2

Vs Mn 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 2θ) c
Rθ
=
1
Mw
(1 + 2Γ2c + --- ) ( 1+ S sin
2
( θ2 ) ) (10.61)

Experimentally Dependence on
measured parameters angle of observation

Virial expansion
 THE EXPERIMENT

Sample
cell
Incident Transmitted
beam θ beam

Detector
 THE ORIGIN OF LIGHT SCATTERING
Z
λ E0

time

LIGHT AS AN OSCILLATING ELECTRIC FIELD

Classical description -
The electric field of
P
The incident light induces
θz Oscillations of the
Electrons in the molecule,
θ
So that the molecule now
x Emits light in all directions
Incident beam polarized
in the zx plane

y
SCATTERING FROM A GAS

FOR SCATTERING FROM A BUNCH

OF RANDOMLY LOCATED OSCILLATORS

. .
.
.
. .

( ) ( ) ( )
4
N I0 8π
( α2 ) 1 + cos2θ
i'θ = (10.46)
V 4
r2
λ

# scatterers Polarizability
per unit volume
Geometry of
Characteristics of observation
the incident beam