Chemical Engineering 160/260

Polymer Science and Engineering

Lecture 5 - Indirect Measures of
Lecture 5 - Indirect Measures of
Molecular Weight: Intrinsic Viscosity
Molecular Weight: Intrinsic Viscosity
and Gel Permeation Chromatography
and Gel Permeation Chromatography
J anuary 26, 2001
J anuary 26, 2001
End-to-end Distance of a Random Coil
r
In general, we will express the end-to-end distance in terms
of the root-mean-square statistical average.
r
2 1 2 /
Freely Jointed Model Polymer Chain:
Mean-squared End-to-end Distance

r
r
r l
i
i
n
=
=

1

r r r l l l l l
i j
i j
i
i
i j
i j n
2 2
0
2 = = = +

< <
r r
r r r r
,

= +

< <
r l l l
i
i
i
i j n
j
2
2
0
2
r r

= + =
<

r nl l l nl
i
i j
j
2 2 2
2
r r

r
r
Average over all
configurations.
There is no bond
correlation.
Vector sum
Outline
! ! Definitions Definitions
! ! Equivalent sphere and Einstein relationship Equivalent sphere and Einstein relationship
! ! Effect of concentration Effect of concentration
! ! Mark- Mark-Houwink Houwink-Sakurada equation -Sakurada equation
! ! Gel permeation chromatography Gel permeation chromatography
! ! Molecular weight summary Molecular weight summary
Definitions
Relative viscosity
Specific viscosity
Reduced viscosity
Inherent viscosity
Intrinsic viscosity

rel
o o
solution
solvent
t solution
t solvent
= =
( )
( )
( )
( )

sp
o
o
rel
solution solvent
solvent
=

=
( ) ( )
( )
1

inh
rel
c
=
ln

red
sp
c
=

sp
c
c
|
|
|
|
|
|

[ ]
=0
Equivalent Sphere
Einstein Relationship
= +
[ ]
o
1
For a suspension containing volume fraction of suspended
material with shape factor , Einstein found that
where is the viscosity of the suspension and
o
is the
viscosity of the suspending fluid. For a sphere or
random coil, = 2.5.
If the polymer is treated as an equivalent hydrodynamic
sphere with volume V
e
and radius R
e
we obtain

sp
p
e
n
V
V =
[
\
|

)
j
2 5 .
V R
e e
=
[
\

)
4
3
3

n
V
cN
M
p
A
v
=

sp
c
A e
v
c
N V
M
|
|
|
|
|
|

[ ]
=
=0
2 5 .
Excluded Volume
That portion of the solution volume that is inaccessible to
polymer chain segments due to prior occupancy by other
chain segments is known as the excluded volume.
As a consequence of the volume exclusion, the overall
spatial dimensions of a real polymer chain must increase
relative to those predicted by the simple chain models.
One can compensate for chain expansion due to excluded
volume through placing the polymer in a poor solvent
such that interactions between polymer segments and
solvent molecules are thermodynamically unfavorable.
Such a solvent, at a given temperature, is a theta solvent.
Excluded Volume of a Flexible Chain
= r r
o
2 2 2

= expansion factor
For large ,
M
0 10 .
Effect of solvent on chain dimensions:
Good solvent - chain expansion
Poor solvent - chain contraction
Theta solvent - chain contraction exactly compensates
for excluded volume effect
=
=
r r
o
2 2
1
A
2
= 0 for theta solvent
Expansion Factor
V
M
R
M
R
M
M
e
v
e
v
e
v
v
= =
[
\
|

)
j
4
3
4
3
3 2
3 2
1 2

/
/
~ constant
Define an expansion factor for a coil in a good solvent
compared to a theta solvent.
R R
e eo
=

[ ]
=
[
\

)
[
\
|

)
j
2 5
4
3
2
3 2
1 2 3
.
/
/
N
R
M
M
A
eo
v
v

3
=
[ ]
[ ]

Interrelationships Among Parameters

For dilute solutions,

ln ln( )

rel sp sp
sp
= + + 1
2
2
L
ln

rel
c
c
|
|
|
|
|
|
=
[ ]
=0

sp
c
c
|
|
|
|
|
|

[ ]
=0
Compare this to
Effect of Concentration in Dilute Solution
Huggins Equation
Kraemer Equation
For many polymers in good solvents
k
H
= 0.4 +/- 0.1 k
K
= 0.05 +/- 0.05

sp
H
c
k c =
[ ]
+
[ ]
2
ln

rel
K
c
k c =
[ ]

[ ]
2
Intrinsic Viscosity and Molecular Weight
An empirical relationship that works well for correlating
intrinsic viscosities and molecular weights of fractionated
samples is the Mark-Houwink-Sakurada equation.

[ ]
=
i
i
a
KM
For a sample at infinite dilution,

sp
i
i
i H
i
i
i
i i
a
i
c k c c KM c
( )
=
[ ]
+
[ ]

[ ]
=
2
2

sp i
a
i
i
K M c =

For the unfractionated solution,
Intrinsic Viscosity and Molecular Weight
The observed intrinsic viscosity may be obtained from

[ ]
=
|
|
|
|
|
|
=
[
\

)

lim( ) c
c
K M
c
c
sp
i
a
i
i
0
Since
c
c
c
c
i i
i
i
=

the weight ratio is

w
w
w
w
i i
i
i
=

[ ]
= =

K w M
w
K WM
i i
a
i
i
i
i
i
i
a
and
Viscosity Average Molecular Weight
M WM
v i i
a
i
a

( )

1/
Define the viscosity average molecular weight by

[ ]
= KM
v
a
The intrinsic viscosity then is related to molecular weight by
Typically, 0.5 < a < 0.8 for flexible polymers, with
a = 0.5 for theta conditions and increasing with
increasing solvent quality. Also, a = 1 for semicoils
and a = 2 for rigid rods.
Mark-Houwink-Sakurada Parameters
Polymer Solvent Temp. Mol. Wt. 100K a
PMMA
chloroform 25 C 80,000-
1,400,000
0.48 0.80
methyl
ethyl
ketone
25 C 80,000-
1,400,000
0.68 0.72
acetone 25 C 80,000-
1,400,000
0.75 0.70
PS
benzene 20 C 1,200-
140,000
1.23 0.72
toluene 20-30 C 20,000-
2,000,000
1.05 0.72
methyl
ethyl
ketone
20-40 C 8,000-
4,000,000
3.82 0.58
Gel Permeation Chromatography
A mixture of different size solute molecules is eluted
through a column of porous particles. Larger molecules
are swept through unhindered, while small molecules
are retarded in the pores.
GPC Calibration

sp
c
A e
c
N V
M
|
|
|
|
|
|

[ ]
=
=0
2 5 .
The relationship between intrinsic viscosity and hydrodynamic
volume is the basis for a universal calibration procedure.
ln ln . ln lim( )
[ ] ( )
=
( )
+
[ ]
M N c V
A e
2 5 0
Ve
[]M
GPC Calibration
For equal elution volumes of two different polymers,

[ ]
= =
[ ]
=
+ +
1
1 1 1
1
2
2 2 2
1
1 2
M K M M K M
a a
ln ln ln M
a
a
M
a
K
K
2
1
2
1
2
1
2
1
1
1
1
=
+
+
+
+
[
\
|

)
j

[ ]
=
+
i
i i i
a
M K M
i
1
Use the Mark-Houwink-Sakurada relation
Molecular Weight Summary: Averages
M WM
v i i
a
i
a

( )

1/
M
c
c
M
w
M
n
i
i
i
i
i
i
i
i
= =

1
M
c M
c
n M
n M
w
i i
i
i
i
i i
i
i i
i
= =

2
M
n M
n M
z
i i
i
i i
i
=

3
2
M
n M
n
n
i i
i
i
i
=

M M M M
z w v n
> > >
Molecular Weight Summary:
Most Probable Distribution
x
x
M
M
p
w
n
w
n
= = + 1 2
x x p p
p
p
w
x
x
=
( )
=
+

2 1
2
1
1
1
x xp p
p
n
x
x
=
( )
=

1
1
1
1
N p p
x
x
=
( )
1
1
W xp p
x
x
=
( )
1
2
1
Molecular Weight Summary: Osmometry
lim( ) c
c
RT
M
n

|
|
|
|
|
|
= 0

c
RT
M
A c A c
n
|
|
|
|
|
|
= + + +
[
\
|

)
j
1
2 3
2
L
Under theta conditions, A
2
= 0. For a particular polymer,
the temperature at which this occurs depends on the solvent.
Mean-squared Radius of Gyration
s
ms
m
m s
m n n
s
i i
n
i
n
i
n
i
n
2
2
0
0
2
0
2
0
1
1
1
= =
+
=
+

( )
A
1
A
n
A
o
A
n-1
A
n-2
s
1
s
n
s
n-2
s
0
s
n-1
Center of mass
s R
g
2 1 2 /
Molecular Weight Summary:
Light Scattering
Hc
R M
A c
w
( )

|
|
|
|
|
|
= +
=0
2
1
2

Hc
R M
R
c o
w
g
( )
sin

|
|
|
|
|
|
= +
[
\

)
[
\

)
+
|
|
|
|
|
|
=
1
1
1
3
4
2
2
2 2
L
R
I w
I V
o s
( )

=
2
H
n
dn
dc
N
o
A
=
[
\

)
2
2 2
2
4

Hc
R RT c
T
( )

=
[
\
|

)
j
1
Molecular Weight Summary:
Intrinsic Viscosity

[ ]
= KM
v
a

sp
o
o
rel
solution solvent
solvent
=

=
( ) ( )
( )
1

sp
c
c
|
|
|
|
|
|

[ ]
=0
Molecular Weight Summary:
Gel Permeation Chromatography

sp
c
A e
c
N V
M
|
|
|
|
|
|

[ ]
=
=0
2 5 .