Chemical Engineering 160/260

Polymer Science and Engineering

Lecture 5 - Indirect Measures of
Molecular Weight: Intrinsic Viscosity
and Gel Permeation Chromatography
January 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.
2 1/ 2
〈r 〉
 Freely Jointed Model Polymer Chain:
Mean-squared End-to-end Distance

r n r
r = ∑ li Vector sum
r i =1
r
2 r r r r r r 2
r = r • r = ∑l • l = ∑l + 2 ∑l • l
i j i i j
i, j i 0<i < j ≤n

r r
2
Average over all 2
〈 r 〉 = ∑ 〈li 〉 + 2 ∑ 〈li • l j 〉
configurations. i 0<i < j ≤n

r r
〈 r 〉 = nl + 2 ∑ 〈li • l j 〉 = nl 2
2 2 There is no bond
i< j correlation.
 Outline

! Definitions
! Equivalent sphere and Einstein relationship
! Effect of concentration
! Mark-Houwink-Sakurada equation
! Gel permeation chromatography
! Molecular weight summary
 Definitions
η( solution) t ( solution)
Relative viscosity ηrel = =
ηo ( solvent ) to ( solvent )

η(solution) − ηo (solvent )
Specific viscosity ηsp = = ηrel − 1
ηo (solvent )
ηsp
Reduced viscosity ηred =
c
ln ηrel
Inherent viscosity ηinh =
c

 ηsp 
Intrinsic viscosity  c  ≡ [η]
 c = 0
Equivalent Sphere
 Einstein Relationship
For a suspension containing volume fraction φ of suspended
material with shape factor ω, Einstein found that
η = ηo [1 + ωφ ]
where η is the viscosity of the suspension and ηo is the
viscosity of the suspending fluid. For a sphere or
random coil, ω = 2.5.
If the polymer is treated as an equivalent hydrodynamic
sphere with volume Ve and radius Re we obtain

 np  n p cN A  4π  3
ηsp = 2.5  Ve = Ve = Re
V V Mv  3
 ηsp  2.5 N AVe
 c  ≡ [ ]
η =
 c = 0 Mv
 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
2 2 2
〈r 〉 = α 〈r 〉o
α = expansion factor
0.10
For large α, α ∝M
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 2 〉 = 〈r 2 〉o A2 = 0 for theta solvent

α =1
 Expansion Factor
3/ 2
3 2
Ve 4π R 4π  R 
= = e
 
e
Mv1 / 2
Mv 3 Mv 3  Mv 
~ constant
Define an expansion factor for a coil in a good solvent
compared to a theta solvent.
Re = Reoα
3/ 2
2
 4π   R  1/ 2 3
[η] = 2.5  N A   eo
M v α
3  Mv 

α 3
=
[η]
[η]Θ
 Interrelationships Among Parameters
For dilute solutions,

ηsp2
ln ηrel = ln(ηsp + 1) ≅ ηsp − +L
2

 ln ηrel  = η
 c  c = 0 [ ]

 ηsp 
 c  ≡ [η]
Compare this to
 c = 0
Effect of Concentration in Dilute Solution
Huggins Equation ηsp 2
= [η] + kH [η] c
c

Kraemer Equation
ln ηrel 2
= [η] − kK [η] c
c
For many polymers in good solvents
kH = 0.4 +/- 0.1 kK = 0.05 +/- 0.05
 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.
a
[η]i = KM i

For a sample at infinite dilution,

( sp )i
η = [η ] c
i i
+ k H [η ] c
i i
2
2
≅ [η ] c
i i
= KM a
i ci

For the unfractionated solution,

ηsp = K ∑ i Mia ci
Intrinsic Viscosity and Molecular Weight

The observed intrinsic viscosity may be obtained from

 ηsp  a  ci 
[η] = lim(c → 0)  = K ∑i Mi  
 c  c
ci ci wi wi
Since = the weight ratio is =
c ∑i ci w ∑i wi
K ∑ i wi Mia
and [η] = = K ∑ i Wi Mia
∑w i i
 Viscosity Average Molecular Weight
Define the viscosity average molecular weight by
1/ a
Mv ≡ (∑ W M )
i i i
a

The intrinsic viscosity then is related to molecular weight by

a
[η] = KM v

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- 0.48 0.80
1,400,000
methyl 25 C 80,000- 0.68 0.72
ethyl 1,400,000
ketone
acetone 25 C 80,000- 0.75 0.70
1,400,000
PS benzene 20 C 1,200- 1.23 0.72
140,000
toluene 20-30 C 20,000- 1.05 0.72
2,000,000
methyl 20-40 C 8,000- 3.82 0.58
ethyl 4,000,000
ketone
 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
The relationship between intrinsic viscosity and hydrodynamic
volume is the basis for a “universal” calibration procedure.

 ηsp  2.5 N AVe

 c  ≡ [η] = M
 c = 0

ln([η]M ) = ln(2.5 N A ) + ln[lim(c → 0)Ve ]

[η]M

Ve
 GPC Calibration
Use the Mark-Houwink-Sakurada relation
a i +1
[ ]i i i i
η M = K M
For equal elution volumes of two different polymers,
a1 +1 a 2 +1
[η]1 M1 = K1 M 1 = [η]2 M2 = K2 M 2

1 + a1 1  K1 
ln M2 = ln M1 + ln 
1 + a2 1 + a2  K2 
Molecular Weight Summary: Averages

∑i ni Mi Mn =
∑ c i i
=
1
Mn = c wi
∑n i i ∑M i
i
∑i M
i i

2 3

Mw =
∑i ci Mi =
∑i i i
n M
Mz =
∑ nM i i i

∑i ci ∑i ni Mi ∑ nM i i i
2

1/ a
Mv ≡ (∑ W M )
i i i
a

M z > M w > Mv > Mn

 Molecular Weight Summary:
“Most Probable” Distribution
x −1 2
Nx = p (1 − p) Wx = xp x −1
(1 − p)
x −1 1
xn = ∑ x xp (1 − p) =
1− p
2 x −1 2 1+ p
xw = ∑ x x p (1 − p) =
1− p
x w Mw
= =1+ p → 2
x n Mn
 Molecular Weight Summary: Osmometry

 π  RT
lim(c → 0)  =
 c  Mn

 π  = RT  1 + A c + A c 2 + L
 c   2 3 
 Mn 

Under theta conditions, A2 = 0. For a particular polymer,

the temperature at which this occurs depends on the solvent.
 Mean-squared Radius of Gyration
Ao
A n-2
A1
s1 s0
sn-2
sn Center of mass
sn-1
An
A n-1

n n
2
∑ ii
m s m ∑ si 2 n
2 1 2 〈 s 2 〉1 / 2 ≡ Rg
s = 0
n = 0
= ∑
m(n + 1) n + 1 0
si

∑m 0
i
 Molecular Weight Summary:
Light Scattering

2
Iθ w2 2 dn 
2 Hc 1  ∂π 
R(θ ) = 2π n o
 dc  =  
IoVs H= R(θ ) RT  ∂c  T
N A λ4

 Hc  1
 R(θ )  = M + 2 A2 c
 θ = 0 w

2
 Hc  1  1  4π  2 2  θ  
 R(θ )  = M 1 + 3  λ© Rg sin  2  + L
 c = o w  
 Molecular Weight Summary:
Intrinsic Viscosity

η(solution) − ηo (solvent )
ηsp = = ηrel − 1
ηo (solvent )

 ηsp 
 c  ≡ [η]
a
 c = 0
[η] = KM v
 Molecular Weight Summary:
Gel Permeation Chromatography

 ηsp  2.5 N AVe

 c  ≡ [η] = M
 c = 0