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Lecture5 PDF
Lecture5 PDF
Lecture5 PDF
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.
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
( sp )i
η = [η ] c
i i
+ k H [η ] c
i i
2
2
≅ [η ] c
i i
= KM a
i ci
ηsp = K ∑ i Mia ci
Intrinsic Viscosity and Molecular Weight
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
a
[η] = KM v
[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
π RT
lim(c → 0) =
c Mn
π = RT 1 + A c + A c 2 + L
c 2 3
Mn
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