PracticalConsiderationsforLightScattering

unfavourable Ideal() favourable

AdvantagesofLS
DisadvantagesofLS
LightScattering(Mw)
AdvantagesofGPC
DisadvantagesofGPC
PracticalConsiderationsforGPC
GPCCalibration UniversalCalibration
MeasurementMethodsforMolecularWeight
GelPermeationChromatography(Mn,Mw,andMz)
PolymerSolventInteractionImplications
IntroductiontoPolymers
PolymerStereoisomerism
MolecularWeight
MeasurementMethodsforMolecularWeight(cont)
AdvantagesofMO
DisadvantagesofMO
OsmoticPressure(Mn)
PracticalConsiderationsforMembraneOsmometry
0
th
ruleofpolymers :Thechemicalmakeupoftheatomiccompositionandconfigurationina
polymergreatlyaffectsthepolymerproperties
1
st
ruleofpolymers :Thelengthofthepolymerchainisthemostimportantvariable(i.e.MW)
2
nd
ruleofpolymers :Thelengthisnottheonlyfactorthatisimportant(eg.tacticity)
Polymers
Natural Polymers
cellulose
polysaccharides
natural rubber
DNA/Proteins
Synthetic Polymers
thermosets
thermoplastics elastomers
crystalline amorphous
isotactic syndiotactic
molecular
homopolymer copolymer
headtail
headhead
tailtail
isotactic syndiotactic atactic
isotactic cancrystalize
syndiotacticcanrystallizein1D
actacticcannotcrystallize
notenopolymercanfullycrystallize!
Mn
Mv
Mw
Mz
H = x H
0
H
n
=
N

H
w
=
N

2
N

H
z
=
N

3
N

2
H

=
N

1+u
N

1u
H
n
=

-1
H
w
=

H
H
z
=

=
H
w
H
n
_
= 1 monoJispcrsc
1.1 norrow bonJ
> 1.S brooJ bonJ
Dispersity
h

[
m
m
]
~
C
o
u
t
ElutionTime
H
n
=
b

H
w
=
b

H
z
=
b

2
b

Thecalibrationplotisspecificto
thepolymerunder study.Aplotof
Log(M)vs.retentionvolumeshould
beroughlylinear(assignment4).
pg.322
Gives thecompletemolecularwt.
distribution
Equipment isveryexpensive
Calibrationisrequired
It isessentialthatthesolventpumpsareabletogivepulsefreeflowrates
Pump mustbecapableofgeneratinghighpressures(414MPa)requiredtoforce
thesolventthroughthecolumn.
TheGPCunitistypicallyplacedinsideofanovensoitisisothermal.Alsohelps
toreducetheviscosityofsolventandtoassistindissolvingthepolymer.
Calibration requiredto
relateelutiontimeto
polymerMW.
Pure
Solvent
DilutePolymer
Solution
h
p
1
(I, P
0
)
o
p
1
(I, P
0
+n)
n = p
o
gb
p
o
n
CRI
=
1
H
n
+ A
2
C
n
CRI
C
1
Hn
A2
Smallcontaminantspass through
Nosimplifying modelorcalibrationisrequired
CanbeusedtoevaluatetheFloryHuggins
interactionparameter
LowMW polymersmaypassthroughmembrane
OnlygetMn
Canbedifficulttomeasurehfor largeMW
Inorderto minimizeequilibrationtimes(typically3060mins),cellsaresmallandmembrane
surfaceareaishigh
Sinceosmotic pressureissensitivetotemperature,goodtempcontrolisessential(0.01C)
IflowMWpolymerspassthroughmembrane,theycanimpacttheMnsignificantlysincethere
aremanyofthem...Thususingamoreretentivemembraneiswise.
assumeelastic
scattering( stays
thesame)
z =
c
u
I
0
I
o
=
8n
4
o
2
1 +cos
2
(0)
z
4
r
2
RayleighScattering SINGLE smallparticle
i
0
I
o
=
2n
2 Jn
Jc
,
2
H C 1 +cos
2
(0)
z
4
r
2
N
A
RayleighScattering DILUTEGASofsmallparticles
R =
i
0
r
2
I
o
1 + cos
2
(0)
RayleighRatio
R = R
soIuton
-R
soIcnt
ExcessRayleighRatio(liquids/solutions)
z =
z
o
n
K =
2n
2
n
o
2
Jn Jc
2
N
A
z
4
OpticalConstant
K C
R
0
=
1
H
w
+2A
2
C + SA
3
C
2
+ 1 +
16n
2
n
o
2
sin
2
(
0
2
)
Sz
2
s
2
z
Tryk'=0.1whenthe
unitsofCareg/dm
3
A
2
=
k
2
J KCR
0 00
J k
i
C
C0
s
2
z
=
Sz
2
H
w
16n
2
n
o
2
J KCR
0 C0
J sin
2
(
0
2
)
00
CanbeusedtoevaluatetheFloryHuggins
interactionparameter and<s
2
>
No calibrationisrequired
Gatherinformationregardingmolec.struct.
Samplemustbeveryclean(smallscatterers)
Equipmentisexpensive
Samplemustbethermostatted(0.01C)
Mustbeabletoprecisely measurethedetectedscatteringangleandlightintensity
Solventsthathaverefractiveindicessubstantiallydifferentthanthepolymershouldbe
chosensuchthatdn/dcisatleast0.0001dm
3
g
1
Solvent,standards,andsolutionsmustbeclarifeidviamicroporefiltrationtogetridofdust
p
1
H
1
= p
2
H
2
K
1
H
1
1+u
1
= K
2
H
2
1+u
2
ln H
2
=
1 +o
1
1 +o
2
ln H
1
+
1
1 +o
2
ln
K
1
K
2
wecangetMforANYpolymerbasedonGPC
calibration ofonlyonepolymeraslong
asweknowtheMarkHouwinkcoefficients
forbothpolymers
K C
R
0
LowT
r<1
>0.5
1
E
>0
A2<0
Med T()
r=1
=0.5
1
E
=0
A2=0
a=0.5
High T
r>1
<0.5
1
E
<0
A2>0
considerphasesep
FloryHugginsTheoryforPolymerSolutions
PolymerChainStatistics
FreelyJointedChainModel(f )
FixedBondAngleModel(fa )
HinderedRotationModel(o)
DiluteSolutionViscometry(Mv)
AdvantagesofSV
DisadvantagesofSV
PracticalConsiderationsforSV
ChainswithExcludedVolume(real)
PolymerSolutionThermodynamics
IdealSolutionsofIndenticalSmallMolecules
FloryHugginsTheoryforIdealPolymerSolutions
MeasurementMethodsforMolecularWeight(cont) PolymerChainStatistics(Continued)
p

=
p
p
o
,
relative viscosity
p
sp
=
p -p
o
p
o
specific viscosity
p
cd
=
p
sp
C
reduced viscosity
p
nh
=
ln (p

)
C
,
inherent viscosity
Intrinsic viscosity
p = lim
C0
p
cd
= lim
C0
p
nh
p = K(H

)
u
MarkHouwinkEquation
SeeTable 13.2pg.302
p
cd
=
p
sp
C
p
p
nh
=
ln p

C
C [gdm
3
]
H

=
p
K
c
Careful,Kandaaretemperature dependent!
p
sp
=
p -p
o
p
o
=
pt -p
o
t
o
p
o
t
o

t -t
o
t
o
Veryfastmeasurement
Veryinexpensive
Good forroutineanalysis
smallimpurities don'taffectresultmuch
ThemolecularweightMviskindofhokey
Needcalibration,constantsareafunctionof
polymer/solventandtemperature
Cannotbecalculateddirectlyfromtheory
Pressureheaddependent onvolumeofsolutioninthe
viscometer initialvaluemustbeexactlythesamefor
eachrun.
ViscometerMUSTbethoroughly cleanotherwise
erraticflowtimescanbeanticipated.
Viscometershouldbethermostatted(0.01C)since
viscosityittempdependent
Measurementsofflowtimeshouldbereproducibleto
~0.1%whenmeasuredvisuallywithastopwatch
p
cd
= p +K
H
p
2
C p
nh
= p + K
k
p
2
C
KH HugginsConstant Kk Kramer Constant
K
H
- K
K
= u.S
Ifthisrelationdoesnothold,itindicatesthat
theparticlescannotbemodelledasnoninteracting
spheres>Polymeragglomeration/ionicinteraction
p H
w
3.4
ruleofthumb
r
2
= _ r
2
w r Jr

0
w x, y, z = P x, y, z JxJyJz
w r Jr = w x, y, z 4nr
2
_ w r Jr = 1

0
x y
z
W(r)
contour lcngtb = nl
w r = 4n
[
n
3
r
2
cxp -[
2
r
2
[ =
S
2nl
2
12
r
2
]
12
= n l
s
2 12
=
r
2 12
6
x
2
=
r
2

ow(r)
or
= u
Mostprobable r
=109.5
r
2
]u
= nl
2
1 -cos 0
1 +cos 0
lc-c=0.154nm
bondscanfreelyrotateabouta
fixedangle(valenceangle)
r
2
o
= nl
2
1 -cos 0
1 +cos 0
1 +cos
1 -cos
r
2
o
= o
2
nl
2
1 - cos 0
1 + cos 0
Table10.3pg259
C

=
r
2
o
r
2
]
=
r
2
o
nl
2
Characteristic Ratio
Thecharacteristicratioisa
functionoftemperature. Higher
valuesofC denotehigher
polymerstiffness.
highstiffness=>hightransitions
r
2
cuI
= o

r
2
o
Chainexpansionfactor
o

1
r
2
cuI
= o

2
r
2
o
= o

2
C

nl
2
GetnfromMWexperiments
s
2
cuI
= o
s
2
s
2
o
applies
generally!
Assumptions:1)Themoleculeshaveidenticalsize2)Molecularinteractionsareindistiguishable
0
m
= E
m
-IS
m
0(assumption2)
0
m
= -IS
m
comb
S
m
comb
= -R n
1
ln x
1
+n
2
ln x
2
S
m
comb
= k
B
ln
12

12
=
N
1
+N
2
!
N
1
! N
2
!
0
m
= RI n
1
ln x
1
+n
2
ln x
2
kB=1.38e23J/K
ln N! = N ln N -N
StirlingApproximation
Assumptions:1)Eachpolymersegmentissamesizeassolventmolecules2)Molecularinteractionsareindisguisable
x
s
=
Polymcr Hw
Sol:cnt Hw
# ofSegments
0
m
= E
m
-IS
m
0(assumption2)
S
m
comb
= k
B
ln
12
- ln
1
+ ln
2 1> solvent
2>polymer
0(one microstate)

1
=
N
1
N
1
+x
s
N
2
2
=
N
2
N
1
+x
s
N
2
S
m
comb
= -R n
1
ln
1
+n
2
ln
2
k
B
=
R
N
A
0
m
= RI n
1
ln
1
+n
2
ln
2
x=molefraction
=volumefraction
N number ofmolecules
n numberofmoles
Assumptions:1)Eachpolymersegmentissamesizeassolventmolecules2)NearestNeighbourInteractionsOnly
g
12
= g
12
-|g
11
+g
22
]
0
m
contuct
E
m
p
12
g
12
p
12=
z -2 N
1

2
= z -2 x
s2
N
2

1
Introduce theFloryHugginsSolutionParameter
_ =
(z -2)g
12
kI
zero forathermalmixing
positiveforendothermicmixing
negativeforexothermicmixing
0
m
= E
m
-IS
m
0
m
totuI
= RI|n
1
ln
1
+n
2
ln
2
+n
1

2
_]
0
m

RI
= |
1
ln
1
+

2
x
s
ln
2
+
1

2
_]
entropicpart enthalpicpart
-
S
m

R
E
m

RI
x
s
=
Hw
PoImc
Hw
soIcnt
_
H
=
I
1
o
1
-o
2
2
RI
_ = _
H
+_
S
See page252for
solubilityparams

S
0.2
0
1
=
o0
on
1
_
P,1,n
]=i
= p
1
-p
1
o
= ln
1
+ 1 -
1
x
s

2
+_
2
2
0
1
=
o0
on
1
_
P,1,n
]=i
= p
1
-p
1
o
= -RI ln

2
x
s
+RI(_ - u.S)
2
2
ln
1
= ln 1 -
2
= -
2
-
q2
2
2
+...
Thesevaluesareforathetasolvent??