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Macrolab:DilutesolutionViscosity

MolecularWeightDeterminationByDiluteSolutionViscosityMeasurements
Objectives
1. Determineintrinsicviscositiesforapolymersolventsystem.
2. DetermineMarkHouwink"K"and"a"valuesforapolymersolventsystem.
3. Determinemolecularweightofanunknownpolymerusing"K"and"a"values.
Introduction
Allpolymersincreasetheviscosityofthesolventinwhichtheyaredissolved.Thisincrease
allowsforaconvenientmethodofdeterminingthemolecularweightofpolymers.Sincethe
viscositymethodisnotbasedonrigorousphysicallaws,itmustbecalibratedbystandardsof
knownmolecularweightwithnarrowmolecularweightdistributions.
Severalimportantviscosityfunctionsareusedinviscositystudies.Therelativeviscosity,r
=/o,isthedimensionlessratioofsolutionviscosity,,tosolventviscosity,o.The
specificviscosity,sp=(o)/o,isrelatedtothefluidviscosityincreaseduetoall
polymersolutemolecules.Thereducedviscosity,red=sp/c,isthefluidviscosity
increaseperunitofpolymersoluteconcentration,c.Theintrinsicviscosity,[]isthelimit
ofthereducedviscosityasthepolymersoluteconcentrationapproacheszero.Theintrinsic
viscosityisalsothelimitoftheinherentviscosity,ln(/o),asthesolutionpolymer
concentrationapproacheszero.

Extrapolationtozeropolymerconcentrationisintendedtoeliminatepolymerintermolecular
interactions.Whenthepolymerconcentrationisexpresseding/dl,theunitsof[]willbe
dl/g.TheplotsusedtofindtheintrinsicviscosityarecalledtheHugginsplot(redvs.c)
andtheKraemerplot(ln(/o)vs.c).AsshowninFigure1,thecurvesofbothplots
shouldbelinearandhaveacommoninterceptthatistheintrinsicviscosity.

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Figure1:TypicalHugginsandKraemerPlots(notecommoninterceptforbothcurves)
Theintrinsicviscosity(alsotermedthelimitingviscositynumber)shouldbeindependentof
thefluidshearrate.Inotherwords,thesolutionviscositiesmeasuredandusedtofindthe
intrinsicviscosityintheHugginsorKraemerplotsmustbethe"zero"shearviscosities
determinedinthelowshearorfirstNewtonianregionsofflowcurves.Aflowcurveisaplot
ofapparentfluidviscositiesversusshearrate.Eachflowcurveisexperimentallydetermined
usingafixedpolymerconcentration.Ifthepolymersolutionconcentrationsarelowandthe
polymermolecularweightsarealsolow,thenthesolutionviscositiesmeasuredfortheflow
curveareconstantorindependentoftheshearrate.Thesolutionviscositiesmeasuredunder
theseconditionsarefirstNewtonianviscositiesorthezeroshearviscosities.However,as
thepolymerconcentrationincreasesand/orthepolymermolecularweighincreases,theflow
curvesbecomesheardependentornonNewtonian.Usually,fornonNewtonianpolymer
solutionstheapparentsolutionviscositydecreasesastheshearrateincreases.Thistypefluid
isusuallyreferredtoasshearthinningorpseudoplasticfluidflowbehavior.SeeFigure2.To
minimizetheunwantedshearthinningeffect,itisdesirabletooperateaviscometeratlow
shearrates.

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Figure2:TypicalFlowCurve(notethatasthemolecularweightdecreases,shearthinning
behaviorstartsatgreatershearrates)
Frompolymerdilutesolutionviscosityexperiments,manymacromolecularcharacteristicsof
apolymercanbedeterminedsuchasmolecularweightandcertainpolymerhydrodynamic
dimensions.Theseexperimentsarenottimeconsuminganddonotrequireexpensive
equipment.
Theintrinsicviscositymeasuredinaspecificsolventisrelatedtothemolecularweight,M,
bytheMarkHouwinkequation.
[]=KMa
whereKandaareMarkHouwinkconstantsthatdependuponthetypeofpolymer,solvent,
andthetemperatureoftheviscositydeterminations.Theexponentaisafunctionof
polymergeometry,andvariesfrom0.5to2.0.Theseconstantscanbedetermined
experimentallybymeasuringtheintrinsicviscositiesofseveralpolymersamplesforwhich
themolecularweighthasbeendeterminedbyanindependentmethod(i.e.osmoticpressure
orlightscattering).Usingthepolymerstandards,aplotofthelog[]vslogMusuallygives
astraightline.Theslopeofthislineisthe"a"valueandtheinterceptisequaltothelogof
the"K"value.SeeFigure3.

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Figure3:TypicalMarkHouwinkPlot(notethatthefitlineslopeistheavalue)
Thefactthattheintrinsicviscosityofagivenpolymersampleisdifferentindifferent
solventsgivesoneinsightintothegeneralshapeofpolymermoleculesinsolution.Along
chainpolymermoleculeinsolutiontakesonasomewhatkinkedorcurledshape,
intermediatebetweenatightlycurledmass(coil)andarigidlinearconfiguration.All
possibledegreesofcurlingmaybedisplayedbyanyonemolecule,buttherewillbean
averageconfigurationwhichwilldependonthesolvent.Inagoodsolvent,onethatshows
azeroornegativeheatofmixingwiththepolymer,themoleculeisfairlylooselyextended,
andtheintrinsicviscosityishigh.TheMarkHouwink"a"constantiscloseto0.75orhigher
forthese"good"solvents.Ina"poor"solvent,onethatshowsapositiveheatofmixing,
segmentsofapolymermoleculeattracteachotherinsolutionmorestronglythantheyattract
surroundingsolventmolecules.Thepolymermoleculeassumesatighterconfiguration,and
thesolutionhasalowerintrinsicviscosity.TheMarkHouwink"a"constantiscloseto0.5in
"poor"solvents.Forarigidorrodlikepolymermoleculethatisgreatlyextendedinsolution,
theMarkHouwinkaconstantapproachesavalueof2.0.
Thisexperimentallowsstudentstocarryoutclassiccapillaryviscosityexperimentson
polymerstandardstodetermineMarkHouwinkconstants.Theseconstantsarethenusedto
determinetheviscousaveragemolecularweightofanunknownpolymer.
Experimental
1. Selectoneoftheaqueouspolyethyleneoxide(PEO)solutionsprovided.Several
solutionshavebeenmadeusingdifferentpolymermolecularweightsandatdifferent
concentrations.Recordthespecificationsofthepolymersolutionyouselected.
2. Pourintoaworkingcupabout25mLoftheselectedpolymersolution.Usethisfluid
tomaketheviscositymeasurementsexplainedbelow.
3. CannonFenskeOperatingInstructions:(SeeFigure4andTableI)
a. SelectaCannonFenskeviscometerthatwillgiveaeffluxflowtimegreaterthan
200secortheminimumtimespecifiedinTableI,shownbelow.TheMathCad
worksheet"PEO_Solution_Viscosities.mcd"canbeusedtohelpdeterminethe
appropriateviscometersize.SeeAppendixA.YouwillutilizeaNo.25size
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CannonFenskeviscometerforallsolutions
usedthisexperiment.Cleantheviscometerwith
suitablesolvents(waterandacetone)andblow
dry,clean,filterednitrogengasthrough
viscometertoremovealltracesofsolvent.
b. Introducethefluidsamplefromtheworking
cupintotheviscometerbypipetting10mlinto
TubeL.
c. Placetheviscometerinaconstanttemperature
bath.Mounttheviscometeruprightinthebath
keepingTubeLvertical.Allowtime(about15
minutes)forthesamplefluidtoattainbath
temperatureandbecomefreeofairbubbles.
d. ApplysuctiontoTubeNorpressuretoTubeL
toforcethefluidsampleintoBulbDabout2
cmaboveuppertimingMarkE.
e. Removethepressureorvacuumandallowthe
fluidsampletoflowdownthroughCapillaryR
bytheforceofgravity.Measuretheeffluxtime,
tothenearest0.1second,requiredforthe
leadingedgeofthefluidmeniscustopassfrom
timingMarkEtotimingMarkF.Iftheefflux
timeislessthantheminimum(250secforthe
No25viscometer),selectasmallersizecapillaryviscometerandrepeatstepsa
throughe.
f. Repeatstepsdandemakingatleastthreemeasurementsofthefluideffluxtime.
Thereadingshouldagreetowithin0.1%oftheaverageflowtime.Ifflowtime
variationisnoted,repeateffluxtimemeasurementsixtimesandtakethe
averageofthreereadingsthatarewithin0.1%ofeachother.Recordtheefflux
times.Recallthatafluidseffluxflowtimeisproportionaltothefluids
viscosity.
4. Repeatsteps1through3forfoursolutionconcentrationshavingaconstantpolymer
molecularweight.
5. Repeatsteps1through4forasecondsetofmolecularweightpolymerstandard
solutions.
6. Repeatsteps1through4fortheunknownmolecularweightpolymersolutions.
7. Repeatstep3usingonlythesolvent(water).Theeffluxtimeforwaterisproportional
tothewatersviscosityatthetemperatureofthemeasurement.At20.2oCtheviscosity
ofwateris1.0000centipoise,at23oCtheviscosityis0.9358centipoise,andat25oC
theviscosityis0.8937centipoise.
TableI:PropertiesofCannonFenskeViscometers(seeFigure4)
Approximate
Size
Constant,
No.
cSt/s
25 0.002

Kinematic
Viscosity
Range,cSt
0.5Ato2

InsideDiameter
ofTubeR,
mm(+2%)
0.30

InsideDiameterof
TubesN,E,andP,
mm
2.6to3.0

Bulb
Volume,
ml(5%)
3.1 1.6

50

0.8to4

0.44

2.6to3.0

3.1

0.004

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75 0.008
100 0.015
150 0.035

1.6to8
3to15
7to35

0.54
0.63
0.78

2.6to3.2
2.8to3.6
2.8to3.6

3.1
3.1
3.1

3.1
3.1
3.1

200 0.1
300 0.25
350 0.5

20to100
50to250
100to500

1.01
1.27
1.52

2.8to3.6
2.8to3.6
3.0to3.8

3.1
3.1
3.1

3.1
3.1
3.1

400 1.2
450 2.5
500 8

240to1200
500to2500
1600to8000

1.92
2.35
3.20

3.0to3.8
3.5to4.2
3.7to4.2

3.1
3.1
3.1

3.1
3.1
3.1

600 20

4000to
200000

4.20

4.4to5.0

4.3

3.1

A250sminimumflowtimeforallotherunits.
Calculations
Makeatableofconcentration(g/100ml),effluxtime(sec.),/0,sp/c,andln(r/c).
Foreachmolecularweightpolymerstandard,plotsp/cvs.candln(r/c)onthesameplot.
Thereafteruseeachplottodeterminetheintrinsicviscosityofeachpolymerstandard.
Usingtheintrinsicviscositiesandthecorrespondingpolymermolecularweights,plotlog[]
vs.logMWandthenusethisplottodeterminetheMarkHouwinkKandaconstantsfor
thepolyethylenewatersystem.
Finally,calculatethemolecularweightoftheunknownPEOfromtheMarkHouwink
equationandtheintrinsicviscosityoftheunknown.
Discussion
Compareyourpolyethylenewatercalculated5andavalueswithreportedliteraturevalues
(SeePolymerHandbook).
Discusstheeffectofavariationinfluidtemperatureonsolutionviscosityfromamolecular
viewpoint.
Fromamolecularviewpoint,discussthesolutionviscositydifferencesyouwouldexpectina
goodsolventversususingapoorsolvent.
Discussanyexperimentalerrorassociatedwithmeasuringthesolutionviscosities.Doyou
haveanysuggestionsthatwouldreduceexperimentalerrororsimplifytheexperimentation?
DiscussyourestimateofthemolecularweightoftheunknownPEOsample.What
quantitativeconfidenceintervalwouldyoureportforthemolecularweightvalueyou
estimatedfortheunknownPEO?

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Copyright2001 |Dr.RogerHester|DepartmentofPolymerScience|UniversityofSouthernMississippi

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