8/10/2016

AnalyzingWaterinOil

AnalyzingWaterinOil
MichaelSternandLarryGirdler,EMDChemicals,Inc.
Tags:waterinoil,oilanalysis

PracticingOilAnalysis(1/2007)

Highwatercontentoflubricatingoilsnegativelyimpactstheoperationandlongevityoftheoilsandthe
mechanicalequipmentcomponentsbeinglubricated.Waterincreasestheoxidationrateofoils,thus
prematurelyusinguptheoils
oxidationinhibitors.Additionally,waterhasbeenknowntocausecertainoiladditivestoprecipitateout,
aswellastochemicallyattacksomeadditives.Someofthemodesbywhichwaterexistsinlubricating
oilscanleadtocatastrophicequipmentfailure.Theseincludecorrosion,erosion,etchingandhydrogen
embrittlement.
Waterinoilscanoccurindissolved,emulsifiedandfreestates.Visualindicationisreliablefor
quantifyingwatercontentonlyinthefreestate,whilethehotplatecrackletestcanbeusedtodetect
freeandemulsifiedwater.However,neitherofthesemethodscandetectdissolvedwateror
reproduciblydetecttracelevelsofemulsifiedwater.Furthermore,neithervisualindicationnorthehot
platetestcanbeusedtoreliablyquantifythewaterpresent.Distillationmethods,suchasASTMD95
andD4006providebetterquantitativedataintherangeofapproximately500ppmto25percent,but
requirelargesamplesizesandinvolvelonganalysistimes,typically60to110minutes.
SinceitsinventionbyGermanpetroleumchemistDr.KarlFischerin1935,KarlFischer(KF)analysis
hasprogressedfromanesotericlaboratoryproceduretoawidelyacceptedinstrumentalmethod
routinelyusedforwaterdeterminationinthepetrochemicalindustry.Itisestimatedthatnearly
500,000KFdeterminationsareperformeddailyaroundtheworld.Themethodformsthebasisof
severalcommonlyusedASTMstandardsforwaterdeterminationinoils,includingASTMD1533,D1744,
D4377,D4928andD6304.TheKFmethoddoesnotsufferfromthesameissuesandlimitations
associatedwiththeothertechniquesdescribedabove,andanumberofrecentadvancesintitrator
instrumentationandreagentformulationshavefurtherimprovedtheaccuracyandreproducibilityofKF
analyses.

ChemistryandPrinciples
KarlFischertitrationproceedsaccordingtoareactionwithatwostepmechanisminwhichsulfur
dioxideinitiallyreactswithanalcohol(ROH)toformanesterintermediatewhichisneutralized,or
buffered,byanappropriateorganicbase(RN).Thesubsequentoxidationofthealkylsulfitesalttoan
alkylsulfatesaltbyiodineconsumeswaterina1:1ratiotoiodine,thusmakingthequantificationof
waterpossible.Thefollowingreactionsrepresentthistwostepmechanism.
ROH+SO2+RN(RNH)SO3R
(RNH).SO3R+2RN+I2+H2O+(RNH)SO4R+2(RNH)I
TheendpointdeterminationinKFtitrationoccursbymeansofbivoltametricindication.Thatis,while
theiodineintheKFreagentisreactingwithwater,thereisnofreeiodinepresentinthetitrationcell,
andahighvoltageisrequiredtomaintainthesetpolarizationcurrentatthedoubleplatinumpin
indicatorelectrode.Onceallthewaterhasreactedwiththeiodine,tracequantitiesoffreeiodine
appearinthetitrationcell,causingadropinvoltagenecessarytokeepthepolarizationcurrent
constant,whichinturnsignalstheendpointofthetitration.

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TypesofTitration
VolumetricKF
VolumetricKFproceedsintheconventionalmannerofaclassictitration,inthatthetitrantcontaining
iodineisaddedmechanicallytothesolventcontainingthesamplebythetitrator'sburette(Figure1).
ThetwotypesofvolumetricKFdifferintheexactcompositionoftitrantandsolvent.Inonecomponent
KF,thetitrant(usuallyreferredtoasaCombiTitrantoracomposite)containsalltheingredients
neededfortheKFreaction,namelyiodine,sulfurdioxide,baseandasuitablealcohol,whilethesolvent
istypicallydrymethanol.IntwocomponentKF,thetitrantcontainsonlyanalcoholicsolutionofiodine,
whilethesolventcontainstheotheringredientsneededforthereaction.Withbothtypesofvolumetric
KF,imidazoleisthebaseusedmostfrequentlyasabuffertomaintainoptimalpHforthereaction.
ThemostwidelyusedstandardmethodsbasedonvolumetricKFareASTMD1533(MethodA),D1744
andD4377.VolumetricKFismostaccurateintherangeof500ppmto100percentwater.

Figure1.KeyComponentsofaModernVolumetricKFTitrator

CoulometricKF
IncoulometricKF,theiodineneededbytheKFreactionisnotpresentintheKFreagent,butisinstead
generatedelectrochemicallyinsitufromiodideattheanodeofthegeneratorelectrode,acomponentof
thecoulometrictitrationcell(Figure2).Correspondingreductionofhydridetohydrogentakesplaceat
thecathode.Incoulometry,thequantityofiodinegeneratedcorrespondingtotheamountofwater
presentiscalculatedbythetitratoronthebasisofcurrent(mA)andtime(sec).CoulometricKFis
consideredanabsolutemethodbecausetimeandcurrentcanbothbeaccuratelymeasured.Themost
widelyusedstandardmethodsbasedoncoulometricKFareASTMD1533(MethodB),D4928andD6304
(MethodA).CoulometricKFismostaccurateintherangeof1ppmto5percentwater.

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Figure2.KeyComponentsofaModernCoulometricKFTitrator

OilSampleChallenges
Solubility
IfasampledoesnotdissolvefullyduringKFanalysis,thenonlypartofthewatercontentwillbe
determined,leadingtoerroneouslylowresults.Oilshavelimitedsolubilityinalcohols,suchas
methanol,whicharetypicallyusedincommonKFreagentformulations,whiletheyarefullysolublein
organicsolventslikechloroform,tolueneandxylene.However,alcoholscannotbecompletelyremoved
fromKFreagents,becausethepresenceofalcoholisrequiredbythemechanismoftheKFreaction.
Reactivity
Certaincompoundsintheoilwillundergointerferingsidereactionseitherwithmethanoloriodine
componentsofKFreagents.Anumberoflubricatingoiladditivesarereactiveandareknownto
interferewithdirectKFtitration.Theseincludealdehydes,higherphenols,modifiedmercaptans,
ketoacids,polysiloxanes,sulfidesandmetaloxides.Usedoilsmayalsocontaincontaminantsthatcan
potentiallyinterferewithdirectKFanalysis,suchastracemetals,polyaromatichydrocarbons,
polychlorinatedbiphenyls,aswellasvariousproductsofincompletecombustion.
SampleSizeandReproducibility
Aswithanyanalyticaltechnique,thesamplingerrorinKFanalysisisinverselyproportionaltothe
samplesize.Inotherwords,thelargerthesample,thelesserrorisintroducedintotheanalysisby
sampleweighing,transferandotherhandling.However,duetosolubilityandreactivityissues
describedabove,analystsoftendrasticallyreducesamplesize,whichtendstoreducethe
reproducibilityoftestresults.

TechniquesforSuccessfulKFofOilSamples
DirectTitration
Samplesolubilityissuesmaybeovercomebyusingcosolventssuchaschloroform,tolueneorxylene
toincreasethesolventcapacityofconventionalKFreagentsinthetitrationcell.Alternatively,specially
preformulatedKFreagentsincorporatingoneorseveralofthesesolventsarecommerciallyavailable
forbothvolumetricandcoulometricKF.
ForthoseoilsampleswhichfailtoadequatelydissolveevenwhenusingKFreagentsformulatedwith
organiccosolvents,orthosethataresuspectedofcontaininginterferingcompounds,anindirectKF
analysisusinganoilevaporatorisrecommended,asdescribedbelow.

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Figure3.OilEvaporatorforIndirectKFAnalysisofOils
IndirectTitrationUsinganOilEvaporator
Theindirecttitrationmethodutilizesaspecialtyaccessory,theoilevaporator,whichisconnectedtoa
volumetricorcoulometricKFtitrator(Figure3).ThisinnovativeKFtechniqueisincorporatedinASTM
D6304(MethodB)andisapplicabletonearlyalloilbasedsamples.
Theprocedureinvolvesaddingtheoilsampletothesolventpresentintheevaporationchamberwhere
itdissolvesinthesolvent,andintheprocessformsabinaryazeotropebetweenthesolventandthe
sample'swatercontent.Thesolvent/samplemixtureisthenheatedtoneartheazeotropicpointand
keptatthattemperaturewhileadry,inertcarriergas,suchasnitrogen,isusedtocarrytheazeotropic
vaporintothetitrationcelloftheKFtitrator,wherethewatercontentisquantified.Thismethodthus
combinesthebestfeaturesofbothKFtitrationanddistillationtechniques,suchasASTMD95,because
theoilevaporatorissimplyaminiaturizedDean&Starkdistillationapparatus.Thedistillation
componentoftheindirecttitrationmethodensuresthatthehardtodissolveoilsamples,orthose
containingpotentiallyinterferingcompounds,arenotintroducedtothetitrationcell,whiletheKF
titrationcomponentofthemethodaccuratelyquantifiesthewatercontentoftheazeotropicvapor
carriedintothetitrationcellbythedrygas.
Additionally,becausetheoilevaporatorcontainsaminiaturizeddistillationsetup,onlysmallsample
(0.1to2.5g)andsolvent(10to15mL)quantitiesarerequired.

Table1.RecommendedSampleSizesforKFAnalysis
SampleSizeSelection
ForbothdirectandindirectKFmethods,samplesizeselectioniscriticalforminimizingerrors
associatedwithsampleweighing,transferandinjection.Asaguideline,samplesizesshowninTable1
arerecommendedforvolumetricandcoulometricKF,respectively.
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KFanalysisisaversatileandrobustanalyticaltoolforwatercontentanalysisinoilsamples,andcan
detectwaterinanyofthreestatescommonlyfoundinoils.Thetechniquealsooffersothersubstantial
advantagesovermoreconventionalhotplatecrackletestanddistillationmethods,andithasbeen
incorporatedintonumerousASTMstandards.VolumetricorcoulometricKFmethods,utilizingeither
directtitrationortheoilevaporatortechnique,canbeusedtoquantifywaterinoilsamplesfromtrace
amountsto100percent.
References>
1.Slater,K.RealTimeMonitoringofWaterinOil.LubricationExcellence2005Conference
Proceedings.April2005.
2.Duncanson,M.DetectingandControllingWaterinOil.PracticingOilAnalysismagazine.
SeptemberOctober2005.
3.Gebarin,S.ACloserLookatKarlFischerCoulometricTitration.PracticingOilAnalysis
magazine.MarchApril2004.
4.Kunkel,S.andDeSandro,J.TitrationMethodImprovesWaterMeasurement.Oil&GasJournal.
December1986.
5.Rouessac,F.andRouessac,A.ChemicalAnalysis:ModernInstrumentalMethodsandTechniques.
(2000).
6.McClure,M.andSteffen,R.WaterTestinginPharmaceuticalProducts.CurrentSeparations.
August2005.
7.MettlerToledoGmbH.Applicationbrochure26.FundamentalsofVolumetricKarlFischerTitration.
1999.

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