8/9/2016

ACloserLookatKarlFischerCoulometricTitration

ACloserLookatKarlFischerCoulometric
Titration
NoriaCorporation
Tags:waterinoil,oilanalysis

PracticingOilAnalysis(3/2004)

Watercontaminationisacauseformajorconcerninalargenumberofapplications.Insomeindustriesand
environments,waterisafarmoredamagingcontaminantthansolidparticlesandisoftenoverlookedasaprimary
causeofcomponentfailure.Forcertainapplications,evenasmallamountofwatermayhavedamagingeffectson
productionorequipment.
Watercanexistinthreestatesorphases.Dissolvedwaterischaracterizedbyindividualwatermoleculesdispersed
throughouttheoil.Similartohumidityintheair,dissolvedwatercannotbeseenintheoil.Iftoomuchwateris
presentintheoil,thedispersedwatermoleculesbegintosaturatethisissimilartotheformationoffog.Whenthis
occurs,thewaterisconsideredemulsified.Freewaterisformedwhentheadditionofwaterleadstoaphase
separationofbothliquidcomponentsproducingalayerofwater.
Severalmethodsareavailabletodeterminethewatercontaminationlevelinfluids.AKarlFischer(KF)coulometric
titratorisoneofthemostaccuratemethods.Unlikeothertechniques,itcantracelowlevelsoffree,emulsifiedand
dissolved(whichcannotbedetectedwithothermethodssuchasacrackletest).Whenusedcorrectly,thetestis
capableofmeasuringwaterlevelsaslowas1ppmor0.0001percent.

Coulometricvs.Volumetric
Titrationisachemicalanalysisthatdeterminesthecontentofasubstance,suchaswater,byaddingareagentof
knownconcentrationincarefullymeasuredamountsuntilachemicalreactioniscomplete.TherearetwotypesofKarl
Fischertitrators:volumetricandcoulometrictitrators.Themaindifferencebetweenthetwoisthatwiththevolumetric
method,thetitrantisaddeddirectlytothesamplebyaburette.Conversely,withthecoulometricmethod,thetitrantis
generatedelectrochemicallyinthetitrationcell.Thecoulometricmethodmeasureswaterlevelsmuchlowerthanthe
volumetricmethod.

TitrationChemistryFundamentals
ThefollowingreactionschemehasbeenproposedfortheKarlFischertitration:

ROHrepresentsanalcohollikemethanolorethanol.
Inthecoulometricmethod,thetitrationcellconsistsoftwoparts:ananodicandacathodiccompartment.Figure1
showsbothcompartmentsseparatedbyaceramicdiaphragm.Theanodiccompartmentcontainstheanolytesolution
whichincludessulfurdioxide(SO2),iodide(I)andimidazoleneededinthechemicalreaction.Methanolorethanol
(ROH)isusuallyusedasasolvent.

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Figure1.TitrationCell(CourtesyofMettlerToledo)
IncoulometricKarlFichertitration,iodine(I2)isgeneratedelectrochemicallyfromiodide(I).Wheniodine(I2)comes
incontactwiththewaterinthesample,wateristitratedaccordingtotheabovementionedreactionscheme
(equationsNo.1andNo.2).Onceallofthewateravailablehasreacted,thereactioniscomplete.Theamountof
waterinthesampleiscalculatedbymeasuringthecurrentneededfortheelectrochemicalgenerationofiodine(I2)
fromiodide(I)accordingtothefollowingreaction(equationNo.3):

CoulometricTitratorFeatures
ThereareseveralfeaturestoconsiderwhenselectingaKarlFischercoulometrictitrator.Table1listsanumberof
manufacturersthatofferKarlFischercoulometrictitrators.Eachmanufactureroffersdifferentfeatures.
SensitivitytoHumidity
Humidityisprobablythelargestsourceoferrorduringthetitration.Specialprecautionsshouldbetakenduringsetup
andtesting,especiallyincoastalortropicalregions.Theairconditioningsystemshouldbeequippedwithamoisture
condenser.Also,aKarlFischertitratorshouldnotbeinstallednearanairconditionervent.
Thetitrationcellsareenclosedtohelpensurethatwaterdoesnotenterfromtheatmospherehowever,averysmall
amountofwateralmostalwaysmakesitintothetitrationcell.Theamountofwaterthatentersoveraperiodoftimeis
knownasthedrift.Manymanufacturerswillgivespecificationsondriftvaluesandmaximumallowableairhumidity.
SensitivitytopH
Thechemicalreactionissensitivetothesolutionsacidityoralkalinity.TheoptimumpHrangeofthesamplesolution
forefficientKarlFischertitrationisbetweenpH5.5and8.WhenthepHisgreaterthan8.5,thereactionrate
increasesduetochemicalsidereactions.Thisresultsinamoresluggishendpointandhigheriodineconsumption,
whichwillaffectresults.BufferingagentsareavailableforacidicorbasicsamplestokeepanidealpHbetween5.5
and8.
Diaphragmvs.DiaphragmlessTitration
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Thediaphragmseparatestheanodicandcathodiccompartments.Itspurposeistopreventtheelectrochemically
generatediodinefromreversingbacktoiodideatthecathodeinsteadofreactingwiththewater.Thediaphragmless
titratorusesadifferentgeometricconstructiontopreventthegeneratediodinefromreversingbacktoiodide(Figure
2).Ashydrogengasisgeneratedinthecathodiccompartment,itcreatesalayerofgasbubblesonthesurfaceofthe
cathode.Thislayerofgaspreventstheiodinefrombeingreducedatthecathode.However,itisstillpossiblefor
smallamountsofiodinetobereversedtoiodidewhenreachingthecathode.

Figure2.DiaphrapmandDiaphragmlessConfigurations
(CourtesyofMettlerToledo)
Diaphragmlesstitrationisadvantageousbecausethereisnodiaphragmtobecomecontaminateditiseasierto
cleanandalowerdriftcanbeused(thisrelatestohowquicklythereactioncompletes).
Adiaphragmlesscellisaccurateenoughformanyapplications.However,checkwithyourKarlFischerTitrator
suppliertoverifywhetheryourapplicationsrequireadiaphragm.
CodistillationMethod
Somesamplesmayreleasewaterslowlyorhavesidereactionswiththereagents.Inthiscase,theASTMD6304
withcodistillationisamorereliabletechniqueandwillmitigatethechancesofthisoccurring.Withthismethod,theoil
sampleisheatedunderavacuumsothatanywaterinthesamplewillevaporate.Watervaporsarecondensedand
dissolvedintoluene.
ThisisthentitratedusingtheASTMD6304procedure.Becauseadditivesandotherinterferingcontaminantsthat
maybepresentinausedoilsampleremaindissolvedorsuspendedintheoil,thecondensedwaterinthetolueneis
freefrominterferenceeffectsandisatruecountofwaterinthesample.Manycompaniesofferoptionaldryingovens
forthispurpose.
ProgrammableorBuiltinMethods
TheKarlFischercoulometrictitratormethodcanbeadjusteddependingontheapplicationandaccuracyneeded.
Adjustmentrequiressomeunderstandingofthetitratorsworkingandcontrollingprinciples.Tohelpensureaccurate
adjustment,manytitratorshavemethodsbuiltinthatcanbeusedformorecommonapplications.Thismoreuser
friendlymethodmakesitpossibleforapersonwhodoesnthavealotofexperiencetousetheinstrument.
Forspecialapplications,aparticularmethodmaynotbebuiltin.Inthiscase,manytitratorsallowtheusertoprogram
amethod.Onceallofthesettingsareinplace,thatspecificmethodcanbeselectedeachtimetheapplicationis
needed,andthetitratorwillrunonitsown.
Thenumberofbuiltinandprogrammablemethodsvaryamonginstruments.Itisusefultodetermineapproximately
howmanyapplicationsareavailable,andtobecomefamiliarwitheachapplicationsspecialties.
BuiltinPumps
Itisimportantthatthereagentsdonotbecomecontaminated.Somecoulometrictitratorscomewithabuiltinpump
thatcanfillanddrainreagents.Thishelpseliminatereagentcontaminationandreducesthenumberofstepsrequired
fortheprocedure.
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TitrationSpeeds
Titrationspeedsvaryforeachunit.Whilespeedmaybeimportant,thefastertheunittitrates,thelessaccurateitwill
be.Forsampleswithlowlevelsofwater(lessthan50g),thetitrationshouldtakeplaceslowly.Itisalsobestto
titratethesampleslowlyifthewaterlevelaccuracyiscritical.Ifhighlevelsofwater(greaterthan1,000gper
sample)arebeingmeasured,thetitrationcanbequicker.
MemoryStorageCapacity
Mostunitscomewithaconnectionforacomputerorprinterandsomehavebuiltinprinters.Eachunithasadifferent
memorystoringcapacity.Ifitwillnotbeattachedtoapersonalcomputer,thenitsmemorystoragecapacitymaybe
animportantconsideration.
References
1.ASTMD6304:StandardTestMethodforDeterminationofWaterinPetroleumProducts,LubricatingOils,and
AdditivesbyCoulometricKarlFischerTitration.
2.(2003,JulyAugust).WaterOilAnalysis101.PracticingOilAnalysis.
3.(2001,JulyAugust).WaterTheForgottenContaminant.PracticingOilAnalysis.
4.MettlerToledoApplicationsBrochure32,FundamentalsoftheCoulometricKarlFischerTitrationwithSelected
Applications.MettlerToledoInc.RetrievedAugust1,2003fromwww.mt.com.
Sidebar1

KarlFischerMethodMadeEasyThroughAutoSamplingTitration
AutomatedtitrationisanaccessoryofferedbysomeKarlFischermanufacturersthatallowstheusertoperform
multipletitrationswithoutstoppingtoprepareasample.ItiscombinedwitheitheracoulometricorvolumetricKarl
Fischertitratortodeterminetheamountofwaterinthesampleefficientlyandunmonitored,allowingtheanalystto
focusonotherimportantjobswhileitruns.

HowDoesitWork?
Thesamplesareplacedintherotatingtrayandsealed.Oncetheinstrumentstarts,thefirstsampleismovedintoa
temperaturecontrolledoven.Then,thesampleispiercedsothatasthewaterisconvertedintoavapor,itis
transferredintoeitheracoulometricorvolumetrictitratorwhichwilldeterminethewatercontentofthesample.By
controllingthetemperature,onlythewaterevaporateswhiletheremainingsamplestaysinthesamplebottle.Onceall
ofthewaterisremovedandmeasured,thesamplebottleisputbackintoitsoriginalpositiononthetray,andthetray
rotatestothenextsampletobeperformed.

Advantages
Multiplesamplescanbeanalyzedatoncewithoutstoppingtoprepareeachsample.
Thereisnocontaminationintheovenorthetitrationcellbecausetheremainingliquidorsolidsampleremains
inthesamplebottle.
Theresnoneedtoworryaboutanysidereactionsthatmayoccurbetweenthesampleandthetitrating
reagents.
Muchlessreagentisusedintheprocess.

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ACloserLookatKarlFischerCoulometricTitration

TheMettlerToledoDL39
CoulometerwithStromboliandOptionalAirPump

TheMetrohm774KFOven
SampleProcessorwith756
KarlFischerCoulometer

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