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TheoryofLiquidLiquidExtraction
Aswesawinthepreviouslab,inchemistry,extractionisthephysicalprocessbywhicha
compound(oramixtureofcompounds)istransferredfromonephaseintoanother.The
isolationoftrimyristinformnutmegisanexampleofasolidliquidextraction.Itisalso
possibletopartitionthecomponentsofamixturebetweentwoimmiscibleliquids(i.e.,
liquidsthatwillnotdissolveineachotherandformtwodistinctphaseswhencombined).This
processiscalledaliquidliquidextraction.
Therearetwogeneraltypesofliquidliquidextractions:
1.anorganicsolventextraction,inwhichanorganicsolventwithahighaffinity
forthedesiredcompoundisusedtoextractthecompoundfromanothersolution,
and
2.anacidbaseextraction,inwhichanorganicacidorbaseisextractedfroman
organicsolventbyusinganaqueoussolutionofaninorganicbaseoracid,
respectively.Aneutralizationoccurswhichconvertsthecompoundintoanionic,
watersolublesalt,causingittotransferfromtheorganicphasetotheaqueous
phase.

Extractionwithorganicsolvents
Liquidliquidextractionsusuallyinvolvewaterandanorganicsolvent.Mostcommonorganic
solvents(diethylether,ethylacetate,toluene,methylenechloride)areimmiscibleinwater.If
youplace50mLofethylacetateand50mLofwaterinaflaskandstirthesolutiontomixit,
youwillnotobtainahomogeneoussolution.Rather,ifthesolutionisallowedtostandafter
stirring,twodistinctliquidphaseswillformintheflask:themoredensesolventasthelower
layerandthelessdensesolventastheupperlayer.
Mostorganicsolventsaremuchlesspolarthanwater.Ageneralruleofthumbforsolubility
statesthatlikedissolveslike.Polarcompoundsaremoresolubleinpolarsolventsthanin
nonpolarsolvents,andviceversa.Theselectivesolubilityofdifferentcompoundsinpolar
versusnonpolarsolventsallowstheseparationofthecompoundsinamixturebyliquidliquid
extraction.
SupposethatweaddacompoundXtoaflaskcontainingethylacetateandwater,andstirthe
contentsoftheflasktomixthem.Aftermixing,theethylacetateandwaterwillseparateinto
twodistinctphases,andcompoundXwillbefounddissolvedinboththeethylacetatelayer
andinthewaterlayer.HowcompoundXdistributesbetweenthetwosolventsisbasedonthe
solubilityofXineachofthetwosolvents:moreofcompoundXwillbefoundinthesolventin
whichitismoresoluble.TheratiooftheconcentrationsofXineachoftheimmiscible
solventsiscalledthedistributioncoefficientorthepartitioncoefficient,Kd,where

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Thevalueofthedistributioncoefficientdependsonthesolubilityofthecompoundinthetwo
solventsinthesystem.Intheabovesystem,ifcompoundXhasahighersolubilityinethyl
acetatethaninwater,atequilibriumtheconcentrationofXinethylacetatewillbegreater
thantheconcentrationofcompoundXinwater,andthevalueofthedistributioncoefficientKd
willbegreaterthan1.IfinsteadcompoundXhasahighersolubilityinwaterthaninethyl
acetate,atequilibriumtheconcentrationofXinwaterwillbegreaterthantheconcentration
ofcompoundXinethylacetate,andthevalueofthedistributioncoefficientKdwillbeless
than1.
Theefficiencyofaliquidliquidextractiondependsonthedistributioncoefficientofthedesired
compoundbetweenthetwosolvents.Ifwewanttoextractanorganiccompoundfroman
aqueoussolutionintoanorganicsolvent,itisdesirabletouseasolventthathasamuch
higheraffinityforthecompoundthandoeswater.Forexample,at25 o C,thesolubilityof
benzoicacidinwateris3.4gperliterwhilethesolubilityofbenzoicacidinchloroform
(CHCl 3)is222gperliter.Waterandchloroformareimmisciblesolvents.Ifasolutionof1g
ofbenzoicacidin400mLofwaterisextractedwith400mLofchloroform,wewouldexpect
mostofthebenzoicacidtobetransferredtothechloroformlayerinwhichitismoresoluble.
Thebenzoicacidwilldistributeitselfbetweenthetwosolventsintheratioofthesolubilitiesin
eachsolvent:

Nomatterhowmuchbenzoicacidispresentinthesystem,itwillalwaysbedistributed
betweenthechloroformandwatersothattheratiooftheconcentrationineachsolventis
65.3.
Fromthisestimateofthedistributioncoefficient,wecancalculatehowmuchbenzoicacidis
presentinthechloroformandwaterlayersaftertheextraction.Letx=gramsofbenzoicacid
inthewaterlayerandy=gramsofbenzoicacidinthechloroformlayer.Sincewestarted
with1gofbenzoicacid,
x+y=1.Usingthisequationalongwiththevalueforthedistributioncoefficientcalculated
above,wecandeterminetheconcentrationofbenzoicacidineachlayer:

or,sincethevolumesofbothsolventsusedarethesame:

Thetotalamountofbenzoicacidpresentis(x+y)=1.Rearrangingthisequationand
substitutingforxinthepreviousequationgives

Solvingthisequationforygives0.015g(15mg)ofbenzoicacidinthewaterlayer,and,since
thetotalamountofbenzoicacidis1g,thereis0.985g(985mg)ofbenzoicacidinthe
chloroformlayer.

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Multipleextractions
Inthepreviousexample,oneextractionwith400mLofchloroformremoved98.5%ofthe
benzoicacidfromtheaqueoussolution.Ifwedividethe400mLofchloroformusedinhalfand
dotwosuccessiveextractionsoftheaqueousphase,theamountofbenzoicacidextractedwill
increase.
Theequationforthedistributioncoefficientfortwo200mLchloroformextractionsofthe400
mLaqueoussolutionofbenzoicacidis

Inthefirstextraction,1gofbenzoicacidisdistributedbetweenthephases,so(x+y)=1as
before.Solvingthetwoequationsintwounknownsgivesx=0.97(ginCHCl 3)andy=0.03
(ginH2O).Whentheaqueousphaseisextractedasecondtimewithafresh200mLof
chloroform,only0.03gofbenzoicacidisleftintheaqueousphasetodistributebetweenthe
twosolvents.Inthisextractiontheequationforthedistributioncoefficientisthesamebut(x
+y)=0.03,andsolvingforxandy,theamountofbenzoicacidineachlayerafterthe
secondextractiongivesx=0.0291(ginCHCl 3)andy=0.0009(ginH2O).Combiningthe
amountsofbenzoicacidfoundinthetwochloroformextractsgives99.91%(0.9991gofthe
original1g)ofthebenzoicacidextractedintothechloroformlayerbyusingtwo200mL
extractionsinsteadof98.5%removedwithone400mLextraction.Ingeneral,itisalways
moreefficienttocarryoutseveralextractionsusingasmallvolumeofsolventeachtimethan
tocarryoutasingleextractionusingalargevolumeofsolvent.

Acidbaseextraction
Organiccompoundsareclassifiedasbeingneutral,acidic,orbasicdependingonthetypesof
functionalgroupstheycontain.Manyorganiccompounds,althoughjustslightlypolaroverall,
containfunctionalgroupsthatcanactasaBrnstedLowryacidorbase(i.e.,theycandonate
oracceptaproton,respectively).Carboxylicacids,phenols,andthiolsareexamplesofacidic
functionalgroupssubstitutedamines(includinganilines)areexamplesofbasicfunctional
groups.Althoughthewatersolubilityofthesecompoundsisoftenlimitedbecauseoftheir
overallnonpolarcharacter,theiraqueoussolubilitiescanbedramaticallyincreasedthroughan
acidbaseneutralizationreaction.Thischangesthecompoundintoanionicsaltthatisvery
watersolubleandwilldistributealmostcompletelyintotheaqueouslayer.
Toillustratehowanacidbaseextractionworks,considertheextractionofawaterinsoluble
carboxylicacid(RCO2H)fromatoluenesolutioncontainingamixtureofneutralorganic
compounds.Thecarboxylicacid,althoughvirtuallyinsolubleinwater,canbeextractedfrom
thetoluene(organic)solutionintotheaqueousphasebyextractingwithasolutionofsodium
bicarbonate.Thebasicaqueoussodiumbicarbonatesolutionwillreactwiththecarboxylicacid
togiveawatersolublecarboxylatesalt.

Thissaltwillmoveintotheaqueoussolution,leavingtheneutralorganiccompoundsbehindin
thenonpolartoluene.
Thecarboxylicacidhasbeenextractedfromtheorganiclayer,butnowitispresentin
solutionasthecarboxylatesalt.Afterthelayershavebeenseparatedthecarboxylicacidis
regeneratedusinganotheracidbasereaction.Acidifyingthebasicsolutionwithamineralacid
protonatesthecarboxylateion,regeneratingthecarboxylicacidwhichhaslimitedsolubilityin
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theaqueoussolution.Theisolatedcarboxylicacidproductcanthenberecoveredeitherby
filtrationorbyextractingthecarboxylicacidintofreshtolueneandevaporatingthesolvent.
Carboxylicacidsarestrongenoughacids(pKa 35)tobeneutralizedtowatersolublesaltsby
reactionwithaweaklybasicsodiumbicarbonatesolution.Themuchlessacidicphenols(pKa
810)willnotreactwithsodiumbicarbonatesolutionphenolscanbedeprotonatedtogive
watersolublephenolatesaltsbyextractingwithanaqueoussolutionofastrongerbasesuch
assodiumhydroxide.Thedifferenceintheacidityofthesetwoacidicfunctionalgroupsallows
themtobeseparatedfromeachotherinamixturebyusingtheproperalkalinesolutioninthe
acidbaseextraction.
Organicamines,R3N,arebasesthatcanberemovedfromanorganicsolutionbyextracting
themwithaqueousacidicsolutionstoformwatersolubleammoniumsalts.Oncethe
ammoniumsalthasbeen

extractedintotheaqueousphaseandtheorganicandaqueouslayershavebeenseparated,
thefreeaminecanberegeneratedfromtheammoniumionbytreatingtheaqueoussolution
withabase.Thisdeprotonatestheammoniumiontogivethelesswatersolublefreeamine
whichcanbecollectedeitherbyfiltrationorbyextractingtheamineintofreshtolueneand
evaporatingthesolvent.
Asanexampleoftheutilityofacidbaseextractionsinseparatingthecomponentsofa
mixture,considertheseparationofamixtureofanthracene,aniline,benzoicacid,andphenol.

Themixtureisdissolvedintolueneandplacedinaseparatoryfunnel,whereitisfirst
extractedwitha510%aqueoussolutionofHCl.Thisextractionremovesanilinefromthe
organicphaseasthewatersolubleaniliniumchloridesalt,leavingtheotherthreecomponents
intheorganicsolution.Thelayersareseparatedandtheorganicsolutionisthenextracted
usinga5%aqueoussolutionofNaHCO3.Thisremovesthebenzoicacidfromtheorganic
solutionassodiumbenzoatebutleavesthelessacidicphenolbehindintheorganiclayer.The
layersareseparatedagain,andnow,byextractingtheorganicphasewith5%NaOH,phenol
canberemovedfromtheorganicphaseasthewatersolublesodiumphenolatesalt,leaving
theneutralanthraceneasthesolecompoundintheorganicphase.Eachcomponentcannow
beisolatedfromthesolutioninwhichitisthesolecomponentbyusingeitherasecond
extractionfollowedbysolventremoval,orbyneutralizationandprecipitationofthesolid(See
Figure1).

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Whentheexperimentalprocedurecallsforwashingasolution,thatmeansanextraction.An
organiclayercontainingthedesiredmaterialmaybewashedwithaqueoussodium
bicarbonatetoremoveacids,orwashedwithwatertoremovewatersolubleimpurities.An
aqueoussolutioncontainingadesiredorganicsaltmaybewashedwithethertoremove
unwantedneutralorganicimpurities.Theliquidusedforwashingisnormallytheonethatyou
don'tintendtokeep.Asolventusedforextractionisnormallythelayeryousave,containing
thedesiredcompound,buttheoperationisthesame.

Usingaseparatoryfunnel
Thechoiceofapparatusforanextractionisdeterminedbythevolumesofthesolutionbeing
extractedandtheextractingsolutions.Typicalextractionsinthelaboratoryaredoneina
separatoryfunnel,whilemicroscaleextractionsaredoneinaconicalvial.
Aseparatoryfunnelisshowninthefollowingfigure.Thefunnelisfittedwithastopcockand
aglassstopper.Makesurethattheholeinthestopcockandtheholeintheseparatoryfunnel
lineupandthatthestopcockfitssnuglyandturnssmoothlywithoutleaking.Ifthestopcockis
madeofglass,itshouldbelubricatedwithasmallamountofstopcockgreasesothatitdoes
notstick.MostnewerstopcocksaremadeofTeflonandneednogrease.Asmallmetalclip,
rubberring,orTeflonnutwithawasherandaringattheendholdsthestopcockinplace.
Thestoppershouldalsofitsnugly.Avoidusingstopcockgreaseonthestoppersincethe
greasemightdissolveintheorganicsolventandcontaminatethesolution.Forstorage,
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removethestopperandthestopcock,orwrapeachwithpaperbeforeinsertingthemintothe
funneltopreventsticking.

Aseparatoryfunnelistopheavy,especiallywhennearlyfilledwithliquid.Standingitupright
inabeakerisaprecarioussituationatbest.Theseparatoryfunnelshouldbesupportedinan
ironringofpropersizeattachedtoaringstand.Beforeaddinganyliquidtotheseparatory
funnel,makesurethatthestopcockisclosed.
Oneofthemostcommonerrorsinextractionispouringaliquidintotheseparatoryfunnel
withoutfirstmakingsurethatthestopcockisclosed.Oops!Theregoesyourcompoundonto
thebenchtop.
Addthetwoimmiscibleliquidsfortheextractionthroughafunnelintotheseparatoryfunnel,
fillingtheseparatoryfunnelonlyaboutthreefourthsfulltoallowroomformixing.Placethe
stopperintheseparatoryfunneland,holdingthestopperfirmlyinplacewiththeindexfinger
ofonehand,removetheseparatoryfunnelfromtheironring.

Invertthefunnel,pointingthestemupawayfromyou(butnotatsomeoneelse!),and
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carefullyopenthestopcocktoventanygases.Youmayhearahissingsoundasthegasesare
releasedthroughthestopcock.Closethestopcockandgentlyswirlthetwoliquidstogetherto
mixthem.Vigorouslyshakingthecontentsisnotonlyunnecessarybutmayprovedeleterious
bycreatingemulsions.Itiscommonforpressuretobuildupintheseparatoryfunnelduring
mixing,especiallywhenusingavolatilesolventsuchasetherorwhenneutralizingacidswith
carbonateorbicarbonatesalts(thatreactwiththeacidtoformCO2gas)soitisnecessary
periodicallytostopmixingandopenthestopcocktoventanypressurethathasbuiltup.After
mixingiscomplete,closethestopcockandplacetheseparatoryfunnelintheironring,
removethestopperandallowthelayerstosettleandseparateacleaninterfaceshouldform
betweenthetwolayers.
PlaceanErlenmeyerflaskorabeakerunderthefunnel,openthestopcockanddrainthe
lowerlayerintothebeakerorflask.Astheinterfacebetweenthetwosolventsapproachesthe
stopcock,slowtherateofdrainingbyadjustingthestopcockyouwanttoremoveallofthe
lowerlayerandretainalloftheupperlayerintheseparatoryfunnelafterdraining.
Ifyouaregoingtodoanotherextractiononthetoplayer,leaveitintheseparatoryfunnel
andaddmoreofthenextextractingsolventtotheseparatoryfunnel.If,however,youare
goingtodoanotherextractiononthelowerlayer,pourtheremainingupperlayeroutthetop
oftheseparatoryfunnelintoaflaskandthenreturnthelowerlayertotheseparatoryfunnel
forthenextextraction.

Whichlayeriswhich?
Acommonproblemthatyoumayfaceindoingextractionsistryingtodeterminewhichoneof
thetwolayersintheseparatoryfunnelistheaqueouslayerandwhichoneistheorganic
layer.Theheavierlayer(i.e.,themoredenseliquid)isthelowerlayer,ofcourse,butsome
organicliquids(e.g.,benzene,diethylether,ethylacetate)arelighterthanwaterandsome
(e.g.,chloroform,dichloromethane)areheavierthanwater,so,dependingonthesolvents
beingused,theorganicphasemightbetheupperorthelowerlayerintheseparatoryfunnel.
Youcouldlookupthedensitiesofthetwoliquidstodeterminewhichisgreater,but
sometimesahighconcentrationofdissolvedsubstancesintheaqueousphasecancauseitto
bemoredensethanexpectedandtobefoundasthelowerlayerintheseparatoryfunnel,
evenwhenextractingwithanorganicsolventwithadensitygreaterthanwaters.Ifyouare
unsureaboutwhichlayeriswhich,carryoutasimpletest:mixasmallsampleofeachlayer
withafewdropsofwaterinatesttubeandseeifthetwoliquidsaremiscibletheaqueous
solutionwilldissolvethewaterdropsbuttheorganicsolutionwillbeimmisciblewiththe
addedwater.
TheGoldenRuleofExtractionis:Neverthrowalayerawayuntiltheendoftheexperiment,
oruntilyouareabsolutelycertainthatyounolongerneedit.Themostcommonmistake
madeduringextractionisthrowingthewronglayerdownthedrainorinthewastebottle,
whichmeanslossofmaterialandstartingtheexperimentoverfromthebeginning.

Emulsions
Thebugabooofextractionsisemulsions,foggylookingmixturescontainingtinydropletsof
oneliquidsuspendedinanotherthatdonotseparateeasily.Iftimepermits,patienceisthe
bestsolutionletthemixturestanduntiltheemulsionbreaksupandthetwolayersclearly
separate.Sometimesaddingsaltorasaturatedsaltsolutionwillhelpbreakuptheemulsion,
aswilladdingalittlelighterorheaviersolventtotheorganiclayertoincreasethedifference
betweenthedensitiesofthetwolayers.Thebestwaytodealwithemulsionsistoavoidthem.
Gentlyswirlingthecontentsoftheseparatoryfunnelduringmixinginsteadofvigorously
shakingthemwillhelppreventemulsionsfromforminginthefirstplace.

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