Experiment

SeparationbySolventExtraction
3

Objectives
Toseparateamixtureconsistingofacarboxylicacidandaneutralcompoundbyusing
solventextractiontechniques.

Introduction
Frequently, organic chemists must separate an organic compound from a mixture of
compounds, often derived from natural sources or products of synthetic reactions. One
techniqueusedtoseparatethemixturecompoundsiscalledextraction.Extractionisaprocess
thatselectivelydissolvesoneormoreofthemixturecomponentsintoanappropriatesolvent.
Thesolutionofthesedissolvedcompoundsisoftenreferredtoastheextract.
Extractionprocessesincluderemovalofsolublecompoundsfromasolidmatrix,suchas
in the brewing of coffee or tea, or in decaffeinating coffee with liquid carbon dioxide. In the
organic chemistry laboratory, however, extraction almost always refers to the transfer of
compoundsfromoneliquidsolventtoanother.
Acompoundcanbeseparatedfromimpuritiesinasolutionbyextractingthecompound
from the original (or first) solvent into a second solvent. For the process to be selective, the
compound must be more soluble in the second solvent than in the first solvent, and the
impuritiesmustbeinsolubleinthesecondsolvent.Additionally,thetwoselectedsolventsmust
beimmiscible,ornotsolubleinoneanother,sothattheyproducetwoseparatesolventlayers.
Afterdissolvingthemixtureinthefirstsolvent,thesolutionisaddedtoasecondsolvent.The
two layers are vigorously mixed to maximize the surface area between them. This mixing
facilitates the transfer of a dissolved compound from one solvent layer to another. Once the
transfer process is complete, the layers are again allowed to form, as shown in Figure 1.
Separationofthetwolayersthencompletestheseparationofthedesiredcompoundfromthe
impurities.

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Washing is the reverse process, in which the impurities are removed to the second
solvent,leavingthedesiredcompoundintheoriginalsolvent,asshowninFigure2.
Extractions using large quantities of solvents, tens or hundreds of milliliters, require a
separatoryfunnel,asshowninFigure3.Thesolventlayersaremixedbyshakingtheseparatory
funnel. Then the layers are allowed to reform. The bottom layer is drained through the
stopcock;thetoplayerispouredfromthetopoftheseparatoryfunnel.

Figure3.Separatoryfunnelforextractions

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 Thefirstrequirementintheextractionprocessistoselecttwoimmisciblesolvents.One
solvent,usuallyaqueous(waterbased),shouldbepolarinnature.Thesecondsolventshould
benonpolarandmightbehydrocarbon,ether,orchlorinatedsolvent,suchasdichloromethane.
When the two immiscible solvents are placed into a container, two liquid layers are formed.
Themoredensesolventisalwaysthebottomlayer.
It is important to identify the solvent in each layer. Hydrocarbons and ethers are less
dense than water or the dilute aqueous solutions used in extractions. When one of these
nonpolarsolventsisused,thewaterlayeristhebottomlayer,asshowninFigure4.
However,dichloromethaneisdenserthanwater.Whendichloromethaneisusedasthe
nonpolarsolvent,thewaterlayerwillbethetoplayer,asshowninFigure5.

Althoughtheidentityofeachlayercanbeestablishedfromthedensityofeachsolvent,
theiridentitiesshouldbeconfirmed.Toconfirmtheidentitiesofthelayers,oneortwodropsof
waterareaddedjustbelowthesurfaceofthetoplayer.Ifthedropsofwaterfallthroughthe
toplayertothelayerbelow,thenthewaterlayeristhebottomone.Itisagoodpracticeto
savealllayersinlabeledcontainersuntiltheexperimentiscompleteandthedesiredproduct
isisolated.
Oftenthetwosolventswillnotcompletelyseparateaftershaking,duetotheformation
ofanemulsionattheinterfacebetweenthem.Anemulsionisasuspensionofsmalldropletsof
oneliquidinanotherliquid.Emulsionsaregenerallyopaqueorcloudyinappearanceandare
oftenmistakenasathirdlayer.
Thesmallsizeofthedropletsinanemulsioncausestheseparationofthetwosolvents
to take place very slowly. Several procedures may be helpful to facilitate this separation. For
example,gentleswirlingofthecontainer,additionofafewdropsofsaturatedaqueoussodium
chlorideorethanol,oradditionofmoresolventtodilutethesolutionsmayhelp.Inparticularly
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difficult cases, it may be necessary to filter the mixture to remove small solid particles that
promoteemulsionformation.
A simple, but useful, guide to solubility is like dissolves like. That is, nonpolar
compounds,includingorganiccompounds,aremoresolubleinnonpolarsolventsthaninpolar
solvent.Ontheotherhand,ionicandpolarcompoundsaremoresolubleinpolarsolvents,such
aswater.Thesesolubilitydifferencescanbeexploitedtoseparatenonpolarcompoundsfrom
ionicorpolarcompounds.
Forexample,syntheticreactionsoftenproduceionic,inorganicsaltsasbyproductsof
the desired nonpolar organic product. In such cases, these salts are removed by washing the
nonpolarsolventwithwater.Theorganiccompoundremainsdissolvedinthenonpolarsolvent.
Someorganiccompoundsaresufficientlypolartobequitesolubleinwater.Extraction
of such polar compounds into a nonpolar solvent is often difficult. The process can be
facilitatedbyusingthetechniquecalledsaltingout.Inorganicsalts,suchasNaCl,aredissolved
in water to reduce thesolubility of the organic compound in the aqueous layer. Under these
conditions,theorganiccompoundpreferentiallydissolvesinthenonpolarlayer.
Extraction is a particularly effective means of separating organic compounds if one
compound in the mixture can be chemically converted to an ionic form. The ionic form is
solubleinanaqueouslayerandcanbeextractedintoit.Othernonionizedorganiccompounds
inthemixturewillremaindissolvedinthenonpolarsolventlayer.Separationofthetwolayers
resultsintheseparationofthedissolvedcompounds.
Ionic forms of some organic compounds can be produced by reacting them with
aqueous acids or bases (Figure 6). Treatment of organic acids with bases such as sodium
hydroxide (NaOH) converts these acids to watersoluble anions. Reacting basic amines with
dilute aqueous acid solutions such as hydrochloric acid (HCl) converts the amines to water
solublecations.

Figure6.Conversionoforganiccompoundstoionicformsbyreactionwithbaseoracid

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 The extent to which an acidbase reaction proceeds to completion depends upon the
relative acidity and basicity of the reactants and products. Reactions occur so that stronger
acids and bases react to produce weaker conjugate bases and acids. Recall that the pKa is a
measureoftheacidityofanacid,asshowninEquation1.

StrongeracidshavesmallerpKasandtheirconjugatebasesareinherentlyweaker.The
positionofanacidbaseequilibriumcanthenbepredictedfromaknowledgeofthepKasofthe
acidsinvolved.Strongeracids,thosewithasmallerpKa,willreactwiththeconjugatebasesof
weakeracids,thosewithalargerpKa.
AnanalysisofpKasindicatesthataqueousNaOHcanbeusedtoextractbothptoluic
acid and ptertbutylphenol from a nonpolar solvent, as shown in Equation 2 and 3. The
strongerbase,OH,removesahydrogenion,H+,fromptoluicacidtoformthesalt,ptoluate.
Thepolarsaltissolubleinaqueoussolution.BothOHandptoluatearebases.ThepKaof16
indicatesthatOHisastrongerbasethanptoluate,withapKaof4.2.Thestrongerbasetakes
H+fromtheweakerbase.

Similarly, OH is a stronger base than ptertbutylphenoxide ion, with a pKa of 10.2.

Therefore, OH takes H+ from ptertbutylphenol to form the water soluble ptert
butylphenoxideion.

Sodiumhydrogencarbonate(NaHCO3),withapKaof6.4,isaweakerbasethanptert
butylphenoxideion,soHCO3willnottakeH+fromptertbutylphenol,asshowninEquation4.
Asaresultsptertbutylphenolisnotconvertedtoasaltinaqueoussodiumhydrogencarbonate
anddoesnotbecomewatersoluble.

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Although aqueous NaHCO3 is not sufficiently basic to react with ptertbutylphenol, it

willreactwithptoluicacidtoformthewatersolubleptoluate,asshowninEquation5.

TheptoluicacidandptertbutylphenolcanberecoveredbyaddingHCltotheaqueous
solutions.TheptoluateandptertbutylphenoxideionsarestrongerbasesthanisCl,soeach
onetakesH+fromHCl.Theacidformsarenotwatersolubleand,therefore,precipitatefrom
solution.
Theprocedureyouwilluseinthisexperimentexploitsthedifferencesinthesereactions
toseparatesalicylicacidandacetanilidefromthenonpolarsolventinwhichtheyaredissolved.
First,youwillextractonlysalicylicacidintoNaHCO3solution.Sinceacetanilideisneutralandso
does not react with NaHCO3, it remains dissolved in the nonpolar solvent. Then, you will add
HCl to the aqueous layer to precipitate the waterinsoluble salicylic acid. You will isolate the
precipitatesfromthesolutionsbyvacuumfiltration,thenairdrythem.Torecoveracetanilide,
you will dry the nonpolar layer with anhydrous sodium sulfate (Na2SO4) and evaporate the
solventinafumehood.Finally,youwillrecrystallizetheacetanilide.
To facilitate the understanding of the experimental concept, each student should
prepareaflowchartbyfillingintheblankswiththenamesorstructuresofthecompoundsprior
toyourlabsession(nextpage).

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 Laboratoryflowchart

ExperimentalProcedure
1) Performaleaktestonyourseparatoryfunnelbyaddingsomewater,putonthecap,and
closethestopcock.Shakeandplacethefunnelonasupportring.Ifthereisaleak,consult
yourinstructor.
2) Obtaina1:1mixtureofsalicylicacidandacetanilidefromyourinstructor.
3) Weighthebagcontainingthismixtureandtransferthemixtureintotheseparatoryfunnel.
Reweightheemptybagandcalculatetheweightofthemixture.
4) Place10mLofethylacetateintheseparatoryfunnel.Swirlthefunneluntilallofthesolid
compoundsdissolve.
5) Add5mLof10%NaHCO3solution.Putonthecapandshakethefunnelcarefullyforafew
seconds as demonstrated by your instructor. (*Remember to hold the separatory funnel
with both hands and vent it frequently with the stopcock pointed upward and away from
otherpeople.)Settleforafewminutesanddraintheaqueouslayerintoabeaker.

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 6) Extract the ethyl acetate layer with another portion of 5 mL of 10% NaHCO3 solution.
Combine the aqueous layers into the same beaker. Leave the ethyl acetate layer in the
separatoryfunnel.
7) Chill the combined aqueous layer in an icewater bath. Acidify it by slow addition of
concentratedHClsolution.Noticethatfoamingandprecipitationoccur.ContinuetoaddHCl
untilnomoresolidisproduced.
8) Filtertheprecipitate,transferontoapreweighedwatchglass,anddryitonasteambath.
(Whichcompoundshouldbeobtainedatthisstage?)
9) Add10mLofsaturatedNaClsolutionintotheethylacetatelayer(intheseparatoryfunnel)
to wash out polar impurities. Shake the funnel and settle for a few minutes. Drain and
discardtheaqueouslayer.TransfertheethylacetatelayerintoanErlenmeyerflask.
10) Drytheethylacetatelayerwithanhydroussodiumsulfate.Decantthesolutionintoapre
weighedceramicevaporatingdish.
11) Evaporatetheethylacetateonasteambath.(Whichcompoundshouldbeobtainedatthis
stage?)
12) Calculatetherecoverypercentagesofeachcompound.
13) Determinethemeltingpointsoftheseparatedcompounds.

LaboratorySafetyPrecaution
1) Wearsafetygogglesandlabcoatatalltimeswhileworkinginthelaboratory.
2) Acetanilide is toxic and irritating. Concentrated hydrochloric acid is toxic and corrosive.
Magnesiumsulfateisirritatingandhygroscopic.
3) Washyourhandsthoroughlywithsoapordetergentbeforeleavingthelaboratory.

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