ExperimentalProcedures:Recrystallization

Purpose

Toexplorethetechniquesforrecrystallizingsolids.
1
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SafetyAlert

Wearsafetyglassesorgoggleswhileperformingtheexperiments.
Organiccompoundsaremuchmorerapidlyabsorbedthroughtheskinwhenthey
areinsolution,particularlyinwatersolublesolventssuchasacetoneandethanol.
Forthisreason,donotrinseorganicmaterialsoffyourskinwithsolventssuchas
acetone;washyourhandsthoroughlywithsoapandwarmwaterinstead.
Donotuseaburnerintheseproceduresunlessinstructedtodoso.Mostsolvents
usedforrecrystallizationareflammable(Table3.1).
Whenusingahotplate,donotsetitatitshighestvalue.Amoderatesettingwill
preventoverheatingandtheresultantbumpingandsplashingofmaterialsfromthe
flask.Donotemployhotplatesforheatingvolatileorflammablesolvents;rather,
useasteambath.
Donotinhalesolventvapors.Ifahoodisnotavailabletoyou,clampaninverted
funneljustabovetheErlenmeyerflaskinwhichyouwillbeheatingsolvents.
Attachthisfunneltoasourceofvacuumbymeansofrubbertubing(Fig.2.71b).
Neveradddecolorizingcarbontoaboilingsolution;doingsomaycausethe
solutiontoboiloutoftheflask.Addthecarbononlywhenthetemperatureofthe
solventisbelowtheboilingtemperature.Thissameprecautionapplieswhenusing
afilteraidtoassistintheremovalofthecarbonduringthehotfiltrationstep.

SolventSelection

Procedure
Preparation

RefertotheonlineresourcestoanswerPreLabExercises,accessvideos,andread
theMSDSsforthechemicalsusedorproducedinthisprocedure.Readorreview
Sections2.5,2.9,and3.2,andreviewthesolventpropertieslistedinTable3.1.
Althoughdifferentcriteriaareusedfordefiningsolubility,plantousethe
followingdefinitionsinthisexperiment:(a)solublemgofsolutewilldissolve
inmLofsolvent;(b)slightlysolublesomebutnotallofthemgofsolutewill
dissolveinmLofsolvent;(c)insolublenoneofthesoluteappearstodissolvein
mLofsolvent.Becertaintorecordallyourobservationsregardingsolubilitiesin
yournotebook!

Apparatus
Testtubes

,hotwaterorsteambath.

Protocol
Forknowncompounds,placeaboutmg(amicrospatulatipfull)ofthefinely
crushedsolidinatesttubeandaddaboutmLofwaterusingacalibratedPasteur
pipet.Stirthemixturewithaglassrodormicrospatulatodeterminewhetherthe
solidissolubleinwateratroomtemperature.Ifthesolidisnotcompletelysoluble
atroomtemperature,warmthetesttubeinthehotwaterorsteambath,andstiror
swirlitscontentstodeterminewhetherthesolidissolubleinhotwater.
Ifanyofyoursolutesaresolubleinthehotsolventbutonlyslightlysolubleor
insolubleatroomtemperature,allowthehotsolutiontocoolslowlytoroom
temperatureandcomparethequantity,size,color,andformoftheresulting
crystalswiththeoriginalsolidmaterial.
Repeatthesolubilitytestforthesolutesusingethanolandthenpetroleumether
(bp,torr).Aftercompletingtheseadditionaltests,recordwhichofthethree
solventsyouconsiderbestsuitedforrecrystallizationofeachofthesolutes.
Compounds14containavarietyoffunctionalgroupsthatimpartdiffering
solubilitypropertiestothemoleculesandarepossiblesubstratesonwhichto
practicethetechniqueofdeterminingsolubilities.Otherknowncompoundsmay
beassignedbyyourinstructor.

Forunknowncompounds,asystematicapproachisimportantfordeterminingtheir
solubility.First,selectthesolventsfromTable3.1tobeusedinthetests.Itshould
notbenecessarytotestallthesolvents,butyoushouldconsidertryingthosethat
aredenotedwiththesymbolinthetable.Yourinstructormayalsosuggest
solventstoevaluate.
Afterselectingthesolvents,obtainenoughclean,drytesttubessothatthereisone
foreachsolventtobetested.Placeaboutmg(amicrospatulatipfull)ofthefinely
crushedunknownineachtesttubeandaddaboutmLofasolventtoatube
containingthesolid.Stireachmixtureanddeterminethesolubilityofthe
unknownineachsolventatroomtemperature.Usethedefinitionsofsoluble,
slightlysoluble,orinsolublegivenearlier.
Iftheunknownisinsolubleinaparticularsolvent,warmthetesttubeinthehot
waterorsteambath.Stirorswirlthecontentsofthetubeandnotewhetherthe
unknownissolubleinhotsolvent.Ifthesolidissolubleinthehotsolventbutonly
slightlysolubleorinsolubleatroomtemperature,allowthehotsolutiontocoolto
roomtemperatureslowly.Ifcrystalsforminthecoolsolution,comparetheir
quantity,size,color,andformwiththeoriginalsolidmaterialandwiththose
obtainedfromothersolvents.
Itisagoodideatotestthesolubilityofasoluteinavarietyofsolvents.Even
thoughnicecrystalsmayforminthefirstsolventyoutry,anotheronemightprove
betterifitprovideseitherbetterrecoveryorhigherqualitycrystals.Toassistin
determiningthebestsolventtouseinrecrystallizinganunknown,youshould
constructatablecontainingthesolubilitydatayougatherbythesystematic
approachdescribedabove.
Ifthesesolubilitytestsproducenoclearchoiceforthesolvent,mixedsolvents
mightbeconsidered.Reviewthediscussionpresentedearlierinthissectionforthe
procedureforusingamixtureoftwosolvents.Beforetryinganycombinationsof
solventpairs,takeaboutmLofeachpuresolventbeingconsideredandmixthem
toensurethattheyaremiscibleinoneanother.Iftheyarenot,thatparticular
combinationcannotbeused.

RecrystallizingImpureSolids

MiniscaleProcedures
Preparation

RefertotheonlineresourcestoanswerPreLabExercises,accessvideos,andread
theMSDSsforthechemicalsusedorproducedinthisprocedure.Readorreview
Sections2.6,2.7,2.9,2.11,2.17,and2.18.

1.BenzoicAcid
Apparatus

TwomLErlenmeyerflasks,graduatedcylinder,icewaterbathapparatusfor
magneticstirring,vacuumfiltration,andflamelessheating.

Dissolution
PlacegofimpurebenzoicacidinanErlenmeyerflaskequippedformagnetic
stirringorwithboilingstones.MeasuremLofwaterintothegraduatedcylinder
andaddamLportionofittotheflask.Heatthemixturetoagentleboiland
continueaddingwaterinmLportionsuntilnomoresolidappearstodissolvein
theboilingsolution.Recordthetotalvolumeofwaterused;nomorethanmL
shouldberequired.Caution:Becausethesamplemaybecontaminatedwith
insolublematerial,paycloseattentiontowhetheradditionalsolidisdissolvingas
youaddmoresolvent;ifitisnot,stopaddingsolvent.

Decoloration
Purebenzoicacidiscolorless,soacoloredsolutionindicatesthattreatmentwith
decolorizingcarbon(Sec.2.18)isnecessary.Caution:Donotadddecolorizing
carbontoaboilingsolution!Allowthesolutiontocoolslightly,adda
microspatulatipfullofcarbon,andreheattoboilingforafewminutes.Toaidin
removingthefinelydividedcarbonbyfiltration,allowthesolutiontocool
slightly,addaboutgofafilteraid(Sec.2.17),andreheat.

HotFiltrationandCrystallization
Ifthereareinsolubleimpuritiesordecolorizingcarboninthesolution,performa
hotfiltration(Sec.2.17)usingamLErlenmeyerflasktoreceivethefiltrate(Fig.
2.52).RinsetheemptyflaskwithaboutmLofhotwaterandfilterthisrinseinto
theoriginalfiltrate.Ifthefiltrateremainscolored,repeatthetreatmentwith
decolorizingcarbon.Covertheopeningoftheflaskwithapieceoffilterpaper,an
invertedbeaker,orloosefittingcorktoexcludeairborneimpuritiesfromthe
solution,andallowthefiltratetostandundisturbeduntilithascooledtoroom
temperatureandnomorecrystalsform.Tocompletethecrystallization,placethe
flaskinanicewaterbathforatleastmin.

IsolationandDrying

CollectthecrystalsonaBchnerorHirschfunnelbyvacuumfiltration(Fig.2.54)
andwashthefiltercakewithtwosmallportionsofcoldwater.Pressthecrystalsas
dryaspossibleonthefunnelwithacleancorkorspatula.Spreadthebenzoicacid
onawatchglass,protectingitfromairbornecontaminantswithapieceoffilter

paper,andairdryitatroomtemperatureorinanoven.Becertainthatthe
temperatureoftheovenisbelowthemeltingpointoftheproduct!

Analysis

Determinethemeltingpointsofthecrudeandrecrystallizedbenzoicacid,the
weightofthelattermaterial,andcalculateyourpercentrecoveryusingEquation
3.1.
(3.1)

2.Acetanilide
Apparatus
TwomLErlenmeyerflasks,graduatedcylinder,icewaterbathapparatusfor
magneticstirring,vacuumfiltration,andflamelessheating.

Dissolution

PlacegofimpureacetanilideinanErlenmeyerflaskequippedformagnetic
stirringorwithboilingstones.MeasuremLofwaterintothegraduatedcylinder
andaddamLportionofittotheflask.Heatthemixturetoagentleboil.
Alayerofoilshouldformwhenthestatedamountofwaterisadded.(Ifyouhave
notdonesoalready,reviewthediscussionofCrystallizationinthissection,
focusingonhowtocrystallizecompoundsthatformoils.)Thislayerconsistsofa
solutionofwaterinacetanilide.Morewatermustbeaddedtoeffectcomplete
solutionoftheacetanilideinwater.However,evenifahomogeneoussolutionis
producedattheboilingpointofthemixture,anoilmayseparatefromitascooling
begins.Theformationofthissecondliquidphaseisknowntooccuronlyunder
specificconditions:Theacetanilidewatermixturemusthaveacompositionthatis
betweenandinacetanilideandbeatatemperatureabove.Becausethesolubility
ofacetanilideinwaterattemperaturesnearexceeds,ahomogeneoussolution
formedbyusingtheminimumquantityofwatermeetsthesecriteria.Sucha
solutionwillyieldanoiloncoolingtoabout;solidbeginstoformbelowthis
temperature.
ContinueaddingmLofwaterinmLportionstotheboilingsolutionuntiltheoil
hascompletelydissolved.Caution:Becausethesamplemaybecontaminatedwith
insolublematerial,paycloseattentiontowhetheradditionalsolidisdissolvingas
youaddmoresolvent;ifitisnot,stopaddingsolvent.Oncetheacetanilidehas
justdissolved,addanadditionalmLofwatertopreventformationofoilduring
thecrystallizationstep.Ifoilformsatthistime,reheatthesolutionandaddalittle
morewater.Recordthetotalvolumeofwaterused.
ContinuetheprocedurebyfollowingthedirectionsforDecoloration,Hot
FiltrationandCrystallization,andIsolationandDryinggivenforbenzoicacidin
Part1.

Analysis

Determinethemeltingpointsofthecrudeandrecrystallizedacetanilide,the
weightofthelattermaterial,andcalculateyourpercentrecoveryusingEquation
3.1.

3.Naphthalene
Apparatus

TwomLErlenmeyerflasks,graduatedcylinder,icewaterbathapparatusfor
magneticstirring,vacuumfiltration,andflamelessheating.

Dissolution
Naphthalenemaybeconvenientlyrecrystallizedfrommethanol,ethanol,or2
propanol.Becausethesesolventsaresomewhattoxicand/orflammable,proper
precautionsshouldbetaken.Thesequenceofstepsupthroughthehotfiltration
shouldbeperformedinahoodifpossible.Alternatively,ifinstructedtodoso,
positionaninvertedfunnelconnectedtoavacuumsourceabovethemouthofthe
flaskbeingusedforrecrystallization(Fig.2.71b).
PlacegofimpurenaphthaleneinanErlenmeyerflaskequippedformagnetic
stirringorwithboilingstonesanddissolveitintheminimumamountofboiling
alcohol.Caution:Becausethesamplemaybecontaminatedwithinsoluble
material,paycloseattentiontowhetheradditionalsolidisdissolvingasyouadd
moresolvent;ifitisnot,stopaddingsolvent.ThenaddmLofadditionalsolvent
toensurethatprematurecrystallizationwillnotoccurduringsubsequenttransfers.
Recordthetotalvolumeofsolventused.
ContinuetheprocedurebyfollowingthedirectionsforDecoloration,Hot
FiltrationandCrystallization,andIsolationandDryinggivenforbenzoicacidin
Part1;however,usethesolventinwhichyoudissolvedthenaphthalenerather
thanwater.

Analysis
Determinethemeltingpointsofthecrudeandrecrystallizednaphthalene,the
weightofthelattermaterial,andcalculateyourpercentrecoveryusingEquation
3.1.

4.UnknownCompound
Apparatus
TwomLErlenmeyerflasks,graduatedcylinder,icewaterbathapparatusfor
magneticstirring,vacuumfiltration,andflamelessheating.

Dissolution
Accuratelyweighaboutgoftheunknowncompoundandtransferittoan
Erlenmeyerflaskequippedformagneticstirringorwithboilingstones.Measure
aboutmLofthesolventyouhaveselectedonthebasisofsolubilitytestsintoa
graduatedcylinderandaddmLofittotheflask.Bringthemixturetoagentleboil
usingflamelessheatingunlesswateristhesolvent,addamLportionofthe
solvent,andagainboilthesolution.ContinueaddingmLportionsofsolvent,one

portionatatime,untilthesolidhascompletelydissolved.Bringthesolutionto
boilingafteraddingeachportionofsolvent.Caution:Becausethesamplemaybe
contaminatedwithinsolublematerial,paycloseattentiontowhetheradditional
solidisdissolvingasyouaddmoresolvent;ifitisnot,stopaddingsolvent.
Recordthetotalvolumeofsolventthatisadded.
ContinuetheprocedurebyfollowingthedirectionsforDecoloration,Hot
FiltrationandCrystallization,andIsolationandDryinggivenforbenzoicacidin
Part1.

Analysis

Determinethemeltingpointsofthecrudeandrecrystallizedunknown,theweight
ofthelattermaterial,andcalculateyourpercentrecoveryusingEquation3.1.

5.MixedSolventCrystallization
Apparatus

TwomLErlenmeyerflasks,graduatedcylinderorcalibratedPasteurpipet,ice
waterbathapparatusformagneticstirring,vacuumfiltration,andflameless
heating.

Dissolution
PlacegofimpurebenzoicacidoracetanilideinanErlenmeyerflaskequippedfor
magneticstirringorwithboilingstones.AddmLofethanolandheatthemixture
toagentleboil.Ifnecessary,continueaddingthesolventinmLportionsuntilno
moresolidappearstodissolveintheboilingsolution.Caution:Becausethe
samplemaybecontaminatedwithinsolublematerial,paycloseattentionto
whetheradditionalsolidisdissolvingasyouaddmoresolvent;ifitisnot,stop
addingsolvent.Recordthetotalvolumeofethanolused.

Decoloration

Ifthesolutioniscolored,treatitwithdecolorizingcarbon(Sec.2.18)andafilter
aidaccordingtotheproceduregivenforbenzoicacidinPart1.

HotFiltrationandCrystallization

Ifthereareinsolubleimpuritiesordecolorizingcarboninthesolution,performa
hotfiltration(Sec.2.17)usingamLErlenmeyerflasktoreceivethefiltrate(Fig.
2.52).RinsetheemptyflaskwithaboutmLofhotethanolandfilterthisrinseinto
theoriginalfiltrate.Ifthefiltrateremainscolored,repeatthetreatmentwith
decolorizingcarbon.
ReheatthedecolorizedsolutiontoboilingandaddwaterdropwisefromaPasteur
pipetuntiltheboilingsolutionremainscloudyorprecipitateappears;thismay
requireaddingseveralmillilitersofwater.Thenaddafewdropsofethanolto
produceaclearsolutionattheboilingpoint.Removetheflaskfromtheheating
source,andfollowthesamedirectionsasgivenforbenzoicacidinPart1to
completeboththisstageoftheprocedureandIsolationandDrying.

Analysis

Determinethemeltingpointsofthecrudeandrecrystallizedproduct,theweightof
thelattermaterial,andcalculateyourpercentrecoveryusingEquation3.1.

MicroscaleProcedures
Preparation

RefertotheonlineresourcestoanswerPreLabExercises,accessvideos,andread
theMSDSsforthechemicalsusedorproducedinthisprocedure.Readorreview
Sections2.5,2.6,2.7,2.9,2.17,and3.3.Plantodeterminethemeltingpointsof
boththepurifiedandthecrudesolidsasawaytoshowthebenefitsof
recrystallization.

1.BenzoicAcid
Apparatus
A

testtube,acalibratedPasteurpipetandPasteurfilteringandfiltertippipets,ice
waterbathapparatusforCraigtubefiltrationandflamelessheating.

Dissolution
Placeofbenzoicacidinthetesttube.AddmLofwatertothetubeandheatthe
mixturetoagentleboil.Toaidindissolution,stirthemixturevigorouslywitha
microspatulawhileheating;stirringalsopreventsbumpingandpossiblelossof
materialfromthetesttube.Ifneeded,addmoresolventintomLincrementsto
dissolveanyremainingsolid.Bringthemixturetoboilingandcontinuestirring
aftereachaddition.Onceallthesolidhasdissolved,addanadditionaltomL
portionofsolventtoensurethatthesoluteremainsinsolutionduringtransferof
thehotsolutiontoaCraigtube.Caution:Becausethesamplemaybe
contaminatedwithinsolublematerial,paycloseattentiontowhetheradditional
solidisdissolvingasyouaddmoresolvent.Ifitisnot,stopaddingsolvent.
Recordtheapproximatetotalvolumeofsolventused.

Decoloration
Ifthesolutioniscoloredandtherecrystallizedproductisknownorsuspectedtobe
colorless,treatmentwithdecolorizingcarbon(Sec.2.18)isnecessary.Caution:
Donotadddecolorizingcarbontoaboilingsolution!Coolthesolutionslightly,
addhalfofamicrospatulatipfullofpowderedcarbonor,preferably,apelletor
twoofdecolorizingcarbon,andreheattoboilingforafewminutes.

HotFiltrationandCrystallization
PreheataPasteurfilteringpipetbypullinghotsolventintothepipet.Thentransfer
thehotsolutionintothispipetwithaPasteurpipetorfiltertippipetthathasalso
beenpreheatedwithsolvent,usingthetaredCraigtubeasthereceiverforthe
filtrate(Fig.2.53).Ifdecolorizingcarbonorotherinsolublematterappearsinthe

Craigtube,passthesolutionthroughthefilteringpipetasecondand,ifnecessary,
athirdtime.ConcentratetheclearsolutionintheCraigtubetothepointof
saturationbyheatingittoboiling.Ratherthanusingaboilingstonetoprevent
superheatingandpossiblebumping,continuallystirthesolutionwitha
microspatulawhileheating.Thesaturationpointwillbesignaledbythe
appearanceofcloudinessinthesolutionand/ortheformationofcrystalsonthe
microspatulaattheairliquidinterface.Whenthisoccurs,addsolventdropwiseat
theboilingpointuntilthecloudinessisdischarged.Thenremovethetubefromthe
heatingsource,capthetubewithalooseplugofcottontoexcludeairborne
impurities,andallowthesolutiontocooltoroomtemperature.Ifnecessary,
inducecrystallizationbygentlyscratchingthesurfaceofthetubeattheairliquid
interfaceorbyaddingseedcrystals,iftheseareavailable.Tocomplete
crystallization,coolthetubeinanicewaterbathforatleastmin.

IsolationandDrying

AffixawireholdertotheCraigtubeand,usingthewireasahanger,invertthe
apparatusinacentrifugetube(Fig.2.55).Removethesolventbycentrifugation,
carefullydisassembletheCraigtube,andscrapeanycrystallineproductclinging
toitsuppersectionintothelowerpart.Protecttheproductfromairborne
contaminantsbypluggingtheopeningofthetubewithcottonorbycoveringit
withapieceoffilterpaperheldinplacewitharubberband.Airdrythecrystalsto
constantweighteitheratroomtemperatureorinanoven.Becertainthatthe
temperatureoftheovenisbelowthemeltingpointoftheproduct!

Analysis

Determinethemeltingpointsofthecrudeandrecrystallizedbenzoicacid,the
weightofthelattermaterial,andcalculateyourpercentrecoveryusingEquation
3.1.

2.Acetanilide
Apparatus
A

testtube,acalibratedPasteurpipetandPasteurfilteringandfiltertippipets,ice
waterbathapparatusforCraigtubefiltrationandflamelessheating.

Dissolution
Placemgofacetanilideinthetesttube.AddmLofwatertothetubeandheatthe
mixturetoagentleboil.Toaidindissolution,stirthemixturevigorouslywitha
microspatulawhileheating;stirringalsopreventsbumpingandpossiblelossof
materialfromthetesttube.Alayerofoilshouldformwhenthestatedamountof
waterisadded.Anexplanationforthisphenomenonisfoundunderthe
DissolutionstageofPart2oftheMiniscaleProcedures.Continueaddingwaterin
mLportionstotheboilingsolutionuntiltheoilhascompletelydissolved.

Caution:Becausethesamplemaybecontaminatedwithinsolublematerial,pay
closeattentiontowhetheradditionalsolidisdissolvingasyouaddmoresolvent;if
itisnot,stopaddingsolvent.
Oncetheacetanilidehasjustdissolved,addanadditionalmLofwatertoprevent
formationofoilduringthecrystallizationstep.Ifoilformsatthistime,reheatthe
solutionandaddalittlemorewater.Recordtheapproximatetotalvolumeofwater
used.
ContinuetheprocedurebyfollowingthedirectionsforDecoloration,Hot
FiltrationandCrystallization,andIsolationandDryinggivenforbenzoicacidin
Part1.

Analysis

Determinethemeltingpointsofthecrudeandrecrystallizedacetanilide,the
weightofthelattermaterial,andcalculateyourpercentrecoveryusingEquation
3.1.

3.Naphthalene
Apparatus
A

testtube,acalibratedPasteurpipetandPasteurfilteringandfiltertippipets,ice
waterbathapparatusforCraigtubefiltrationandflamelessheating.

Dissolution
Naphthalenemaybeconvenientlyrecrystallizedfrommethanol,ethanol,or2
propanol.Becausethesesolventsaresomewhattoxicand/orflammable,proper
precautionsshouldbetaken.Ifinstructedtodoso,positionaninvertedfunnel
connectedtoavacuumsourceabovethemouthofthetesttubebeingusedfor
recrystallization(Fig.2.71b)tominimizereleaseofvaporsintothelaboratory.
Placemgofnaphthaleneinthetesttubeanddissolveitinaminimumamountof
boilingsolvent.Caution:Becausethesamplemaybecontaminatedwithinsoluble
material,paycloseattentiontowhetheradditionalsolidisdissolvingasyouadd
moresolvent;ifitisnot,stopaddingsolvent.ThenaddmLofadditionalsolvent
toensurethatprematurecrystallizationwillnotoccurduringsubsequenttransfers.
Recordthetotalvolumeofsolventused.
ContinuetheprocedurebyfollowingthedirectionsforDecoloration,Hot
FiltrationandCrystallization,andIsolationandDryinggivenforbenzoicacidin
Part1;however,ratherthanwater,usethesolventinwhichyoudissolvedthe
naphthalene.

Analysis
Determinethemeltingpointsofthecrudeandrecrystallizednaphthalene,the
weightofthelattermaterial,andcalculateyourpercentrecoveryusingEquation
3.1.

4.UnknownCompound
Apparatus
A

testtube,acalibratedPasteurpipetandPasteurfilteringandfiltertippipets,ice
waterbathapparatusforCraigtubefiltrationandflamelessheating.

Dissolution
Ifinstructedtodoso,positionaninvertedfunnelconnectedtoavacuumsource
abovethemouthofthetesttubebeingusedforrecrystallization(Fig.2.71b)to
minimizereleaseofvaporsintothelaboratory.Placemgoftheunknowninthe
testtubeanddissolveitinaminimumamountofboilingsolventyouselectedon
thebasisofsolubilitytests.Caution:Becausethesamplemaybecontaminated
withinsolublematerial,paycloseattentiontowhetheradditionalsolidis
dissolvingasyouaddmoresolvent;ifitisnot,stopaddingsolvent.ThenaddmL
ofadditionalsolventtoensurethatprematurecrystallizationwillnotoccurduring
subsequenttransfers.Recordthetotalvolumeofsolventused.
ContinuetheprocedurebyfollowingthedirectionsforDecoloration,Hot
FiltrationandCrystallization,andIsolationandDryinggivenforbenzoicacidin
Part1;however,ifyouarenotusingwater,usethesolventinwhichyoudissolved
theunknown.

Analysis
Determinethemeltingpointsofthecrudeandrecrystallizedunknown,theweight
ofthelattermaterial,andcalculateyourpercentrecoveryusingEquation3.1.

5.MixedSolventCrystallization
Apparatus
A

testtube,acalibratedPasteurpipetandPasteurfilteringandfiltertippipets,ice
waterbathapparatusforCraigtubefiltrationandflamelessheating.

Dissolution

Placemgofbenzoicacidoracetanilideinthetesttube.AddmLofethanoland
heatthemixturetoagentleboil.Ifnecessary,continuetoaddethanoldropwiseby
Pasteurpipetuntilahomogeneoussolutionisobtained.Caution:Becausethe
samplemaybecontaminatedwithinsolublematerial,paycloseattentionto
whetheradditionalsolidisdissolvingasyouaddmoresolvent;ifitisnot,stop
addingsolvent.Onceallthesolidhasdissolved,addanadditionaltomLportion
ofsolventtoensurethatthesoluteremainsinsolutionduringtransferofthehot
solutiontoaCraigtubeand,ifnecessary,decolorizethesolutionaccordingtothe
directionsinPart1forbenzoicacid.

HotFiltrationandCrystallization

PreheataPasteurfilteringpipetbypullinghotsolventintothepipet.Thentransfer
thehotsolutionintothispipetwithaPasteurpipetorfiltertippipetthathasalso
beenpreheatedwithsolvent,usingthetaredCraigtubeasthereceiverforthe
filtrate(Fig.2.53).Ifdecolorizingcarbonorotherinsolublematterappearsinthe
Craigtube,passthesolutionthroughthefilteringpipetasecondand,ifnecessary,
athirdtime.
ReheatthedecolorizedsolutiontoboilingandaddwaterdropwisefromaPasteur
pipetuntiltheboilingsolutionremainscloudyorprecipitateforms.Ratherthan
usingaboilingstonetopreventsuperheatingandpossiblebumping,continually
stirthesolutionwithamicrospatulawhileheating.Thenaddadroportwoof
ethanoltorestorehomogeneity.Removethetubefromtheheatingsource,capthe
tubewithalooseplugofcottontoexcludeairborneimpurities,andallowthe
solutiontocooltoroomtemperature.Followthesamedirectionsasgivenfor
benzoicacidinPart1tocompleteboththisstageoftheprocedureandIsolation
andDrying.

Analysis
Determinethemeltingpointsofthecrudeandrecrystallizedproduct,theweightof
thelattermaterial,andcalculateyourpercentrecoveryusingEquation3.1.

DiscoveryExperiment
FormationofPolymorphs
Developanexperimentalprocedureforformingpolymorphs(seetheHistorical
HighlightPolymorphism,whichisavailableonline)oftranscinnamicacidor
derivativesthereofbyreferringtothefollowingpublications:Bernstein,H.I.;
Quimby,W.C.,J.Am.Chem.Soc.1943,65,18451848;Cohen,M.D.;Schmidt,
G.M.J.;Sonntag,F.I.,J.Chem.Soc.1964,20002013.Consultwithyour
instructorbeforeundertakingyourproposedprocedure.

WrappingItUp
Flushanyaqueousfiltratesorsolutionsdownthedrain.Withtheadviceofyour
instructor,dothesamewiththefiltratesderivedfromuseofalcohols,acetone,or
otherwatersolublesolvents.Usetheappropriatecontainersforthefiltrates
containinghalogenatedsolventsorhydrocarbonsolvents.Putfilterpapersinthe
containerfornontoxicwaste,unlessinstructedtodootherwise.

ExperimentalProcedures:MeltingPoints

Purpose
Todeterminemeltingpointsusingthecapillarytubemethod.
7
8
9

10

11
12

SafetyAlert

Wearsafetyglassesorgogglesandsuitableprotectivegloveswhileperformingthe
experiments.
Ifaburnerisusedinthisexperiment,besurethatnoflammablesolventsare
nearby.Keeptherubbertubingleadingtotheburnerawayfromtheflame.Turn
offtheburnerwhenitisnotbeingused.
Somekindsofmeltingpointapparatus,suchastheThieletube,usemineralor
siliconeoilsastheheattransfermedium.Theseoilsmaynotbeheatedsafelyif
theyarecontaminatedwithevenafewdropsofwater.Heatingtheseoilsabove
mayproducesplatteringofhotoilasthewaterturnstosteam.Firecanalsoresult
ifspatteredoilcomesincontactwithopenflames.ExamineyourThieletubefor
evidenceofwaterdropletsintheoil.Ifthereareany,eitherchangetheoilor
exchangetubes.Givethecontaminatedtubetoyourinstructor.
Mineraloilisamixtureofhighboilinghydrocarbonsandshouldnotbeheated
abovebecauseofthepossibilityofspontaneousignition,particularlywhena
burnerisusedforheating.Somesiliconeoilsmaybeheatedtoaboutwithout
danger(Sec.2.9).
Becarefultoavoidcontactofchemicalswithyourskin.Cleanupanyspilled
chemicalsimmediatelywithabrushorpapertowel.
IfyouuseaThieletube,handleitcarefullywhenyouarefinished,becausethe
tubecoolsslowly.Toavoidburns,takecarewhenremovingitfromitssupport.

CalibrationofThermometer

Procedure
Preparation

RefertotheonlineresourcestoanswerPreLabExercises,accessvideos,andread
theMSDSsforthechemicalsusedorproducedinthisprocedure.Readorreview
Sections2.7and2.9.

Apparatus

Capillarymeltingpointtubes,packingtube,meltingpointapparatus.

Protocol

Carefullydeterminethecapillarymeltingpointsofaseriesofstandardsubstances.
AlistofsuitablestandardsisprovidedinTable3.2.Thetemperaturesgivenin

Table3.2correspondtotheupperlimitofthemeltingpointrangeforpure
samplesofthesestandards.

Table3.2
StandardsforThermometerCalibration
Compound

MeltingPoint

Icewater

3Phenylpropanoicacid

48.6

Acetamide

82.3

Acetanilide

114

Benzamide

133

Salicylicacid

159

4Chloroacetanilide

179

3,5Dinitrobenzoicacid

205

Plotthecorrectionsinyournotebookasdeviationsfromzeroversusthe
temperatureovertherangeencompassedbythethermometer.Thisallowsyouto
tell,forexample,thatataboutthethermometergivesreadingsthataretoolow,or
thatatthereadingsareabouttoohigh.Thesevaluesshouldthenbeappliedto
correctalltemperaturemeasurementstaken.Thecorrectionsyouobtainarevalid
onlyforthethermometerusedinthecalibration.Ifyoubreakit,notonlyareyou
likelytobechargedforareplacement,butyoumustrepeatthecalibration.

DeterminingCapillaryTubeMeltingPoints

Procedure
Preparation
RefertotheonlineresourcestoanswerPreLabExercises,accessvideos,andread
theMSDSsforthechemicalsusedorproducedinthisprocedure.Readorreview
Sections2.7and2.9.Plantopreparetwomeltingpointtubesifyouare
determiningthemeltingpointsofunknowncompounds.

Apparatus
Capillarymeltingpointtubes,packingtube,meltingpointapparatus.

1.PureCompound
Protocol

Selectoneormorecompoundsfromalistofavailablecompoundsofknown
meltingpointanddeterminethemeltingpointranges.Repeatasnecessaryuntil
youobtainaccurateresultsandareconfidentwiththetechnique.

2.UnknownCompound
Protocol

Accuratelydeterminethemeltingrangeofanunknownpurecompoundsupplied
byyourinstructor.

3.MixedMeltingPoints
SamplePreparation

Prepareasampleformixedmeltingpointdeterminationbyintroducingofa
secondsubstanceasanimpurityintoasolidwhosemeltingpointwasdetermined
inPart1.Intimatelymixthetwocomponentsbygrindingthemtogetherwitha
smallmortarandpestle.Alternatively,useasmall,cleanwatchglassandglass
stirringrodormetalspatulatomixthecomponents.Becarefulnottoapplytoo
muchpressuretotheglassrod,however,becauseitismorefragilethanapestle
andmaybreak.Donotperformthisoperationonapieceoffilterpaper,because
fibersfromthepapermaycontaminatethesample.

Protocol

Accuratelydeterminethemeltingrangeofthesampleandcompareittothatofthe
majorcomponentofthemixturetostudytheeffectofimpuritiesonthemelting
rangeofapreviouslypurecompound.

DiscoveryExperiment
MeltingPointDepression

Obtainapairofsolidswhosemeltingpointsarewithinofoneanotherand
determinewhethertheyindeeddepressoneanothersmeltingpoints.Some
possibleexamplesare3furoicacidandbenzoicacid,1naphthylaceticacidand
2,5dimethylbenzoicacid,transcinnamicacidand2furoicacid,2
methoxybenzoicacidandmalicacid,ordimethylfumarate,9fluorenone,and
methyl4bromobenzoate.Consultwithyourinstructorregardingtheseandother
possibilities.

WrappingItUp
Returnanyunusedsamplestoyourinstructorordisposeofthemintheappropriate
containerfornonhazardousorganicsolids.Discardtheusedcapillarytubesina
containerforbrokenglass;donotleavethemintheareaofthemeltingpoint
apparatusorthrowtheminwastepaperbaskets.

WhoElseHasMyCompound?

DiscoveryExperiment

Scienceisacollaborativeenterprise,andteamsofscientistsoftenworktogetherto
makediscoveries.Itisalsocommonforgroupsofresearchersfromdifferentparts
oftheworldtocollaboratebysharingexperimentaldataandexchangingsamples.
Thegroupsmustthenestablishthatthesampleswithwhichtheyareworkingare
identical.
Howdoyouknowiftwocompoundsarethesame?Amongorganicchemicals,
therearemanycolorless(white)andcoloredsolidsandliquids,soavisual
inspectionisusuallyinsufficienttodetermineidentity.Rather,wemustrelyupon
comparisonofmeasuredphysicalproperties.Inthisexperiment,youwillbe
workingwithyourclassmatestodiscoverwhichofyouhavethesamecompound
andwhatthatcompoundis.Throughsolvingthispuzzle,youwilllearnsomebasic
techniquesforanalyzingandidentifyingorganiccompounds.
Thefirstpartofthepuzzleinvolvesmeasuringphysicalpropertiesofyour
compoundandcomparingthemwithdataobtainedbyotherstudents.Thesecond
partisprovingthatallthesampleswiththesameorsimilarpropertiesareindeed
identical.Underthesameconditions,compoundshavingcomparableproperties
maybethesame,butcompoundshavingdifferentpropertiesareclearlynot.
Completingthepuzzlerequiresthatthecompoundbeidentified.Inthisregard,
singlemeasurementsbythemselvesareinsufficientforidentifyingacompound.
Forexample,justknowingthatacompoundisaclearliquidatroomtemperature
andhasameltingpointofrulesoutmanypossibilities,butavarietyofcompounds
meltat.Knowingthatthecompoundmeltsat,boilsat,hasadensityofg/mL,
andissolubleinmethanolbutnotinhexanegivesusgreaterconfidencethatthe
substanceiswater.Accordingly,asyoucollectmoredata,yourconfidencein
matchingcompoundsthatmaybethesamewillincreaseaswillyourconfidence
inestablishingtheidentityofthecompound.
Youwillbegivenanumberedsampleofacolorlesspuresolidasyourpieceofthe
puzzle.Thefirstgoalinsolvingthepuzzleisfindingwhoelseinthelaboratoryhas
thesamecompoundasyou.Toaccomplishthistask,youwilldeterminesome
propertiesofyoursample,suchasitsmeltingpoint(Section3.3),itssolubilityin
twosolvents(waterandaqueoussodiumhydroxide),anditsonathinlayer
chromatography(TLC)plate(Section6.2).Youwillthenshareyourresultsby
recordingthedatainacentrallocationtofindtheotherstudentswhohavea
compoundwhosepropertiesarethesameasorsimilartoyours.Strategiesfor
makingunambiguouscomparisonsthatwillultimatelyprovetheidentityof
differentsamplesareprovidedbelow.
Yourlaboratorynotebookshouldcontainallthedatayouobtained,aswellasa
briefcompilationofthedatareportedbytheotherstudentswhosedataare
comparabletoyours.Theselabmatesandyouwillhaveasecondgoalof
determiningexactlywhichcompoundyourgrouphas.Toaccomplishthis

objective,thegroupwillbegivenalistofpossiblecomparisonsubstancestouse
formakingafinalidentificationofthecompound.Thesesubstanceswillalsobe
availableforactuallymakingthecomparisons.Asbefore,suggestionswillbe
providedthatallowyoutoprovetheidentityofyoursampleandthecomparison
compound.

ExperimentalProcedures

Purpose
Todemonstratetheequivalenceofdifferentsamplesandprovetheir
structure.
13
14
15

SafetyAlert

Wearsafetyglassesorgogglesandsuitableprotectivegloveswhileperformingthe
experiments.
ThesolventsusedforTLCanalysisarehighlyflammable,sodonothandlethese
liquidsnearopenflames.
TheMsolutionofsodiumhydroxideiscaustic.Donotallowittocomeinto
contactwithyourskin.Ifthisshouldhappen,thoroughlyrinsetheaffectedarea
withwater.

Preparation

RefertotheonlineresourcestoanswerPreLabExercises,accessvideos,andread
theMSDSsforthechemicalsusedorproducedinthisprocedure.ReviewSections
3.2,3.3,and6.2.

DeterminingMeltingPoints

Apparatus

Apparatusfordeterminingmeltingpoints.

Analysis

Accuratelydeterminethemeltingpointofyourunknownsolid.

TestingSolubility

Apparatus
Two

testtubes,calibratedPasteurpipet,microspatula.

Dissolution

PlaceapproximatelymLofwaterinthefirsttesttube.Addaboutamicrospatula
tipfulloftheunknownsolidtothetesttubeandgentlystirthemixturewiththe
spatula.PlacemLofMaqueoussodiumhydroxideinthesecondtesttube.Add
aboutamicrospatulatipfulloftheunknownsolidtothistesttubeandgentlystir
themixturewiththespatula.Forbothtests,recordyourobservationsinyour
laboratorynotebook.

ThinLayerChromatography

Apparatus
Widemouthbottleswithscrewtopcaps,

silicagelTLCplates,capillarypipet,

testtube,microspatula.

SettingUp
DissolveamicrospatulatipfullofyourcompoundinapproximatelymLof
acetoneandstirthemixturetoeffectdissolution.Usingacapillarypipet,spotthe
solutiononeachofthreeTLCplates.

Analysis
Developoneplateinethylacetate,oneplateinhexane,andoneplateinamixture

ofethylacetate:hexane(byvolume).VisualizeyourplatesunderUVlight,
calculatethevalues,andrecordtheresultsinyourlaboratorynotebookandwhere
otherstudentscanseethem.

ComparingDataandDeterminingtheStructureofthe
Unknown

Apparatus

Apparatusfordeterminingmeltingpoints,several

testtubes,calibratedPasteurpipets,microspatula,widemouthbottlewithscrew
topcap,

silicagelTLCplates,capillarypipet.

GroupAnalysis

Workingwithmembersofyourgroup,obtainmixedmeltingpointsforeach
combinationofsamplesinthegrouptoprovethattheyarethesamecompound.
Usingthesolventsystemyoudeterminedtobethebestforyourcompound,
performaTLCanalysisbyspottingtheTLCplatewithtwodifferentsamplesand
athirdcospot(Section6.2)thathasbothsamplesspottedatthesamelocation.
Thistechniqueminimizesthepossibilitythatdifferingvaluesforthetwosingle
spotsresultfromvariationsinwherethespotswereappliedtotheplateortothe
concentrationofthesamplebeingspotted,asdiscussedinSection6.2.Theresult
oftheTLCanalysisshouldreinforcetheconclusionyoureachontheidentityof
samplesbasedontheresultsofmeasuringmixedmeltingpoint.
UsingthemeltingpointandTLCdatayourgrouphasobtainedandcomparingitto
theknowncompoundsprovidedbyyourinstructor,decidewhichcompoundyou
arelikelytohaveandobtainanauthenticsampleofit.Demonstratetheidentityof
yoursampleandtheknowncompoundbyperformingappropriatemixedmelting
points,solubilitytests,andTLCanalysis.

WrappingItUp

PuttheorganicsolventsfromTLCanalysisintheappropriatecontainerfor
nonhalogenatedorganicliquids.Disposeoftheaqueoussolutionsfromthe
solubilitytestsintheappropriateaqueouswastecontainer.DiscardTLCplatesin

theappropriatesolidwastecontainerandthecapillarypipetsinthebrokenglass
container.