Experiment

PurificationbyRecrystallization

Objectives
1)

Tobeabletoselectanappropriaterecrystallizingsolvent.

2)

Toseparateandpurifyacetanilidebyrecrystallization.

3)

Tocomparethemeltingpointsofimpureandrecrystallizedacetanilide.

Introduction

Impurities often contaminate organic compounds that have been synthesized in the

laboratory or isolated from natural sources. Recrystallization is a purification process used to

removeimpuritiesfromorganiccompoundsthataresolidsatroomtemperature.Thisprocess
is based on the premise that the solubility of a compound in a solvent increases with
temperature.Conversely,thesolubilityofthecompounddecreasesasthesolutioncools,and
thatswhenthecrystalsareformed.

Verypurecompoundscanbeproducedbyrecrystallization.Asaheatedsolutionofthe

desired compound cools, a small, pure seed crystal of the compound forms in the solution.
Layerbylayer,additionalmoleculesattachtothiscrystal,formingagrowingcrystallattice,as
showninFigure1.Themoleculesinthecrystalhaveagreateraffinityforothermoleculesof
thesamekindthantheydoforanyimpuritiespresentinthesolution.Ineffect,theprocessof
crystalformationremovesonekindofmoleculefromthesolution.

Figure1.(a)Identicalmoleculesattachtooneanother,formingacrystallattice;
(b)impuritieshavedifferentshapesorsizesanddonotpacktogether.

Selectinganappropriaterecrystallizingsolventtouseisprobablythemostdifficultstep

of recrystallization. The primary consideration when choosing a recrystallizing solvent is the

extent to which the compound and impurities are soluble in the solvent at high, and low
temperatures.ThegraphinFigure2showsthreepossiblescenariosforhowthesolubilitiesof
thecompoundandtheimpuritiesdependontemperature.

Ideally,thecompoundtoberecrystallizedshouldbeverysolubleinthechosensolvent

at elevated temperatures, but almost insoluble in the cold solvent, as shown by line A.
Impuritiesshouldbesolubleinthechosensolventatalltemperaturessothatimpuritiesstayin
solutionasshownbylineB.Alternatively,impuritiesshouldbeinsolubleatalltemperaturesso
theycanbefilteredoutofthehotsolution,asshownbylineC.

Figure2.Idealsolubilitypatternsofacompound,lineA,andaccompanyingimpurities,
linesBandC,atvaryingtemperatures

Experimentation is needed to select an appropriate recrystallizing solvent. Typically,

severalsolventsareusedtotesttheextentofsolubilityofthecompound.Asmallamountof
the compound is mixed with a few milliliters of each solvent. The compounds solubility is
observedatroomtemperatureandnearthesolventsboilingpoint.Ifthecompoundissoluble
inasolventatroomtemperature,thesolventisnotsuitable.Ifthecompoundisinsolubleat
room temperature and soluble near the solvents boiling point, the solvent is a suitable
candidate.

Insolubleisarelativeterm.Forexample,benzoicacidinwaterhasasolubilityof6.80

gramsper100millilitersat100C.However,benzoicacidhasasolubilityofonly0.34gramper
100millilitersat25C.Benzoicacidistypicallylistedasinsolublein25Cwater.

When considering the solubility of a compound, a general rule is like dissolves like.

Polarorganicmoleculescontainfunctionalgroupsthatcanhydrogenbond,suchasOH,NH2,
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and COOH. Polar molecules are generally most soluble in polar solvents. Many organic
moleculesarenonpolarandaremostlysolubleinnonpolarsolvents.Alistofcommonlyused
recrystallizationsolventsisshowninTable1.

Table1.Commonlyusedrecrystallizationsolvents,inorderofdecreasingpolarity

Theboilingpointoftherecrystallizationsolventshouldbelowerthanthemeltingpoint

of the compound to be recrystallized. If the solvents boiling point is higher than the
compoundsmeltingpoint,thecompoundwilloilout.Oilingoutoccurswhenacompoundis
insolubleinasolutionatatemperatureabovethecompoundsmeltingpoint.Asaresult,the
compoundisdepositedasanoil,andnotascrystals.

Anotherimportantcriterionforselectingarecrystallizingsolventrelatestorecoveryof

the compound. An abundant quantity of crystals must be produced as the solution cools to
room temperature or below. Here is a summary of the four major criteria for selecting a
recrystallizingsolvent:
1. Compoundbeingpurifiedmustbeinsolubleinsolventatroomtemperature
2. Compoundmustbesolubleathightemperatureorinboilingsolvent
3. Solventsboilingpointmustbelowerthanthecompoundsmeltingpoint
4. Anabundantquantityofcrystalsmustberecoverablefromthecoolsolvent

Often, the requirements necessary for successful recrystallization are not met by a

single solvent. In these cases, a mixture of two solvents, called a solvent pair, is used. Two
solventsareselectedthataremisciblewitheachother,buthaveoppositeabilitiestodissolve
thecompound.Thecompoundtoberecrystallizedshouldbesolubleinonesolvent(A)orthe
pairandshouldberelativelyinsolubleinthesecondsolvent(B).

Todeterminethepropercombinationsofthetwosolvents,thecompoundisdissolved

inaminimumvolumeofsolventAneartheboilingtemperatureofthissolvent.Next,solventB
isaddedtotheboilingmixtureuntilthemixturebecomescloudy,indicatingthatthecompound
isprecipitatingfromsolution.AfewdropsofsolventAareaddedtoredissolvetheprecipitate,
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producing a clear solution. Then the solvent pair is treated just like a single recrystallization
solvent.Commonsolventpairsareethanolandwater,acetoneandether,andaceticacidand
water.

Onceasuitablesolventisfound,therecrystallizationprocessiscontinuedbydissolving

the compound in a minimum volume of boiling solvent. Then a five percent excess of the
solventisaddedtothesaturatedsolutiontopreventprematurecrystallization.Forexample,if
10mLofaboilingsolventisrequiredtojustdissolveacompound,fivepercentof10mLor0.5
mLwouldbeaddedtobringthetotalvolumeto10.5mL.

Occasionally, a sample may contain an insoluble impurity that can be removed by

filtration. The hot solution is filtered by gravity filtration through a funnel containing a fluted
filter paper. If no undissolved impurities are present, the filtration step can be omitted. A
typicalgravityfiltrationapparatusisshowninFigure3.Thefunnel,filterpaper,andcollecting
flaskareheatedwithboilingsolventpriortofiltratingthesolutiontopreventprematurecrystal
formation. Usingaflutedfilterpaperincreasessurfaceareainsidethefunnelandspeedsthe
filteringprocess.Figure4showshowtomakeaflutedfilterpaper.

Afterthecompoundisdissolvedinaminimalamountofboilingsolventandthesolution

isfiltered,asnecessary,thesolutionisallowedtoslowlycooltoroomtemperature.Ifcrystal
formationoccurstoorapidly,impuritiesmaybecometrappedinthecrystals.Therefore,placing
thesolutioninanicewaterbathwillcompromisethepurityofthecrystalssincetheyusually
formfasteratlowertemperatures

Glass funnel
with fluted
filter paper

Solution to be
filtered
Solvent for
heating the
funnel and
filter paper

Collecting
flask

Figure3.Gravityfiltrationapparatusofhotfiltration

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Figure4.Foldingaflutedfilterpaper

Sometimes,crystalsdonotformeveninthecooledsolution.Inthiscase,twomethods

can be used to induce crystallization. One method involves scratching the inside of the flask
withaglassstirringrod.Thefreshlyscratchedglasssuppliedsitesforseedingcrystalformation.
Alternatively,aseedcrystalofthepurecompoundcanbeplacedintothesolutiontopromote
crystalgrowth.

Filteredpaper
(Trimmedtofit
bottomoffunnel)

Figure5.Vacuumfiltrationapparatus

After letting the compound crystallize, vacuum filtration is the best method for

separatingthecrystalsfromthemotherliquor,orremainingsolvent.Atypicalvacuumfiltration
apparatusisshowninFigure5.Afilterflask(orsuctionflask)isconnectedtoavacuumsource.
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Themostcommonsourceofvacuumisawateraspirator.ABchnerfunnelisfittedtothefilter
flask with a rubber stopper or filter adapter. To recover the pure crystals, the perforated
Bchner funnel plate is covered with a filter paper, which is moistened with recrystallizing
solvent. With vacuum applied, the solution containing the suspended crystals is poured onto
thefilterpapersothatauniformthicknessofcrystalscollectsonthepaper.Afterthemother
liquor has been pulled through the filter, the crystals are washed with small portions of cold
solvent. Then the crystals are dried and their mass is measured. The efficiency of the
recrystallization can be determined by calculating the recovery percentage as shown in the
equationbelow.

Purityofarecrystallizedcompoundisaccessedbyobservingitscolorandbymeasuring

itsmeltingpointrange.Ifacompoundisdescribedinthechemicalliteratureashavingwhite
crystals,therecrystallizedcompoundshouldappearwhite.Also,apurecompoundmeltsovera
narrowrangeof13Cnearitsreportedmeltingpoint.

ExperimentalProcedure
1) Labelfourtesttubesasacetone,ethanol,ethylacetate,andwater.
2) Placeapproximately50mgofacetanilideintoeachtesttube(50mgisaboutthesizeofone
grainofrice).
3) Place 1 mL of the corresponding solvent into each test tube. Thoroughly shake each
mixture. Record whether the acetanilide is soluble or insoluble in each solvent at room
temperature.
4) Select the test tube(s) containing the solvent(s) in which acetanilide did not dissolve at
roomtemperature.Placethetubeinasteambathforafewminutesandrecordwhether
acetanilideissolubleorinsolubleineachhotsolvent.
5) Allowtheheatedtesttube(s)tocooltoroomtemperature.Placethetube(s)intotheice
water bath for a few minutes and observe whether recrystallization occurs. Record your
observation.
6) Based on your observations, choose an appropriate solvent from which to recrystallized
acetanilide.Consultyourinstructorregardingyoursolventofchoicebeforeproceeding.
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7) Obtainasampleofimpureacetanilidefromyourinstructor.
8) Place the rest of the sample in a preweighed Erlenmeyer flask. Weigh and record the
weightofthesampleintheflask.
9) Add 10 mL of the solvent. Heat the mixture on a hotplate and swirl occasionally. Do not
allowthemixturetoboilvigorously.Ifsampledoesntcompletelydissolvewhenthesolvent
starts to boil, add a small amount of solvent until a clear solution is obtained. However,
impuritiesorsomeblackparticlesmaystillexist.
10) SetupahotfiltrationapparatusasshowninFigure3.Heatthefunnelbyusingapipetteto
transfer510millilitersoftheextrahotsolventinthebeakertothefunnel.
11) Use beaker tongs to pick up the flask containing the sample solution. Slowly pour the
solutionontothefunnel.Donotallowthesolutiontooverflowoutoftheflutedfilterpaper.
12) Whenthefiltrationiscompleted,rinsethefilterpaperandthefunnelwithafewmilliliters
ofhotsolventinthebeaker.Combinetherinseinthecollectingflask.
13) Turnoffthehotplate.Carefullyremovethecollectingflaskfromthehotsurface.Allowthe
solutiontocooltoroomtemperature.Thismaytakeupto30minutes.
14) Iftheformationofcrystalsdoesnotoccurevenatroomtemperature,placetheflaskinan
icewaterbathfor1015minutes.
15) SetupavacuumfiltrationapparatusasshowninFigure5.Turnonthewateraspiratorand
moistenthefilterpaperwithsomecoldsolvent.
16) Swirl the flask to facilitate the transfer of the suspension. Carefully pour the content into
theBchnerfunnelandrinsetheflaskwithcoldsolvent.
17) AllowthecrystalstoairdryontheBchnerfunnelforafewminutes.Transferthecrystals
ontoawatchglass.
18) Placethewatchglassonasteambathinordertodrythecrystals.Useaspatulatoensure
thatthecrystalsaredriedthoroughly.
19) Set aside 50 mg of the crystals for the determination of the postcrystallization melting
point. Put the rest of the dry crystals in a preweighed plastic bag. Weigh and record the
weightofyourcrystallizedproduct.Calculatetherecoverypercentage.

LaboratorySafetyPrecaution
1) Wearsafetygogglesandlabcoatatalltimeswhileworkinginthelaboratory.
2) Acetanilide is toxic and irritating. Acetone, ethanol, and ethyl acetate are flammable and
irritating.

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3) Toavoidshortcircuitingormeltingofwires,makesurethattheelectricalwireofthehot
plateisfullyuncoiledfromthemetalpart..
4) Washyourhandsthoroughlywithsoapordetergentbeforeleavingthelaboratory.
5) Takecaretoavoidburningyourselfwhenusingelectrichotplates.

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