1

EXP1
AnswerstoPrelabQuestions

1.Theproperprocedureforrecrystallizationistoallowthehotsolutiontocoolto
roomtemperature,thentochillthesolutioninanicebath.Whydowenot
simplychillthehotsolutioninanicebathinitially?
Ans.Ifthehotsolutionischilledrapidly,precipitation(crystalsizesareverysmall)
occursinsteadofcrystallization,andtheproductwillprobablybecontaminated
withimpurities.

2.Explainwhetherornoteachofthefollowingpairsofsolventsmightbeuseful
asasolventpairforrecrystallization.

(a)ethanolmethanol (b)hexanecyclohexane (c)acetone

ethanol
(d)waterethanol (e)watercyclohexane

Ans.
a. ethanolmethanolNo.Thereisnodifferenceinpolarity(botharepolar
andprotic)
b. hexanecyclohexaneNo.Thereisnodifferenceinpolarity(bothare
nonpolar).
c. acetoneethanolNo.Sameas(a).
d. waterethanolYes.Waterandethanolaremiscibleandhavedifferent
solvatingcharacteristics(ethanolislesspolaranddissolvesorganic
compoundswhilewaterdoesnot)
e. watercyclohexaneNo.Thispairofsolventsisnotmiscible.

PostlabAssignment
AnswertoQuestions1&3inTechniques..,p116
**Findawaytoincorporatetheseintopostlabdiscussion!
1. Describethecharacteristicsofagoodrecrystallizationsolvent.
Ans.Agoodrecrystallizationsolventis
a. Thesolidtoberecrystallizedisverysolublewhenthesolventisnearitsboiling
temperatureandonlysparinglysolublewhenthesolventisatroomtemperature
orbelow.
b. Thesolidiseitherverysolubleincoldsolventorinsolubleinhotsolvent.

51LAW07TANote
 2
c. Thesolidshouldnotreactwiththesolvent.
d. Thesolventshouldbereasonablyvolatile,nontoxic,nonflammable,and
inexpensive.

3. Explainhowtherateofcrystalgrowthcanaffectthepurityofarecrystallized
compound.
Ans.Ifacompoundiscrystallizedtooquickly,impuritiescanbetrappedinthecrystal
lattice.Slowcrystallizationallowsformaximumselectivity(purity)incrystalformation.

51LATANotesExp#2
IdentificationofaWhiteSolid
PreandPostLabQuestions

AnswerstoPrelabQuestions

1.Whatmeltingpointrangeistypicalforapurecompound?
Ans.Ameltingrangeof2oCorlessor1.0~2.0oC.
2.Towhatdepthshouldthecapillaryisloadedwithsample?
Ans.Theheightofthesampleshouldbebetween12mm.
3.Whenclose(within10oC)tothemeltingpoint,howfastshouldyouallowthe
temperaturetorise?
Ans.Rateofheatingshouldbe1oC/minutewithin10oCtothemeltingpoint.
However,itsgenerallyacceptedtoraisethetemperatureattherateof23degree
perminute.

PostlabAssignment
AnswertoPostLabQuestions

1.Twosubstances,AandB,havethesamemeltingpoints.Howcanyoudetermine
iftheyarethesame?
Ans.CheckthemixedmeltingpointofAandBmixture.Ifthemixedmpisthesame
asthepureonewithoutanydepression,AandBaresame.Ifthemixedmpshowsa
lowermpwithwidermeltingrangethanthatofthepure,AandBarenotsame.
51LAW07TANote
 3

2.Whyisitnecessarytodrytherecrystallizedproductbeforetakingameltingpoint?
Ans.Theresidualsolventisapartofimpuritiesthatwouldaffectthemp.

AnswerProblem1onpage127inTechniques

1.Astudentperformedtwomeltingpointdeterminationsonacrystallineproduct.Inone
determination,thecapillarytubecontainedasampleabout12mminheightandthe
meltingrangewasfoundtobe141o142oC.Intheotherdetermination,thesampleheight
was45mmandthemeltingrangewasfoundtobe141o145oC.Explainthebroader
meltingpointrangeobservedforthesecondsample.Thereportedmeltingpointofthe
compoundis143oC.
Ans.Thiskindofphenomenon(theobservedmeltingrangeislowerthanitactually
is)isexpectedwhentherateofheatingisextremelyrapidbecauseofthe
thermometerlag,aconditioncausedbythefailureofthemercuryinthethermometer
torisequicklyenoughtoaccuratelyshowthetemperatureofthemetalheatingblock.
Thebroadermeltingrangeobservedforthesecondsampleisduetotheamountof
sampleusedinthedetermination.Themeltingprocessisbyaheattransferprocess
formtheheatertothesample.Whentherearetoomuchsample,itshouldtakea
longertime(awidermeltingrange)toturnthesolidtoliquidcompletely.

AnswerstoPrelabQuestions

1.Eachofthefollowingsolventsisusedcommonlyintheexperimentstoextract
organiccompoundsfromaqueoussolutions.

a)methylenechloride(dichloromethane)
b)toluene
c)diethylether
d)hexane

Willtheorganicphasebetheupperorlowerlayerwheneachoftheseorganic
solventsismixedwithwater?Explainyouranswerforeachsituation.
Ans.Theorganiclayerwillbethelowerphaseonlywhenusingmethylenechloride
(d201.3078).Theotherfoursolventswouldbetheupperphasebecausetheir
densitiesaresmallerthanthatofwater.

51LAW07TANote
 4
2.Explainwhythefollowingsolventsarenotusedintheexperimentstoextractorganic
compoundsfromaqueoussolutions.
a)ethanol b)acetone
Ans.EthanolisnotusedbecauseitiswatersolubleandhasahighB.P.Acetoneis
alsonotusedbecauseitiswatersoluble.

EXP3
PrelabAssignment
AnswerQuestions1,4,and5,pp.99100inTechniques

1.Anextractionprocedurespecifiesthattheaqueoussolutioncontainingdissolved
organicmaterialbeextractedtwicewith10mLportionsofdiethylether.Astudent
removedthelowerlayerafterthefirstextractionandaddedthesecond10mLportion
ofethertotheupperlayerremainingintheseparatoryfunnel.Aftershakingthe
funnel,thestudentobservedonlyonephasewithnointerface,Explain.
Ans.Thestudentremovedthewronglayer.Theaqueouslayerwasremovedleaving
theorganiclayer.Therefore,anotheradditionofetherwouldgiveonlyonephaseand
nointerface.

4.Whenthetwolayersformduringanether/waterextraction,whatwouldbeaneasy,
convenientwaytotellwhichlayeriswhichifthedensitieswerenotavailable?
Ans.Addingafewdropsofwaterandobservingwhichlayerismisciblewiththe
dropsofwaterisaneasyandconvenientway.

5.Youhave100mLofasolutionofbenzoicacidinwater;theamountofbenzoicacidin
thesolutionisestimatedtobeabout0.30g.Thedistributioncoefficientofbenzoic
acidindiethyletherandwaterisapproximately10.Calculatetheamountofacidthat
wouldbeleftinthewatersolutionafterfour20mLextractionswithether.Dothe
samecalculation,usingone80mLextractionwithether,todeterminewhichmethod
ismoreefficient.
Ans.
Forfourextractionswithfour20mlportionsofdiethylether:

1stextraction:k=10=(0.30x1)g/20mL x1=0.10g
x1g/100mL

2ndextraction:k=10=(0.10x2)g/20mL x2=0.033g
x2g/100mL

3rdextraction:k=10=(0.033x3)g/20mL x3=0.011g
51LAW07TANote
 5
x3g/100mL

4thextraction:k=10=(0.011x4)g/20mL x4=0.004g
x4g/100mL
Totalremoved=0.296g
Amountleftinwater=0.004g

Foranextractionwithone80mLportionofdiethylether:

1stextraction:k=10=(0.30x)g/80mL x=0.033g
xg/100mL

Totalremoved=0.267g
Amountleftinwater=0.033g

Therefore,theextractionusingfour20mLportionsisfarbetterthantheonewith80
mLportion.

PostlabAssignment
AnswertoQuestions14inpage8inModernProjects..

1. Whyistheteaboiledwithwaterinthisexperiment?
Ans.Caffeineiswatersoluble,whilesomeoftheothercomponentsofteasuchas
cellulosearenot.Thusboilingwaterinitiatestheseparationprocess.

2. Whyistheaqueousteasolutioncooledto1520oCbeforethedichloromethaneis
added?
Ans.Decreasingthetemperatureoftheaqueoussolution
1) preventsdichloromethanefromboiling(evaporating)awayand
2) minimizesthewatersolubilityofcaffeinesothatitismorereadilyextractedinto
thedichloromethanelayer.

3.Whydoestheadditionofsalt(NaCl)totheaqueouslayersometimeshelptobreakup
anemulsionthatformsinanextraction?
Ans.MakingtheaqueouslayerhighlyionicbydissolvingNaClwillhelptobreakup
theemulsion.

4.Thedistributioncoefficientforcaffeineindichloromethaneandwateris4.6.Assume
thatyour100mLteasolutioncontained0.3gofcaffeine.Ifyouhadextractedwith

51LAW07TANote
 6
onlyone15mLportionofdichloromethane,howmuchcaffeinewouldhavebeenleft
inthewatersolution?Howmuchcaffeinewouldbeleftinthewaterafterthesecond
15mLdichloromethaneextraction?Howmuchcaffeinewouldbeleftinthewater
solutionifonlyoneextractionwith30mLofdichloromethanewasperformed?
Ans.
Forthefirst15mLextraction:

conc.indichloromethane = (0.3x1)g/15mLCH2Cl2
k=4.6= conc.inwater x1g/100mLwater
Solvingforx1showsthat0.122gisthemountofcaffeineremovedbyoneextractionof15mL.
Therefore,x1is0.178gofcaffeineleftintheaqueoussolution.
Forthe2nd15mLextraction:

4.6= (0.178x2)g/15mLCH2Cl2
x2g/100mLwater

Nowx2=0.105gofcaffeinethatisleftintheaqueoussolutionafter2nd
extraction.
Ifextractedoncewith30mLportiononly.

(0.3x)g/30mLCH2Cl2
4.6=
xg/100mLwater

Solvingforxshowsthat0.126gofcaffeinewillbeleftintheaqueoussolution.

EXP4
PrelabAssignment
AnswerQuestions1&2,page189inTechniques.

1. When2propanolwasusedasthedevelopingsolvent,twosubstancesmovedwiththe
solventfront(Rf=1)duringTLCanalysisonasilicagelplate.Canyouconcludethat
theyaretheidentical?Ifnot,whatadditionalexperiment(s)wouldyouperform?
Ans.Youcannotconcludethatthetwosubstancesareidenticalbecause2propanolisa
highlypolarsolventandmaynotseparatethesetwocompounds.Furtherexperiments
shouldinvolvechangingthesolventsystemtoasolventorsolventmixturewithalower
polarity.Examplesofpossiblesolventstobeusedaloneorinamixtureincludehexane,
dichloromethane,diethylether,and/orethylacetate.

2. TheRfvalueofcompoundAis0.34whendevelopedinhexaneand0.47when
developedindichloromethane.CompoundBhasanRfvalueof0.42inhexaneand
0.69indichloromethane.Whichsolventwouldbebetterforseparatingmixtureof
compoundsAandB?Explain.

51LAW07TANote
 7
Ans.DichloromethanewouldbeabettersolventfortheseparationofAandBbecause
thereisalargerdifferencebetweentheRfvalues(0.22)thaninhexanes(0.08).Alarger
differencebetweenRfvaluestranslatestobetterseparationofthecompounds.

PostLabAssignment
AnswerQuestions13,page14inModernProjects..

1. WhydoescaffeinehavealargerRfvaluethanchlorophyll?
Ans.Chlorophyllisamuchlargermoleculewithsimilarpolarity(comparethefunctional
groups)thancaffeine.Therefore,itisnaturallyexpectedthatcaffeinewillhavealargerRf
value.AlargerRfvaluemeanscaffeineisnotastightlyboundtothepolaradsorbentas
ischlorophyll.Therefore,chlorophyllmusthaveahigherpolaritythancaffeine.

2. WhycantherebenobreaksinthethinlayersurfaceofaTLCplate?
Ans.DiscontinuitiesintheTLCsurfacewoulddisruptpassageofcompoundsalong
thesurface,invalidatingTLCRfvalue

3.TwocompoundshavethesameRf(0.87)underidenticalconditions.Doesthisshow
thattheyhaveidenticalstructures?Explain.
Ans.JustbecausethecompoundshavethesameRfvaluedoesnotnecessarilyindicate
thatthecompoundshaveidenticalstructures.TheentirerangeofRfvaluesis0.01.0,
andmillionsoforganiccompoundsareknown.Thesolventusedmaynotbesufficient
enoughtoseparatethesecompounds.HighRfvalueisduetothechoiceofsolvent.
Choosingalesspolarsolvent,givingaRfof<0.5mayseparatetwospotsiftheyarenot
thesamecompound.

EXP 5
PrelabAssignment
AnswertoQuestions2,3,and6onpage99100inTechniques...

2. Acrudenonacidicproductmixturedissolvedindiethylethercontainsaceticacid,
Describeanextractionprocedurethatcouldbeusedtoremovetheaceticacid.
Ans.Thebestwaytoremoveaceticacidfromtheethersolutionistoconvertitto
itsconjugatebase,theacetateanion,byextractingtheethersolutionwitha5%
NaHCO3solution.Sodiumacetateisverysolubleinwaterbutnotsolubleindiethyl
ether.

51LAW07TANote
 8
3. Whatprecautionsneedtobeobservedwhenanaqueoussodiumcarbonate
solutionisusedtoextractanorganicsolutioncontainingtracesofacid?
Ans.Aqueoussodiumcarbonatewillreactwithorganicsolutionscontaining
tracesofacidandformcarbondioxidegas.Theadditionshouldbedoneslowly
tominimizeanyexothermicreactions.CO2gasshouldbereleasedfromthe
separatoryfunnelbyopeningthestopcockaftereachshake.

6. K2CO3isanexcellentdryingagentforsomeclassesoforganiccompounds.
Woulditbeabetterchoiceforanacid(RCOOH)oranamine(RNH2)?Why?
Ans.Potassiumcarbonateisaneffectivedryingagentthatforms2K2CO3.3H2O
(potassiumcarbonatesesquihydrate)afterabsorbingwatermolecules.However,
potassiumcarbonateisbasicinaqueoussolutionand,therefore,cannotbeused
withanacid.Itcanbeusedforaminesandneutralcompounds.

PostLabAssignment
AnswerforQuestions14,and6,page246inModernProjects..

1. Whydoesnttheneutralorganiccompounddissolvein1.5Msodiumhydroxide
solution?
Ans.Amajorityoforganiccompoundsareinsolubleinwater:onlythosethatare
ionicorarehydrogenbondingcompoundsarewatersoluble.Ifanorganiccompound
isanacid,however,NaOHwillconvertittoawatersolubleionicsalt.

2. Whyisdiethyletheragoodchoicefortheorganicsolventinthisexperiment?
Ans.Diethyletherisalargelywaterinsolublecompoundofintermediatepolarity,
whichdissolvesawiderangeoforganiccompounds.Sinceetherhasalowboiling
point(34oC),itiseasilyseparatedfromtheorganiccompoundbyevaporationor
distillation.

3. Whatexperimentaldifficultywouldyouencounterifyouhadneglectedtoincludeadrying
stepbeforeevaporatingtheethersolutionoftheneutralorganiccompound?
Ans.Withoutincludingthedryingstep,therewillbewaterpresentinthesampleof
theneutralorganiccompound,duetosomewatersolubilityinetherandincomplete
separationoftheetherandwaterlayersintheextraction.Thiswaterisverydifficultto
evaporate.Thustheneutralorganiccompoundwillbeimpure,anditmaybemore
difficulttodissolveitinethanolusedforitsrecrystallization.Itwillalsotakelongerto
drythesolidafterrecrystallization.

51LAW07TANote
 9

4. Whyarethetwoorganiccompoundsrecrystallizedbeforetheirmeltingpointsare
determined?
Ans.Meltingpointscanbeverysensitivetotraceimpurities.Presenceofevena
smallquantityofimpurityusuallydepressesthemeltingpointafewdegreesand
causesmeltingtooccuroverarelativelywidetemperaturerange.

6.Describethecharacteristicsofagoodrecrystallizationsolvent.
Ans.Agoodrecrystallizationsolventhas:
1) Highsolubilityofthecompoundinhotsolvent
Lowsolubilityofthecompoundincoldsolvent
2) Similarstructureandpolaritytothecompoundtoberecrystallized
3) Easilyevaporated/removedfromtherecrystallizedproduct

EXP6
AnswertoPrelabQuestions

1. Whydoweaddboilingchipsorboilingstonesbeforethedistillationstarts?Boiling
chipsshouldneverbeaddedtoahotsolution!Why?

Ans.Solutioncanbecomesuperheated,i.e.,heatedaboveitsboilingpointwithout
actuallyboiling.Whenboilingdoessuddenlyoccur,itcanhappenwithalmost
explosiveviolence.Topreventthisfromhappening,boilingchipsorstonesshouldbe
addedbeforetheheatingbegins.Ifboilingshipswereaddedtoahotsolution,the
solutionwouldboiloverorexplode.

2. Whywoulditbedangeroustoheataliquidinadistillingapparatuswhichhadno
ventoropeningtothelaboratory?

Ans.Pressurewouldbuildupasthesubstancevaporized.Eventuallytheapparatus
wouldblowup.

3.Whatistheeffectoftheboilingpointofasolution(forexample,water)produced
byasolublenonvolatilesubstance(forexample,sodiumchloride)?Whatistheeffect
ofaninsolublesubstancesuchassandorcharcoal?Whatisthetemperatureofthe
vaporabovethetwoboilingsolutions?

51LAW07TANote
 10
Ans.Asolublenonvolatilesubstancelikesodiumchloridewillraisetheboilingpoint
ofanaqueoussolution.Aninsolublesubstancewillhavenoeffect.Thebpofa
solutioncontainingasolublesubstancewillbehigherthanthepuresolution.

3) Explainwhyrefractiveindexvaluesofliquidsarenumericallygreaterthanone.

Ans.Refractiveindexisdefinedasn=Vvac/Vlig,wherenisrefractiveindex,Vvac=
velocityoflightinavacuum(orair),Vliq=velocityoflightintheliquid.Thevelocityof
lightinaliquidisalwayslessthanthatoflightinavacuum.

5.Asolutionconsistingofisobutylbromideandisobutylchlorideisfoundtohavea
refractiveindexof1.3931at20oC.Therefractiveindicesat20oCofisobutylbromide
andisobutylchlorideare1.4368and1.3785,respectively.Determinethemolar
composition(inpercent)ofthemixturebyassumingalinearrelationbetweenthe
refractiveindexandthemolarcompositionofthemixture.

Ans. 1.3931x100= 1.4368x+1.3785y

x+y=100
wherexandyaremolar%compositionof
isobutylbromideandisobutylchloride,
respectively.
Solution:
1.4368x+1.3785(100x)
1.3931x100=
139.31137.85 1.46
x= = =25.04%
1.43681.3785 0.0583
Molar%compositionofisobutylbromideis25.04%
andisobutylchlorideis74.96%.

AnswertoPrelabAssignment
Question3,page157inTechniques..

3.Astudentcarriedoutasimpledistillationonacompoundknowntoboilat124oCand
reportedanobservedboilingpointof116117oC.Gaschromatographicanalysisofthe
productshowedthatthecompoundwaspure,andacalibrationofthethermometer
indicatedthatitwasaccurate.Whatproceduralerrordidthestudentmakeinsetting
upthedistillationapparatus?

51LAW07TANote
 11
Ans.Thethermometermaynothavebeenincorrectplace.Itisverylikelythatthe
thermometerwasplacedlowerthanitshouldbe.

AnswertoPostlabAssignment
PostLabAssignment

1.Plotadistillationcurvebasedonyourexperimentalresultsforbothsimpleand
fractionaldistillationasshowninFig.11.14(page143)inTechniques...
2.Determinethe%compositionofthe"unknown"liquidmixtureusingthefractional
distillationcurve.
3.Identifythetwocomponentsfromtheboilingpointsandrefractiveindicesofthe
lowandhighboilingcomponents.
4.Discusstheefficiencyofsimpleandfractionaldistillationsforseparatingthemixture.

Therearenopostlabquestionsassigned.Studentsshouldsubmitthepost
labdiscussionincludingtheidentity,the%compositionofacetoneinwater,
anddifferencebetweenthesimpleandfractionaldistillations.

EXP7
OPTICALISOMERISM

1.Constructamodelthathasacentralcarbonatomswith4differentcoloredspheres
attachedtoit,representingfourdifferentatomsorgroups.Drawasolid/dashedwedge
structureofthismodelhereandanswerthefollowingquestions.

C(ablueball)

B D Fig.1
A

a. Doesthemodelhaveaplaneofsymmetry? Yes______No__X___

Thecentralcarbonissaidtobeastereocenter,stereogeniccenterorchiralcarbon.
Changeoneofthecoloredspheressothattwoofthefourspheresarethesameand
examinethestructureatdifferentangles.
.
b. Doesthemoleculenowpossessymmetry? Yes__X___No______

51LAW07TANote
 12
Whatkind?
Planeofsymmetry___




___

c. Inviewofyouranswerstoaandb,whatconditionisnecessaryforacarbontobe
stereogeniccenter? Acarbonisbondedto4differentgroups.

d. Drawastructuralformulaforeachofthefollowingandindicateallstereogeniccarbon
withanasterisk:

2bromobutane 3bromopentane

*
Br Br

1bromo2chloropropane 2,3dibromobutane

Br
Br *
* *
Cl Br

2.Reconstructtheoriginalstereogeniccarbonwiththefourdifferentcolored
ballsagain.Setthemodelonthetablesothattheblueball(CintheFig1)points
upwards.

a. Lookingdownonthemodelfromabove,recordthecolorsoftheballs,
e.g
proceedinginaclockwisedirection. .
orange,purple,green
_

Constructanothermodelthatisthemirrorimageofthefirstandplaceitonthetable
withtheblueballup.

b. Inwhatdirectionmustyouproceedtoobservethesameorderof
substituentsasrecordedfor2a? counterclockwise__X___clockwise_____
c. Trytosuperimposethe2models.Aretheythesame?Yes_____No_X__
Ifnot,howaretheydifferent?
Nonsuperimposablemirrorimages

__________________________

d. Whatisthestereochemicaltermthatrelatesthesetwomodels?
Enantiomers






___________

51LAW07TANote
 13
e. Whattwoimportantpropertiesmustthetwomolecules(models)eachhavetoberelated
bythetermthatistheanswerto2d?
Eachmodelconsistsofthesamecoloredballsbutshowsdifferentspacial
arrangements.

f. Onyourmirrorimagemodel,switchanytwogroups.Isthismodelstillthemirrorimage
oftheoriginalmodel? Yes______No___X___

g. Trytosuperimposethetwomodels.Aretheysuperimposable?
Yes__X____No______
h. Whatisthestereochemicaltermthatrelatesthesetwomodels?

____Identicalcompounds,superimposablemirrorimage

_
________

Changetheredballoneachmodeltoablueone(Nowmodelscontaintwoblueballs)
i. Arethemodelsstillmirrorimages? Yes__X___No______
j. Dothemodelshaveaplaneofsymmetry? Yes__X___No______
Aplanebisectsthemodelintotwohalves.The
Ifso,describeitslocation.
planecontainsthecarbonandtwoballs(noneblue).
____


k. Arethemodelssuperimposable? Yes__X___No_____
l. Dothemodelsrepresentidenticalordifferentmolecules?___Identical________
Explain. Twomodelssuperimposewitheachother.

m. Eachofthefollowingmoleculeshasonestereocenter,andisthereforechiral.Draw
stereorepresentations(dashwedgeformulas)fortheenantiomersofeach.

Br Br or Br
Br H Br H or
H Br Cl H Cl H H Cl

Mirrorplane Mirrorplane
2bromobutane 1bromo2chloropropane

3.DiastereomersandMesoForms.Whenamoleculehastwoormorestereogenic
centers,stereoisomersthatarenotmirrorimagescanexist;thesearecalled
diastereoisomers.Withinthisgeneralclass,therearespecialtypesofstereoisomersthat
arealwaysopticallyinactiveandarecalledmesoforms.

51LAW07TANote
 14
Constructamodelwithfourdifferentcoloredballsaboutacarboncenter.Construct
anotheridenticaltothefirstandverifythisbythesuperimpositiontest.Nowremovethesame
coloredballs,blue(CfromFig1)forexample,fromeachmodelandjointhetwocarbonsat
thevacantvalencesitesasshowninFig2.

B D
A
D Fig2
A B
a. Howmanystereogeniccarbonsdoesthismodelhave?Notethateachcarbonhasthe
samethreegroupsattachedtoit.
Two
__


______

b. Conformationallyadjust(byrotationaboutthecentralCCbond)themodelinasearch
forsymmetry.Doesthemoleculehaveaplaneofsymmetry?
_
Yes_____No___X _

Constructthemirrorimageofthismolecule.
c. Arethemirrorimagesidentical? _
Yes_____No___X _
d. Whattermisusedtodescribetherelationshipbetweenthetwomoleculesin3c?
Enantiomers____








e. Examineeachofthesemodelstodeterminewhethertheyarechiralorachiral.
Chiral________

Interchangetwoballs(AandBforexampleasshowninFig3)ononecarbonofonemodel.

B D B D
A B
D D A
A B A
Fig2 Fig3

f. Arethetwomodelsidenticalnow? Yes_____No__X_
g. Aretheymirrorimages? Yes_____No__X_
h. Aretheystereoisomers? Yes__X__No_____
i. Whatstereochemicaltermdescribesthetwomoleculesthatarerelatedinthis
way?

Diastereomers







j. Examinevariousconformationsofthemodelwherethetwoballswereinterchanged.
Canyoufindaconformationwithaplaneofsymmetry?Yes__X_No_____
k. Doesthissameconformationhaveaplaneofsymmetry?Yes__X_No_____

51LAW07TANote
 15
Aplanebisectingthetwocarbonsresultstwohalvesthatbecome
Explain.
themirrorimmageswitheachother.
_________________
_

l. Predictwhetherthismolecule'smirrorimagewillbeidenticalwithor
nonsuperimposableontheoriginal.Explainthebasisofyourprediction.Testthe
validityofyourpredictionbyconstructingthemirrorimageandconductingthe
superimpositiontest.Recordyourobservations.
Themirrorimageissuperimposable.___



_______

m. Isthismolecule(Fig3)chiral? Yes_____No__X__
n. Isthiscompoundopticallyactive? Yes_____No__X___
o. Whatisthestereochemicaltermusedtodescribethistypeofstereoisomer?
Mesocompound

Tartaricacid,2,3dihydroxybutanedioicacid,cancomeinthreedifferentforms,
correspondingtothemodelsassembledin2ao:apairofopticallyactiveenantiomersanda
thirdopticallyinactiveformcalledthemesoform.Thelatterisadiastereomerofthe
opticallyactiveenantiomers.

HO OH
* *
C C Tartaricacid
HOOC COOH
H H

p. Drawsolid/dashedwedgestructuresforthethreetartaricacidforms.
Labeleachformsandshowtherelationshipwitheachotherasenantiomers,
diastereomers,andthemesoform.

HO H H OH HO OH
C C C C C C
HOOC COOH HOOC COOH HOOC COOH
H OH HO H H H
A B C(meso)

A&B:enantiomers;A&CandB&C:diastereomers

Whenamoleculehastwodifferenttypesofstereogeniccenters,itcanexistin2n
stereoisomericforms,wherenisthenumberofstereogeniccarbons.Removeanyone
ballfromanyonecarboncenterandreplaceitwithacolornotalreadybeingused.Your
modelshouldhavetwostereogeniccenters,withtwoofthethreecoloredballsonone
centerbeingthesameasontheother.Constructthefourstereoisomersnowpossible.

51LAW07TANote
 16

q. Recordthediagramsforthese4stereoisomers;labelenantiomersanddiastereomers.

X W W X W X X W
C C C C C C C C
Y Y Y Y Y Z Z Y
Z Z Z Z Z Y Y Z
A B C D
A&BandC&D:enantiomers;
A&C,A&D,B&C,andB&D:diastereomers

r. Explainwhy4stereoisomerscannotbeachievedwithtartaricacid.
Amongfourstereoisomerstwoaremesoformwhicharesuperimposablemirror
imageseachother.




4. AbsoluteConfigurationandR/SSequenceRules.In3qyouconstructedmodels
withtwostereocentersthatrepresented4stereoisomers.2,3Dibromobutanoicacid
exemplifiessuchacompound.Makemodelsfortheisomersofthiscompound.

a. Drawsolid/dashedwedgestructuresforthe4possiblestereoisomersand
labeltheenantiomersanddiastereomers.

H3 C COOH HOOC CH3 H3 C COOH HOOC CH3

C C C C C C C C
H H H H H Br Br H
Br Br Br Br Br H H Br
A B C D
A&BandC&D:enantiomers;
A&C,A&D,B&C,andB&D:diastereomers

b. Specifythesequencepriorityforthesubstituentsoncarbon2andcarbon3.
Carbon2:Br,CH(Br)CH3,COOH,H;Carbon3:Br,CH(Br)COOH,CH3,H

c. LabeleachstructurewiththeproperR/Snotationinthedrawingsabove,forexample
(2R,3S).
H3 C COOH HOOC CH3 H3C COOH HOOC CH3
C C C C C C C C
H H H H H Br Br H
Br Br Br Br Br H H Br
A B C D

(2R,3S) (2S,3R) (2S,3S) (2R,3R)

d. DrawNewmanprojectionsforall4possiblestereoisomers.

51LAW07TANote
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COOH COOH COOH COOH
H Br Br H H Br Br H
Br H H Br H Br Br H
CH3 CH3 CH3 CH3
(2R,3S) (2S,3R) (2S,3S) (2R,3R)

A B C D
e. SpecifythesequenceofpriorityforthesubstituentsonC2andC3for
tartaricacid(see3p).Writeyouranswerfor3p.
Carbon2:OH,COOH,CH(OH)COOH,H;Carbon3:OH,COOH,CH(OH)COOH,H

5.ConformationalEnantiomersandCyclicCompounds

a. Constructamodelofmethanol(CH3OH).Ismethanolchiral?Whyorwhynot?
_No.Itsachiralbecausethecarboncarries3Hsand,therefore,itdoesntmeet
therequirementforastereocenter.

b. Orientyourmodelsothattheplaneofsymmetry(indicatedbythedottedrectangle)
containstheHCOHbondsthatareintheplaneofthepaper,asshownbelow:

H
H C O H
H

NowrotatetheCObond,sothattheplanenolongercontainstheOHbond.Allofthe
bondsinmethanolfreelyrotateatroomtemperature,soyouarejustshowinga
differentconformationofmethanol.Doesthisconformationofmethanolhaveaplane
ofsymmetry?

Yes_____No_____couldbeyesornodependingonhowfaryourotatethe
CObond

c. Eventhoughoneconformationofmethanolhasaplaneofsymmetry,andonedoesnt,
methanolisstillconsideredtobeachiral.Itisonlynecessarytofindoneconformation
withaplaneofsymmetryforamoleculetobeachiral.

d. Nowconsidercyclohexanol,shownbelow.Lookingattheflat,hexagonal
representationofcyclohexanol,doescyclohexanolcontainaplaneofsymmetry?
Yes_X
__
No_____

51LAW07TANote
 18
H OH

e. Ofcourse,cyclohexanolneverexistsinaflathexagonalform.Itisjustdrawnthiswayfor
convenience.Itexistsinoneoftwochairconformationswhicharerapidlyinterconverting
atroomtemperature,theconformationwiththehydroxylintheequatorialpositionbeing
favored.

OH H
OH

MakeamodelofcyclohexanolwiththeOHintheequatorialposition.Nowdoachair
flip,sothattheOHisintheaxialposition.Canyoufindaplaneofsymmetryforeach
configuration?Iscyclohexanolchiral?

_______No._____________________________________________________

f. Nowconsideradisubstitutedcyclohexanederivative,cis1,2dibromocyclohexane:

Br

Br

Lookingattheflat,hexagonalrepresentationofcis1,2dibromocyclohexane,does
thismoleculecontainaplaneofsymmetry?Yes_X__No_____

g. Onceagain,weknowthatcyclohexaneringsneverexistinaflathexagonalform.They
existasrapidlyinterconvertingchairconformations.Onlyatabsolutezerocanyou
isolateasinglechairconformationofanycyclohexanederivative.

Ifyouconvertcis1,2dibromocyclohexanetoachairconformation,however,both
chairconformationsarechiral:

51LAW07TANote
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H H

H H
CH3 CH3
CH3 CH3

Bothchairconformationsarenonsuperimposablemirrorimagesofeachotherand
thereisnoplaneofsymmetry,BUT,theyareinterconvertiblebyaringflip!

Makeamodelofeachofthechairconformationsofcis1,2dibromocyclohexane,
andshowthattheyarenonsuperimpoasblemirrorimagesofeachother.

Iscis1,2dibromocyclohexaneisomeropticallyactive?Theplanarstructurehas
aplaneofsymmetry,butthechairconformationdoesnt!

Yes_____No__
X
_

Althougheachconformerischiral,therapidinterconversionbetweenthetwoat
roomtemperaturemeanstheycannotbeseparated.Thecompoundisnotchiral.

Identifyingchiralityincyclohexanederivativescanseemdaunting.Fortunately
wecangreatlysimplifybymakingusingthefollowingrule:

Ifyoucanfindaplaneofsymmetryintheflathexagonaldrawingofasubstituted

cyclohexanering,themoleculeisachiral.Ifyoucannotfindaplaneofsymmetry,itis

chiral.

51LAW07TANote
 20
h. Usingthissimplification,determinewhetherthefollowingsubstitutedcyclohexane
ringsarechiralorachiral.Drawplaneofsymmetryforanyachiralmolecules.

Cl

HO OH

Chiral Achiral Achiral Achiral

EXP8
PreLabQuestions

1. WriteamechanismtoillustratewhatwillhappeniftheadditionofBr2totrans
cinnamicacidissyn;Whatdoyouexpectthemeltingpointofthesynaddition
producttobe?
Ans.
d+ d
Br Br
C6H5 H Br Br
C C C C H
C6H5
H COOH H COOH
and 2S,3S aracemicmixture
C6H5 H mp93.5oC
C6H5 H
C C H C C COOH
H d+ d COOH Br Br
Br Br
2R,3R

synAdditiongivesaracemicmixtureof(2R,3R)and(2S,3S)2,3dibromo3
phenylpropanoicacid(mp93.594.5oC)

2.WriteamechanismtoillustratewhatwillhappeniftheadditionofBr2totrans
cinnamicacidisanti;Whatdoyouexpectthemeltingpointoftheantiaddition
producttobe?
Ans.

51LAW07TANote
 21
+
C6H5 C6H5 Br H C 6H5 Br
H d+ d H
C C C C + C C
Br Br
H COOH H COOH H Br COOH
Br +
aracemicmixtureofbridgedbromonuimion
intermediatesisattackedbyBrandringopeningoccurs

C6H5 Br Br H
H COOH
C C C C
H C 6H5
Br H Br
COOH
2S,3R 2R,3S
aracemicmixture
mp203oC

antiAdditiongivesaracemicmixtureof(2S,3R)and(2R,3S)2,3dibromo3
phenylpropanoicacid(mp202203oC)

3.Describethemeltingpointyouexpecttoobserveiftheisolatedproductisthemixture
ofbothsynandantiadditionofBr2.

Ans.Iftheadditionofbromineproceedsviabothsynandantiaddition,amixtureof
2,3dibromo3phenylpropanoicacidwillbeformedand,therefore,themeltingpoint
willbelowerthanthe93oCexpectedfromthepuresynadduct.

4.ExplainwhytheadditionofBr2totranscinnamicacidtakesplacemoreslowlythan
theadditionofBr2toa"normal"alkene.
Ans.Thecarboxylgroupoftranscinnamicacidisanelectronwithdrawinggroup
thatslowstheadditionofbrominetothealkene.

EXP9
AnswerstoPrelabQuestions
Questions14,page174inTechniques..

1. Asampleof2butanolshowsanopticalrotationof+3.25o.Determinethe%eeandthe
molecularcompositionofthissample.Theopticalrotationofpure(+)2butanolis
+13.0o.
Ans.

51LAW07TANote
 22
+3.25o
x100% =25.0%eedetrorotatoryor(+)
+13.0o

Molecularcomposition:
100+25
=62.5%dextrotoratoryor(+)
2 37.5%levorotatoryor()

or 10025 37.5%of(+)and()tomaketheracemicmixture
=
2 thatgives0oopticalactivityreading.
Therefore,(+)enantiomerof2butanolis

37.5+25.0=62.5%is(+)enatiomerand37.5%is()enantiomer.

2. Asampleof2butanol(Seequestion1)showsanopticalrotationof9.75o.
Determinethe%eeandthemolecularcompositionofthissample.

%ee:
9.75o
x100% =75.0%eelevorotatoryor()
13.0o
Molecularcomposition:
100+75
=87.5%levorotatoryor()
2 12.5%dextrotoratoryor(+) Ans.

3. Anopticalrotationstudygivesaresultofa=+140o.Suggestadilutionexperimentto
testwhethertheresultisindeed+140oandnot220o.
Ans.Iftheconcentrationofthesamplesolutionwerehalved,therotationwould
eitherbe+70oor290oifthe=140oreadingisoriginallycorrect.If220owerecorrect
reading,thenewreadingwouldbe110oor+250o.

Pre-Lab Question
Question 1, p 46 in Techniques..

1. (R)-(+)-limonene has a boiling point of 176oC. What made it possible to steam distill it
at 100oC?
Ans. Because the limonene is not miscible with water, the vapor pressures of
limonene and water add together. When the combined pressure equals the
51LAW07TANote
 23
atmospheric pressure, distillation occurs. The distillate contains limonene and water
in proportion to their vapor pressures at the boiling point

51LAW07TANote