StructuralEquivalenceandNonequivalenceofGroups

StructuralClassificationofAtomsorGroups
Wenotedearlierthatnotallmethyl(ormethyleneormethyne)groupsinamoleculearenecessarilythesame(structurallyequivalent).Dependingonthe
molecularconstitutionandconfiguration,similaratomsorgroupsofatomsmayoccupydifferentstructuralenvironments.Thesymmetryofamoleculeishelpful
inevaluatingstructuralequivalence,sincegroupsthatareinterchangedbyasymmetryoperationmusthaveacharacteristicrelationship.Asillustratedbythe
followingexamples,atomsorgroupsthatarestructurallyinterchangedbyarotationalsymmetryoperationotherthanC1areclassifiedashomotopicandare
consideredstructurallyequivalent(e.g.thehydrogensindichloromethane).Ligandsthatarenothomotopicmaybereferredtogenerallyasheterotopic.Ifa
pairofatomsorgroupsareinterchangedbyareflectivesymmetryoperationtheyaretermedenantiotopic(e.g.thehydrogensinbromochloromethane).Itis
instructivetoconfirmtheseassignmentsbyconsideringtheresultofahypotheticalsubstitution.IfhomotopicgroupsarereplacedinturnbyanXsubstituent
theproductswillbeidentical.However,ifenantiotopicgroupsaresimilarlysubstitutedtheproductsareenantiomers.Enantiotopicatomsorgroupsare
structurallyequivalentinasymmetricalenvironmentorinreactionswithsymmetricalreagents.Byclickingonthenameofeachexampleshownbelow,the
symmetryoperationandhypotheticalsubstitutionwillbedisplayedingreaterdetail.The"Restore"buttonreturnstheoriginaldisplay.
Restore Chart

Inthecaseofbromoethane(the2ndexample)thethreemethylhydrogensarenotstructurallyequivalentinafrozenconformation,butbecomesoasthis
grouprapidlyrotatesaboutitsCCsigmabond.Thisequivalenceremainsevenwhenthemethylisbondedtoachiralcenter.Thelasttwoexamplesonthe
rightillustrateadiastereotopicrelationshipofatoms.InthesecasesHaandHbarenotinterchangedbyasymmetryoperation,andsubstitutionofeachgives
diastereomersasproducts.Althoughdiastereotopicatomsorgroupsaresimilar,theyarestructurallynonequivalentandoftenexhibitdifferentproperties,such
asnmrchemicalshiftsorreactionrates.Adiagramsummarizingthisclassificationwillbedisplayedbypressingthe"Chart"button.
Inevaluatingthestructureandconfigurationofmolecularcomponents,itisusefultodefinetheconceptofprostereoisomerism.Anatombondedto
heterotopicligandsmaybeconsideredaprostereogeniccenter.Iftheligandsareenantiotopic,asinthecaseofbromochloromethaneshownabove,thecenter
iscalledprochiral,sincereplacementofoneoftheatoms(orgroups)withadifferentsubstituentwouldconvertthecarbontoachiralcenter.Casesinwhich
theligandsarediastereotopic,ratherthanenantiotopic,aredescribedtobythegeneraltermprostereogenic.
Planarsp2carbonfunctionshavingthreedifferentsubstituentsatonecarbonaresimilarlyconsideredtohaveprochiralfaces.Thusadditionofhydridetothe
achiralketone,2butanone,producesthechiralalcohol2butanol.Inthiscasetheplanarcarbonylcarbonhasthreedifferentsubstituents(oxygen,methyland
ethyl),andthereforehasprochiralfaces(commonlydesignatedreandsi).

SelectanExample
Themoduleontherightprovidesexamplesof
homotopicandheterotopicligandpairsforanalysis.
Thesearedisplayedasthreedimensionalstructures
inwhichthepairsarelabeledAandB.The
structuresmaybemovedaboutandexaminedfrom
variouspointsofview.Byusingthisresourcethe
readershouldbeabletoclassifythenatureofthe
relationshipashomotopic,enantiotopicor
diastereotopic.
ThisvisualizationmakesuseoftheJmolapplet.With
somebrowsersitmaybenecessarytoclickabutton
twiceforaction.

ClicktheShowExampleButton
Athreedimensionalmolecularstructurewillbedisplayed
here,andmaybemovedaboutwiththemouse.Carbon
isgray,hydrogeniscyan,oxygenisred,andchlorineis
green.
CharacterizetherelationshipofligandsA &B by
selectingoneofthethreetermslistedbelow.Aresponse
toyouranswerwillappearbyclickingtheCheck
Answerbutton.

homotopic
enantiotopic
diastereotopic

ShowExample
CheckAnswer

Example1
Example2
Example3
Example4
Example5
Example6
Example7
Example8
Example9
Example10
Example11
Example12
Example13
Example14
Example15

Aresponsetoyourselectionwillappearhere.

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MesoCompounds
MesoDiastereomers
Thefourdiastereomericaldopentosespresentedearlierandrepeatedaboveareallchiral.Eachofthesecompoundshasanenantiomerso,asexpected,there
areeightstereoisomersinall.Byreducingthealdehydefunctiontoa1alcohol,theendsofthefivecarbonchainsbecomeidenticalandthesymmetry
characteristicsoftheoverallstructurearesuchthatthenumberofconfigurationalstereoisomersfallsfromeighttofour.Thesefourisomers,shownbelow,are
apairofenantiomersandtwomesocompounds.
Intheenantiomericpairontheleft,carbon#3isnotastereogeniccenter,sinceinterchangingtheHandOHsubstituentsatthiscarbondoesnotchangethe
overallconfiguration.Thisisnottrueforthemesocompoundsontheright.InterchangingtheHandOHsubstituentsoncarbon#3convertsoneisomerintoits
achiralpartner.StereogeniccenterssuchasC#3havebeencalledpseudoasymmetriccenters,andaconfigurationalnotation(rors)maybeassignedby
notingthatanRsubstituentisaboveanequivalentSsubstituentinthesequencerule(notethelowercaselettersusedforthisnotation).Thechainnumbering
ontherighthaschanged,becauseinnearlysymmetricalcasesthenearestRcenterhasprecedentoverasimilarlyorientedScenterindeterminingthe
primaryendofthechain.
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IsomerSummary
GeneralSummaryofIsomerismandMolecularDescriptors
MethodsofDescribingMoleculeswithIncreasingRefinement
1.Composition
Thenumberandkindsofatomsthatmakeupamolecule.Thisinformationissuppliedbyamolecularformula.
2.Constitution
Thebondingpatternoftheatomsofamolecule(ie.whichatomsareconnectedtowhichotheratomsandbywhat
kindofbonds).Differentbondingconstitutionsareinterconvertedonlybybreakingandreformingcovalentbonds.
Thisinformationissuppliedbyastructuralformula,andisimplicitintheIUPACname.
3.Configuration
Thepermanentspatialrelationshipoftheatomsofamoleculetoeachother.Differentconfigurationsare
interconvertedonlybybreakingandreformingcovalentbonds.Thisinformationisgiveninastereoformula,andis

alsoprovidedbyaprefixtotheIUPACname(eg.cis&trans).
4.Conformation
Thevariablespatialorientationoftheatomsofamoleculetoeachotherthatoccursbyrotationortwistingofbonds.
Differentconformationsareinterconvertedwithoutbreakingcovalentbonds.Thisinformationissuppliedby
conformationalformulas,andalsobynomenclatureterms(eg.gauche&anti).

RelationshipofConstitutionalandStereoisomers

RelationshipsofStereoisomers

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IntermolecularForces
IntermolecularForces
Themoleculeisthesmallestobservablegroupofuniquelybondedatomsthatrepresentthecomposition,configurationandcharacteristicsofapure
compound.Ourchieffocusuptothispointhasbeentodiscoveranddescribethewaysinwhichatomsbondtogethertoformmolecules.Sinceallobservable
samplesofcompoundsandmixturescontainaverylargenumberofmolecules(ca.!020),wemustalsoconcernourselveswithinteractionsbetweenmolecules,
aswellaswiththeirindividualstructures.Indeed,manyofthephysicalcharacteristicsofcompoundsthatareusedtoidentifythem(e.g.boilingpoints,melting
pointsandsolubilities)areduetointermolecularinteractions.
Allatomsandmoleculeshaveaweakattractionforoneanother,knownasvanderWaalsattraction.Thisattractiveforcehasitsoriginintheelectrostatic
attractionoftheelectronsofonemoleculeoratomforthenucleiofanother.IftherewerenovanderWaalsforces,allmatterwouldexistinagaseousstate,
andlifeasweknowitwouldnotbepossible.Itshouldbenotedthattherearealsosmallerrepulsiveforcesbetweenmoleculesthatincreaserapidlyatvery
smallintermoleculardistances.

Boiling&MeltingPoints

BoilingandMeltingPoints
Forgeneralpurposesitisusefultoconsidertemperaturetobeameasureofthekineticenergyofalltheatomsandmoleculesinagivensystem.As
temperatureisincreased,thereisacorrespondingincreaseinthevigoroftranslationalandrotationmotionsofallmolecules,aswellasthevibrationsofatoms
andgroupsofatomswithinmolecules.Experienceshowsthatmanycompoundsexistnormallyasliquidsandsolidsandthatevenlowdensitygases,suchas
hydrogenandhelium,canbeliquifiedatsufficientlylowtemperatureandhighpressure.Aclearconclusiontobedrawnfromthisfactisthatintermolecular
attractiveforcesvaryconsiderably,andthattheboilingpointofacompoundisameasureofthestrengthoftheseforces.Thus,inordertobreakthe
intermolecularattractionsthatholdthemoleculesofacompoundinthecondensedliquidstate,itisnecessarytoincreasetheirkineticenergybyraisingthe
sampletemperaturetothecharacteristicboilingpointofthecompound.
Thefollowingtableillustratessomeofthefactorsthatinfluencethestrengthofintermolecularattractions.Theformulaofeachentryisfollowedbyitsformula
weightinparenthesesandtheboilingpointindegreesCelsius.Firstthereismolecularsize.Largemoleculeshavemoreelectronsandnucleithatcreatevan
derWaalsattractiveforces,sotheircompoundsusuallyhavehigherboilingpointsthansimilarcompoundsmadeupofsmallermolecules.Itisveryimportantto
applythisruleonlytolikecompounds.Theexamplesgiveninthefirsttworowsaresimilarinthatthemoleculesoratomsaresphericalinshapeanddonot

havepermanentdipoles.Molecularshapeisalsoimportant,asthesecondgroupofcompoundsillustrate.Theupperrowconsistsofroughlyspherical
molecules,whereastheisomersinthelowerrowhavecylindricalorlinearshapedmolecules.Theattractiveforcesbetweenthelattergrouparegenerally
greater.Finally,permanentmoleculardipolesgeneratedbypolarcovalentbondsresultinevengreaterattractiveforcesbetweenmolecules,providedthey
havethemobilitytolineupinappropriateorientations.Thelastentriesinthetablecomparenonpolarhydrocarbonswithequalsizedcompoundshavingpolar
bondstooxygenandnitrogen.Halogensalsoformpolarbondstocarbon,buttheyalsoincreasethemolecularmass,makingitdifficulttodistinguishamong
thesefactors.

BoilingPoints(C)ofSelectedElementsandCompounds
IncreasingSize
Atomic Ar(40)186
Molecular CH4(16)161

Kr(83)153

Xe(131)109

(CH3)4C(72)9.5

(CH3)4Si(88)27

(CH3)2CCl2(113)69

(CH3)3CC(CH3)3(114)106

CCl4(154)77

MolecularShape
Spherical: (CH3)4C(72)9.5
Linear: CH3(CH2)3CH3(72)
36

Cl(CH2)3Cl(113)121 CH3(CH2)6CH3(114)126

MolecularPolarity
Nonpolar: H2C=CH2(28)104
Polar: H2C=O(30)21
HCN(27)26

F2(38)188

CH3CCCH3(54)32 CF4(88)130

CH3CH=O(44)20

(CH3)3N(59)3.5

(CH3)2C=O(58)56

CH3CN(41)82

(CH2)3O(58)50

CH3NO2(61)101

Themeltingpointsofcrystallinesolidscannotbecategorizedinassimpleafashionasboilingpoints.Thedistancebetweenmoleculesinacrystallatticeis
smallandregular,withintermolecularforcesservingtoconstrainthemotionofthemoleculesmoreseverelythanintheliquidstate.Molecularsizeisimportant,
butshapeisalsocritical,sinceindividualmoleculesneedtofittogethercooperativelyfortheattractivelatticeforcestobelarge.Sphericallyshapedmolecules
generallyhaverelativelyhighmeltingpoints,whichinsomecasesapproachtheboilingpoint.Thisreflectsthefactthatspherescanpacktogethermoreclosely
thanothershapes.Thisstructureorshapesensitivityisoneofthereasonsthatmeltingpointsarewidelyusedtoidentifyspecificcompounds.Thedatainthe
followingtableservestoillustratethesepoints.
Compound

Formula

pentane

CH3(CH2)3CH3

36C

130C

hexane

CH3(CH2)4CH3

69C

95C

heptane

CH3(CH2)5CH3

98C

91C

octane

CH3(CH2)6CH3

126C

57C

nonane

CH3(CH2)7CH3

151C

54C

decane

CH3(CH2)8CH3

174C

30C

106C

+100C

tetramethylbutane (CH3)3CC(CH3)3

BoilingPoint MeltingPoint

Noticethattheboilingpointsoftheunbranchedalkanes(pentanethroughdecane)increaserathersmoothlywithmolecularweight,butthemeltingpointsof
theevencarbonchainsincreasemorethanthoseoftheoddcarbonchains.Evenmemberedchainspacktogetherinauniformfashionmorecompactlythan
dooddmemberedchains.Thelastcompound,anisomerofoctane,isnearlysphericalandhasanexceptionallyhighmeltingpoint(only6belowtheboiling
point).

HydrogenBonding

HydrogenBonding
Themostpowerfulintermolecularforceinfluencingneutral(uncharged)moleculesisthehydrogenbond.Ifwecomparetheboilingpointsofmethane(CH4)
161C,ammonia(NH3)33C,water(H2O)100Candhydrogenfluoride(HF)19C,weseeagreatervariationforthesesimilarsizedmoleculesthan
expectedfromthedatapresentedaboveforpolarcompounds.Thisisshowngraphicallyinthefollowingchart.MostofthesimplehydridesofgroupIV,V,VI&
VIIelementsdisplaytheexpectedriseinboilingpointwithmolecularmass,butthehydridesofthemostelectronegativeelements(nitrogen,oxygenand
fluorine)haveabnormallyhighboilingpointsfortheirmass.

Theexceptionallystrongdipoledipoleattractionsthatcausethisbehaviorarecalledthehydrogenbond.Hydrogenformspolarcovalentbondstomore
electronegativeatomssuchasoxygen,andbecauseahydrogenatomisquitesmall,thepositiveendofthebonddipole(thehydrogen)canapproach
neighboringnucleophilicorbasicsitesmorecloselythancanotherpolarbonds.Coulombicforcesareinverselyproportionaltothesixthpowerofthedistance
betweendipoles,makingtheseinteractionsrelativelystrong,althoughtheyarestillweak(ca.4to5kcalpermole)comparedwithmostcovalentbonds.The
uniquepropertiesofwaterarelargelyduetothestronghydrogenbondingthatoccursbetweenitsmolecules.Inthefollowingdiagramthehydrogenbondsare
depictedasmagentadashedlines.

Themoleculeprovidingapolarhydrogenforahydrogenbondiscalledadonor.Themoleculethatprovidestheelectronrichsitetowhichthehydrogenis
attractediscalledanacceptor.Waterandalcoholsmayserveasbothdonorsandacceptors,whereasethers,aldehydes,ketonesandesterscanfunction
onlyasacceptors.Similarly,primaryandsecondaryaminesarebothdonorsandacceptors,buttertiaryaminesfunctiononlyasacceptors.Onceyouareable
torecognizecompoundsthatcanexhibitintermolecularhydrogenbonding,therelativelyhighboilingpointstheyexhibitbecomeunderstandable.Thedatain
thefollowingtableservetoillustratethispoint.
Compound

Formula

Mol.Wt. BoilingPoint MeltingPoint

dimethylether

CH3OCH3

46

24C

138C

ethanol

CH3CH2OH

46

78C

130C

propanol

CH3(CH2)2OH

60

98C

127C

diethylether

(CH3CH2)2O

74

34C

116C

propylamine

CH3(CH2)2NH2

59

48C

83C

methylaminoethane CH3CH2NHCH3

59

37C

trimethylamine

(CH3)3N

59

3C

117C

ethyleneglycol

HOCH2CH2OH

62

197C

13C

aceticacid

CH3CO2H

60

118C

17C

ethylenediamine

H2NCH2CH2NH2

60

118C

8.5C

Alcoholsboilconsiderablyhigherthancomparablysizedethers(firsttwoentries),andisomeric1,2&3amines,respectively,showdecreasingboiling
points,withthetwohydrogenbondingisomersbeingsubstantiallyhigherboilingthanthe3amine(entries5to7).Also,OHOhydrogenbondsareclearly

strongerthanNHNhydrogenbonds,asweseebycomparingpropanolwiththeamines.Asexpected,thepresenceof
twohydrogenbondingfunctionsinacompoundraisestheboilingpointevenfurther.Aceticacid(theninthentry)isan
interestingcase.Adimericspecies,shownontheright,heldtogetherbytwohydrogenbondsisamajorcomponentofthe
liquidstate.Ifthisisanaccuraterepresentationofthecompositionofthiscompoundthenwewouldexpectitsboilingpointto
beequivalenttothatofaC4H8O4compound(formulaweight=120).Asuitableapproximationofsuchacompoundisfoundintetramethoxymethane,
(CH3O)4C,whichisactuallyabitlarger(formulaweight=136)andhasaboilingpointof114C.Thus,thedimerichydrogenbondedstructureappearstobea
goodrepresentationofaceticacidinthecondensedstate.
Arelatedprincipleisworthnotingatthispoint.Althoughthehydrogenbondisrelativelyweak(ca.4to5kcalpermole),whenseveralsuchbondsexistthe
resultingstructurecanbequiterobust.Thehydrogenbondsbetweencellulosefibersconfergreatstrengthtowoodandrelatedmaterials.
ForadditionalinformationonthissubjectClickHere.

WaterSolubility

SolubilityinWater
Waterhasbeenreferredtoasthe"universalsolvent",anditswidespreaddistributiononthisplanetandessentialroleinlifemakeitthebenchmarkfor
discussionsofsolubility.Waterdissolvesmanyionicsaltsthankstoitshighdielectricconstantandabilitytosolvateions.Theformerreducestheattraction
betweenoppositelychargedionsandthelatterstabilizestheionsbybindingtothemanddelocalizingchargedensity.Manyorganiccompounds,especially
alkanesandotherhydrocarbons,arenearlyinsolubleinwater.Organiccompoundsthatarewatersoluble,suchasmostofthoselistedintheabovetable,
generallyhavehydrogenbondacceptoranddonorgroups.Theleastsolubleofthelistedcompoundsisdiethylether,whichcanserveonlyasahydrogenbond
acceptorandis75%hydrocarboninnature.Evenso,diethyletherisabouttwohundredtimesmoresolubleinwaterthanispentane.
Thechiefcharacteristicofwaterthatinfluencesthesesolubilitiesistheextensivehydrogenbondedassociationofitsmoleculeswitheachother.Thishydrogen
bondednetworkisstabilizedbythesumofallthehydrogenbondenergies,andifnonpolarmoleculessuchashexanewereinsertedintothenetworkthey
woulddestroylocalstructurewithoutcontributinganyhydrogenbondsoftheirown.Ofcourse,hexanemoleculesexperiencesignificantvanderWaals
attractiontoneighboringmolecules,buttheseattractiveforcesaremuchweakerthanthehydrogenbond.Consequently,whenhexaneorothernonpolar
compoundsaremixedwithwater,thestrongassociationforcesofthewaternetworkexcludethenonpolarmolecules,whichmustthenexistinaseparate
phase.Thisisshowninthefollowingillustration,andsincehexaneislessdensethanwater,thehexanephasefloatsonthewaterphase.

Itisimportanttorememberthistendencyofwatertoexcludenonpolarmoleculesandgroups,sinceitisafactorinthestructureandbehaviorofmanycomplex
molecularsystems.Acommonnomenclatureusedtodescribemoleculesandregionswithinmoleculesishydrophilicforpolar,hydrogenbondingmoieties
andhydrophobicfornonpolarspecies.
ForadditionalinformationonthissubjectClickHere.

PracticeProblems

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MoreaboutIntermolecularForces
IntermolecularForcesandPhysicalProperties
Theattractiveforcesthatexistbetweenmoleculesareresponsibleformanyofthebulkphysicalpropertiesexhibitedbysubstances.Somecompoundsare
gases,someareliquids,andothersaresolids.Themeltingandboilingpointsofpuresubstancesreflecttheseintermolecularforces,andarecommonlyused
foridentification.Ofthesetwo,theboilingpointisconsideredthemostrepresentativemeasureofgeneralintermolecularattractions.Thus,ameltingpoint
reflectsthethermalenergyneededtoconvertthehighlyorderedarrayofmoleculesinacrystallatticetotherandomnessofaliquid.Thedistancebetween
moleculesinacrystallatticeissmallandregular,withintermolecularforcesservingtoconstrainthemotionofthemoleculesmoreseverelythanintheliquid
state.Molecularsizeisimportant,butshapeisalsocritical,sinceindividualmoleculesneedtofittogethercooperativelyfortheattractivelatticeforcestobe
large.Sphericallyshapedmoleculesgenerallyhaverelativelyhighmeltingpoints,whichinsomecasesapproachtheboilingpoint,reflectingthefactthat
spherescanpacktogethermorecloselythanothershapes.Thisstructureorshapesensitivityisoneofthereasonsthatmeltingpointsarewidelyusedto
identifyspecificcompounds.
Boilingpoints,ontheotherhand,essentiallyreflectthekineticenergyneededtoreleaseamoleculefromthecooperativeattractionsoftheliquidstatesothatit
becomesanunencumberedandrelativeindependentgaseousstatespecies.Allatomsandmoleculeshaveaweakattractionforoneanother,knownasvan
derWaalsattraction.Thisattractiveforcehasitsoriginintheelectrostaticattractionoftheelectronsofonemoleculeoratomforthenucleiofanother,and
hasbeencalledLondondispersionforce.
Thefollowinganimationillustrateshowcloseapproachoftwoneonatomsmayperturbtheirelectrondistributionsinamannerthatinducesdipoleattraction.
Theinduceddipolesaretransient,butaresufficienttopermitliquefactionofneonatlowtemperatureandhighpressure.Clickingonthediagramwillreactivate
theanimation.

Ingeneral,largermoleculeshavehigherboilingpointsthansmallermoleculesofthesamekind,indicatingthatdispersionforcesincreasewithmass,number
ofelectrons,numberofatomsorsomecombinationthereof.Thefollowingtableliststheboilingpointsofanassortmentofelementsandcovalentcompounds
composedofmoleculeslackingapermanentdipole.Thenumberofelectronsineachspeciesisnotedinthefirstcolumn,andthemassofeachisgivenasa
superscriptnumberprecedingtheformula.
#Electrons

Molecules&boilingpointsC

10

20

Ne24616CH4162

18

40

Ar18632SiH411230C2H68938F2187

3444

84

Kr15258C4H100.572(CH3)4C1071Cl23588CF4130

6676

114

[(CH3)3C]2106126(CH2)9174160Br259154CCl477138C2F678

Twotenelectronmoleculesareshowninthefirstrow.Neonisheavierthanmethane,butitboils84lower.Methaneiscomposedoffiveatoms,andthe
additionalnucleimayprovidegreateropportunityforinduceddipoleformationasothermoleculesapproach.Theeasewithwhichtheelectronsofamolecule,
atomorionaredisplacedbyaneighboringchargeiscalledpolarizability,sowemayconcludethatmethaneismorepolarizablethanneon.Inthesecond
row,foureighteenelectronmoleculesarelisted.Mostoftheirboilingpointsarehigherthanthetenelectroncompoundsneonandmethane,butfluorineisan
exception,boiling25belowmethane.Theremainingexamplesinthetableconformtothecorrelationofboilingpointwithtotalelectronsandnumberofnuclei,
butfluorinecontainingmoleculesremainanexception.
Theanomalousbehavioroffluorinemaybeattributedtoitsveryhighelectronegativity.Thefluorinenucleusexertssuchastrongattractionforitselectronsthat
theyaremuchlesspolarizablethantheelectronsofmostotheratoms.
Ofcourse,boilingpointrelationshipsmaybedominatedbyevenstrongerattractiveforces,suchasinvolvingelectrostaticattractionbetweenoppositely
chargedionicspecies,andbetweenthepartialchargeseparationsofmoleculardipoles.Moleculeshavingapermanentdipolemomentshouldthereforehave
higherboilingpointsthanequivalentnonpolarcompounds,asillustratedbythedatainthefollowingtable.
#Electrons

Molecules&boilingpointsC

1418

30C

28
26
30
27
34
2H 689 H 2C=CH 2104 HCCH84 H 2C=O21 HCN26 CH 3F78

2226

42

CH3CH=CH24840CH3CCH2344CH3CH=O2141CH3CN8146(CH3)2O2450.5CH3Cl2452CH2F252

3244

58

(CH3)3CH1256(CH3)2C=CH2758(CH3)2C=O5659(CH3)3N395CH3Br4585CH2Cl24070CHF384

Inthefirstrowofcompounds,ethane,etheneandethynehavenomoleculardipole,andserveasusefulreferencesforsingle,doubleandtriplebonded
derivativesthatdo.Formaldehydeandhydrogencyanideclearlyshowtheenhancedintermolecularattractionresultingfromapermanentdipole.Methyl
fluorideisanomalous,asaremostorganofluorinecompounds.Inthesecondandthirdrows,allthecompoundshavepermanentdipoles,butthoseassociated
withthehydrocarbons(firsttwocompoundsineachcase)areverysmall.Largemoleculardipolescomechieflyfrombondstohighelectronegativeatoms
(relativetocarbonandhydrogen),especiallyiftheyaredoubleortriplebonds.Thus,aldehydes,ketonesandnitrilestendtobehigherboilingthanequivalently
sizedhydrocarbonsandalkylhalides.Theatypicalbehavioroffluorinecompoundsisunexpectedinviewofthelargeelectronegativitydifferencebetween
carbonandfluorine.

HydrogenBonding
MostofthesimplehydridesofgroupIV,V,VI&VIIelementsdisplaytheexpectedrisein
Group
Molecules&boilingpointsC
boilingpointwithnumberofelectronsandmolecularmass,butthehydridesofthemost
electronegativeelements(nitrogen,oxygenandfluorine)haveabnormallyhighboilingpoints,
VII
HF19HCl85HBr67HI36
depictedearlierasagraph,andalsolistedontheright.Theexceptionallystrongdipole
dipoleattractionsthatareresponsibleforthisbehaviorarecalledhydrogenbonds.Whena
H2O100H2S60H2Se41H2Te2
VI
hydrogenatomispartofapolarcovalentbondtoamoreelectronegativeatomsuchas
oxygen,itssmallsizeallowsthepositiveendofthebonddipole(thehydrogen)toapproach
NH333PH388AsH362SbH318
V
neighboringnucleophilicorbasicsitesmorecloselythancancomponentsofotherpolar
bonds.Coulombicforcesareinverselyproportionaltothesixthpowerofthedistancebetweendipoles,makingtheseinteractionsrelativelystrong,although
theyarestillweak(ca.4to5kcalpermole)comparedwithmostcovalentbonds.Thetableofdataontherightprovidesconvincingevidenceforhydrogen
bonding.Ineachrowthefirstcompoundlistedhasthefewesttotalelectronsandlowestmass,yetitsboilingpointisthehighestduetohydrogenbonding.
Othercompoundsineachrowhavemoleculardipoles,theinteractionsofwhichmightbecalledhydrogenbonding,buttheattractionsareclearlymuch
weaker.ThefirsttwohydridesofgroupIVelements,methaneandsilane,arelistedinthefirsttableabove,anddonotdisplayanysignificanthydrogen

bonding.
OrganiccompoundsincorporatingOHandNHbondswillalsoexhibitenhancedintermolecularattractionduetohydrogenbonding.Someexamplesaregiven
below.
Class

Molecules&boilingpointsC

Oxygen
Compounds

C2H5OH78(CH3)2O24(CH2)2O11

(CH2)3CHOH124&(CH2)4O66

ethanoldimethyletherethyleneoxide

cyclobutanoltetrahydrofuran

Nitrogen
Compounds

C3H7NH250C2H5NH(CH3)37(CH3)3N3

(CH2)4CHNH2107&(CH2)4NCH380

propylamineethylmethylaminetrimethylamine

cyclopentylamineNmethylpyrrolidine

C2H5CO2H141&CH3CO2CH357

C3H7CONH2218&CH3CON(CH3)2165

propanoicacidmethylacetate

butyramideN,Ndimethylacetamide

Complex
Functions

WaterSolubility
Wateristhesinglemostabundantandimportantliquidonthisplanet.Themiscibilityofotherliquidsinwater,andthesolubilityofsolidsinwater,mustbe
consideredwhenisolatingandpurifyingcompounds.Tothisend,thefollowingtableliststhewatermiscibility(orsolubility)ofanassortmentoflowmolecular
weightorganiccompounds.Theinfluenceoftheimportanthydrogenbondingatoms,oxygenandnitrogenisimmediatelyapparent.Thefirstrowlistsafew
hydrocarbonandchlorinatedsolvents.Withoutexceptiontheseareallimmisciblewithwater,althoughitisinterestingtonotethattheelectronsofbenzene
andthenonbondingvalenceelectronsofchlorineacttoslightlyincreasetheirsolubilityrelativetothesaturatedhydrocarbons.Whencomparedwith
hydrocarbons,theoxygenandnitrogencompoundslistedinthesecond,thirdandfourthrowsareoverahundredtimesmoresolubleinwater,andmanyare
completelymisciblewithwater.

WaterSolubilityofCharacteristicCompounds
CompoundType

SpecificCompounds

Grams/100mL

Moles/Liter

SpecificCompounds

Grams/100mL

Moles/Liter

Hydrocarbons&
AlkylHalides

butane
hexane
cyclohexane

0.007
0.0009
0.006

0.0012
0.0001
0.0007

benzene
methylenechloride
chloroform

0.07
1.50
0.8

0.009
0.180
0.07

Compounds
Having
OneOxygen

1butanol
tertbutanol
cyclohexanol
phenol

9.0
complete
3.6
8.7

1.2
complete
0.36
0.90

ethylether
THF
furan
anisole

6.0
complete
1.0
1.0

0.80
complete
0.15
0.09

Compounds
Having
TwoOxygens

1,3propanediol
2butoxyethanol
butanoicacid
benzoicacid

complete
complete
complete
complete

complete
complete
complete
complete

1,2dimethoxyethane
1,4dioxane
ethylacetate
butyrolactone

complete
complete
8.0
complete

complete
complete
0.91
complete

Nitrogen
Containing
Compounds

1aminobutane
cyclohexylamine
aniline
pyrrolidine
pyrrole

complete
complete
3.4
complete
6.0

complete
complete
0.37
complete
0.9

triethylamine
pyridine
propionitrile
1nitropropane
DMF

5.5
complete
10.3
1.5
complete

0.54
complete
2.0
0.17
complete

Somegeneraltrendsareworthnotingfromthedataabove.First,alcohols(secondrowleftcolumn)areusuallymoresolublethanequivalentlysizedethers
(secondrowrightcolumn).Thisreflectsthefactthatthehydroxylgroupmayfunctionasbothahydrogenbonddonorandacceptorwhereas,anetheroxygen
mayserveonlyasanacceptor.Theincreasedsolubilityofphenolrelativetocyclohexanolmaybeduetoitsgreateracidityaswellasthepielectroneffect
notedinthefirstrow.
ThecyclicetherTHF(tetrahydrofuran)ismoresolublethanitsopenchainanalog,possiblybecausetheoxygenatomismoreaccessibleforhydrogenbonding
towatermolecules.Duetothedecreasedbasicityoftheoxygeninthearomaticcompoundfuran,itismuchlesssoluble.Theoxygenatominanisoleis
likewisedeactivatedbyconjugationwiththebenzenering(note,itactivatestheringinelectrophilicsubstitutionreactions).Asecondoxygenatomdramatically
increaseswatersolubility,asdemonstratedbythecompoundslistedinthethirdrow.Againhydroxylcompoundsarelistedontheleft.
Nitrogenexertsasolubilizinginfluencesimilartooxygen,asshownbythecompoundsinthefourthrow.Theprimaryandsecondaryamineslistedintheleft
handcolumnmayfunctionasbothhydrogenbonddonorsandacceptors.Aromaticitydecreasesthebasicityofpyrrole,butincreasesitsacidity.The
compoundsintherightcolumnareonlycapableofanacceptorrole.Thelowsolubilityofthenitrocompoundissurprising.

ThispageisthepropertyofWilliamReusch.Comments,questionsanderrorsshouldbesenttowhreusch@msu.edu.
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Endofthissupplementarytopic