Beruflich Dokumente
Kultur Dokumente
StructureofMolecules
SOLUTIONStoChapter5Problems
Section5.1.
Isomers
5.1.
Thisisthestructureof2methyl1propanol,C4H10O.
H H H
H C C C O H
H
H
H C H
H
Whichofthesestructuresisalsoacorrectrepresentationof2methyl1propanol?
Explainyourdecisionineachcase.Usemodels,ifnecessary,foryourexplanation.
H
O
C
(i)
H
H
H C
C H
H
H
H C H
H
H
H C H
(ii)
H H
H O C C C H
H H H
H
H C
H
(iii)
H
H C O H
C H
H C H
H
Answerto5.1:Structure1isnotacorrectrepresentation.NotethattheOHgroupis
attachedtothe2ndcarbonatom,notthefirst.Youcancheckthisbymakingmodelsof2
methyl1propanolandofstructure1.Youwillfindthatyoucannotsuperimposethetwo
models.Thisis2methyl2propanol.
Structure2isnotacorrectrepresentation.AlthoughtheOHgroupiscorrectlyattached
tothe1stcarbonatom,thefourcarbonsareattachedsequentially.Thefactthatthelast
CH3groupisbentisjustadifferentpaperandpencilrepresentationandtheCH3group
isnotattachedtothe2ndcarbonatom.Youcancheckthisbymakingmodelsof2
methyl1propanolandofstructure2.Youwillfindthatyoucannotsuperimposethetwo
models.Thisis1butanol.
Structure3isacorrectrepresentation.NotethattheOHgroupisattachedtothe1st
carbonatom,andtheCH3groupisattachedtothe2ndcarbonatom.Youcancheckthis
bymakingmodelsof2methyl1propanolandofstructure3.Youwillfindthatyoucan
superimposethetwomodels.Thisis2methyl1propanol.
5.2.
Both1pentanoland2pentanolhavethesamemolecularformula,C5H12O.
(a) Drawthestructureofeachalcohol.
(b) Predictwhichofthesetwoalcoholshasthehigherboilingpoint.Explainthereason
foryourprediction.
(c) DrawallalcoholswiththeformulaC5H12O.Hint:thereareeighttotalincluding
1pentanoland2pentanol.
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Answerto5.2:
H H H H H
H C C C C C O H
(a)Structureof1pentanol
H H H H H
H H H H H
Structureof2pentanol
H C C C C C H
H H H O H
H
(b)Basedonacomparisonwith1butanoland2butanolinTable5.1,theprediction(and
fact)isthattheboilingpointofthestraightchainalcohol,1pentanol,islikelytobe
greaterthanthatofthebranchedalcohol,2pentanol.Thebasicreasonisthatthe
dispersionforcesbetweenmoleculesofstraightchainalcoholsaregreaterthanthe
dispersionforcesbetweenbranchedalcohols.Therefore,moreenergyisrequiredto
changefromtheliquidtothegasphase,reflectedinhigherboilingpointsforstraight
chainalcoholscomparedtobranchedalcoholsofthesamemolecularweights.
OH
OH
OH
(R/S)
OH
(R/S)
OH
OH
OH
HO
(R/S)
Astudentfollowedtheprocedureinalaboratorymanualtoprepareanioniccompound,a
greensolidwiththecomposition,Co(H2NCH2CH2NH2)2Cl3.Shedissolvedthecompound
inwater,warmedthesolution,andfoundthatthesolutionturnedreddishpurple.She
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evaporatedthewater,recrystallizedthereddishpurplecrystals,andanalyzedthemfor
cobalt,chloride,and1,2diaminoethane,H2NCH2CH2NH2.Shefoundthatthereddish
purplecompoundhadthecomposition,Co(H2NCH2CH2NH2)2Cl3.Whatconclusion(s)
canyoudrawabouttherelationship(s)betweenthegreenandreddishpurplecompounds?
Explainyourreasoning.
Answerto5.3:Sincethemolecularformulasofthegreenandreddishpurplecompounds
arethesame,thecompoundsmustbeisomers.(InChapter6,metalioncomplexesare
introduced.Thecompoundsherearemetalioncomplexeswitheachofthe1,2
diaminoethane(ethylenediamine)moleculesbondedattwoofthesixoctahedralpositions
aroundacentralCo(III)ionandchloridesbondedattheothertwopositions.Thegreen
compoundhasthechloridesbondedonoppositesides(trans)ofthemetalionasfarfrom
oneanotheraspossibleinthisstructure.Inthereddishpurplecompoundthetwo
chloridesarebondedatadjacentpositions(cis).)
Section5.2.
LewisStructuresandMolecularModelsofIsomers
5.4.
Predicttherelativevaluesfortheboilingpointsof1propanoland2propanol.
OH
1propanol
OH
2propanol
Answerto5.4:Whencomparingisomericbranchedandstraightchainalkanes,the
branchedalkanesinvariablyhavelowerboilingpointsthantheirstraightchainisomeric
cousins.Asimilareffectappliestotheisomericvariantsofotherfunctionalgroups.
Therefore,wepredictthat2propanolboilsatalowertemperaturethan1propanol.This
predictionisborneoutbyexperiment.Theyboilat82Cand97Crespectively.
5.5.
ThisistheLewisstructureforpropane,C3H8:
H H H
H C C C H
H H H
(a) Useyourmodelkittomakethismodel,andthendrawarepresentationofthis
structureinthreedimensions.
(b) Whatistheshape(geometry)aroundthecentralcarbonatom?
(c) Arethereanyotherisomersforpropane,C3H8?
Answerto5.5:
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H
(a)
CH3
CH3
(b)tetrahedral
(c)Therearenootherisomers.Atleastfourcarbonsarenecessarybeforeanotherorder
oflinkageofcarbonatomsispossibleforanalkane.
5.6.
ThisistheLewisstructureofnpentane,C5H12.
H H H H H
H C C C C C H
H H H H H
(a) Howmanyvalenceelectronsarerepresentedinthisstructure?
(b) Includingelectronsinatomiccores,whatisthetotalnumberofelectronsimplicitly
represented?
Answerto5.6:
(a)12(1)+5(4)=32valenceelectrons
(b)12(1)+5(6)=42totalelectrons
5.7.
TheboilingpointsofthethreepentaneisomersaregiveninTable5.2.Makemolecular
modelsofthesecompoundsandcoverthemwithplasticwraporaluminumfoilto
representthesurfaceofeachmolecule.Explainwhynpentanehasthehighestboiling
pointandneopentanehasthelowestboilingpointofthissetofisomers.Hint:Consider
theamountofsurfaceeachmoleculehastointeractwithitsneighborsintheliquids.
Answerto5.7:Becausehydrocarbonsarenonpolar,theonlyintermolecularforcesare
dispersionforces.Themolecularvolumeofeachpentaneisomermustbethesame
becausethevolumeofeachsimplyconsistsoffivecarbonsandtwelvehydrogens.
However,thesurfaceareaisnotthesameforthethreeisomers.Themostnearlylinear
isomer(npentane)hasthegreatestsurfaceareaandthereforehasthemostintermolecular
attractionsduetodispersionforces.Thisinturnleadstothehighestboilingpoint.
Neopentanehasthemostnearlysphericalshapeandhasthesmallestsurfaceareaofthe
threepentaneisomers.Therefore,itwillhavethelowestboilingpoint.(Recallfrom
geometrythatthesphereisthegeometricsolidthatminimizesthesurfaceareaforany
givenvolume.)Ingeneral,branchingleadstomorecompactstructuresand
correspondinglylowerboilingpoints.
5.8.
InCheckThis5.11,youwereaskedtoexplaintheboilingpointdata(Table5.1)forthe
fourC4H10Oalcohols.DrawthethreeethersthatalsohavetheformulaC4H10Oand
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predictwhichonewillhavethelowestboilingpoint.Explainthereasoningforyour
selection.Hint:SeeProblem5.7.
Answerto5.8:Allthreeisomershavepolarcarbonoxygenbonds,butonlythecircled
isomerisbranched.
O
5.9.
InCheckThis5.7youwroteLewisstructuresandmademodelsofthefourisomeric
amineshavingtheformulaC3H9N.Predictwhichonewillhavethelowestboilingpoint
andexplainthereasoningforyourselection.Hint:Considerallthepossible
intermolecularinteractionsintheliquids.
Answerto5.9:Twooftheaminesarelinear(AandB)andtwoarebranchedtothesame
extent(CandD).However,branchingisnotthemostimportantfactorinfluencing
boilingpointinthiscomparison.CompoundsA,B,andCareallcapableofforming
intermolecularhydrogenbonds,whereascompoundDisnot.Sincehydrogenbondingis
astrongerintermolecularforcethandispersion,compoundD(lackinghydrogenbonds)
hasthelowestboilingpoint.
NH2
NH2
A
N
H
B
N
D
Section5.3.
SigmaMolecularOrbitals
5.10.
Whichelectrons,coreorvalence,aregenerallyresponsibleforchemicalbonding?
Explainwhy.
Answerto5.10:
Valenceelectrons.
5.11.
Explainthedifference(s)betweenanatomicorbitalandamolecularorbital.
Answerto5.11:Atomicorbitalsdescribetheenergyandspatialdistributionofelectrons
withrespecttoasingleatomicnucleus.Molecularorbitalsdescribetheenergyand
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spatialdistributionofvalenceelectronswithrespecttotwo(ormore)atomiccores.
Molecularorbitalsareformedfromatomicorbitals.
5.12.
Explainthedifference(s)betweenabondingandanonbondingmolecularorbital.
Answerto5.12:Bondingorbitalscontainthevalenceelectronsinvolvedinchemical
bonds.Nonbondingorbitalscontainvalenceelectronswhichremainassociatedwitha
particularatomiccoreandarenotinvolvedinbonds.
5.13.
Whydotwohydrogenatomscombinetoformahydrogenmolecule(H2)?Explainusing
(a) aLewisstructureforbonding.
(b) theMOmodelforbonding.
Answerto5.13:
TheLewismodelplacesthetwoseparateselectronsofthestartinghydrogenatomsinto
asinglebondlinkingthetwoatoms(H+H>HH).Inthespecialapplicationof
theoctetruleforfirstrowatoms,acompleteoutershellofelectronsconsistsofjusttwo
electrons.TheMOmodelplacesthetwoseparateselectronsofthestartinghydrogen
atomsintoamolecularorbital.The*orbitalisemptyandthebondorderforthe
moleculeis1.0.
5.14.
Whydonttwoheliumatomscombinetoformaheliummolecule(He2)?Explainusing
(a) aLewisstructureforbonding.
(b) theMOmodelforbonding.
Answerto5.14:
Atomicheliumhastwoelectronsandalreadysatisfiestheoctetrule.Inthespecial
applicationoftheoctetruleforfirstrowatoms,theMOmodelplacestwoselectronsof
thestartingheliumatomsintoamolecularorbital.The*orbitalalsohastwo
electronsandthebondorderforthemoleculeiszero.Thereforeithasnotendencyto
remainbonded.
5.15.
Explainwhyitispossibleformoleculestoexist,ifthereisalwaysarepulsiveforce
betweenpositivelychargednuclei?
Answerto5.15:
Eventhoughbothrepulsionofnucleiandkineticenergyofelectronwavesmustbe
accountedfor,theattractivecontributionsofthepotentialenergymakesthetotalenergy
ofthemoleculelowerthanthecombinedenergiesoftheseparatedatoms.
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5.16.
StructureofMolecules
Identifythenumberofvalenceelectronsineachofthefollowing:
(a) Na
(b)CO2
(c)NH3
(d)Se
Answerto5.16:
Foratoms,seewhatcolumn(group)theelementbelongsto.Forcompounds,anyshared
orunsharedelectrons(asshowninaLewisstructure)count.Becarefulnottodouble
countthesharedelectrons.
(a)1(b)16(c)8(d)6
5.17.
ConsiderFigure5.4,Relativeenergies
foratwonucleioneelectronmolecular
orbitalsystem.Ithasbeenredrawnhere
withcurves14labeled.
(a)Whatinformationdoesline1give
youastwonucleimovetowardseach
other?
(b)Whatinformationdoesline2give
youastwonucleimovetowardseach
other?
(c)Whatinformationdoesline3give
youastwonucleimovetowardseachother?
(d)Whatinformationdoesline4giveyouastwonucleimovetowardseachother?
Answerto5.17:
(a)Line1tellsmethatastwonucleiapproacheachother,thekineticenergyoftheone
electronmolecularorbitalsystemincreases.
(b)Line2isthereferencebaselineforenergyanddoesnotchangeasthetwonuclei
approacheachother.
(c)Line3tellsmethatastwonucleiapproacheachother,thetotalenergyoftheone
electronmolecularorbitalsystemfallstoaminimumandthenincreasessignificantly.
(d)Line4tellsmethatastwonucleiapproacheachother,thepotentialenergyofthe
systemdecreases.
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Section5.4.
SigmaMolecularOrbitalsandMolecularGeometry
5.18.
Incertaingasphasereactions,methanecanloseahydrogencation,H+,toformthe
methideanion,CH3.
(a) WritetheLewisstructureforthemethideanion.
(b) Howwouldyoudescribethegeometryofthesigmaorbitalsinthemethideanion?
(c) Howwouldyoudescribethegeometryofthemethideanion?
(d) Areyouranswerstoparts(b)and(c)thesame?Explainwhyorwhynot.
Answerto5.18:
H
(a)
(b)Thesigmaorbitals,threebondingandonenonbonding,aretetrahedrallyarranged
aroundthecarbon.
(c)Thegeometry(thearrangementofthenuclei)isatrigonalpyramidwithcarbonatthe
apexandthehydrogensformingthebase:
H
H
(d)Thearrangementofsigmaorbitalsandthegeometryarenotthesame,becausethe
nonbondingelectronpairisnotincludedinthegeometricdescription.Thestructureofthe
methideionismuchlikethestructureofammonia,Figure5.10.
5.19.
Sodiumamide,NaNH2,isawhitecrystallineioniccompound.
(a) WritetheLewisstructurefortheamideanion,NH2.
(b) Howwouldyoudescribethegeometryofthesigmaorbitalsintheamideanion?
(c) Howwouldyoudescribethegeometryoftheamideanion?
(d) Areyouranswerstoparts(b)and(c)thesame?Explainwhyorwhynot.
Answerto5.19:
N
(a)
(b)Thesigmaorbitals,twobondingandtwononbonding,aretetrahedrallyarranged
aroundthenitrogen.
N
(c)Thegeometryoftheamideionisbent:
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(d)Thearrangementofsigmaorbitalsandthegeometryarenotthesame,becausethe
nonbondingelectronpairsarenotincludedinthegeometricdescription.Thestructureof
theamideionismuchlikethestructureofwater,Figure5.10.
5.20.
(a) HowmanyvalenceelectronsarethereintheLewisstructureforIF5?
(b) Howmanytotalelectrons,includingallofthecoreelectrons,arethereinamolecule
ofIF5?
(c) WriteaLewisstructureforIF5.
(d) ThegeometryofthefluorineatomsintheIF5moleculeissquarepyramidal(a
pyramidwithasquarebase).WhyisthisdifferentfromthemolecularshapeofPF5,in
whichthegeometryofthefluorineatomsistrigonalbipyramidal,asshowninFigure
5.11(b)?
Answerto5.20:
(a)
F
I
F
F
(b)Thereare1(7)+5(7)=42valenceelectronsintheLewisstructureforIF5.
(c)Thereare1(53)+5(9)=98totalelectronsinamoleculeofIF5.
(d)NotethattheLewisstructureforIF5has42valenceelectrons,butforPF5has40
valenceelectrons.ThisdifferenceiscausedbythefactthatiodineisinGroupVIIAand
phosphorusisinGroupVA.Therefore,whilethereare12electronsaroundthecentral
atominIF5,thereareonly10electronsarrangedaroundthecentralatominIF5.
5.21.
Foreachofthefollowingmoleculesorions,writeaLewisstructure,includingall
nonbondingpairsofelectrons.
(a) I3
(b) BF4
(c) SF4
(d) XeF4
(e) PF6
Answerto5.21:
(a) I3has28valenceelectronstotal(4and18n).Theextraelectronisassociated
withthecentraliodine,whichcarriestheformalcharge(1).Thecentraliodineis
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surroundedbyfivepairsofelectronsthatwilladoptatrigonalbipyramidal
arrangementwiththetwootheriodines180apartattheoppositeendsofthe
structure.Forclarity,onlytheelectronpairsonthecentraliodineareshowninthe3
dstructureontheright.
(b) BF4has32valenceelectronstotal(8and24n).Theextraelectronisassociated
withthecentralboron,whichcarriestheformalcharge(1).Theboronissurrounded
byfourpairsofbondingelectronsinatetrahedralarrangement.
F
B
S
F
F
F
S
F
F
F
(c) SF4has34valenceelectronstotal(8and26n).Thesulfurhasfivepairsof
electronsthatwilladoptatrigonalbipyramidalarrangementaboutthiscentralatom.
Thenonbondingpairislocatedatoneofthesitesonthetriangularbasesharedbythe
twopyramids.Theremainingsigmabondsdefinethegeometrythatlookslikea
seesaw.
(d) XeF4has36valenceelectronstotal(8and28n).Thexenonhassixpairsof
electronsthatwilladoptanoctahedralarrangementwiththetwononbondingpairsof
electrons180apartattheoppositesidesofthestructure.Theremainingbonded
substituentsareinasquareplanararrangementwithrespecttothexenon.
F
F
Xe
F
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PF6has48valenceelectronstotal(12and36n).Theextraelectronis
associatedwiththephosphorus,whichcarriestheformalcharge(1).Thephosphorusis
surroundedbysixpairsofbondingelectronsinanoctahedralarrangement.
F
F
P
F
5.22.
F
F
P
F
F
F
ForeachmoleculeorioninProblem5.21,explainwhythesearetheobservedgeometries
(shapes).
(a) I3islinear.
(b) BF4istetrahedral.
(c) SF4isshapedlikeaseesaw,
,withSatthefulcrum.
(d) XeF4issquareplanar,withtheXeatthecenterofthesquare.
(e) PF6isoctahedralwiththePinthecenteroftheoctahedron.
Answerto5.22:Seeanswerto5.21.
Section5.5.
MultipleBonds
5.23.
Whichsecondperiodelementsarecapableofmakingdoublebondsundernormal
conditions?Whyaretheothersnotincluded?Explainthereasoningforyourchoices.
Answerto5.23:
Carbon,Nitrogen,Oxygen.Othersarenotincludedbecausethemolecularorbitalsare
largerinhigherperiodatoms.Thus,theyaremoreavailabletoreactandformproducts
withbondingorbitals.
5.24.
Whichelementsnevermakedoublebonds?Explainthereasoningforyourchoices.
Answerto5.24:
Hydrogenandthehalogens(Fluorine,Chlorine,Bromine,andIodine).Hydrogenonly
hasonevalenceelectron.Thehalogenshave7valenceelectrons.Thus,onlyone
electronfromanotheratomcanformasinglebondwiththehalogens.
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5.25.
StructureofMolecules
Foreachmolecule,writeaLewisstructureanddeterminethemoleculargeometryfor
eachcarbonatom.Hint:eachmoleculehasamultiplebond.Molecularmodelsmaybe
helpful.
(a) C3H6(propenehasonecarboncarbondoublebond)
(b) C3H4(propynehasonecarboncarbontriplebond)
(c) C3H4(allenehastwocarboncarbondoublebonds)
(d) C2H4O(ethanalhasonecarbonoxygendoublebond)
(e) C2H3N(acetonitrilehasonecarbonnitrogentriplebond)
Answerto5.25:
(a)
C3H6(propene)
trigonal planar
H
H
H H
tetrahedral
(b)
trigonal planar
tetrahedral
linear
C
linear
C3H4(allene)
trigonal planar
H
C
(d)
C3H4(propyne)
H
(c)
H
H
linear
C2H4O(ethanal)
trigonal planar
H
H
tetrahedral
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C2H3N(acetonitrile)
tetrahedral
H
H
C
H
linear
Section5.6.
PiMolecularOrbitals
5.26.
Whatis(are)thedifference(s)betweenasigma()andapi()orbital?
Answerto5.26:Botharemolecularorbitals.Sigmaobitalsarecylindricallysymmetric
abouttheaxisconnectingtwoatomiccores.Pibondsareformedfrompatomicorbitals.
Theyareoffaxisandhavetwohalvesseparatedbyanodalplanewhichincludesthetwo
atomiccores.Sigmabondsaretypicallystrongerthanpibonds.
5.27.
Whydoallmoleculeshavesigmabondingorbitals,butnotnecessarilypibonding
orbitals?
Answerto5.27:Thereisatwoelectronsigmabondingorbitalbetweeneverypairof
bondedatomcoresinamolecule.Asigmaorbitalhasthegreatestelectrondensityalong
thebondaxis,formingabondwiththelowestpossibletotalenergyforthetwonuclei
system.Apibondingorbitalisnotneededifsigmabondingorbitalssuccessfullyaccount
forallofthevalenceelectronsandeverysecondperiodelementhasanoctetofelectrons.
5.28.
Iftwocarbonatomsarebondedbyasigmabondingorbital,whyisasecondbond
betweenthosetwoatomsapiorbitalratherthananothersigmabondingorbital?
Answerto5.28:Thepibondingorbitalhasgreaterelectrondensityawayfromthebond
axis,notdirectlybetweenthebondedatomcores.Theriseinelectronwaveinteractions
wouldmaketwosigmabondsbetweenatomcoresenergeticallyimpossible.
5.29.
Whyaremoleculeswithmultiplebondsgenerallymorereactivethansimilarcompounds
withoutmultiplebonds?
Answerto5.29:Thepibondingorbitals,havingaconsiderableamountofelectron
densityawayfromthebondaxis,aremorereadilyavailableforinteractionswithother
molecules.
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Section5.7.
DelocalizedOrbitals
5.30.
Considerthefollowingmoleculesandions.Circleeachonethatcontainsabond.For
thosemoleculeswithabond,placeaDnexttooneswherethebondisdelocalized
andanLnexttooneswherethebondislocalized.Buildingmodelsmaybehelpful.
(a) H2CCH2
(d) NH3
(g) CH4
(b) H2CO
(e) CO2
(h) SO2
(c) NO3
(f) CH3C(O)OH
(i) H2O
Answerto5.30:
Moleculesorionswithbonds:(a)H2CCH2L
(b)H2COL(c)NO3D
(e)CO2D(orL)(f)CH3COOH D(h)SO2D
5.31.
Considerthehydrogencarbonateanion,(HO)CO2,andtheozonemolecule,O3.
(a) Whatisthetotalnumberofvalenceelectronsineachspecies?
(b) DrawtheLewisstructureforeachspecies.
(c) Howmanybondingorbitalsaretherearoundthecentralatomineachspecies?
(d) Whatgeometryispredictedforeachspecies?
(e) Howmanybondingorbitalsaretherearoundthecentralatomineachspecies?
(f) Howmanylocalizedandhowmanydelocalizedbondingorbitalsarethereineach
species?Explainhowyouarriveatyouranswer.
(g) Whatarethebondordersforcarbontooxygenin(HO)CO2andoxygentooxygen
inO3?Usesketchesofthedelocalizedorbitals,ifany,toillustrateyouranswer.What,if
any,similaritiesaretherebetweenthedelocalizedorbitalsandthebondordersinthese
twospecies?Explain.
Answerto5.31:
(a)HOCO2has24valenceelectronsandO3has18.
H
O
C
(b)
O
O
(c)ThecentralCatominHOCO2issurroundedbythreesigmabondingorbitalsandthe
centralOatominO3hastwosigmabondingorbitals(andonesigmanonbondingorbital).
(d)TheOatomsaroundtheCinHOCO2arearrangedinaplaneat120angles;the
geometryabouttheCatomistrigonalplanar.Ozone,O3,isabentmolecule;thethree
sigmaorbitalsarearrangedroughlytrigonally(buttheanglesarenotallequal).
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(e)Thereisonepibondingorbitalaroundeachcentralatominthesespecies.
(f)Eachspecieshasonedelocalizedpiorbital.IntheHOCO2,thepiorbitalis
delocalizedoverthecentralCatomandthetwoOatomsnotbondedtoanHatom.In
ozone,thepiorbitalisdelocalizedoverallthreeatoms.Ineachcase,asecondLewis
structure,identicalinenergytotheonesabove,canbewritten:
H
O
C
O
O
WhenevertwoormoreLewisstructureswiththesameenergycanbewrittenfora
species,neitherisanaccuraterepresentation;thepiorbitalsinvolvedaredelocalized.
(g)ThebondordersbetweentheCatomandthetwoOatomsnotbondedtoanHatomin
HOCO2areeach1.5,oneandonehalfbonds.Thesameistrueforthebondsbetween
thecentralOatomandtheotherOatomsinozone.Inbothcases,thesigmabond
betweentheatomsisafullbondandthedelocalizedpibondcontributesonehalfabond
toeachbond,fora1.5bond.Althoughthesespeciesarequitedifferentinmanyways,
someaspectsoftheirbonding(delocalizationand1.5orderbonds)areverymuchalike.
5.32.
(a) Wehavesaidthatmoleculesarelikelytohavedelocalizedpiorbitals,ifthereis
morethanoneenergyequivalentwaytowritelocalizedpiorbitals.WritetheLewis
structureforcarbondioxide,asyoudidinConsiderThis5.38.Wouldyouexpectthe
moleculetohavedelocalizedpiorbitals?Explainwhyorwhynot.
(b) Themolecularorbitalpictureforcarbondioxide,Figure5.24,showstwopiorbitals
delocalizedoverallthreeatomiccoresinthemolecule.Isthisconsistentwithyour
answerinpart(a)?Explainwhyorwhynot.
(c) Anotherwaytorepresentthelocalizedpiorbitalsin
carbondioxideisshowninthismolecularmodel.(Thesigma
nonbondingelectronsarenotrepresentedinthemodel.)Is
theremorethanoneequivalentwaytomodelthesepiorbitals?
Explainwhyorwhynotandconstructamodel(ormodels)to
demonstrateyourexplanation.
(d) Isyouranswerinpart(c)consistentwiththedelocalizedpiorbitalpictureforcarbon
dioxide?Explainwhyorwhynot.Doesitexplaintheobservedbondlengths(Check
This5.39)?
Answerto5.32:
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(a)TheLewisstructureforCO2is:
.Theredoesnotappeartobeanyotherway
toarrangetheelectronsthatisequivalenttothisone,sodelocalizedpiorbitalsarenot
predictedbytheLewisstructure.
(b)TheLewisstructureappearstohavethetwopairsofpielectronslocalizedintwo
centerbondsbetweenthecarbonandanoxygenatom.Thisisnotconsistentwiththe
delocalizedpiorbitalsinFigure5.24wherethepielectronpairsspreadoverallthree
atoms.
(c)Themodelshownisonewaytoarrangethepiorbitalsthatareperpendiculartoone
another.Thesecondpicturehererepresentsanotherway.
Inthesetwomodels,theatomshavenotswitchedplaces,butthelocalizedpiorbitalsare
shownondifferentpairsofatoms.Therearetwoenergyequivalentwaystoarrangethe
piorbitals.
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(d)Sincetherearetwoenergyequivalentwaystoarrangethepiorbitals(whicharenot
representedbythetwodimensionalLewisstructure),delocalizationofthepielectrons
occursandlowersthetotalenergyofthemolecule.Carbondioxideismorestable(lower
energy)thanlocalizedpiorbitalswouldpredict.Thedelocalizationimpliedbyhaving
twoequivalentwaystoarrangethepibondpaddlesisthesameasthatshowninFigure
5.24andtheexplanationfortheCObondlengthsthatareshorterthanforaCObond
withalocalizedpibond,isgivenintheanswertoCheckThis5.39(b).
5.33.
Considerthenitrateion,NO3,thenitriteanion,NO2,andthenitroniumcation,NO+.
(a) Whatisthetotalnumberofvalenceelectronsineachion?
(b) DrawtheLewisstructureforeachion.
(c) Howmanybondingorbitalsaretherearoundthecentralatomineachion?
(d) Whatgeometryispredictedforeachion?
(e) Howmanybondingorbitalsaretherearoundthecentralatomineachion?
(f) Howmanylocalizedandhowmanydelocalizedbondingorbitalsarethereineach
ion?Explainhowyouarriveatyouranswer.
(g) Whatisthebondorderfornitrogentooxygenineachion?Usesketchesofthe
delocalizedorbitals,ifany,toillustrateyouranswer.
(h)Whatdoyoupredictfortherelativebondlengths,shortesttolongest,intheseions?
Answerto5.33:
a.totalnumberofvalencee
b.Lewisstructure
nitrateion
nitriteion
1(5)+3(6)+1=24e
1(5)+2(6)+1=18e
O N O
trigonalplanar
bent
f.localized,delocalized
0,1
0,1
g.bondorder
(a)NO2+has16valenceelectrons.
11/3
11/2
c.bondingorbitals
d.geometry
e.bondingorbitals
(b)
(c)TherearetwosigmabondingorbitalsonthecentralNatom.
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(d)Theionispredictedtobelinearwithtwosigmabondingandnosigmanonbonding
orbitalsonthecentralNatom.
(e)TherearetwopibondingorbitalsaroundthecentralNatom.
(f)Therearenolocalizedpiorbitalsandtherearetwopiorbitalsthataredelocalizedover
allthreeatomsandperpendiculartooneanother.(SeethesolutiontoProblem5.34(c).)
(g)Thebondsarebothdoublebonds.ThesigmaorbitalbetweenthecentralNatomand
eachOatomcontributeafullbond.Eachofthetwopidelocalizedorbitalsspreadover
thethreeatomscontributeshalfabondbetweenthecentralNatomandeachOatom,for
atotalofonemorefullbond.
(h)Wewouldpredictthatthebondlengthswouldfollowtheprogressionofbondorders,
11/3,11/2,and2fornitrate,nitrite,andnitroniumion,sonitroniumwouldhavethe
shortestNObondsandnitratethelongest.
5.34.
AsingleLewisstructureforthenitrateiondoesntrepresentthedistributionofthe
bondingorbitaloverallfouratomcores,analternativethathasbeenextensivelyusedis
todrawmorethanoneLewis(or3d)structure:
O
Thedoubleheadedarrowsareusedtoindicatethatthebestrepresentationissome
intermediatestructure(thatisimpossibletowrite).
(a) Ifallthreeofthesestructuresexistedseparately,theywouldhaveidenticalenergies.
Explainwhy.
(b) Ifthestructureshaveidenticalenergies,thenwewouldexpectanintermediate
structurebasedonthemtohaveequalcontributionsfromeachstructure.Whatfraction
contributionwouldeachmaketotheintermediatestructure?Whatisyourreasoning?
(c) Thedelocalizedbondingstructure,Figure5.23(a),ledustotheconclusionthatall
threeofthenitrogenoxygenbondsinnitratecanbethoughtofas11/3bonds.Showhow
thesameconclusioncanbereachedhere,basedonequalcontributionsfromthesethree
structurestotheproposedintermediatestructure.
Answerto5.34:
(a)Theenergiesareequalbecausethestructuresallhaveexactlythesamebonding,just
electronsshiftedaround.
(b)Sincetherearethreeidenticalstructures,eachwouldbeexpectedtocontribute
exactlyonethirdtotheintermediate.
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(c)Ifwefocusononeoftheoxygenatoms,saytheoneatthebottom,weseethatitis
singlybondedintwostructuresanddoublybondedinthethird.Thus,thesumofits
bondinginthethreestructuresis4,buteachcontributesonlyathird,soitsnetis4/3or1
/3.
5.35.
Whensomematerialisconnectedbetweentheterminalsofabattery,thereisanelectrical
potentialdifferencebetweenthetwoconnectionstothebattery.Ifelectronscanenterthe
materialatthenegativeterminalandleaveatthepositiveterminaltocompletethe
electriccircuit,wecallthematerialanelectricalconductor.Metalsaregoodelectrical
conductors.Howdoesthedelocalizedmolecularorbital(seaofelectrons)modelof
metallicbondinghelpyouunderstandthehighconductivityofmetals?Presentyour
reasoningclearly.
Answerto5.35:Theelectronsinthediffusecloudrepresentingthedelocalizedelectrons
inFigure5.27arerelativelyfreetomoveaboutanywherewithinthemetalcrystallattice.
Ifanextraelectronenterstheseaofelectronsfromanegativeelectricalterminal,another
canimmediatelyleavetheelectronseaatthepositiveterminal,inordertomaintainthe
electricalneutralityofthecrystal.Theelectronthatentersdoesnothavetobetheone
thatleaves,whichmakestheflowofelectronsthroughthecrystalrelativelyeasyand
rapid.Thatis,themetalisagoodconductorofelectricity.
5.36.
Youcanoftenbreakapieceofwireorthinstripofmetalbybendingitbackandforth
repeatedly.Thisactioncausesdislocationsofatomsinthecrystallikethoseyousee
representedinFigure5.26.Explainhowthiseffectcaneventuallyleadtobreakingthe
pieceofmetal.
Answerto5.36:Dislocationsinametalcrystallatticeweakenthelatticebecausethe
atomiccentersarenolongersymmetricallysurroundedbyotheratomcentersandthe
delocalizedmolecularorbitalsaredisrupted.Adiscontinuityinthebondingoccursat
dislocationsand,iftheygrowbyfurthermechanicalmanipulationofthemetal,the
overallbondingbecomessoweakenedthatthepieceofmetalcanbreakalongthe
discontinuities.
Section5.8.
RepresentationsofMolecularGeometry
5.37.
Thenumberofisomerspossibleforanyparticularmolecularformuladependsonthe
geometryabouttheatomsthatmakeupthemolecule.Foreachofthefollowing
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compounds,useyourmodelstofigureouthowmanyisomersarepossibleifthefour
bondsaboutthecentralcarbonatom(showninbold)haveasquareplanarmolecular
shape?Howmanyisomersarepossibleifthefourbondsaboutthecentralcarbonatom
haveatetrahedralmolecularshape?
(a) CH3Br,(methylbromide,afumigant)
(b) CH2Cl2,(dichloromethane,asolventusedinsemiconductorprocessing)
(c) CH3CH(OH)CH2OH,(propyleneglycol,ashampooadditive)
Answerto5.37:
The3dshapeofamoleculedeterminesthetotalnumberofisomersthatarepossible.
Thisisoneofthewayschemistsofthelastcenturyfiguredoutthatcarbon(andother
atoms)assumedatetrahedralandnotasquareplanargeometry.Seeforyourself!
5.38.
squareplanargeometry
tetrahedralgeometry
(a)1isomerpossible
1isomerpossible
(b)2isomerspossible
1isomerpossible
(c)3isomerspossible
2(optical)isomerspossible
Skeletalstructuresforseveralmoleculesaregiven.Drawthecondensedrepresentations
foreachmolecule.Whatisthemolecularformulaineachcase.
O
O
O
(a) aspirin
(b) nicotine
N
HO
HO
(c) vitaminC
(d) cholesterol
HO
O
OH
HO
Answerto5.38:
Recallthateachvertexorlineend(whichdoesnothaveaparticularatomindicated)is
understoodtorepresentacarbonatom.Becausecarbonswillalwaysformfourbondsin
stableorganicmolecules,allunspecifiedvalencesareunderstoodtobehydrogenatoms.
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Thenumberofhydrogensatanyparticularcarbonatomyouchoosetoexamineissimply
themathematicaldifferencebetweenthenumberfourandthenumberofbondsalready
specifiedatthatcarbonatom.
(a)C9H8O4
(b)C10H14N2
(c)C6H8O6
(d)C27H46O
5.39.
Conformationsareformsofamoleculethatdifferonlyinthattherehavebeenrotations
aboutsinglebonds.Identifywhichofthefollowingpairsofstructuresareconformers
(i.e.,thesamemolecule)andwhichareactuallydifferentmoleculesthatarenot
interconvertiblebyanycombinationofrotationsaboutsinglebondsormotionsofthe
moleculeasawhole.Buildingmolecularmodelsmightbehelpfulinsomecases.
(a)
(b)
(c)
(d)
OH
OH
H
CH2 CH3
H 3C
H 3C
OH
H 3C
(e)
(f)
CH2 CH3
H
CH2 CH3
H
CH2 CH3
H 3C
OH
H
Br
Br
Br
Br
Br
Br
Br
Br
Answerto5.39:
Itisextremelydifficulttoanswerquestionsaboutmolecularstructurewithouttheaidof
molecularmodels.Ifyoubuildandmanipulatemolecularmodelsalot,thetwo
dimensionaldrawingswilleventuallytakeonthreedimensionalsignificance.Eventhe
mostexperiencedchemistsstillresorttophysicalmodelswheninvestigatingnewor
unusualstructures.Theanswerstoquestionssuchasthisonecanonlybearrivedat
confidentlyifyouhavebuiltthemodels.
(a)conformers(i.e.,thesamecompound)
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(b)conformers
(c)mirrorimageisomers(i.e.,differentcompoundsrelatedasright/leftisomers)
(d)samecompound(simplyorienteddifferentlyinspace)
(e)samecompound
(f)mirrorimageisomers
5.40.
Rotationsaboutsinglebondsarerapid.Thisallowsmoleculeseasilytoassumedifferent
conformations.(Seeproblem5.39.)Foreachofthefollowingmolecules,canyoufinda
conformationthatallowsallthecarbonstolieinasingleplane?Draw3dstructuresto
illustrateyouranswers.Hint:molecularmodelsareextremelyvaluableinansweringthis
question.
(a) butane,CH3CH2CH2CH3
(b) 2methylpropane,CH(CH3)3(commonname:isobutane)
(c) 1,3butadiene,CH2CHCHCH2
(d) 1,2propanediene,CH2CCH2(commonname:allene)
Answerto5.40:(a)possible(b)impossible(c)possible(d)possible
5.41.
Foreachofthefollowingmolecules,canyoufindaconformation(Seeproblem5.39.)
thatallowsallthecarbonsANDallthehydrogenstolieinasingleplane?Draw3d
structurestoillustrateyouranswers.
(a) butane,CH3CH2CH2CH3
(b) 2methylpropane,CH(CH3)3
(c) 1,3butadiene,CH2CHCHCH2
(d) 1,2propanediene,CH2CCH2
Answerto5.41:(a)impossible(b)impossible(c)possible(d)impossible
5.42.
Foreachofthefollowingmolecules,canyoufindaconformation(Seeproblem5.39.)
thatallowsalltheatomiccenterstolieinasingleplane?DrawtheLewisstructuresfirst
tohelpanswerthisquestion.Draw3dstructurestoillustrateyouranswers.
(a) methanol
CH3OH
(woodalcohol)
(b) hydrogenperoxide
H2O2
(usedasadisinfectantandtobleachhair)
(c) hydrogencyanide
HCN
(poisonousgas)
(d) nitricacid
(HO)NO2
(usefulindustrialacid)
(e) nitrousacid
(HO)NO
(nitritesaltsaresuspectedcarcinogens)
Answerto5.42:(a)impossible(b)possible(c)possible(d)possible(e)possible
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Section5.9.
Stereoisomerism
5.43.
Stereoisomers(isomersthatsharethesameconnectivityoftheirbonds,butdifferintheir
3dshapes)canbesubcategorizedasopticalisomers(thosestereoisomersthatbeara
mirrorimagerelationshiptooneanother)andthosethatarenotopticalisomers.Identify
whichofthefollowingpairsofstructuresareidentical,whichareopticalisomers,and
whichareothertypesofstereoisomers.Buildingmodelscouldbeveryhelpful.
(a)
(b)
Br
Br
Br
Br
Br
Br
Br
Br
(f)
OH
OH
OH
(g)
Cl
(c)
(h)
Cl
Cl
Cl
(d)
OH
OH
(i)
OH
OH
(j)
Cl
Cl
Cl
Cl
(e)
OH
Cl
Cl
Cl
Cl
Answerto5.43:(a)opticalisomers(b)othertypeofstereoisomers(c)identical(d)
othertypeofstereoisomers(e)opticalisomers(f)identical(g)opticalisomers(h)
opticalisomers(i)othertypeofstereoisomers(j) opticalisomers
5.44.
(a) Completethistablebyfillingintheblankswitheitherthesameordifferent.
Property
Structural
Isomers
Stereoisomers
OpticalIsomers
Other
Molarmass
Boilingpoint
Density
Bondconnectivity
(b) Foroneofthesedatacolumns,alltheentriesarethesame.Bydefinition,two
compoundscannotbeisomersifalloftheirpropertiesarethesame.Whatistheproperty
thatallowsustodistinguishtheisomersinthiscolumn?
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Answerto5.44:
Properties
StructuralIsomers
MolecularWeight
BoilingPoint
Density
ConnectivityofBonds
ChemicalReactivity
same
different
different
different
different
Stereoisomers
OpticalIsomers
OtherStereoisomers
same
same
same
different
same
different
same
same
same
different
(b)Opticalrotation(measuredbyapolarimeter)distinguishestherightandleft
handedopticalisomersfromoneanother.Whatevertheextentofrotationofplane
polarizedlightbyoneisomer,theotherrotatesplanepolarizedlightanequalamount,but
intheoppositedirection.Onerotatesclockwise;theothercounterclockwise.
5.45.
UseyourmolecularmodelstomakeasmanymodelsofisomersofC5H10asyoucan.
Howmanyarethere?(Ifitiseasyforyoutovisualizemolecularstructures,likeLewisor
condensedstructures,writtenonapieceofpaper,youcandothisproblemwithapencil
andpaper.)HowdoesyourresultcomparewiththenumberofC4H8isomersyouobtained
inInvestigateThis5.55?Whatconclusion(s)canyoudrawabouttherelationship
betweennumberofcarbonsandnumberofisomers?Doesthisconclusionmakesense?
Explainwhyorwhynot.
Answerto5.45:
Thenoncyclicisomersare:
1pentene
trans2pentene
cis2pentene
2methyl1butene
3methyl1butene
2methyl2butene
Thecyclicisomersare:
cyclopentane
methylcyclobutane
1,1dimethylcyclopropane
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trans1,2dimethycyclopropane
cis1,2dimethycyclopropane
ThereareelevenC5H10isomerscomparedtosixC4H8isomers(InvestigateThis5.55).As
thenumberofcarbonatomsincreases,thenumberofpossibleisomersincreases.This
makessensebecausetherearemorewaysforthecarbonchaintobranchandringsto
formaswellasmorepossibleplacesformultiplebondstobelocatedinmoleculeslike
these.
Section5.10.FunctionalGroupsMakingLifeInteresting
5.46.
(a) Useyourmolecularmodelkittoconstructamodelofcyclopentane.(SeeInvestigate
This5.45.).Howflexibleisthering?
(b) RemoveoneoftheCH2groupsandreconnecttheringtomakeafourcarbonring,
cyclobutane.Howeasyisittodothis?Howflexibleisthering?
(c) RemoveanotherCH2groupandreconnecttheringtomakecyclopropane.Howeasy
isittodothis?Howflexibleisthering?Wouldyouexpectcyclopropanetobemore
reactive,lessreactive,oraboutthesameascyclopentane?Givethereasoningforyour
answer.
Answerto5.46:Thisisamodelbuildingproblem.Youshouldbeabletoobservehow
muchharderitistogetathreememberedringbemorepronetoreact,sinceitsbonds
seemreadytoburstapart.
5.47.
Useyourmodelkittomakeacyclopentanemodel.
(a) ReplaceoneofthehydrogenswithanOHgroup;themodelnowrepresents
cyclopentanol.Istheremorethanonestructureforcyclopentanol?Whyorwhynot?If
so,makeseparatemodelsofeachone.Areanyofthemopticalisomers?Howcanyou
tell?
(b) AddasecondOHgrouponthecarbonadjacenttothefirstOHgroup.Thenew
modelis1,2cyclopentanediol(di=two).Istheremorethanonestructureforthediol?
Whyorwhynot?Ifso,makeseparatemodelsofeachone.Areanyofthemoptical
isomers?Howcanyoutell?
Answerto5.47:Probablyyoucantimmediatelyseetherelationshipsamongthepartsof
moleculesandneedthissortofmodelbuildingexercisetohelpthemdevelopaninner
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eyeforstructure.Thereis,ofcourse,onlyonestructureforcyclopentanol,butthings
getmoreinterestingforthediol,whichhascisandtransisomers.Itismuchmore
difficulttofindthatthetransisomerisamixtureofmirrorimageisomers(anenatiomeric
pair).Thustherearethreeisomersofthediol.ThisisVERYhardtoseewithout
modeling.Theeasiestwaytoseemirrorimageisomersistobuildboth,showthatthey
areinfactmirrorimages,thenshowthattheyarenonsuperimposible.Alternatively,try
usingamirrorandbuildingthemodeloftheimageyouseeinthemirror.
5.48.
Table5.4catalogsanumberofimportantfunctionalgroups.Usethetabletoanswerthe
followingquestions.
(a) Whichfunctionalgroupscontainoxygen?
(b) Whichfunctionalgroupscontainnitrogen?
(c) Whichfunctionalgroupsinthetablearemostlikelytoionize?(Youmayhaveto
referbacktoChapter2.)Explainyourreasoning.
Answerto5.48:
(a)alcohol,ether,aldehyde,ketone,carboxylicacid,ester,amide
(b)amine,amide
(c)carboxylicacid,amine[Inthisquestion,thewordionizereferstothereactionof
electricallyneutral,polarmoleculeswithwatertoformions.]
5.49.
CanyoudiscoveramathematicalrelationshipbetweenthenumberofCsandthenumber
ofHsinanalkane?[Becausethisisaratherabstractquestion,wewillgiveyouan
exampletoillustratewhatwemean.Ifyouwishedtoknowthenumberoftoesina
crowdedroom,youcouldsimplycountthenumberoffeetandmultiplyby5.
Mathematically,thenumberoftoesisafunctionofthenumberoffeet.Notethatthis
relationshipisindependentofthenumberoffeetintheroom(assumingnothreetoed
aliensorotherexceptions)!]
(a) CanthenumberofHsinanalkanebedescribedasafunctionofthenumberofCs?
Youwillneedtoexamineanumberofalkanestobecertainthatyouhavediscovereda
generalrelationship.Yourrelationshipshouldfitbranchedaswellasstraightchain
alkanes.
(b) CanthenumberofHsinanalkenebedescribedasafunctionofthenumberofCs?
(c) CanthenumberofHsinanalkynebedescribedasafunctionofthenumberofCs?
Answerto5.49:(a)alkanes:CnH2n+2(b)alkenes:CnH2n(c)alkynes:CnH2n2
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StructureofMolecules
Certaintermsusedinthenomenclatureofcarboncontainingcompoundssoundvery
muchalikebutdonotmeanthesamethingatall.Clearlyexplainthedifferencesbetween
thesepairsofwordsanddrawaspecificcompoundillustratingeach.
(a) alkane
alkene
(b) alcohol
aldehyde
(c) ether
ester
(d) amine
amide
(e) carboxyl
carbonyl
Answerto5.50:(a)Analkaneisanacyclichydrocarbon(compoundconsistingofonly
hydrogenandcarbon)inwhicheverycarbonisconnectedtofourotheratoms.These
connectionsareentirelybymeansofsinglebonds.Closelyrelatedarecycloalkanes
whichhaveoneormoreringsintheirstructures.Analkeneisahydrocarbonwhichhas
atleastonedoublebondaspartofitsstructure.Thedoublybondedcarbonsare
connectedtoonlythreeotheratomsbecauseoneofthoseconnectionsismadewithfour,
nottwo,electrons.Acycloalkene,asyoumightexpect,hasatleastoneringandone
doublebond.
(b)Analcoholhasanoxygenatomlinkedbysinglebondstoahydrogenatomanda
carbonatom;twopairsofnonbondingelectronscompleteitsoctet.Anequivalent
descriptionofanalcoholfocusesonthecarbonatom.Inthisdefinition,thekeyfeatureis
acarbonatomsinglybondedtoanOHgroup(alsoknownasahydroxylgroup)and
havingallthreeofitsotherbondstoeithercarbonorhydrogen.Analdehydehasan
oxygenatomlinkedbyadoublebondtoacarbonatom.Aswithalcohols,twopairsof
nonbondingelectronscompletetheoctetonoxygen.TheC=Odoublebondisknownas
acarbonylgroupandisfoundasasubstructureinmanyfunctionalgroups.Inan
aldehydethecarbonylcarbonislinkedbysinglebondsto(1)ahydrogenand(2)a
carbon.
(c)Anetherhasanoxygenatomlinkedbysinglebondstotwocarbonatoms;twopairs
ofnonbondingelectronscompleteitsoctet.Anesterischaracterizedbyacarbonylliked
bysinglebondsto(1)acarbonatomand(2)anoxygenalsoboundtocarbonwithits
othersinglebond(alsoknownasanalkoxygroup).
(d)Anaminehasanitrogenatomlinkedbythreesinglebondstoeithercarbonor
hydrogenatoms.Anamidehasanitrogenatomlinkedbyasinglebondtoacarbonyl
carbon.Theothertwosinglebondsmayconnectthenitrogentoeithercarbonor
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hydrogenatoms.Thedefinitionsofaminesandamidessoundsurprisinglysimilar,yet
theirphysicalandchemicalpropertiesaredramaticallydifferent.
(e)Thecarbonylgroupwasdefinedinsection(b)above,Acarboxylgroup(ormore
precisely,acarboxylicacidfunctionalgroup)consistsofacarbonylsinglybondedtoa
hydroxylgroupandalsotoacarbonorhydrogen.
5.51.
DrawtheLewisstructuresandstructuralformulasforeachofthefollowingcompounds.
Drawbonddipolesonthestructuralformulas.Identifytheshapeofeachcompound.
Identifyifthecompoundispolarornonpolar.
(a) H2CO(formaldehyde)
(b) HO(O)CCH(NH2)CH2C(O)OH(asparticacid)
(c) H2NCH2CH2NH2(1,2diaminoethane)
Answerto5.51:Althoughcarbonisslightlymoreelectronegativethanhydrogen,the
differenceissmallandwewillignoretheeffectoftherelativelysmallbonddipoles
whichresult.Indrawingstructuresweoftenwritepartiallycondensedstructures,as
shownforasparticacidand1,2diaminoethane.
5.52.
(a) InProblem5.2,youdrewstructuresforisomericalcoholswithformulaC5H12O.
TherearesixotherstructuresthathavetheformulaC5H12O.Drawtheirstructuresand
identifythefunctionalgroup(s)inthesemolecules.
(b) Predictwhichoneofthesixmoleculesinpart(a)willhavethelowestboilingpoint.
Explainthereasoningforyourchoice.
Answerto5.52:
(a)ethers
O
(b)Themosthighlybranchedofthissetofethersismethylterbutylether(MTBE;structure
shown).
O
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Section5.11.MolecularRecognition
5.53.
InadoublehelixofDNA,thenitrogenous
basecytosineisheldtothenitrogenousbase
N H
guaninebyhydrogenbonds.(SeeInvestigate
N
attached
O
todeoxyribose
inDNAchain
This1.33.)Dashedlinesinthediagram
representhydrogenbonds.
Cytosine
(a)Howmanyhydrogenbondscanform
H N
H N
N
H
N
attached
todeoxyribose
inDNAchain
Guanine
between,thymineandadenine?Usethesetwostructuresforthymineandadeninetodraw
adiagramshowingthehydrogenbondingthatcantakeplacebetweenthymineand
adenine.
H 3C
N H
N
attached
N
todeoxyribose
inDNAchain
attached
O
todeoxyribose
inDNAchain
Thymine
H
N H
N
Adenine
(b) Thyminedoesnotpairwithguanine.Offerapossibleexplanationforthis
observation.
(c) DNAhastheabilitytoreplicate(makecopiesofitself)accuratelyandreproducibly.
Howcanthisberelatedtobasepairing?Explainyourreasoning.
Answerto5.53:(a)Thisdiagramshowsthatthymineandadenineformtwohydrogen
bonds.
H 3C
H
O
N H
N
attached
O
todeoxyribose
inDNAchain
Thymine
H N
N
N
N
attached
todeoxyribose
inDNAchain
Adenine
(b)Thymineandguaninedonothavepolargroupsstrategicallyarrangedtofacilitate
multiplehydrogenbonding.Makingmodelsofthesebaseswillhelpyouvisualizethe
possibilitiesofbasepairing.
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(c)Thespecificityofbasepairingiscausedbyhydrogenbonding.Althoughthereare
errorsinreproducingDNA,considerablerepetitionisbuiltintotheDNAdoublehelix,
helpingtoreducethenumberoferrorsduringthereplicationprocess.
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5.54.
StructureofMolecules
WEB
WEBChap5,Sect5.11.13.Workthroughthesepagesbeforeansweringthefollowing
questions.
(a) ExplaintherelationshipoftheactivityinSect5.11.3totheoneyoudidinCheck
This5.72.
(b) Makeamodelofaspartame.AballandstickmodelisshownrotatinginSect5.11.1
andhereisa3drepresentationofthemolecule:
HC CH
HC
CH
HC C
O
CH2
+
H3N
C
C H
N
C O
H C
CH2 H
OCH3
O(O)C
Animportantpointtonoteaboutthestructureofthisdipeptide(aspartylphenylalanine
methylester)isthatthefouratomsinthecenterofthestructure,O=CNH(shownin
red),lieinaplaneandrotationabouttheCNbondisveryrestricted.Thisbondacts
muchlikeadoublebondbecauseinteractionsbetweenthepibondinthecarbonylandthe
nonbondingelectronsonthenitrogenatomdelocalizetheelectronsoverthethreesecond
periodatomsandmaketheirstructurerigid.
Twopossiblewaystoconstructthesix
memberedringareshowninthese
photographs.Usewhicheveroneyouwish.
(c) Assweetreceptor,cutanappropriate
sizeholeinapieceofpaperandcoloritsedgered,blue,andgreenasinsweetreceptor
showninSect5.11.3(orsimplylabeltheedgewithcharges).Showthatyouraspartame
modelcomplementsthereceptor,asdoesthecorrectphenyalanineisomerintheweb
activity.
(d) ExchangetheHandNH3+,onyourmodel(lefthandsideofthestructureabove)
andtrypart(c)withthenewisomer.Willthisisomerstilltastesweet?Explainwhyor
whynot.
(e) Undotheexchangeinpart(d)andthenexchangetheHandoneoftheothergroups
attachedtothecentralcarbonattherighthandsideofthestructureabove.Trypart(c)
withthenewisomer.Willthisisomerstilltastesweet?Explainwhyorwhynot.Discuss
thesimilaritiesanddifferencesbetweenyourobservationsinparts(d)and(e).
Answerto5.54:
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(a)Bothactivitiesinvolveamolecularstructurewithfourdifferentgroupsbonded
tetrahedrallytoacentralatom.Therearetwopossiblearrangementsofthefourgroups
(thetwoopticalisomers).Onlyoneoftheisomershasthefourgroupsarrangedsothat
threeofthemcaninteractwiththreecomplementarygroupsonanothermolecule.
(b)Twoviewsofthemodelareshownhere.Oneisstretchedouttoshowthepartsabit
betterandthesecondiscurledaround,asitwillhavetobetointeractwiththesweet
receptor:
(c)Sheetsofcoloredpaper,red,blue,andlightgreen,representthenegative,positive,
andneutral(hydrophobic)sitesonthesweetreceptor.Themolecularstructureisshown
herewithitsnegativecarboxylategroup,C(O)O,interactingwiththepositivesite,the
positiveammoniumlikegroup,NH3+,interactingwiththenegativesite,andthe
unchargedphenylring,C6H5,interactingwiththeneutralsite.Thehydrogenatomatthe
carbonwhosestereochemistryiscriticalismarkedwithanarrow.Notethatthishydrogen
atomispointingouttowardyou.Thisisomerfitsthesweetnesstriangleandwilltaste
sweet.
(d)ThemodelwiththeHandNH3+switchedisshownhereinteractingwiththesweet
receptor.Thehydrogenatomonthecriticalcarbonisagainmarkedandshowninthe
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sameposition,pointingoutatyou,asinthepictureinpart(c).NowtheC(O)Oand
NH3+cannotproperlyinteractwithsweetreceptorandthisisomerwillnottastesweet.
(e)Exchangeattheotherstereocenterinthemolecule(afterthefirstisrestoredtoits
originalform)givesathirdisomershownhere.Again,thearrowidentifiesthehydrogen
atthecriticalcenter.Thehydrogenispointingouttowardyouandbothofthepolar
groupsareinteractingwiththeiroppositelychargedcounterpartsonthesweetreceptor.
Theotherendofthemoleculecanberotatedsothatthephenylringcaninteractwiththe
neutralsiteonthesweetreceptor.Thisisomeralsooughttotastesweet.
Thedifferencebetweentheresultsinpart(d)andpart(e)hastodowithwhereinthe
moleculethestructuralchangeismade.Ifitismadeatthecriticalstereocenter(asin(d)),
thenthemoleculewillnotfitthereceptor.Thereisnowayforthemoleculetomaintain
thesamegeometricrelationshiptothereceptor(shownbythepositionofthehydrogen
atomwithrespecttothereceptor)andalsohavetheappropriateinteractionsofthe
chargedgroupswiththereceptor.Whenthechangeismadeattheotherstereocenter,the
structurecanrotatetoputthephenylringinthecorrectgeometrytointeractfavorably
withthesweetreceptorwhiletheoverallmoleculemaintainsitsgeometricrelationshipto
thereceptor.
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Section5.13.EXTENSIONAntibondingOrbitals:TheOxygenStory
5.55.
ThedoublebondinO2andatriplebondbetweentwocarbonshavealmostthesamebond
length,121and120pm,respectively.Ifbondlengthsgetshorterasbondorderincreases,
whyisthedoublebondbetweenoxygenatomsthesamelengthasthetriplebond
betweencarbonatoms?Hint:Recallthetrendinatomicsizesandthereason(s)foritas
yougoacrossaperiodoftheperiodictable.
Answerto5.55:Oxygenatomsaresmallerthancarbonatomsbecauseofhighernuclear
chargeactingonelectronsinsameshell.Thissamefactorispresentinthesigmaandpi
molecularorbitalsinoxygenvs.carbon.Theorbitalvolumesaresmallerinoxygen
(increasedattractioncanbalancegreaterkineticenergy)andthenucleiareclosertogether
forthesamebondorder.Thedoublebondincarbonisabout134pm.
5.56.
Fluorine(F2)isthemostreactiveofthehalogens.AccordingtotheLewismodel,each
fluorineatomofthiscovalentcompoundhasthreenonbondingpairsofelectrons.
(a) Howmanyvalenceelectronsarethereindiatomicfluorine?
(b) AssumethatthemolecularorbitaldiagramshowninFigure5.42isalsoapplicableto
molecularfluorine.DrawadiagramlikeFigure5.42thatshowshowthevalence
electronsareassignedtothevariousmolecularorbitals.(Rememberthattwononbonding
sigmaorbitalsarenotshowninthediagram.)
(c) WhatisthebondorderoftheFtoFcovalentbondthatyouderivefromyourresults
inpart(b)?Explainclearly.
(d) HowdoesthemolecularorbitalbondingmodelcorrelatewiththeLewismodelfor
fluorine?
Answerto5.56:(a)Molecularfluorinehas14valenceelectrons.Themolecularorbitals
formedfromtheoriginalporbitalsaresimilartothoseofmolecularoxygen(Fig4.31).
(b)Thereare2electronsinamolecularorbital,and4electronssplitbetweentwo
molecularorbitals.Thereareadditionally4electronssplitbetweentwo*molecular
orbitals.
(c)Sincetheelectronsintheand*molecularorbitalseffectivelycancelout,the
molecularorbitalmodelpredictsabondorderof1.
(d)TheLewismodelalsopredictsabondorderof1.
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GeneralProblems
5.57.
(a) WriteaLewisstructureforthecyanateanion,OCN.Canyouwritemorethanone
satisfactorystructure?
(b) Whatgeometrydoes(do)yourLewisstructure(s)predictforthecyanateanion?How
doesthestructureandgeometryofthisioncomparetothestructureandgeometryofthe
carbondioxidemolecule?
(c) Wouldyouexpectthecyanateaniontohavedelocalizedelectrons?Explainthe
reasoningforyourresponse.
(d) Answerthesesamequestionsfortheisocyanateanion,ONC.
(e) Wouldyouexpectthecyanateorisocyanateaniontobethemorestableisomer?
Givethereasoningforyourchoice.
Answerto5.57:
(a)TwoLewisstructuresforthecyanateionare:
(i)
(ii)
Ineachstructure,werecognizeatomsthatdonothavetheirusualcomplementof
bondingorbitals.Instructure(i),theNatomhasonlytwobondingorbitals,butwe
usuallyseetheNatomwiththreebondingorbitals,asinNH3.TheNatomhereislikethe
Natomintheamideion,NH2,sowecanthinkoftheNatominstructure(i)carryingthe
overallnegativechargeoftheion.Instructure(ii),theOatomhasonlyonebonding
orbital,soitisliketheOatominthehydroxideion,OH,andwecanthinkoftheO
atominstructure(ii)carryingtheoverallnegativechargeoftheion.
(b)Inbothstructures(i)and(ii),thecentralCatomisbondedtotheOandNatomsby
sigmabondsandithasnononbondingelectronpairs.Thegeometryoftheionislinear
(Figure5.21andTable5.3),justlikethestructureofcarbondioxide.
(c)Structure(i)willhavetwodelocalizedpiorbitalslikecarbondioxide.Theseare
shownforcarbondioxideinFigure5.24andfurtherrepresentedinthesolutionto
Problem5.34.Thetwopiorbitalsinstructure(ii)aremorelocalizedbetweentheCandN
atoms.
(d)TwoLewisstructuresfortheisocyanateionare:
(iii)
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Again,werecognizeatomsinbothstructuresthatdonothavetheirusualcomplementof
bondingorbitals.Instructure(iii),theCatomhasonlytwobondingorbitals,butwe
usuallyseetheCatomwithfourbondingorbitals,asinCH4.TheCatominstructure(iii)
isliketheCatominthemethylideion,CH22,sowecanthinkofthisCatomascarrying
a2charge.TheNatomhasfourbondingorbitals,asinNH4+,sowecanthinkoftheN
atominbothstructuresascarryinga+1charge.Instructure(iii),the2and+1charges
sumtoanoverall1charge,astheymustbetogivethecorrectoverallchargeontheion.
Instructure(iv),theOatomisliketheoneinstructure(ii)andcanbeconsideredtocarry
a1charge.TheCatominstructure(iv)isliketheCatominthemethideion,CH3,so
wecanthinkofthisCatomascarryinga1charge.Thesumofthechargesinstructure
(iv)is(1)+(+1)+(1)=1,asitmustbetogivethecorrectoverallchargeontheion.
Thesigmabondingframeworkforthesetwostructuresis,again,likethatincarbon
dioxideandtheisocyanateionislinear.Thepielectrondistributionsinstructures(iii)
and(iv)arelikethoseinstructures(i)and(ii),respectively,soweexpectdelocalizedpi
orbitalsinstructure(iii).
(e)Thecyanateionislikelytobemorestablethantheisocyanateion.Twooftheatoms
inthecyanateion(eitherLewisstructure)areinabondingenvironmentsimilartothat
theywouldexperienceinstable,neutralmolecules.Thethirdatomisinabonding
environmentsimilartowhatitwouldexperienceasanion.Atleastoneatominany
Lewisstructureforanionhastobeinabondingenvironmentlikethatofanion,since
thestructurecarriesanoverallcharge.IntheisocyanateionLewisstructure(iii),twoof
theatomsareinbondingenvironmentslikethatofionsandoneoftheseisamultiply
chargedion.IntheisocyanateionLewisstructure(iv),allthreeatomsareinbonding
environmentslikethatofions.Lewisstructureswithbondingenvironmentsthataremost
likestable,neutralspeciesaremorestable.(InChapter6,wewillintroducetheconcept
offormalchargeandthesesamekindsofargumentscanthenbemadeintermsofformal
charge.)Lewisstructure(i)forcyanateionisfurtherstabilizedbythedelocalizationof
thepiorbitals.Experimentally,weobservethatisocyanatesusuallyreadilyisomerizeto
cyanates.
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5.58.
StructureofMolecules
(a) Atroomtemperature,berylliumfluoride,BeF2,isawhitecrystallinesolidandboron
trifluoride,BF3,isagas.Whatconclusionscanyoudrawaboutthebondinginthese
compounds?Explain.
(b) WritetheLewisstructureforBF3.WhatgeometrydoyoupredictforBF3?What
figureinthechapterhelpsyouexplainyourchoiceofgeometry?Explain.Hint:This
compounddoesnotobeytheoctetrule.
(c) UndercertainconditionsBeF2moleculescanbeobservedinthegasphase.Writethe
LewisstructureforBeF2.WhatgeometrydoyoupredictforBeF2?Whatfigureinthe
chapterhelpsyouexplainyourchoiceofgeometry?Explain.Hint:Thiscompounddoes
notobeytheoctetrule.
Answerto5.58:
(a)Thegaseouscompound,BF3,islikelytobeamolecularcompoundcovalently
bonded,sincethemoleculesmoveaboutindependentlyofoneanotherasagas.The
solid,crystallinecompound,BeF2,islikelytobeionic(oratleasthavealargedegreeof
electrontransferfromtheberylliumatomtothehighlyelectronegativefluorineatoms).
Perhapsitcanbecharacterizedas,(Be2+)(F)2.
F
B
(b)TheLewisstructureis:
Sincetherearethreesigmabondingorbitals
aroundthecentralBatom,thegeometryoftheBandFatomsshouldbetrigonalplanar
asinFigure5.18andTable5.3.
(c)TheLewisstructureis:
Be
Sincetherearetwosigmabondingorbitalsaround
thecentralBeatom,thegeometryoftheBeandFatomsshouldbelinearasinFigure
5.21andTable5.3.(a)Thegaseouscompound,BF3,islikelytobeamolecular
compoundcovalentlybonded,sincethemoleculesmoveaboutindependentlyofone
anotherasagas.Thesolid,crystallinecompound,BeF2,islikelytobeionic(oratleast
havealargedegreeofelectrontransferfromtheberylliumatomtothehighly
electronegativefluorineatoms).Perhapsitcanbecharacterizedas,(Be2+)(F)2.
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F
B
(b)TheLewisstructureis:
Sincetherearethreesigmabondingorbitals
aroundthecentralBatom,thegeometryoftheBandFatomsshouldbetrigonalplanar
asinFigure5.18andTable5.3.
(c)TheLewisstructureis:
Be
Sincetherearetwosigmabondingorbitalsaround
thecentralBeatom,thegeometryoftheBeandFatomsshouldbelinearasinFigure
5.21andTable5.3.
5.59.
WriteLewisstructuresformethanoicacid,HC(O)OH,andthemethanoateanion,
HC(O)O.TheCOsingleanddoublebondlengthsintheacidare134and120pm,
respectively.WhatdoyoupredictfortheCObondlengthsintheanion?Explainthe
basisforyourprediction?
Answerto5.59:ThereisasingleLewisstructurefortheacid,buttwoequivalent
structuresfortheanion:
O H
H C
O
O
H C
O
O
H C
O
and
Thus,thepielectronsintheanionaredelocalizedoverthreeatomcenters,OCO,sothe
electronsaresharedbetweentwoCObondsandeachhasabondorderof11/2.Thus,
wewouldpredictabondlengthintermediatebetweenasingleanddoubleCObond
about127pm.Theexperimentalvalueis126pm.
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