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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)

8 different structural (constitutional) isomers for C5H12O alcohols;

those with "(R/S)" to the right of the structure can exist in two
enantiomeric (right/left stereoisomeric) forms
(c)
5.3.

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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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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