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Answers to SelectedTextbook Questions
Chapter1
Therearenoinchapteranswersnecessaryforthischapter.
REVIEWQUESTIONS

1.1 PDTorphotodynamictherapyrequiresaphotosensitizer,lightandoxygen.
1.3 Thetumourmustbelocatedinaplacethatcanbesubjectedtolight.
1.5 Toxicologyisthestudyoftheilleffects(toxicity)ofsubstancesonthebody.Beforeintroducing
aporphyrinintothebodyforPDT,itmustbeestablishedthattheporphyrin,byitself,isnon
toxic.
1.7 Chemotherapyistheuseinmedicineofsubstancesthatareselectivelytoxictomalignantcells
ortoadiseasecausingvirusorbacterium.Assuch,avaccinewouldnotbeconsidered
chemotherapy.Theuseofgarlictotreatgangrene,ontheotherhand,isanexampleof
chemotherapy.Garlicisamildantisepticwhichkillsbacteriainfectingtissueleadingto
gangrene.
1.9 Yes,arsenicisgenerallyconsideredtobetoxic.However,Sec.6.1discusseshowthetoxicityof
arsenicvariesdramaticallydependingonthespeciescontainingthearsenicatoms.For
example,whereaselementalarsenicistoxic,thearseniccontainingspeciesinlobsterarenot.
1.11 BothVitaminB12andVisudyneareporphyrinbased.
1.13 Anaturalproductisacompoundproducedbyalivingorganism.
1.15 (a)TheHaberprocesscombineshydrogenandnitrogentomakeammonia.Ammoniaisusedto
makefertilizer.
(b)IntheBohrmodel,ahydrogenatomconsistsofanelectroninacircularorbitabouta
proton.
(c)Aconicalflaskusedinchemistrylabstocarryoutreactions.
(d)vanderWaalsequationisarelationbetweenthepressure,temperatureandvolumeofa
gasthataccountsforthenonzerosizeofthegasmoleculesandtheattractiveforcesbetween
them.
(e)Gibbsfreeenergy,G=HTS,combinesenthalpyandentropytogiveaquantitywhichmust
decreaseforanyprocessesthatactuallyhappens.
(f)Lewisiteisachlorinatealkylarseniccompoundwhichwasproducedasachemicalweapon
causingblistersandlungirritation.
(g)ALewisbasehasalonepairofelectronsthatitcandonatetoanelectronpairacceptora
Lewisacid.
(h)Schrodingersequationdeterminesthewavefunctionthatdescribesthestateofanatom.
Copyright2011byNelsonEducationLimited 1
1.17 Anorganiccompoundconsistsofmoleculesmadefromcarbon,hydrogenandoxygenatoms.
Therecanbeotheratomsforexample,nitrogen,sulfur.
1.19 1.Acetylsalicylicacid,thecommonmildpainreliever,isaderivativeofthenaturalproduct,
salicin,obtainedfromwillowbark.
2.Morphine,obtainedfrompoppies,isapowerfulpainreliever.
3.Cocaine,obtainedfromthecocaplant,isalsoapainrelieverstillusedfortopicalpainrelief.
4.Quinine,anantimalariaagent,wasisolatedfromthebarkofcinchonatrees.
5.Menthol,isolatedfrommintleaves,isatopicalpainrelieverwhichalsorelievesitching.
1.21 Thechemicalstructureofthesyntheticdrugsisidenticaltothoseextractedfromplants.Itisthe
impuritiesassociatedwiththesyntheticprocedure,inthecaseofsyntheticdrugs,andthose
associatedwiththebiologicalsourceandthemeansofextraction,inthecaseofnatural
products,thataredifferent.
1.23 Mycotoxinsaretoxinsproducedbyfungisuchaspoisonousmushrooms.Penicillinisa
mycotoxinthatistoxictobacteria,makingittheoriginalantibiotic.Itisanaturalproductand
anorganiccompound.
SUMMARYANDCONCEPTUALQUESTIONS
1.25 Duetotheirsensitivity,porphyriasuffererswouldavoidsunlightlikethevampiresoflegend.
1.27 Infraredlightexcitesbendsandvibrationsofmolecularbonds.Infraredspectraareusedto
determinethetypesofbondspresentinamolecule.
Chapter2
2.1
Pure Mixture
Compounds Solutions
(h)
testosterone (b)air (a)mud
(f)sodium (c)vinegar (e)milk
chloride (g)athletesurine
Elements sample

(d)gold
Homogeneous Heterogeneous
2 Chemistry,FirstCanadianEdition
2.2 (a)symbolic,
(b)observable
(c)molecular
2.3 (a)Na,ClandCrarethesymbolsforsodium,chlorineandchromium,respectively.
(b)Zn,NiandKarethesymbolsforzinc,nickelandpotassium.
2.4 Sucroseisacolorlessmolecularsolidwithamoderatemeltingtemperature.Carbonisablack
solid(graphite)orahardcrystallinematerial(diamond).Botharenetworksolids.Hydrogenand
oxygenarebothcolorlessdiatomicgases.
2.5 (a)InCO,thereisonecarbonatomforeveryoxygenatom(ortheratioofCtoOatomsis1:1).
(b)InCH4,theCtoHatomratiois1:4.
(c)InC2H2,theCtoHatomratiois1:1.
(d)InC6H12O6,C,HandOatomsareinproportionto1:2:1.
2.6 Sixcarbondioxideandsixwatermoleculescombinetoformoneglucoseandsixoxygen
molecules.
2.7 Ozoneandnitricoxidegasescombinetoformoxygenandnitrogendioxidegases.Therelative
numbersofmoleculesofthefourrespectivespeciesare1:1:1:1i.e.thestoichiometric
coefficients.
2.8 Theatomisbiggerthanthenucleusbythefactor,100pm/0.001pm=105.Iftheradiusofthe
atomwere100m,thenthenucleusradiuswouldbe100m/105=0.001m=1mm.Verysmall
pebblesandsmallpeasarethissize.
2.9 (a)56
(b)30protons,34neutrons,30electrons
2.12 (a)3618Ar,3818Ar,4018Ar.%abundanceof4018Ar=99.600%
(b)69Ga:31protons,38neutrons
71Ga(%abundance,39.9%):31protons,40neutrons
2.13 (a)1.99875
(b)2.16522
(c)1.08329
75.77 24.23
2.14 Atomic weight of chlorine = 34.96885 + 36.96590 = 35.45
100 100
2.18 10
2.19 (a)59g
(b)1.90x1024atoms
2.20 0.97g

REVIEWQUESTIONS
2.27 Thepieceoftablesaltisthemacroscopicview.Therepresentationofitsinternalstructureis
theparticulateview.Themacroscopicviewariseswhenthenumberofparticlesisverylarge
vast.
2.29 (a)physicalproperty
(b)chemicalproperty
(c)chemicalproperty
(d)physicalproperty
(e)physicalproperty
(f)physicalproperty
2.31 (a)colourlessisaphysicalproperty;burnsinairisachemicalproperty
(b)shinyandmetalarephysicalpropertiesofaluminium;orangeandliquidarephysical
propertiesofbromine;aluminiumreactsreadilywithbromineisachemicalpropertyof
aluminiumandbromine.
2.33 (a)27
(b)48
(c)62
57 58 60
2.35 27 Co , 27 Co , 27 Co
205
2.37 Tl
2.39 50%.
2.41
65 86 195 81
Symbol Cu Kr Pt Br
Number of protons 29 36 78 35
Number of neutrons 36 50 117 46
Number of electrons in the neutral atom 29 36 78 35
Name of element copper krypton platinum bromine
2.43 2
2.45 1
2.47 134.9g
2.49 Twoperiodshave8elements,twoperiodshave18elements,andtwoperiodshave32
elements.
2.51 (a)Bk
(b)Br
(c)B
(d)Ba
(e)Bi
2.53 (a)Siisametalloid,whilePisanonmetal
(b)Sihassomeelectricalconductivity,whilePdoesnot
(c)BothSiandParesolidsat25C
2.55 (a)anythingfromberyllium,Be,toradium,Ra
(b)anythingfromsodium,Na,toargon,Ar
(c)carbon,C
(d)sulphur,S
(e)iodine,I
(f)magnesium,Mg
(g)krypton,Kr
(h)germanium,Ge,orarsenic,As.
2.57 Boron
2.59 9.42x105mol
5.67x1019atoms
2.61 (a)Ar(1H)=1,Ar(11B)=10.9241,Ar(24Mg)=23.7994,andAr(63Cu)=62.4525
(b)Ar(1H)=1.0088,Ar(11B)=11.0199,Ar(24Mg)=24.0080,andAr(63Cu)=63
(c)Ar(1H)=1.0084,Ar(11B)=11.0162,Ar(24Mg)=24,andAr(63Cu)=62.9790

2.63 13C = -28.90 is consistent with a thermogenic sample
2.65 Weneedthedensityofiron,(d),inordertodeterminethemassof1cm3ofiron.Dividingthis
massbythemolarmassofiron,(b),determinesthenumberofmolesin1cm3ofiron.
MultiplyingthatnumberbyAvogadrosconstant,(c),providesthefinalanswerthenumberof
atomsin1cm3ofiron.
2.67 Youcouldcounthowmanyjellybeansittakestofillasmallercontainerfewerjellybeans,
easiertocountthenmultiplybytheratioofthevolumeofjartothatofthesmallercontainer.
Ifyouonlyhavethepicture,youcouldcountthenumberofjellybeanshalfwayaroundthe
perimeterofthecylindricaljar,andfrombottomtotopofthejar.Youhavedetermined
radiusofjarandtheheightofthejarinjellybeanlengthunits.Squaringthefirstquantity,then
dividingbyandmultiplyingbythesecondquantityprovidesanestimateofthenumberofjelly
beansinthejar.
Chapter3
3.1 BN
3.2 Sodiumchlorideisheldtogetherinalatticebystrongionicbondsattractionbetween
positivelyandnegativelychargedions.Siliconcarbideisanetworksolid.Theatomsare
similarlyheldtogetherinalattice,butinthiscaseitisbycovalentbonds.Covalentbondsare
generallystrongerthanionicbonds.Siliconcarbideisexpectedtohavethehighermelting
point.Thisisinfactthecasesiliconcarbidedecomposesat2730C,whilesodiumchloride
meltsat800C.
3.3 (a)Shas16protonsand16electrons.S2has16protonsand18electrons.
(b)Alhas13protonsand13electrons.Al3+has13protonsand10electrons.
(c)Hhas1protonand1electron.H+has1protonandnoelectrons.

3.4 N3,O2,F,Na+,Mg2+,andAl3+have7,8,9,11,12and13protons,respectively.Allofthese
specieshave10electrons,thenumberofelectronsinaneutralNeatom(10protons).
3.6 (a)equalamountsofNa+andFinNaF;twiceasmuchNO3asCu2+inCu(NO3)2;
equalamountsofNa+andCH3CO2inNaCO2CH3
(b)FeCl2andFeCl3arethecompoundsformedbyFe2+andFe3+,respectively
(c)Na2S,Na3PO4,BaSandBa3(PO4)2
3.10 (a)119.0gmol1
(b)53.5gmol1
(c)213gmol1
(d)120.3gmol1
3.11 (a)0.0250mol
(b)6.95x105mol
(c)5x103mol
3.14 (a)electrons
(b)electronsandtoalesserextentMg2+ions(theyarelessmobile)
(c)Mg2+andClions
(d)Mg2+andClions
3.15 (b),(d)and(e)aremolecularsubstances.
3.16 Siliconhasamuchhighermeltingpointbecauseitisanetworksolid.Itdoesnotconsistof
discretemolecules.Covalentbondingextendsthroughoutalatticegivingthematerial
exceptionalstrength.SulfurconsistsofdiscreteS8moleculeswhichare,inturn,heldinalattice
byweakerintermolecularbonds.
12
3.17 C,16Oand1Harethemostcommonisotopesofcarbon,oxygenandhydrogen.Themolarmass
ofthemostabundantisotopologue,12C21H616O,is46.04189gmol1.Thisisnotinexact
agreementwiththeexperimentalvalue.
3.18 (a)16.043gmol1
(b)58.080gmol1
(c)93.129gmol1
3.19 (a)1.53g
(b)4.60g
(c)4.59g
3.23 Asinglechlorineatom
C6H5Cl
112.008002;114.005052
3.24 C6H5CHCH2orC8H8
3.25 (a)C=Ostretchketone,aldehydeorcarboxylicacid
(b)CNHbendofanamine
(c)CNstretchofanitrile
(d)C=OandOHstretchesofacarboxylicacid
(e)NHandC=Ostretchesofanamide
REVIEWQUESTIONS
3.27 (a)molecular
(b)covalentnetwork
(c)molecular
(d)ionic(withsomecovalentcharacter)
3.29 (a)Se2
(b)F
(c)Fe2+andFe3+
(d)N3
3.31 (a)ammonium,NH4+,hasonemoreprotonthanelectronhencethe+1charge.
(b)phosphate,PO43,hasthreemoreelectronsthanprotonshencethe3charge.
(c)dihydrogenphosphate,H2PO4,hasonemoreelectronthanprotonshencethe1charge.
3.33 Na2CO3sodiumcarbonate
BaCO3bariumcarbonate
NaIsodiumiodide
BaI2bariumiodide
3.35 (a)chlorinetrifluoride
(b)nitrogentrichloride
(c)strontiumsulphate(ionic)
(d)calciumnitrate(ionic)
(e)xenontetrafluoride
(f)oxygendifluoride
(g)potassiumiodide(ionic)
(h)aluminiumsulphide(ionicwithsomecovalentcharacter)
(i)phosphorustrichloride
(j) potassium phosphate (ionic)
3.36 (a)NaOCl(ionic)
3.37 (iii)electronsaresetfreewithinalatticeofpositiveions
3.39 Achemicalreactionofoxygenrequiresbreakingtheoxygenoxygendoublebond,andgenerally
formingotherbonds.Assuch,thepropensityofoxygentoreactdependsonthestrengthofthe
O=Obond,aswellasthestrengthofbondsformedinthereaction.Theboilingpointofoxygen
dependsonlyonthestrengthoftheweakintermolecularbondsbetweenneighbouringoxygen
molecules.
3.41 Onlythecalculatedmolecularmass,28.03132,ofC2H4comesreallyclosetothisvalue.Ifthe
datawerefromalowresolutionspectrometer,wecouldnotruleoutH2CN(molecularmass=
28.01873),N2(molecularmass=28.00614)andCO(molecularmass=27.99491).
3.43 Infraredspectroscopyandstructure
(a)absorptionfrequenciesincm1:
28502980 duetoalkylCHstretches
30003100 duetoaromaticCHstretches
27002850 duetoaldehydeCHstretch
17201740 duetoaldehydeC=Ostretch
17001725 duetocarboxylicC=Ostretch
675900,14001500and15851600 duetoaromaticCCbendsandstretches
(b)
30203100 duetoalkeneCHstretches
17301750 duetoesterC=Ostretch
16401670 duetoC=Cstretch
10001300 duetoesterCOstretch
(c)
32003550 duetoalcoholOHstretch
17051725 duetoketoneC=Ostretch
10001260 duetoalcoholCOstretch
3.45 (a)carboxylicacidandaromaticring
absorptionwavenumbersincm1:
(b)esterandaromaticring
(c)alcohol,nitrile,andaromaticring
32003550 broadpeakduetoalcohol(phenol)OHstretch
22102260 duetonitrileC Nstretch
(d)ketoneandalkene
28502980 duetoalkaneCHstretches
(e)ketoneandester
28502980 duetoalkaneCHstretches
17001725 duetoesterC=Ostretch(wouldprobablyoverlapwiththeketone
stretch)
10001300 duetoesterCOstretch
3.47 (a)159.688gmol1
(b)117.170gmol1
(c)176.1241gmol1
3.49 21millionkMol
3.51 CaS(c)
3.53 (a)305.4119gmol1
(b)1.8104mol
(c)39mg
3.55 (a)0.0130mol
(b)NiF2
(c)Nickel(II)fluoride
3.57 Sodiumchlorideisionic.Itssolidisheldtogetherbythestrongattractionbetweenoppositely
chargedions.ChlorineisamolecularsubstanceitconsistsofCl2molecules.Inthesolidstate,
themoleculesareheldtogetherbyweakintermolecularforces.
3.59 (a)silicondioxideisacovalentnetworksolidwhichmeltsatveryhightemperature
carbondioxideisamolecularsubstancewhichmelts(sublimesat1atmpressure)atverylow
temperature
(b)sodiumsulfideisanionicsubstancemeltingathightemperature
hydrogensulfideisamolecularsubstancewhichmeltsatverylowtemperature
3.61 (a)calciumandchlorideionsareina1:2ratioinCaCl2
(b)calcium,carbonandoxygenatomsareina1:1:3ratioinCaCO3
(c)nitrogenandhydrogenatomsareina1:3ratioinNH3
(d)siliconandcarbonatomsareina1:1ratioinSiC
(e)hydrogenandchlorineatomsareina1:1ratioinHCl
3.63 Al3+ismostattractedtowaterbecauseithasthelargestmagnitudecharge.
3.65
(a)
OH
HH
O
Cl
Clostebolhasalkylgroups,analkene,aketone,achlorideandanalcoholgroupthelastfour
groupsarecircled.
(b)Thetestosteronemolecularionpeakisat288,whereastheclostebolmolecularionpeakis
at322.Therearepeaksatboththesepositions,thoughthepeakat322issmaller.Itwould
appearthatthismassspectrumdoesnotruleoutclostebol.However,chlorinatedcompounds
generallyshowpeaksassociatedwithlossofachlorineatomfromthemolecularion.We
thereforewouldexpecttoseeapeakat287.Nosuchpeakisseen.Thepeakat322mustbe
duetosomeothercompound.Thedataisconsistentwiththeexpertanalysis.
3.67 absorptionfrequenciesincm1
22102260 duetonitrileCNstretchnotgiveninTable3.5
16401670 duetoC=Cstretch
3.69 (a)LookfortheNHstretchofCH3CH2NHCH3apeakaround32503400cm1notseenfor
(CH3)3N.
(b)LookfortheketoneC=OstretchofCH3COCH3apeakaround17051725cm1ortheOH
stretchabroadpeakaround25003300cm1.
(c)LookforthealdehydeCHpeaks(2ofthem)ofCH3CH2CHO,around27002850cm1.
Chapter4
4.1 Covalentforcesholdthecarbonandhydrogenatomstogetherwithinamethanemolecule.
4.2 Weakdispersionforcesatypeofintermolecularornonbondingforceholdneighboring
methanemoleculestogether
4.3 The CFCs do not have H atoms bonded to C. Such H atoms readily react with hydroxyl radicals.
4.4 Mostgreenhousegasabsorptiontakesplaceintroposphere.ThisiswheremostoftheIR
absorbingcompoundsarefound.IRabsorbingmoleculesaregenerallyheavierthanmostair
molecules,andarefoundwithinthelowestlayeroftheatmosphere.
4.5 NitrousoxideabsorbsstronglyinregionsoftheIRspectrumemittedbytheearththatcarbon
dioxideandwaterdonotabsorb.
4.6 8.4x1017g
4.7 Today, I drank from a plastic cup. The plastic material was polymerized from monomers
obtained from fractionation and cracking, etc., of petroluem extracted from fossil deposits. I am
using a number of plastic products today for example, the keyboard keys I am typing on, and
the computer monitor I am viewing. Another fraction of the same petroleum was used to drive
my car. Natural gas from fossil deposits of mostly methane is used to heat my house.
4.8
H3C CH3
CH3
H3C
H3C CH3 H3C CH3
CH3 CH3
H3C H3C CH3
CH3 CH3 CH3

4.11 4
4.12
F F F
F F F
F F F
F F F
REVIEWQUESTIONS
4.13 (a)CovalentbondsholdthenitrogenatomstogetherintheN2molecules,insidetheclathrate
hydrate.
(b)DispersionforcesattracttheN2andH2Omoleculeswithintheclathratehydratecage.
(c)HydrogenbondingholdsneighboringH2Otogethermoleculestomaketheclathratehydrate
cage.
(d)DispersionforcesattracttheN2andO2moleculeswithintheclathratehydratecage.
4.15 Agreenhousepreventsconvectionofheatakeycomponentoftheheatflowfromtheearths
surfaceoutintotheatmosphere.Greenhousegasesdonotpreventconvection.However,like
thegreenhousewallsandroof,theyreflectsomeoftheradiationemittedbytheearthback
downagain.Thisoccursbecausemuchoftheabsorbedenergyisreemitted(arandomprocess)
backtowardstheearth,orspreadtosurroundingmoleculesbycollisionaldeexcitation.
4.17 CH3CH3(g);ozone,O3(g);andchloroform,CHCl3
4.19 1750isthebeginningoftheindustrialrevolution.Radiativeforcingofourclimatewassubject
onlytonaturalfluctuationsbeforethattime.
4.21 Cloudscausecoolingbyreflectingincomingsunlightbackoutintospace.
4.23 Increasinglevelsoftroposphericozonehasapositiveradiativeforcingeffect.
4.24 Stratosphericozonehasanegativeradiativeforcingeffect.ItabsorbsUVlightpreventingit
fromreachingtheearthssurface.Thestratosphereisheated,butthesurfacecools.
4.25 Inthetroposphere.
4.27 Theradiativeforcingandglobalwarmingpotentialofmethanearebothenhancedbymethanes
strongabsorptionofIR.However,theglobalwarmingpotentialalsodependsuponhowlong
methanestaysintheatmospherebeforebeingeliminatedbyoxidationandsubsequently
returningtothesurfaceinrain.Theglobalwarmingpotentialofmethaneisanestimateofhow
muchagivenmassofmethanewillcontributetoglobalwarmingrelativetothesamemassof
carbondioxide.
4.29 ConsultingtherankingoflevelsofscientificuncertaintyinFigure2.20ofthe2007IPCCsummary
report:
troposphericcarbondioxide>troposphericnitrousoxide>stratosphericozone>jetcontrails
(weunderstandthatitseffectisverysmall)>solarirradiance
4.31Theadvantagesofusingbiofuelsareasfollows:
(1)Theyarerenewablewegetanewcropeachyear.
(2)Thereisnonetadditiontoatmosphericcarbondioxide.AtmosphericCO2isconsumedas
theplantgrows.Itisreturnedtotheatmospherewhenthefueliscombusted.
(3)Biofuelcanbeproducedinmostplacesprovidedasuitablecropcanbefound.Fossilfuels
arefoundonlyincertainplaces.

Thedisadvantagesofthebiofuelstrategy,inpractice,areasfollows:
(1)Energyisneededtoproducethecropandmanufacturethebiofuel.Theseenergydemands
mustbeminimizedtomakebiofuelproductionworththeeffort.
(2)Onlyasmallportionofcorn,forexample,canbeusedtoproducebiofuels.Thecellulosic
partoftheplant(itsbulk),issimplyplowedbackintothefield.Thissignificantlyreducesthe
viabilityofbiofuelasanalternativeenergystrategy,ascurrentlyproducedinNorthAmerica.
(3)Biofuelproductiontakeslandawayfromfoodproduction.Thishasdrivenupfoodpricesin
NorthAmericainrecentyears.
4.33 TheprincipaldifferencebetweenthedatasetsisthesizeoftheannualoscillationinCO2level.
TheCO2leveldropsinthespringinsummermonthsduetothegrowthofvegetationontheland
massesofthenorthernhemisphere.Itrisesagainwhenthisgrowthstops.Theantarcticdatais
lesssensitivetothisoscillationsinceitissofarawayfromthenorthernhemisphere.
4.35
O
(a) (b)
CH3

(c) CH3
Cl
Cl
4.37 (a)alkane
(b)alkeneandalkane
(c)alkene,alkaneandalcohol
(d)Benzaldehyde has aromatic and aldehyde functional groups
4.39
(a)
CH3
H3C CH3
CH3
(b)
CH3
CH3
H3C CH3 CH3

(c)
H3C
CH3
H3C
CH3
CH3
(d)
H3C
CH3
H3C
CH3 CH3

4.41
4.43 Presenceofastrongoxidizingagentonmarsmeanstheenvironmentishostiletomanyfragile
moleculesfoundonearth.Ontheotherhand,togetherwithsuitablereducingagents,astrong
oxidizingagentsuchashydrogenperoxideprovidesapotentialrapidsourceofenergythat
evolvinglifeformsmightexploit.Hereonearth,animalformsoflifeexploitthereadily
available,strongoxidizingagent,O2,toprovideaquicksourceofenergy.
4.45 Table7.3showsthebondenergiesofCH,CFandCClbondstobe413,485and339kJmol1,
respectively.WhenahydroxylradicalreactsitbreakstheCXbondandformsanOXbond.The
bondenergiesofthebondswithOare463forOHand218forOCl.Thereisnoenergygiven
fortheOFbond.Here,weseethatthemostfavorablereactionisthatwhichbreakstheCH
bondtoformthestrongerOHbond.
4.47 SF6hasmorebondsthanCO2andconsequentlymorevibrationalmodesandmoreassociated
IRabsorptionpeaks.Thisanditslonglifeintheatmosphereincreaseitsglobalwarming
potential.
4.49 Perhapsweshouldlookforoxygen,waterandcarbondioxideatleastiftheimportanceof
thesemoleculestolifeonearthisaguide.Plantsuselightandcarbondioxidetodrivetheirlife
processes.Animalsreactfuels(food)withoxygentodrivetheirprocesses.Wateristhe
mediuminwhichthechemistryprimarilytakesplace.
4.51 2106g.(Basedontheassumptionsthatmycarconsumesabout10Lofgasolineper100km
travelled,andItravelabout10000kmperyear.Densityofgasoline=0.7g/mL)
4.53 Fossilfuelsaremorevaluableasfeedstocksfortheproductionofpolymers.Thisshouldbethe
mostimportantuse.
4.55 No,weshouldnotbeconcernedabouthumanbreathingasasourceofatmosphericcarbon
dioxide.Themainpointofconcernsaboutglobalwarmingistheimpactonhumanlife(yes,
otherspeciesarealsoaffected).Floodingofcoastalareas,associatedwithglobalwarming,isa
concernbecauseofthenegativeimpactonhumanslivingintheseareas.Humanbreathinghas
tobeanacceptablevariable,asthereisnoalternative.
Chapter5
5.2 (a)balancedforelectricalchargeandforallrelevantatoms
(b)balancedforelectricalchargeandforallrelevantatoms
(c)NOTbalancedforelectricalcharge;balancedforCaandC,butNOTforOatoms
5.4 4.5molofO2(g)
3.0molofAl2O3(s)
5.5 (a)Asmallamountofsolidsodiumchlorideinwaterhasahigherchemicalpotentialthana
dilutesolutionofsodiumchloride.
(b)Adilutesolutionofsodiumchlorideismorestablethanasmallamountofsolidsodium
chlorideinwater.
5.6 (a)Neither.Chemicalpotentialonbothsidesofthesereactionsareequal.
(b)Amixtureofsolidcalciumcarbonateinpurewaterhasahigherchemicalpotentialthana
mixturecontainingsolidcalciumcarbonateandCa2+(aq)ionsandCO32(aq)bothata
concentrationof6105molL1.
(c)AmixturecontainingsolidcalciumcarbonateandCa2+(aq)ionsandCO32(aq)bothata
concentrationof6105molL1ismorestablethanamixtureofsolidcalciumcarbonateinpure
water.
5.7 26.7gofoxygenreactswith25.0gofglucose.36.7gofCO2and15.0gofH2Oareformed.
5.11 (a)COisthelimitingreactant
(b)407gofCH3OHproduced
(c)14gofH2remain
5.12 (a)Fe2O3isthelimitingreactant
(b)35.0gofFe

5.17 Theoreticalyieldofhydrogen=15.7g
Percentyieldofhydrogen=86.6%
5.19 MasspercentofNiS=13.8%
5.20 (a)Fortheproductionofmaleicanhydridebyoxidationofbenzene
(i)theCatomefficiency=66.7%
theOatomefficiency=33.3%
theHatomefficiency=33.3%
(ii)theoverallatomefficiency=44.1%
(iii)theEfactor=1.27
(b)Fortheproductionofmaleicanhydridebyoxidationofbutene
(i)theCatomefficiency=100.0%
theOatomefficiency=50.0%
theHatomefficiency=25.0%
(ii)theoverallatomefficiency=64.5%
(iii)theEfactor=0.55
REVIEWQUESTIONS
5.21 (a)balancedforelectricalchargeandforallrelevantatoms
(b)balancedforelectricalchargeandforallrelevantatoms
(c)balancedforelectricalchargeandforallrelevantatoms
5.23 (a) H 2 O(g)

H 2O(l) isthespontaneousdirectionofreaction
(b)Watervapourat1barpressurehasahigherchemicalpotentialthanliquidwaterat25C.
5.25 (a)Amixturecontainingapieceofcopperina1molL1aqueoussilvernitratesolutionhasa
higherchemicalpotentialthanamixturecontainingsomesolidsilverinanaqueoussolutionin
whichtheconcentrationofCu2+(aq)ionsisabout0.5molL1andtheconcentrationofAg+(aq)
ionsisabout1x1010molL1.
(b)Amixturecontainingsomesolidsilverinanaqueoussolutioninwhichtheconcentrationof
Cu2+(aq)ionsisabout0.5molL1andtheconcentrationofAg+(aq)ionsisabout1x1010molL1is
morestablethanamixturecontainingapieceofcopperina1molL1aqueoussilvernitrate
solution.
5.27 theoreticalyieldofCO2=36.6g
5.29 massofargininerequired=275mg
massofornithineproduced=210mg
5.31 Thetotalmassofthebeakersandsolutionsafterreactionisthesameasitwasbeforereaction
(167.170g)
5.33 (a)1.76kg
(b)1.19kg
5.35 617kg
5.37 TiO1.5orTi2O3
5.39 11.2%
5.41 66.7kg
5.43 weightpercentCuSinore=30%
weightpercentCu2Sinore=70%
5.45 (a)8.8g.
(b)1.5
(c)FeBr3
(d)2Fe(s)+3Br2()2FeBr3
(e)iron(III)bromide
(f)(i)TRUE
(ii)FALSE
(iii)FALSE
(iv)FALSE
5.47 (a)65.0%Ptbyweight.
9.3%Nbyweight.
23.6%Clbyweight.
(b)massofammoniarequired=1.31g.
massofPt(NH3)2Cl2produced=11.6g.
5.49 (1)Thereismorethanenoughzinc.Inthiscase,HClisthelimitingreactantallofitreacts,
producingenoughH2toinflatetheballoon.0.1070.050mol=0.057molofzincremains.
(2)Inthiscase,thereisjustenoughzinctoconsumealloftheHCl.ThesameamountofH2is
producedasinpart(1)i.e.enoughtoinflatetheballoon.Nozincremains.
(3)Inthiscase,thereisnotenoughzinctoconsumealloftheHCl.Zincisthelimitingreactant.
Only40%asmuchH2isproducedasinpart(1)i.e.notenoughtoinflatetheballoon.Nozinc
remains.
Chapter6
6.1 (a)108.99mL
(b)109.06mL
(c)100.01mL
(d)100.00mL
(e)100.03mL
6.2 35s
6.3 (a)1.10x103kJ
(b)727kJ
6.4 diethylether>carbondisulfide>acetone>bromine>hexane>ethanol>water
6.5 Theorderofnormalboilingpointsisthesameastheorderofenthalpychangesofvaporization.
Thisiswhatweexpectbecausebothboilingpointandenthalpychangeofvaporizationincrease
withincreasingstrengthofintermolecularforces.
6.6 Thesurfacetensionisthatwhichpullsthedropintoasphericalshapeminimizingsurfacearea.
Sincethisforceissmallerfordiethyletherweexpectitsdropstobeevenmoredistortedby
gravitythanthoseofwater.
6.7 (a)Theintermolecularforceofattractionbetweenwatermoleculesandotherwatermolecules
orthemoleculesonthesurfaceofthebladeofgrassissufficienttoallowwatermoleculesto
sticktogetheronthebladeofgrass.
(b)Whenapieceofpaperburns,carboncarbonandcarbonhydrogenbondsarebrokenwhile
newbondswithoxygenareformed.Intramolecularforcesarethelosing(inthebreaking
reactantbonds)andwinningforces(inthemakingofbonds)atworkwhenpaperburns.
(c)Intermolecularforcesholdingwatermoleculestogether,andnexttoclothesfibermolecules,
areovercomewhenwetclothesarehungouttodry.
(d)Intermolecularforcescausewatermoleculestoarrangethemselvesintoalatticeoflowest
potentialenergy.Thefreezertakesawaythekineticenergytherebyliberated,leavingwaterin
itscrystalline,solidformice.

6.9 (a)HFismorepolarthanHI
(b)BCislesspolarthanBF
(c)CSiismorepolarthanCS
6.10 (a)TheC=OandCHbondsarepolar,whileCCandC=Carenonpolar.
(b)TheC=Obondisthemostpolar,withOatthenegativeend.
6.12 CS2andCO2arenonpolarbecauseoftheirlinearshape.SO2andH2Oarepolarbecauseoftheir
bentshape.Thetwobonddipolesvectorsonlypartiallycancelout,leavingaNETdipole
moment.
6.13 (a)BFCl2istrigonalplanar.IthasaNETdipolebecauseoneofthethreebondsisdifferent
morepolarthantheothertwo.IfthethreesubstituentsonBwerethesame,asinBCl3,then
thebonddipoleswouldcancel.
(b)NH2Clistrigonalpyramidal.IthasaNETdipolebecauseitisasymmetricalandhasonebond
differentfromtheothertwoNClvs.NH.
(c)SCl2isbentlikewater.IthasaNETdipolebecausetheSClbonddipolesonlypartiallycancel
out.
6.15 (a)BentSO2hasanetdipole.So,therearedipoledipoleforcesbetweenneighboring
molecules.
(b)LinearCO2hasnonetdipole.Therearenodipoledipoleforcesbetweenthesemolecules
onlydispersionforces.
(c)HClhasjustonepolarbond,andsohasadipolemoment.Therearedipoledipoleforces
betweenneighboringmolecules.
6.17 CH3OOH
|
CH3CH3
showsthehydrogenbondingbetweenneighbouringmethanolmoleculesastheymovepast
eachother.
6.19 (a)bromine
(b)butane
6.23 (a)ICl
(b)Krypton
(c)ethanol
6.24 (a)dispersionforces
(b)hydrogenbondsanddispersionforces
(c)dispersionforces
6.27 Mg2+(aq)andBr(aq)arethemainspeciespresentinsolutionwhensomemagnesiumbromide,
MgBr2(s),isdissolvedinwater.
6.28 (a)soluble
LiNO3 s
H 2O
Li (aq) NO3 (aq)
(b)soluble
CaCl2 s
H 2O
Ca 2 (aq) 2 Cl (aq)
(c)insoluble
(d)soluble
NaCH 3COO s
H2O
Na (aq) CH 3COO (aq)
6.29 (a)Ammonia,NH3(g),issolubleinwaterbecausewatermoleculescanmakestronghydrogen
bondswithammoniamoleculesOHandHN.
(b)Hydrogenchloride,HCl(g),issolubleinwaterbecausewatermoleculescanmakestrong
hydrogenbondswithHClmoleculesOHonly.
(c)Iodine,I2(s),isnonpolarandinsolubleinwater.Onlydispersionlikeforcescanbemade
betweenwaterandI2.ThisinteractionisweakerthanthedispersionforcebetweenI2
molecules.
(d)Octane,C8H18()isnonpolarandinsolubleinwater.Onlydispersionlikeforcescanbemade
betweenwaterandoctane.Thisinteractionisweakerthanthedispersionforcebetween
octanemolecules.
6.30 (a)Benzene,C6H6(),isnonpolarandsolubleinnonpolaroctane.Dispersionforcesareallthat
areatplayinthepuresubstancesandmixtures.Theentropyofmixingissufficienttodrive
dissolution.
(b)Waterispolarandinsolubleinnonpolaroctane.Itturnsoutthatreasonforthisismore
subtlethanappears.Dissolvingoctaneinwaterdecreasestheentropyofneighboringwater
molecules.Thiseffectoverwhelmstheentropyofmixing,anddissolutionisnotspontaneous.
(c)Iodine,I2(s),isnonpolarandsolubleinnonpolaroctane.Dispersionforcesareallthatareat
playinthepuresubstancesandmixtures.Theentropyofmixingissufficienttodrive
dissolution.
6.31 Butan1ol,CH3CH2CH2CH2OH(),shouldbemoresolubleinhexanethanbutan2,4diol,
HOCH2CH2CH2CH2OH().Thelattercompoundhastwohydroxyl(OH)groupsvs.onlyonefor
theformer.LiketheOHofwater,thesehydroxylsdonotspontaneouslymixwithhexane
thatis,notwithoutthehelpofthefavorabledispersioninteractionsofthealkylchains.
6.32 (a) HBr(g) + H 2 O(l)

H3O+ (aq) + Br - (aq)
only some ionised

(b) HF(aq) + H 2 O(l) + -
H 3O (aq) + F (aq)
only some ionised

(c) HCOOH(aq) + H 2 O(l) - +
HCOO (aq) + H 3O (aq)
(d) C12 H 22 O11 (s) C12 H 22 O11 (aq)
H O
2
6.36 (a) Cu 2+ (s) + CO32 (aq) CuCO3 (s)

+
Na andCl arespectatorions

(b)Noprecipitateforms

(c) Ni 2+ (s) + 2 OH (aq) Ni(OH) 2 (s)
+
K and Cl are spectator ions
6.37 Fe2+isoxidizedtoFe3+.TheoxidizingagentisMnO4.MnO4isreducedtoMn2+.Fe2+isthe
reducingagent.
6.38 (a)HCOOHistheacidreactant,whileOHisthebasereactant.
(b)H2CO3istheacidreactant,whileNH3isthebasereactant.
(c)H2C4H4O6istheacidreactant,whileHCO3isthebasereactant.
(d)H3O+istheacidreactant,whileCH3NH2isthebasereactant.
6.39 (a) H 3O + (aq) + OH (aq) 2 H 2 O(l)
Li+andBrarespectatorions
(b) H 2 CO3 (aq) + OH (aq)

HCO3 (aq) + H 2 O(l)
and HCO3 (aq) + OH (aq) CO32 (aq) + H 2 O(l)
K+isaspectatorion.
(c) H 3O + (aq) + CH 3 NH 2 (aq)

H 2 O(l) + CH 3 NH 3+ (aq)
NO3isaspectatorion
(d) H 3Citrate(aq) + OH (aq)

H 2 Citrate (aq) + H 2 O(l)
H 2 Citrate (aq) + OH (aq)
HCitrate 2 (aq) + H 2 O(l)
HCitrate 2 (aq) + OH (aq)
Citrate3 (aq) + H 2 O(l)
Na+isaspectatorion
6.40 (a)Co2+istheLewisacid,whileClistheLewisbase.
(b)Fe2+istheLewisacid,whileCNistheLewisbase.
(c)Ni2+istheLewisacid,whileCH3NH2istheLewisbase.
(d)Cu2+istheLewisacid,whileClandNH3aretheLewisbases.
6.41
H H
O H H H
H O H
O H
O H O
2+
O H
H Fe 2+
H H Mn H
H O
O H O
H O
H O H
H H H O
H H
H H H H
O H O H
H H
O O
O H O H
H 3+ 3+
Al H Cr
H H
H O H O
O O
H H
H O H O
H H H H
6.42 (a)[Co(H2O)6]2+(aq)+4Cl(aq)[CoCl4]2(aq)+6H2O()
Lewisbase,Cl,competessuccessfullywiththeLewisbase,H2O,tocomplexCo2+.
(b)[Fe(H2O)6]2+(aq)+6CN(aq)[Fe(CN)6]4(aq)+6H2O()
Lewisbase,CN,competessuccessfullywiththeLewisbase,H2O,tocomplexFe2+.
(c)[Ni(H2O)6]2+(aq)+2CH3NH2(aq)[Ni(CH3NH2)2]2+(aq)+6H2O()
Lewisbase,CH3NH2,competessuccessfullywiththeLewisbase,H2O,tocomplexNi2+.
(d)[Cu(H2O)6]2+(aq)+4Cl(aq)+2NH3(aq)[Cu(NH3)2Cl4]2(aq)+6H2O()
Lewisbases,ClandNH3,competesuccessfullywiththeLewisbase,H2O,tocomplexCu2+.
6.43 0.478molL1
6.47 (a)(a)
(b)(a)
(c)(b)
(d)(a)
(e)(a)and(b)havethesameconcentration(b)isjustasampleof(a).
6.49 (a)0.50molL1NH4+(aq)and0.25molL1SO42(aq)
(b)0.246molL1Na+(aq)and0.123molL1CO32(aq)
(c)0.056molL1H3O+(aq)andNO3(aq)
REVIEWQUESTIONS
6.51 Waterhasalowervapourpressurethanhexane,3.17vs.20.2kPaat25C.Ittakesahigher
temperaturetoget1atmvapourfromwater,thanitdoesfromhexanei.e.waterhasahigher
boilingpoint.
6.53 (a)Intramolecularforces.
(b)Intermolecularforces.
(c)Intramolecularforces.
(d)Intermolecularforces.
6.55 (a)CO
(b)PCl
(c)BO
(d)BF
6.57 HF>HCl>HBr>HI
6.59 (a)BeCl2isnonpolar.
(b)HBF2ispolar.ThenegativeendisatthetwoFatoms.
(c)CH3Clispolar.ThenegativeendisattheClatom.
(d)SO3isnonpolar.
6.61 H2S(g)
6.63 (b) HCOOH
6.65 (Kr)Itisbiggerwithmoreelectrons
6.67 (a)dispersionforces
(b)metallicbonds
(c)dipoledipoleanddispersionforces
(d)Hbondsanddispersionforces
6.69 (a)<(b)<(c)<(d).(a),(b)and(c)aregasesat25oCand1atm.
6.71 (a)higher.
(b)higher.
(c)unchanged.
(d)higher.
(e)smaller.
(f)higher.
6.73 Propan1ol(CH3CH2CH2OH)hasahigherboilingpointthanmethylethylether(CH3CH2OCH3),a
compoundwiththesameempiricalformula,becausepropan1olmoleculescanformhydrogen
bonds,whereasmethylethylethercannot.
6.75 (a)O2
(b)SO2
(c)HF
(d)GeH4
6.77
6.79 (a)Waterhasahigherviscositythanhexane,inspiteofitssmallerdispersionforces,becauseof
itsstronghydrogenbonds.
(b)Glycerol(propan1,2,3triol,HOCH2CHOHCH2OH)isevenmoreviscousthanwaterbecauseit
hasthreeOHgroupsandcanformmorehydrogenbondsthanwater.
6.81 Themeltingpointoffumaricacid(287C)ismuchhigherthanthatofmaleicacid(131C)even
thoughthesesubstancesarejustcisandtransisomers.
Maleicacidmakesastrongintramolecularhydrogenbondthisreducesopportunitiesfor
intermolecularhydrogenbonds,asanOandHarealreadyhydrogenbonding.Strong
intermolecularpairsofhydrogenbondsareformedbetweenadjacentfumaricacidmolecules.
6.83 (a)TheOend(thenegativeend)ofwaterpointstoCa2+.
(b)TheHend(thepositiveend)ofwaterpointstoBr.
(c)TheHend(thepositiveend)ofwaterpointstoCr2O72.
(d)TheOend(thenegativeend)ofwaterpointstoNH4+(aq).
6.85 H2O(),Ag+(aq),NO3(aq),K+(aq)andCl(aq).
6.87 Cookingoilisnotmisciblewithwaterbecauseitsmoleculesarenonpolar(orveryweakly
polar).Theydonotinteractwithwaterstronglyenoughforwatertosolvatethemwater
moleculesprefertointeractwithotherwatermolecules.Cookingoilissolubleinhexanea
nonpolarsolvent.
6.89 Theconcentrationsofhydroniumionandhydroxideionequalinpurewaterbecauseofthe
stoichiometryoftheselfionizationreaction,
2H2O()H3O+(aq)+OH(aq)
6.91 Sincebariumsulfate,BaSO4(s),precipitatesfromwater,whereasiron(II)sulfatedoesnot,we
concludethatBaSO4(s)isinsolubleinwater(ithasaverylowsolubility)whereasFeSO4(s)is
soluble.
6.93
2 Cr2 O7 2- (aq) + 28 H + (aq) + 12 e-
4 Cr 3+ (aq) + 14 H 2 O()

3C2 H 5OH(aq) + 3H 2 O()
3CH 3COOH(aq) + 12 H + (aq) + 12 e-
Here,ethanol,C2H5OH,isoxidizedtoaceticacid,CH3COOH.Dichromate,Cr2O72,istheoxidizing
agent.Cr2O72isreducedtoCr3+.Ethanolisthereducingagent.
6.95 Whennitricaciddissolvesinwater,nitrateandhydroniumionsareproduced.
Whenbariumhydroxidedissolvesinwater,Ba2+(aq)andOH(aq)areproduced.
6.97 (a)[Fe(NH3)6]2+
(b)[Zn(CN)4]2
(c)[MnF6]4
(d) [Fe(CN)6]3
(e) [CoCl4]2-
(f){Ni(NH3)4(H2O)2]2+
6.99 Topreparethedesiredsolution,carefullyweigh0.849gofAgNO3(s),addittothevolumetric
flask,add~150mLofdeionizedwater,stoppertheflaskandshaketodissolvetheAgNO3and
ensureahomogenenoussolution.AftertheAgNO3hasdissolved,topupthevolumetothe250
mLmarkwithdeionizedwateraddtheadditionaldeionizedwaterinsteps,swirlingbetween
eachsteptoensureahomogeneoussolution.
6.101 1250mLof0.060molL1Na2CO3solutionhasthegreatermassofsolute.
6.103 0.494g
6.105 5.08L
6.107 3.38g
6.109 concentrationofNa2CO3=0.254molL1
concentrationofNa+=0.508molL1
concentrationofCO32=0.254molL1
6.111 (a)Kineticenergyofthewatermoleculeswithinandonthesurfaceofthebubblepreventsits
collapse.Thesehotmoleculessmashintotheirneighbourspushingopenthebubble.
(b)Bubblesformwhenthevapourpressurewithintheheatedliquidslightlyexceeds
atmosphericpressureenoughtopushopenthebubble.
6.113 (a)Hydroniumionsappeartodiffuseveryquicklythroughanaqueoussolutionfasterthan
theyshouldbeabletoviadiffusionbecausethetransferofhydroniumacrossaclusterof
watermoleculesisachievedthroughsuccessiveH+iontransfersbetweenadjacentwater
molecules.
(b)EachprotontransferinvolvesoneOatomofahydroniumiontakingthepairofelectrons
fromanHatombondedtoit,andanotherOatom(onawatermoleculeontheothersideofthe
H)donatingalonepairofelectronstothereleasedprotoni.e.,acceptingtheproton.
6.115 (a)Here,theelectrostaticattractionoftheAg+andClionsovercomesthedipoleionforces
betweensolvatingwatermoleculesandtheionstocausegrowthoftheioniclattice.
(b)ThelatticeisanarrayofAg+andClions.ItdoesnotconsistofdistinctAgClmolecules.
6.117 (a)TheelectronsintheOHbondoftheCH3COOHmoleculegoentirelytotheOatomreleasing
aprotonwhichattachestoalonepairofelectronsonawatermolecule.
(b)Acovalentbondisbrokenandanewonemade.
6.119 (a)AmmoniaistheLewisbase,donatinglonepairsofelectronstothecopperatom,intheform
ofacoordinatebond.Cu2+istheLewisacid.
(b)AmmoniamoleculesreplacewatermoleculesbecausetheNinammoniaformsastronger
coordinatebondwithcopperthantheOinwaterammoniaisabetterligand.
6.121 (a)anacidbasereaction
(b)precipitationreaction
(c)acidbase,andcomplexationreaction
(d)oxidationreductionreaction
Chapter7
7.1 (a)1moleachofH+(aq)ionsandOH(aq)ions,thathavenotreacted,havemoreenergythan1
molofwater.
(b)Yourfingerswouldfeelhot.Thisisbecausethenegativeenergychangerequiresremovalof
excessenergy.
7.3 Thechemicalpotentialenergystoredinabatterycanbeconvertedtothemechanicalenergyof
soundwavesfromyourmp3playertheelectricalandmagneticenergyofanimagetakenby
yourdigitalcamera,orthelightenergyemittedbyaflashlighttonameafewpossibilities.
7.4 Heatalwaysflowsfromhighertemperature(water)tolowertemperature(air).
7.5 (a)Thesystemisthecontentsofthecombustionchamberofthegasfurnaceamixtureofair
andmethane.Thesurroundingsarethefurnaceandeverythingaroundit.
(b)Thesystemisthewaterdropsplustheairaroundyou.Thesurroundingsconsistofyour
bodyandthesuntheyprovidetheheatthatevaporatesthewaterdrops.
(c)Thewater,initiallyat25C,isthesystem.Thecontainerandtherestofthefreezercontents
includingtheairarethesurroundings.
(d)ThealuminumandFe2O3(s)mixtureisthesystem(initiallylateritconsistsofAl2O3(s)and
iron).Theflaskandthelaboratorybencharethesurroundings.
7.6 (a)Thevolumeofaballoonisastatefunction.
(b)ThetimeittakestodrivefromyourhometoyourcollegeoruniversityisNOTastate
function
(c)Thetemperatureofthewaterinacoffeecupisastatefunction.
(d)Thepotentialenergyofaballheldinyourhandisastatefunction.
7.7 333kJ
7.10 32.1kJ
7.11 0.16kJ
7.12 heatevolved=2.38kJ
7.15 56.3kJ
7.16 (a)molecularliquidBr2().
(b)metallicliquid,Hg().
(c)ionicsolidNa2SO4(s).
(dmolecularliquidCH3CH2OH().
(e)1molL1concentrationCl(aq).
7.17 (a)Thestandardenthalpychangeofthisreaction,rH,istheheatabsorbed(henceanegative
numberwhenisevolved)ataconstanttemperatureof25C,whenexactly1.00molofCO(g)
and0.500molofO2(g)bothgasesseparatelyat1barpressurearecombinedinavesselsuch
thatthetotalpressureis1bar(i.e.1thevesselcontainingthecarbonmonoxide),then
reactedcompletelyatfixedpressuretoform1molCO2(g)at1bar.
(b)Thestandardenthalpychangeofthisreaction,rH,istheheatabsorbedunderconstant
pressureconditionsof1bar,andconstanttemperatureat25C,whenexactly1.00molofMg(s)
and2.00molofH+(aq)at1.00molL1concentrationreactcompletelytoform1.00molof
Mg2+(aq)at1.00molL1concentrationand1molH2(g)at1barpartialpressure.
(c)Thestandardenthalpychangeofthisreaction,rH,istheheatabsorbedunderconstant
pressureconditionsof1bar,andconstanttemperatureat25C,whenexactly1.00molof
H+(aq)and1.00molofOH(aq)bothat1.00molL1concentrationreactcompletelytoform1.00
molofH2O().
7.19 (a)1.9kJ
7.20 116.8kJ
7.21 (a)Thestandardmolarenthalpyofformationofbromine,Br2(),isthestandardenthalpy
changeofthefollowingreaction:
Br2()Br2()at25C

(b)Thestandardmolarenthalpyofformationofsolidiron(iii)chloride,FeCl3(s),isthestandard
enthalpychangeofthefollowingreaction:
Fe(s)+Cl2(g)FeCl3(s)at25C

(c)Thestandardmolarenthalpyofformationofsolidsucrose,C12H22O11(s),isthestandard
11
12C(graphite)+11H2(g)+ O2(g)C12H22O11(s)at25C
2
7.22 Thestandardmolarenthalpyofformationofliquidmethanol,CH3OH(),isthestandard
1
C(graphite)+2H2(g)+ O2(g)CH3OH()at25C
2
7.26 3267.4KJ
7.27 53KJ
7.28 694KJ
7.31 (a)FALSE
(b)TRUE
(c)TRUE
(d)TRUE
REVIEWQUESTIONS
7.33 Theliquidwaterhasmoreenergy.
7.35 49.3kJ
7.37 181kJ
7.39 200kJ
7.41 6190kJ
7.43 23kJ
7.45 (a)H2O()
(b)NaCl(s)
(c)Hg()
(d)CH4(g)
(e)2.00molL1istheNa+(aq)concentration
7.47 90.3kJ
7.49 (a)601.24kJmol1
(b)1503.1kJ
7.51 905.47kJ
2 N2(g) + 6 H2(g) + 5 O2(g)

4 fH[NH3(g)] |
4 NH3(g) + O2(g) | |
| | 4rH[NO(g)] + 6rH[H2O(g)]
4rH[NO(g)] + 6rH[H2O(g)] | |
4rH[NH3(g)] | |
4 NO(g) + 6 H2O(g)
7.53 77.69kJ
7.55 rH=352.9kJ.MassofMg(s)=7.24mg.
7.57 Enthalpychangepergofhydrazine=16.67kJg1
Enthalpychangepergof1,1dimethylhydrazine=30.00kJg1
1,1dimethylhydrazineevolvesmoreheatonapergrambasis.

7.59 301kJ
7.61 (a)1070kJ
(b)1352.97kJ
7.63 1273kJ
7.65 (a)Anexothermicreactionreleasesenergywhichmustberemovedtoreturnthesystemtoits
originaltemperatureheatleavesthesystem.Anendothermicreactionabsorbsenergywhich
mustbesuppliedforthesystemtostayatitsoriginaltemperatureheatentersthesystem.
(b)Thesystemisthesetofallsubstancesofintereste.g.thereactantsandproductsofa
reaction.Thesurroundingsconsistofeverythingelse.

(c)Thespecificheatcapacityofsubstanceistheamountofheat(usuallyexpressedinJ)required
toraisethetemperatureofexactly1gofthesubstance1Cassumingnophasetransitions
occurduringheating.

(d)Astatefunctionisanythingthatdependsonlyonthestateofasystem.Astatefunctionis
anypropertyofthesystemsuchastemperature,pressure,volumeorenergy.Achangedvalue
ofastatefunctionindicatesachangeinthestateofthesystem.

(e)Thestandardstateofasubstanceisthestableformofthesubstanceat1atmandunless
specifiedotherwise25C.

(f)Theenthalpychangeofreaction,rH,isthechangeinenthalpywhentheextentofreactionis
1mol(i.e.reactantsformproductswithnumbersofmolesgivenbythestoichiometric
coefficients),andthetemperatureoftheproductsisreturnedtotheinitialtemperatureof
reactants.

(g)Thestandardenthalpychangeofreaction,rH,istheenthalpychangeofreactionunder
standardconditionsallreactantsandproductsareat1atmpressure,andsolutesareat1mol
L1concentration.

(h)Thestandardmolarenthalpychangeofformation,fH,isthestandardenthalpychangeofa
formationreactionwherein1molofasubstanceisformed.
7.67 Aperpetualmotionmachineisimpossibleassoonasthereisfrictionorotherformsofenergy
dissipation.Becauseenergyisconstantlylosttofriction,theremustbeaconstantsupplyof
incomingusefulenergyhereweinvokeconservationofenergy.Forthemachinetorun
forever,itmusthaveaninfinitesupplyofenergyimpossibleinafinitemachine.
7.69 rH=1433.5kJ
7.71 Abonddissociationenergyistheenthalpychangeassociatedwithbreakingasinglebond.All
bondbreakingprocessesareendothermictheenthalpychangeispositive.Italwaystakes
energyinputtobreakabond.
7.73 6.21010kJ
Chapter8
8.1 (a)Elementwithatomicnumber8greaterthanFi.e.atomicnumber=17isCl.
Elementwithatomicnumber18greaterthanCli.e.atomicnumber=35isBr.
Elementwithatomicnumber18greaterthanBri.e.atomicnumber=53isI.
Elementwithatomicnumber32greaterthanIi.e.atomicnumber=85isAt.
Theseareallhalogens.
(b)Theatomicnumbersofthegroup15elements,N,P,As,Sb&Bi,are
7,15,33,51and83
Differencesbetweensuccessiveatomicnumbers=
8,18,18and32.
8.2 (a)Strontium,Sr(s)
(b)Calcium,Ca(s)
(c)Rubidium,Rb(s)
8.3 (a)Bromine,Br2(g)
(b)Sodium,Na(s)
(c)Chlorine,Cl2(g)
(d)Theelementswithatomicnumbers34,35,36,37,and38areSe,Br,KrandRb.Rubidium,
Rb,isthemostpowerfulreducingagent.
8.5 C<Si<Al
8.7 (c) Li<Si<C<Ne
8.8 (a)ThefourthionizationenergyofAlismuchlargerthanthethirdmoresothansuccessive
ionizationenergiesusuallyincrease.Afterremovingthreeelectronsfromanaluminumatom
theresultofthefirstthreeionizationstepstheatom(nowanion)isleftwiththeelectron
configurationofNe,anoblegas.Al3+hasfilledn=1andn=2shells.Thenextelectrontobe
removedisatightlyheldmemberofthesecondshell.Thefirstthreeelectronscamefromthe
thirdshell.
(b)Mg
8.9 (a)+2
(b)2
8.13 (a)Cl
(b)Ba2+
(c)K
(d)Se2
(e)Cl
(f)Pb2+
8.14 (a)O
(b)Cl
8.15 (a)O<C<Si
(b)Si<C<O
(c)Si<C<O
8.16 (a)1.46x105Jmol1=146kJmol1
(b)182KJmol1
8.18 2.043x1018J;308.3THz;97.24nm
8.19 2.2x1025nm
8.20
8.22 (a)valid
(b)notvalid
(c)notvalid
8.24 (a)0or1
(b)1,0or1 psubshell
(c)dsubshell
(d)lis0andmlhasthevalue0
(e)3orbitals
(f)7valuesofml 7orbitals
8.25 (a)n=4,l=2,ml=0,ms=0isnotvalidbecausemsisalwaysbecauses=
foranelectron.msisneverequaltozero.
(b)n=3,l=1,ml=3,ms=isnotvalidbecauseml=3doesnotgowithl=1.ml=1,0,or
1inthiscase.
(c)n=3,l=3,ml= 1,ms=+isnotvalidbecauselmustbelessthanorequalton1.
8.27
(a) 90% isosurface of 1s orbital
50% isosurface of 1s orbital
(b)
8.28
z
s obital 90% isosurface

x
p obital 90% isosurface
8.30 (a)18
(b)10
(c)1
(d)none
8.32 [Ne][][][][]
3s3p
Thelastfiveelectronscorrespondtothequantumnumbers,
n=3,
l=0andml=0,andms=or+ 2electronstates
l=1andml=1,0or1andms=+ 3electronstates
8.34 Z*(12Mg)=+2.85;Z*(15P)=+4.8;Z*(18Ar)=+6.75
8.35 Z*(8O)=+4.55;Z*(8O2)=+3.85
8.36 Although84Pohasalotmoreelectronsthan11Na,theelectronsofPoareheldsomuchmore
tightlythatitissmaller.Theeffectivenuclearcharges,+5.45and+2.2,showthateventhe
valenceelectronsofPoareheldmoretightlythanthevalenceelectronsofNa.Thevalence
electronsdeterminethesizeoftheatom.
8.39 Z*(Na)=+2.2;Z*(Si)=+4.15;Z*(Ar)=+6.75
8.40 Z*(N3)=+2.85;Z*(S3)=0.8
Ncanforma3ionbecausethevalenceelectronsarestillheldbyaneffectivenuclearchargeof
+2.85.Scannotformsuchanionbecauseitsvalenceelectronswouldberepelledbyanet
negativeeffectivenuclearcharge.AddinganelectrontoS2requiresputtingtheelectronina
newshellwhichiswellshieldedbythefilledshells.
8.41 Z*(Na+)=+6.85;Z*(Mg2+)=+7.85;Z*(Al3+)=+8.85
Thevalenceelectronsofthesethreeionsareincreasinglytightlyheld.Thisisconsistentwith
thetrendinsizestheionsdecreaseinsize.

8.42 Z*(Mg)=+2.5;Z*(Cl)=+5.75
ThelargereffectivenuclearchargeinClshowsthatchlorinehasagreaterattractionforan
additionalelectron.Thisisconsistentwithchlorinehavingalargerelectronegativity.
8.43 Z*(Ar)=+1.2
WeseethatArwillholdanextraelectronevenlesstightlythanMg.Argon,beinginert,hasno
electronegativity.Itselectronegativitycannotbedefinedsinceitformsnochemicalbonds.
REVIEWQUESTIONS
8.45 MgCl2isanionicmaterialacompoundofametalandnonmetal.Ithasahighmeltingpoint
i.e.,714Canditconductselectricityinitsmoltenstatebutnotitssolidstate.
PCl3isamolecularsubstanceacompoundoftwononmetals.Itssolidconsistsofmolecules
heldtogetherbyintermolecularforces.Ithasalowmeltingpointi.e.,112Canditdoesnot
conductelectricity.
8.47 C<B<Al<Na<K
8.49 K<Ca<Si<P
8.51 (a)S
(b)Cl
8.53 (a)C<B<Al
(b)Al<B<C
(c)carbon
8.55 (a)S<O<F
(b)O
(c)Cl
(d)O2
8.59 2.179x1018J
8.61 Blue;ninitial=6.
8.63 (a)10
(b)n=5toalevelwithn=1.
(c) n = 5 to the level with n = 4.
8.65 (a)n=4ton=2
(b)n=4ton=1
8.67 0.145nm
8.69
(a) (b)
Thewavelengthofthiswaveis10cm. Thewavelengthofthiswaveis5cm.
(c)Fourwavesfitintheintervalifthewavelengthofthestandingwaveis2.5cm.Thenumber
ofnodesbetweentheendsis241=7.

8.71 n=4,l=1andml=1,0,1
8.73 (a)n=2,l=2,ml=0isNOTallowedbecauselmustbenogreaterthan1whenn=2.
(b)n=3,l=0,ml=2isNOTallowedbecausemlmustequal0whenl=0.
(c)n=6,l=0,ml=1isNOTallowedbecausemlmustequal0whenl=0.
8.77 4
8.81 (a)Thenandlvaluesfor6s,4p,5d,and4fareasfollows:
6smeansn=6,l=0
4pmeansn=4,l=1
5dmeansn=5,l=2
4fmeansn=4,l=3
(b)Fora4porbitaltherearen1=3radialnodes(sphericalinshape)andl=1nodalplanes.
3+1=4altogether
Fora6dorbitaltherearen1=5radialnodes(sphericalinshape)andl=2nodalplanes(or
cones).5+2=7altogether
8.83 (a)energy
(b)quantumnumberl
(c)more
(d)7
(e)1
(f)0,1,2,3and4
(e)1+3+5+7=16
8.87 (a)1s22s22p63s23p4
(b)1s22s22p63s23p1
8.89 (a)1s22s22p63s23p64s23d104p3or[Ar]4s23d104p3
(b) 1s22s22p63s23p64s23d104p6 or [Ar]4s23d104p6 = [Kr]
8.93 (i)Z*(Mg)=+2.85
(ii))Z*(Mg+)=+3.2
(iii)Z*(Mg2+)=+7.85
Theincreasingeffectivenuclearchargeforthesethreespeciescorrelateswiththeirsizes:Mg>
Mg+>Mg2+.Note,especiallythejumpfromMg+toMg2+.
8.95 Z*(N3)=+2.85;Z*(O2)=+3.85;Z*(F)=+4.85
Theseeffectivenuclearchargescorrelatewiththerelativesizesoftheions:F<O2<N3
8.97 (c)Electronsaremovingfromagivenenergyleveltooneoflowern.
8.99 Electronsandothersubatomicparticlesarefoundtoexhibitpropertiesofbothwavesand
particles.Wecanmeasurethepositionoftheparticlesaparticleproperty.However,the
resultsofsuchmeasurementscanshowinterferencepatternscharacteristicofawave.
8.101 Li+ionsaresomuchsmallerthanLiatomsbecauseLihasalonevalenceelectroninthen=2
shell,whereasLi +justhasthetwon=1electrons.Inanycase,withanetpositivecharge,
cationsholdontotheirelectronsmoretightly,andarecorrespondinglymuchsmaller.
FionsaresomuchlargerthanFatoms,becausetheyareanions.Anions,withanetnegative
chargeholdontotheirelectronsmoreloosely,andaremuchlargerthanassociatedneutral
atoms.
8.103 Theionizationenergyofatomsincreasesfromlefttorightacrosstheperiodictable,and
decreasesgoingdownagroup.Thedecreasegoingdownagroupisattributabletothevalence
electronsbeingfurtherfromthenucleus.Theeffectivenuclearchargeisthesame(orsimilar)
becausetheelementsareinthesamegroup.Whatchangesisthedistancefromthenucleus.
Electronsfurtherfromthenucleusaremoreeasilyremoved.
Chapter9
9.1 Thespectraontheleftandrightarethoseofdiethyletherandbutan1ol,respectively.
9.2 Onecoulddistinguishbutan1olanddiethyletherbylookingforthedistinctiveOHstretch
peak(broadpeakaround32003550cm1)ofbutan1olintheIRspectra.
9.3 Thespectraontherightandleftarethoseofpropan2amineandpropan1amine,respectively.
9.4 (a)1
(b)4
(c)3
(d)7
9.5 (a)1peakinbothcarbon13andprotonspectra
(b)1peakinbothcarbon13andprotonspectra
(c)2peaksinbothcarbon13andprotonspectra
(d)1peakinbothcarbon13andprotonspectra
(e)1peakinbothcarbon13andprotonspectra
(f)1peakinbothcarbon13andprotonspectra
(g)2peaksinbothcarbon13andprotonspectra
(h)2peaksinbothcarbon13andprotonspectra
(i)2peaksincarbon13spectrumand1peakinprotonspectrum
9.6
H
CH3
H H
H
H
H
H
HH
HH

Thisistheeclipsedconformationitistheleaststable.
9.7
CH3 H CH3 H CH3 CH3

H H H H
H H
H H CH3 H H H
H
H H H H H
H CH3 H H H H
H
H H H H H
ThesearetheNewmanprojectionsofthethreestaggeredconformations.Theconformationon
thelefthasthelowestenergy.Theothertwohavethesameenergy.
H H
CH CH3 CH3 CH3
H H3 H H H H
H CH H
H H H 3 H
H H
H H H
HH HH HCH
H 3
HH HH H

ThesearetheNewmanprojectionsofthethreeeclipsedconformations.Theconformationon
thelefthasthehighestenergy.Theothertwohavethesameenergy.
9.8 Thereisonlyonestaggeredandoneeclipsedconformationofpropane.
H H HCH3
H
H H H H
H H H
H
H H H
H CH3 HH
H
H HH

Forethaneandbutane,theenergyasafunctionofangleofrotationabouttheCCbond(the23
bondinbutane)lookslike


energyvs.angleforethane energyvs.angleforbutane
9.10 (a)C5H5N:oneHatomisbondedtoeachCatom
(b)C6H12O:twoHatomsarebondedtoeachCatom,excepttheC=Ocarbon
(c)C8H6NH:oneHatomisbondedtoeachCatom,exceptthetwoCatomsbelongingtoboth
rings

9.14
H H3C
CH3 H
9.15
H Br
H
H
H H Br
H H H
H H
H H
H H H
H H
H H
H
H
H
Herearetheequatorial(ontheleft)bromineandaxialbromineconformationsof
bromocyclohexane.Theequatorialpositionsarecircled.
9.17 Since[]D=16ispositiveforcocaine,cocaineistermeddextrorotatory.
9.18 16.1
9.21 (a) Br>CH2CH2OH>CH2CH3>H

(b) OH>CO2CH3>CO2H>CH2OH
(c) Br>Cl>CH2Br>CH2Cl
9.22
Atthecarbonstereocenter,theconfigurationsare(a)S,(b)Sand(c)R
9.23
Atthetopandbottom(respectively)carbonstereocenter,theconfigurationsare(a)RandR
(b)SandR,and(c)RandS
9.24 Atthetopandbottom(respectively)carbonstereocenter,theconfigurationsare
RandR
9.25 (a)isamesocompound
(b)isamesocompound
9.26 (a)and(c)aremesomoleculestheyareR,S.
(b)isanR,Renantiomer.
9.27 Nandrolonehas6stereocenters.Therecouldinprinciplebeasmanyas26=64different
stereoisomers.
9.28 Darvonisthe2R,3S(+)enantiomerofpropoxyphene.
Novradisthe2S,3R()enantiomer.
REVIEWQUESTIONS
9.29 (a)
H
|
CH3CH2C=CCH2CH2CH3
|
H
(b)
CH3CHCH2 CH2 CH3

|
CH3
(c)

O
||
CH3CHCH
|
CH3
9.31 NMRusesphotonswithlowerenergythanthoseusedinIRspectroscopy.400MHzisamuch
lowerfrequencythanthe10100THzrangeofIRspectroscopy.NMRcausestransitions
betweenspinenergylevelsthatareveryclose.IRcausesvibrationalenergytransitionsthatare
muchhigherinenergy.
9.33 Reasonablevaluesforthecarbonatomchemicalshiftsareasfollows:
carbonylcarbonat200ppm
twomethylcarbonsataround20ppmtwodistinctpeaks
twomethylcarbonsataround20ppmtwodistinctpeaks
COmethylenecarbonat70ppm
CClmethinecarbonat50ppm

Thecarbon13spectrummightlooksomethinglike
| | | | |
| | | | |
| | | | |
____________|___________________________________|_____|_______|_|_____
| | | | | | | | | | | | |
240 220 200 180 160 140 120 100 80 60 40 20 0
9.35 (a)77.23ppmdownfieldfromTMS
(b)46338HzdownfieldfromTMS
(c)77.23
9.37 CH4<CH2Cl2<HCCH<benzene<HC(O)C(O)H(twocarbonylsbondedtogether)
9.39 Possibleskeletalstructures:
(a) C4H8
(b) C3H6O
(c) C4H9Cl
9.41
CH3 H CH3 H
H H
H H
H H CH3 H
H
H H H
CH3 H CH3 CH3 H
H H
H
Thestaggeredconformationontheleftisexpectedtohavethelowerenergybecausethe
methylsubstituentonthebackcarbonisclosetobothofthemethylsubstituentsonthefront
carbonintherightconformation,butonlyoneintheleftconformation.
9.43 7.4kJmol1
9.45
cisandtrans2butene
9.47
H
Cl
Cl
H
Cl
H
H
Cl
EitherbothClatomsareequatorial(topconformation)oraxial(bottomconformation)because
onadjacentcarbonatomsthetwoaxialpositionsareonoppositesidesoftheringthetwo
equatorialarenecessarilyalsoonoppositesidesofthering.
9.49 Intheringflippedform,theblueandredsubstituentsareaxialwhereastheyellowisequatorial.
9.51
H
CH3 CH3
H
Themethylgroupsareinequatorialpositions.
9.53 Themethylsubstituenthasgreaterstericrequirementsthantheelectronlonepairtheformer
isinthemoreaccommodatingequatorialposition.
9.55
H CH3
H H
CH3 H
H3C OH H3C OH
H3C H H3C H
H
OH
CH3
H3C H
H3C H

9.57
9.59 37.0O
9.61
9.63 (a)
1 2 3 4
(b) 1 SO3H 2 SH 3 OCH2CH2OH 4NH2
9.65 Theconfigurationsatthechiralcentersare:
(a)S (b)S (c)S
9.67 Thespecificrotationsof(2R,3R)dihydroxypentaneand(2S,3S)dihydroxypentanearethesame
(notequaltozero)exceptforthesign.Thesespeciesareenantiomers.Thespecificrotationof
(2R,3R)dihydroxypentaneiszeroitisamesocompound.
9.69 Thestereochemicalconfigurationsofthetwodiastereomersof(2S,4R)dibromooctaneare
(2R,4R)and(2S,4S).
9.71
H H H OH
HO O
HO H HO H
Ribosethreestereocentersindicatedwithcircles.Theare23=8stereoisomersofribose.
9.73
H H H OH
HO O
H OHHO H
9.75

(a)ThelonestereocenteristheCatombondedtotheNatomofthebicyclicsubstituent.
(b)ThestructureontherightistheSenantiomertheRenantiomeristhestructureontheleft.

9.77
NH2

9.79
Br Br
H H H H
H H H H Br H
H H H H
H Br H H

9.81
CH3 CH3
H H H H
H H H H H H
H CH3 H3C H
H H H H
Thetwoenantiomersoftrans1,2dimethylcyclopentanetheyarethenonsuperimposable
mirrorimagesofeachother.
9.83
Thestereocentersaredenotedbysolidwhitecircles.
9.85 +6.83
9.87
CH3 H CH3
H H H CH3 H CH3
H H H H CH3H H H H
H CH3 H H H H
H H H H H H

Thestereoisomersof1,2dimethylcyclopentane.Fromlefttoright,thestereocentersare
configuredas(R,R),(S,S)and(R,S).
Thetwoontheleft(thetransisomers)areenantiomers.Thestructureoftheright(thecis
isomer)isamesomolecule.
9.89 (a)ThechiralcarbonherehastheSconfiguration.
(b)BothofthechiralcarbonsherehavetheSconfigurations.
9.91 (a)(S)5Chloro2hexeneandchlorocyclohexanearestructuralorconstitutionalisomers.
Specifically,theyareskeletalisomers.
(b)(2R,3R)Dibromopentaneand(2S,3R)dibromopentanearediastereomers.
9.93 Thestereocenter(thetopcarbonintheprojection)isintheSconfiguration.
Chapter10
10.3 NH4+
H H
+ +
N N
H H H H
H H

CO

+
C O C O

SO42

OH
S
HO
OH
HO
10.4
CH3OH NH2OH
C O N O
H H
H H H H

10.5

H
O
P
O
O
O
H

10.6 (a)Acetylideion,C22,isisoelectronicwithN2.
(b)SO2
(c)OH
10.9
O O O
N N N
O O O O O O

Thethreeresonancestructuresofnitrate,NO3
N
O O H

Astructurefornitricacid,HNO3
10.11
H H H H
O O O O

S S S S
O O O O O
O O O
O O
O O H
H H H

Thestructureontheright,withnoformalcharges,isthepreferredLewisstructure.
10.12

O O
O O O O

Equivalentresonancestructuresthattogetherbestdescribethechargedistributionwithin
ozone.
10.13
H
C Cl
H
Cl
Tetrahedralshape.TheClCClbondangleispredictedtobe109.5
10.16
F F

B F
B F
F F F

BF3 BF4
BF3istrigonalplanar.BF4istetrahedral.
10.17
(a)phosphateion, PO43, istetrahedral
P
O
O
O

(b)phosphoricacidmolecule, H3PO4, istetrahedralattheP

H
O
P
O
O
O
H
H

(c)sulfateion, SO42, istetrahedral

O
S
O
O
O


(d)sulfiteion,SO32,istrigonalpyramidal
S
O
O
O

(e)ethanolistetrahedralatthecarbonsandbentattheoxygen
C H
H
C O
H
H H

(f)Acetone,CH3C(O)CH3,istrigonalplanaratthecarbonylcarbonandtetrahedralatthemethyl
carbons.
O
H H
C
C C
H H
H H

10.18
H
+
O C N
H
H H H
H
H H

(a) (b)
Lewisstructuresof(a)hydroniumion,and(b)methylamine
(a)TheOatomofhydroniumhasfourelectronregionsdistributedtetrahedrally.Thismeans
sp3hybridizationatO.Threeofthesp3orbitalsoverlapwithsorbitalsonHatomstoformthe
OHbonds,whilethefourthaccommodatesthelonepaironO.
(b)TheCatomhasfourelectronregionsdistributedtetrahedrally.Thismeanssp3
hybridizationatC.Threeofthesp3orbitalsoverlapwithsorbitalsonHatomstoformtheCH
bonds,whilethefourthmakesabondwiththeNatom.
TheNatomhasfourelectronregionsdistributedtetrahedrally.Consequently,wehavesp3
hybridizationatN.Twoofthesp3orbitalsoverlapwithsorbitalsonHatomstoformtheNH
bonds,oneofthemformsthebondwithcarbon,whilethefourthaccommodatesthelonepair
onN.
10.19
O
H H
C
C C
H H
H H

ThemethylCatomshavethetetrahedraldistributionofelectronregions.Thismeanssp3
hybridizationatthemethylcarbonatoms.Threeofthesp3orbitalsoverlapwithsorbitalsonH
atomstoformtheCHbonds,whilethefourthmakesabondwiththecarbonylCatom.

ThecarbonylCatomhasatrigonalplanararrangementofelectronregionsconsequently,we
usesp2hybridizationhere.TheCCbondsareformedfromcarbonylcarbonsp2orbitals,and
methylcarbonsp3orbitals.Theremainingsp2orbitalformsthebondtooxygen.

Theoxygenatomhasthreeelectronregionsthetrigonalplanararrangementasdepicted
above.ThisOatomusesonesp2orbitaltomakethebondtoC.Theremainingtwosp2
orbitalsaccommodatelonepairs.

TheC=Odoublebondisformedfromtheunhybridizedporbitalsoneachatombothatomsare
sp2hybridizedwithoneunhybridizedporbital.ThisppbondistheCObond.
10.20
N N

TheNatomshavealineararrangementoftwoelectronregions.Thismeanssphybridization.
AnsporbitalfromeachNatomisusedtomaketheNNbond.Theremainingsporbitals
accommodatethelonepairsoneoneachatom.

ThetworemainingporbitalsoneachatomoverlapinpairstoformthetwoNNbonds.
Specifically,thepxorbitalsoverlaptoformthexbond,whilethepyorbitalsoverlaptoformthe
ybond.
10.21
C C N
H
H

TheHCH,HCC,andCCNbondanglesareestimatedtobe109.5,109.5and180,
respectively.

ThemethylCatomhasthetetrahedraldistributionofelectronregionssp3hybridizationatthe
methylcarbonatoms.

ThenitrileCandNatomshavealineararrangementoftwoelectronregions.

ThetworemainingporbitalsonthenitrileCandNatomsoverlapinpairstoformthetwoCN
bonds.
10.22
O
H
C
C O
H
H

ThemethylCatomhasthetetrahedraldistributionofelectronregionssp3hybridizationatthe
methylcarbonatoms.Threeofthesp3orbitalsoverlapwithsorbitalsonHatomstoformtheC
Hbonds,whilethefourthmakesabondwiththecarbonateCatom.

ThecarbonateCatomhasatrigonalplanararrangementofelectronregionssp2hybridization
here.TheCCbondisformedfromoneofthesesp2orbitals,andamethylcarbonsp3orbital.
Theremainingtwosp2orbitalsformbondstooxygenatoms.

Theoxygenatomscanbedescribedassporsp2hybridized.Becauseofsymmetry,weshouldto
usethesamedescriptionforbothatomsincontrasttotheLewisstructurewhichimpliesthat
oneoftheOatomsissp3hybridized.WewillassumesphybridizedOatoms.EachOatomuses
onesporbitaltomakeabondtoC.Theothersporbitaloneachatomaccommodatesalone
pair.Theotherlonepair,oneachOatom,occupiesoneofthetwounhybridizedporbitals.

WhatremainsareaporbitaloneachoftheOatomsandtheunhybridizedporbitalonthe
carbonatecarbonatomthreeorbitalsinall.Twoelectronpairsalsoremain.Inavalencebond
description,abondisformedusingtheporbitalonCandoneoftheOatomporbitals.The
otherOatomporbitalaccommodatestheremaininglonepairofelectrons.Thiscanbewritten
inoneoftwoequivalentwaystheresonancestructuresofcarbonate.However,becauseof
symmetryitismoreaccuratetothinkoftheporbitalonCandbothoftheOatomporbitals
formingadelocalizedbond,thoughthisgoesbeyondvalencebondtheory.Wemustthinkof
thetwoOatomporbitalsbeingcombinedtoformtwodelocalized(overthetwoOatoms)
orbitalsanalogoustoorbitalhybridizationexceptthattheorbitalsareondifferentatoms
(thesearemolecularorbitals).Oneofthedelocalizedorbitalsformsasymmetricbondwith
carbon,theotheraccommodatestheremaininglonepairofelectrons.
10.25 H2+:( 1s )1
He2:( 1s )2( 1s* )1
H2:( 1s )2( 1s* )1
H2+hasabondorderof.Itshouldexist.But,itisweaklybound.He2andH2havethesame
bondorder.
10.26 Li2anionshouldexist.Itisweaklyboundwithbondorder,.
10.27 ElectronconfigurationofgroundstateO2+
[core electrons]( 2 s ) 2 ( 2s ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px ) 2 ( 2p y )1
Bondorder=2
O2+isexpectedtobeparamagnetic.Itselectronconfigurationshowsanunpairedelectron.
REVIEWQUESTIONS
10.31 4

10.33
(a) (b)
N Cl
F O
F O
F O

(c) (d)
Br O S
O
O
H O

10.35
10.37
(a)SO2
+ +
S S S
O O O O O
O

(b)NO2
+ +
N N
O O O O

(c)SCN
+
S C N S C N S C N

10.39

O O
C C
H O H O

AverageCObondorder=3/2
10.41
(a)
+
O N O

FormalchargesarezeroonOsand+1onN.
(b)
N N
O O O O

TheNhasaformalchargeofzero.TheformalchargesonthetwoequivalentOsarezeroand
1.

(c)
N
F
F
F

Allatomshavezeroformalcharge.

(d)

O
N
O
O H

Formalchargesareasshown.
10.43
N N
O O O O

IfHattachestoNO2(toformtheacidHNO2),itattachestoanOatomnotN.
10.45
(a)
O C O

Therearetwoelectronregionsaboutthecarbonatom.Theelectrongeometryandthe
moleculargeometryarelinear.

(b)
N N
O O O O

Therearethreeelectronregionsaboutthenitrogenatom.Theelectrongeometryistrigonal
planar,whilethemoleculargeometryisbentthereisonelonepaironthecentralatom.

(c)

O O
O O O O

Therearethreeelectronregionsabouttheoxygenatom.Theelectrongeometryistrigonal
planar,whilethemoleculargeometryisbentthereisonelonepaironthecentralatom.This
moleculeisisoelectronicwithNO2.TheyhavethesameshapeandLewisstructureasidefrom
theformalchargeonthecentralatom.
(d)
Cl
O O

Therearefourelectronregionsabouttheoxygenatom.Theelectrongeometryistetrahedral,
whilethemoleculargeometryisbenttherearetwolonepairsonthecentralatom.This
moleculeislikelymorebentthanO3orNO2,becausetherearetwolonepairsonthecentral
atominthiscase.
10.47 (1) 120

(2) 109.5
(3) 120
(4) 109.5(actuallythevalueis107theangleissmallerduetogreaterrepulsionofthe
lonepairs)
(5) 109.5(actuallyslightlyless)
10.49
N
F
F
F

Themoleculargeometryistrigonalpyramidalthereisalonepairwhiletheelectron
geometryabouttheNatomistetrahedral.
Atetrahedraldistributionofelectronregionsmeanssp3hybridizationatnitrogen.Threeofthe
sp3orbitalsoverlapwithsporbitalsonFatomsweassumetheFatomstobesphybridized(in
contrasttotheLewisstructuredepictionwhichimpliessp3hybridization).Theremaining
nitrogensp3orbitalaccommodatesthelonepaironN.Theremainingonespandtwoporbitals
oneachFaccommodatesthefluorinelonepairsthreeoneachatom.
10.51 (a)Thecarbonatomsindimethylether,H3COCH3
usesp3hybridizedorbitalstoformbondswithHatoms,andwiththeOatom.
Theoxygenatomindimethylether,H3COCH3usestwosp3hybridizedorbitalstoformbonds
withCatoms.
Theremainingtwosp3orbitalsonOaccommodatethetwolonepairs.
10.53
(a) SO2
TheOSObondangleisabout120.
Thesulfuratomusessp2orbitalstoformtwobondsonewitheachOatom.
Theothersp2orbitalaccommodatesalonepair.WecandescribetheLewis
structurewithonlyonedoubleSObondwiththeremainingunhybridizedp
orbital.ItformsabondwithjustoneoftheOatoms.
However,thestructurewithtwoSOdoublebondsminimizesformalchargesand,
assuch,ispreferred.Todescribethebondinginthiscaserequirestheuseofa1
dorbitalonSsinceinthisstructure,Saccommodates10electronsinitsvalence
shell.TwopdorbitalsonSformtwobondsonewitheachoftheOatoms.

(b) SO3
TheOSObondangleis120.
Thesulfuratomusessp2orbitalstoformthreebondsonewitheachOatom.
Inaccordwiththeformalchargeminimizedstructure,weusethreepd2orbitals
onStoformthreebondsonewitheachoftheOatoms.Otherwise,ifweuse
justtheporbital,thenScanformonlyoneSObond.

(c) SO32
TheOSObondangleis109.5.
Thesulfuratomusessp3orbitalstoformthreebondsonewitheachOatom.
Theothersp3orbitalaccommodatesalonepaironS.
Inaccordwiththeformalchargeminimizedstructure,weusetwopdorbitalsonS
toformtwobondsonewitheachoftwoOatoms.

(d) SO42
TheOSObondangleis109.5.
Thesulfuratomusessp3orbitalstoformfourbondsonewitheachOatom.
Inaccordwiththeformalchargeminimizedstructure,weusetwopdorbitalsonS
toformtwobondsonewitheachoftwoOatoms.

10.55 InlinearCO2thecarbonatomusestwosporbitalstoformbondswitheachOatom.Eachof
thetwounhydridizedporbitalsformsabondwithanOatom.InCO32,therearetwosingleC
ObondsandonedoubleCObond,givingrisetothreeequivalentresonancestructures.The
carbonatomusesthreesp2orbitalstoformbondswitheachofthethreeOatoms.The
unhydridizedporbitalformsabondwithjustoneOatom.Sinceitcanbeanyoneofthe
three,wegetthreeequivalentresonancestructures.
10.57 (a)TheanglesA,B,C,andDareabout120,109.5(actually104),109.5and120,
respectively.
(b)Accordingtothevalencebondmodel,carbonatoms1,2,and3aresp2,sp2andsp3
hybridized,respectively.
10.59
(a)

O O

ThebondorderinO22is1.
(b) The molecular orbital theory electron configuration for O22 is (using unhybridized orbitals)
[core electrons]( 2 s ) 2 ( 2s ) 2 ( 2p y )2 ( 2pz ) 2 ( 2px ) 2 ( 2p y ) 2 ( 2pz ) 2
bond order = ( 2 + 2 + 2 + 2 2 2 2 ) = 1
(c)ForO22,thevalencebonddescriptionandthemolecularorbitaldescriptionpredictthesame
bondorderandthesamemagneticbehaviour(i.e.diamagneticNOTparamagneticthereare
nounpairedelectronsineitherdescription).
10.61 Molecularorbital;theoryelectronconfigurations(coreelectronsomitted):
(a)NO
( 2 s ) 2 ( 2s ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px ) 2 ( 2p y )1
anunpairedelectronparamagnetic
HOMO= 2p y or 2pz sameenergy(bysymmetry)

(b)OF
( 2 s ) 2 ( 2s ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px ) 2 ( 2p y ) 2 ( 2pz ) 2
nounpairedelectronsNOTparamagnetici.e.diamagnetic

(c)O22
( 2 s ) 2 ( 2s ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px ) 2 ( 2p y ) 2 ( 2pz ) 2
nounpairedelectronsNOTparamagnetici.e.diamagnetic

(d)Ne2
( 2 s ) 2 ( 2s ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px )1
HOMO= 2px
(e)CN
( 2 s ) 2 ( 2s ) 2 ( 2p y ) 2 ( 2pz ) 2 ( 2px )1
HOMO= 2px
10.63
N
F
F
F

NF3hasfourelectronpairsaboutthecentralatom,andatrigonalpyramidalshape.

O
Cl Cl

OCl2hasfourelectronpairsaboutthecentralatom,andabentshape.
10.65 TheaverageCObondorderinformate(HCO2is1.5therearetwoequivalentCObonds
representedasasingleandadoublebondinthetworesonancestructures.
Inmethanol(CH3OH),theCObondisjustasinglebondthereisjustonestructure.
Incarbonate(CO32),therearethreeequivalentCObonds.Oneisadoublebond,whilethe
othertwoaresinglebonds.Theaveragebondorderis4/3=1.3333.
FormatehasthestrongestCObond,whichisexpectedtobetheshortest.
MethanolhastheweakestCObond,whichisexpectedtobethelongest.
10.67 NO 2 islinear.ItsONObondangleis180.
NO 2 isbent.ItsONObondangleislessthan120.
10.69 (a)Angles1,2,and3equalabout120,180and120,respectively.
(b)Thecarboncarbondoublebondisshorter.
(c)Thecarboncarbondoublebondisstronger.
(d)TheCNtriplebondisthemostpolarlargestdifferenceinelectronegativity.
10.71 (a)Bondangles1,2and3areabout120,109.5(actually104)and120,respectively.
(b)TheshortestcarbonoxygenbondisthecarbonylC=Odoublebondatthetopofthe
structure.
(c)ThemostpolarbondinthemoleculeistheOHbondatthebottomofthestructure.
10.73 (a)ThegeometryabouttheboronatominH3NBF3istetrahedral.
(b)InBF3,thevalenceorbitalsofboronaresp2hybridized.
InH3NBF3,thevalenceorbitalsofboronaresp3hybridized.
(c)Weexpectthehybridizationofborontochangewhenthiscoordinatebondforms.
Chapter11
11.4 32x104L
11.5 650balloons
11.6 136kPa
11.10 121gmol1
11.13 p(C2HBrClF3)=37.7kPa
P(O2)=364kPa
11.16 0.798
11.17 TakingHeasthereference,RateofeffusionofSF6 =0.166

RateofeffusionofHe
andRateofeffusionofN2 =0.378
RateofeffusionofHe
11.19 160gmol1
11.23 (a)thedispersionforcesinliquidO2<(c)thedipoleinduceddipoleinteractionsofO2
dissolvedinH2O<(b)thehydrogenbondingforcesinliquidCH3OH
11.25 (a)167mmHg
(b)thevapourandliquidareNOTatequilibriumthevapourissupersaturatedandvapour
condensestoformmoreliquid.
11.26 0.50gofwaterisnotenoughtoachieveapartialpressureof19.3kPa.Instead,weachieveonly
15kPa.
With2.0gofwater,thepartialpressureofwaterwouldbe19.3kPa.
11.27 (a)ThedensityofliquidCO2islessthanthatofsolidCO2.
(b)gasphase
(c)No.
11.29 T(80km)<T(25km)<T(110km)<T(5km)
REVIEWQUESTIONS
11.29 T(80km)<T(25km)<T(110km)<T(5km)
11.31 Thetemperaturestopsdecreasing,andstartsincreasing,aswemovefromthetroposphereinto
thestratosphere.AbsorptionofUVlightbyoxygenproducesoxygenatomswhich,inturn,
produceozone(togetherwithotheroxygenmolecules).Theozoneproduceabsorbsadditional
UVlight.Theenergyabsorbedincreasesthelocaltemperature.Thedensityoftheatmosphere
atthetopofthestratosphereandbottomofmesosphereissufficienttoabsorbenoughUVlight
toincreasethetemperature.Aswedescendintothestratosphereandbelow,theintensityof
incomingUVradiationisdiminishedduetoabsorptionathigheraltitudes.At1kmabove
earthssurfaceinthetropospherethereistoolittleUVradiationtocausesignificantabsorption
byoxygentoproduceOatoms,andozoneetc.
11.33 (a)c(CO2)waslowerat30,000yearsagocomparedto125,000yearsago,thenwasloweragain
at260,000yearsago.
(b)Temperaturewaslowerat30,000yearsagocomparedto125,000yearsago,thenwaslower
againat260,000yearsago.
11.35 0.276atm=30.0kPa=0.300bar
11.37 0.117L
11.39 9.7atm
11.41 Molarvolume(at448.15Kand1.00bar)ofH2,CO2andSF6are37.277,37.218and37.157Lmol
1
,respectively.Thethreegasesaremorealikeintermsofmolarvolumeat448.15Kthan
298.15K.
11.43 565kPa
11.45 57.5gmol1
11.47 1.22x107L.Thoughthepressuredroppedbyalmost20%,thedecreaseintemperature
compensatesandthechangeinvolumeisnotverybig.Nevertheless,therewouldhavetobe
allowanceforexpansionoftheballoonathigheraltitudes.
11.49 33.97gmol1
11.51 173g

11.53 171kPa
11.55 PTotal=580kPa
P(H2)=412kPa
P(Ar)=168kPa
11.61 3.65041cms1
11.63 4.58cms1
1.194
11.67 36gmol1
11.69 Usingidealgaslaw,p=4990kPa.UsingvanderWaalsequation,p=2991kPa.
11.71 WhensolidI2dissolvesinmethanol,CH3OH,dispersionforcesholdingI2moleculesintheir
latticepositionsmustbeovercome.Hydrogenbondingforcesbetweenmethanolmoleculesare
disruptedwhenmethanolsolvatesiodine.Thesolvationforcesbetweenmethanolandiodine
aredipoleinduceddipoleinteractions.
11.75 (a)18.7kPa
(b)Atabout75C
(c)Theequilibriumvapourpressureofethanolishigherthanthatofwaterat70C.
11.77 About80kPa.1.0gofdiethyletherismorethanenoughtoachievethispartialpressure.0.24g
ofdiethyletherevaporates,while0.76gremainsintheliquidphasethetwophasesarein
equilibrium.Iftheflaskisplacedinanicebath,thetemperaturelowerscausingthevapour
pressuretolower.Thegasbecomessupersaturatedandliquiddiethylethercondensesoutof
thevapour.
11.81
p/kPa 100
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90
T/K

Thisphasediagramisconstructedby(1)connecting(T=0K,p=0kPa)tothetriplepoint,(T=
54.34K,p=0.267kPa),togetthesolidgascoexistencecurve,(2)connectingthetriplepointto
thenormalmeltingpoint,(T=54.8K,p=100kPa),togetthesolidliquidcoexistencecurve,and
(3)connectingthetriplepointtothenormalboilingpoint,(T=90.18K,p=100kPa),togetthe
liquidgascoexistencecurve.
AtT=196C(i.e.T=77K),p=76.5kPa
11.83 1.624kJ
11.87 CH3Clcanbeliquefiedatoraboveroomtemperature,upto416K(143C)thecritical
temperature.Abovethecriticaltemperature,chloromethanecannotbeliquifieditcanonly
becompressedintoasupercriticalfluid.Belowthetriplepointtemperature,175.4K(97.8C),
chloromethanecannotbeliquifieditsolidifiesuponcompression.However,room
temperatureisbetweentheselimitsonliquification.
11.89 IceVonlyexistsovertherangeoftemperaturesandpressuresshowninthephasediagram.The
lowestpressureatwhichIceVisstableisabout3Mbari.e.about3millionatmospheres.
11.91 306K
11.93 (a)A1.0Lflaskcontaining10.0geachofO2andCO2at25ChasgreaterpartialpressureofO2
thanCO2.Thepartialpressuresdependonthenumbersofmoles10.0gofthelowermolar
massO2hasmoremolesthan10.0gofCO2.
(b)ThelighterO2moleculeshavegreateraveragespeedaveragespeedisproportionalto
M1/2.

11.95 (a)ThisisNOTagas.Anidealgaswouldexpand100foldifitspressurewerechangedfrom100
barto1bar(atmosphericpressure).Onlyaliquidorsolidissoincompressibleastoexpandonly
10%whenrelievedofsuchalargepressure.
(b)ThisisNOTagas.Adensityof8.2gmL1=8200gL1iswaytoohighforsuchagas.
(c)Thereisinsufficientinformation.Chlorineisatransparentandpalegreengas.But,thereare
alsomanytransparentandpalegreenliquidsandsolids.
(d)Amaterialthatcontainsasmanymoleculesin1.0m3asthesamevolumeofair,atthesame
temperatureandpressure,isdefinitelyagas(assumingthetemperatureandpressurearenot
unusual).
11.97 (a)46.0g
(b)
+ + +
N N N N N N N N N

Thestructureontheleftisthemostreasonable.

(c)Theazideionislinear.
11.99 0.61kPacorrespondstoessentiallyzeropressureinthegivenphasediagram.Tosolidifycarbon
dioxiderequiresatemperaturenogreaterthan90C.
11.101 (a) O 2 < B2 H 6 < H 2 O i.e.indescendingorderaccordingtomolarmass

(b)102.3kPa
11.103 64g
11.105 (a)28.7gmol1
(b)x(O2)=0.17;x(N2)=0.83
11.107 21.7kPa
11.109 (a)7.76mgL1
(b)4.61mgL1

Themassdensityofwatervapourishigherat20Cwith45%humiditythan0Cwith95%
humidity.
11.111 5.491019atoms/m3
11.113 Themoleculesofcookingoildonotformhydrogenbondswithwater,anddonothavestrong
dipolestoformsignificantdipoledipoleinteractions.
11.115 (a)27C

(b) At25C,thereisnetevaporationofliquidCCl2F2untilthe
dichlorodifluoromethanepartialpressureinsidethesteelcylinderequalsabout6.5
atm,thevapourpressureofCCl2F2at25C.Hereweassumethatthecylinderisnotso
bigthat25kgofCCl2F2isnotenoughtofillthecylindertothispressurei.e.nobigger
thanabout780L.

(c)TheCCl2F2vapourrushesoutofthecylinderquicklyatfirstbecauseofthelarge
pressure
imbalance.
Theflowslowsastheinsidepressureapproaches1atm.
Theoutsideofthecylinderbecomesicybecausewhenthegasexpands,
intermolecularforcesareovercometheenergyrequiredisdrawnfromthethermal
energyofthegasandcylinder.Expansionofagascancausesignificantcooling.This
expansionisdrivenbytheincreaseinentropy,andtheresultingcoolingisinexorable.

(d) (1)Turningthecylinderupsidedown,andopeningthevalve,wouldproducea
dangeroussituation.Thecylinderwouldbehavelikearocket.Itwouldempty
quicklythough.
(2)Coolingthecylinderto78Cindryice,thenopeningthevalvewouldallow
thecylindertobeemptiedsafely.Itwouldnothappenquicklythoughthe
vapourpressureofCCl2F2at78C(notshowninthefigure)isquitesmall.
(3)Knockingthetopoffthecylinder,valveandall,withasledgehammerwould
providerapidandrelativelysafedischargeofthecylinder.Theflowvelocity
wouldbesmallerbecauseofthelargecrosssectionalareaoftheopentopof
thecylinder.
11.117 90.1kJ
11.119
(a)
O
+
H3N O
NH CH3
-
O O
(b)Aspartameiscapableofhydrogenbonding.Sitesofhydrogenbondingarecircledonthe
structure.
Chapter12
12.2 (a)ThelatticeenthalpyofLiCl(s)islargerthanthatofKCl(s)becausetheLi+ionissmallerthan
K+andsogetsclosertoCl.Theelectrostaticpotentialenergyislowerittakesmoreenergyto
breaktheionicbonds.
(b)TheenthalpyofaquationofLi+andClislargerinmagnitudethanthatofK+andCl(theyare
bothnegative)becausetheLi+ionissmallerthanK+.TheinteractionofwatermoleculeswithLi+
isstrongerthanwithK+becausetheygetclosertothesmallerlithiumions.
12.4 1.12x102molL1
12.5 ThesolubilityofLi2SO4inwaterdecreasesslightlyasweincreasethetemperaturefrom10C.
TheamountofsolidLi2SO4inthesecondbeakerwillincreasealittle.
ThesolubilityofLiClinwaterincreasesslightlyasweincreasethetemperaturefrom10C.The
amountofsolidLiClinthefirstbeakerwilldecrease.
12.7 molefraction=0.00210
molality=0.117molkg1
masspercent=3.85%
12.8 19.85kPa
12.10 4.66kPa
12.12 Thefreezingpointofthesolutionis5.25C.Theaddedethyleneglycolisnotenoughto
preventfreezingat25C.
12.14 472gmol1
12.16 2.81C
12.18 1.40105gmol1
12.19 754kPa
12.20 (a)volume=4.19x106nm3
Surfacearea=1.26x105nm2
(b)2.4x1014spheres;surfacearea=30m2
REVIEWQUESTIONS
12.21 (a)6.20106molL1kPa1.
BecauseO2isagas,itislesssolubleinwaterathighertemperaturesdissolutionisan
exothermicprocess.
12.23 ForasaturatedNaClsolutionat25Cwithnosolidinthebeaker,theamountofdissolvedNaCl
inthesolutionisincreasedby
(c)RaisingthetemperatureofthesolutionandaddingsomeNaCl.
ThesolubilityofNaClinwaterincreaseswithtemperaturenotalot,butsome.
(a)AddingmoresolidNaCldoesnotincreaseNaClinsolutionbecausethesolutionissaturated.
(b)RaisingthetemperatureofthesolutiondoesnotincreaseNaClinsolutionbecausethereis
noextrasolidNaClinthebeakertodissolve.
(d)LoweringthetemperatureofthesolutionandaddingsomeNaCldecreasestheamountof
NaClinsolutionbecausethesolubilitygoesdown.
12.25 molefraction=0.000780
molality=0.0434molKg1
masspercent=0.509%
12.27 2.65g
12.29 5.65molkg1
12.31 (a)16.2molkg1
(b)37.1%
12.35 The0.15molkg1Na2SO4solutionhasthehigherequilibriumvapourpressureofwater.
12.37 (a)8.60molkg1
(b)28.4%
12.41 Inorderofdecreasingfreezingpoint,wehave
(a)0.20molkg1ethyleneglycolsolution
(d)0.12molkg1KBrsolution0.24molkg1ions
(c)0.10molkg1MgCl2solution0.30molkg1ions
(b)0.12molkg1K2SO4solution0.36molkg1ions
i.e.inorderofincreasingconcentrationofaquatedspecies
12.43 510g
12.45 52.9kPa
Therearenosummaryandconceptualanswersnecessaryforthischapter.
Chapter13
[PCl3 ][Cl2 ]
13.3 (a) Q
[PCl5 ]
[CO]2
(b) Q
[CO 2 ]
[Cu 2+ ][NH 3 ]4
(c) Q
[Cu(NH 3 ) 24 ]
[CH 3COO ][H 3O + ]
(d) Q
[CH 3COOH]

13.5 (a)Qc=2.25.NOTatequilibrium.BecauseQc<Kc,thereactionproceedsintheforward
direction.
(b)Qc=3.47.NOTatequilibrium.BecauseQc>Kc,thereactionproceedsinthereversedirection
13.6 (a) [NH 3 ] 6.2 10-4 mol L1

(b)[NH3]=1.8x102molL1
Thecadmiumsolutionhasahigherammoniaconcentration
13.7 (a)[C6H10I2]=0.015molL1
[C6H10]=0.035molL1
(b)K=0.082
13.10 [H2]=[I2]=1.54103molL1
[HI]=8.92103molL1
13.11 (b) K 2 = K12
13.13 (a) K 2 ( K 2 ) 2 = (2.5 1029 ) 2 = 6.3 1058

(b) K 3 ( K 2 ) 1 = (6.3 1058 ) 1 = 1.6 1057
13.14 K 3 K1 K 2 8.12 0.771 13.7

2 2
13.15 [butane]=0.77molL1
[isobutane]=1.93molL1
13.16 (a)WhenextraH2isaddedtoanequilibriummixture,themixtureisshiftedoutofequilibrium
bytheincreaseinH2concentration.Thereisnetforwardreactionuntilanewequilibriumis
attained.Some,butnotall,oftheadditionalH2isconsumed.TheconcentrationofN2
decreases,sinceitisareactant,whiletheconcentrationofproductNH3increases.
WhenextraNH3isadded,netreversereactionfollowsconsumingsomebutnotallofthe
addedammonia.Thefinalequilibriummixturehasahigherconcentrationofbothhydrogenand
nitrogen(reactants)andahigherconcentrationofammoniathantheoriginalequilibrium
mixture.

(b)Whenthevolumeofthesystemisincreased,allconcentrationsaredecreasedbythesame
factor.Sincethereareadifferentnumberofmolesofreactantandproductgases,thiswill
changethevalueofthereactionquotient,shiftingitawayfromitsequilibriumvalue.Inthis
case,therearemorereactantgasesthanproductgases,andthereactionquotientgetsbigger.
Thiscausesthereactiontoproceedinthereversedirection(thereactionquotientmust
decreasetoreverttoitsequilibriumvalue),generatinganetincreaseinmolesofgas.The
reactionproceedsinthedirectionwhichcountersthedecreaseintotalgasconcentration
causedbythechangeinvolume.
13.17 (a)TheequilibriumconcentrationofNOCldecreasesifthetemperatureofthesystemis
increased.
2 NO(g) + Cl2 (g)
2 NOCl(g) rxn H = +77.1 kJ mol-1

(i) Initially,themixtureisatequilibrium.So,Q=K.Whentemperatureincreases,the
equilibriumconstantgenerallychanges.Foranendothermicreactionsuchasthis,the
equilibriumconstantincreases.Now,Q<KwhereKisthenewequilibriumconstant.Q
hasnotchangedatleastatfirst.However,becauseQislessthanK,thereactionmust
proceedintheforwarddirectiontoreturntoequilibriumi.e.increasingQuptoK.This
directionconsumesreactanti.e.theconcentrationofNOCldecreases.
(ii) Thereactionproceedsintheforwardendothermicdirectionafterthetemperatureis
increased.Theendothermicdirectionisthedirectionthatconsumesheatandlowers
temperaturei.e.counteringtheincreaseintemperatureinaccordwithLeChateliers
principle.
(b)TheequilibriumconcentrationofSO3decreasesifthetemperatureisincreased?
2 SO3 (g)
2 SO 2 (g) + O 2 (g) rxn H = -198 kJ mol-1
(i) Initially,themixtureisatequilibrium.So,Q=K.Foranexothermicreactionsuchasthis,
theequilibriumconstantdecreases.Now,Q>KwhereKisthenewequilibriumconstant.
Toreturntoequilibrium,Qmustdecreasei.e.thereactionproceedsinthereverse
directiontoreturntoequilibriumi.e.decreasingQdowntoK.
(ii) Thereactionproceedsinthereverseendothermicdirectionafterthetemperatureis
increased.Theendothermicdirectionisthedirectionthatconsumesheatandlowers
temperaturei.e.counteringtheincreaseintemperatureinaccordwithLeChateliers
principle.

REVIEWQUESTIONS
13.19 BecauseQ(1.4x104)<K(4.0x104),thereactionproceedsintheforwarddirection
13.21 K=1.2
13.25 K=9.3x105
13.29 (a)K=1.6
(b)ThenewequilibriumconcentrationsofH2OandCOareboth0.014molL1
13.31 0.0002g
13.33 [NH3]eqm=0.66molL1
[N2]eqm=0.57molL1
[H2]eqm=1.71molL1
p=17.7MPa
13.35 4.441025
13.37 (a)K=0.041
(b)K=590
13.39 (a)[butane]=1.1molL1
[isobutane]=2.9molL1
(b)sameasinpart(a)
13.41 (a)Allthreegasesincreaseinconcentration.
(b)Allthreegasesincreaseinconcentration.
(c)Anetdecreaseinallgasconcentrations.
(d)Productgasesdecreaseinconcentration,whilereactantgasesincreaseinconcentration.
13.43 (a)(i)nonetreaction
(b)(ii)netreactiontoformmoreBaCO3(s)
(c)(i)nonetreaction
(d)(iii)netreactiontoformmoreBaO(s)andCO2(g).
(e)(iii)netreactiontoformmoreBaO(s)andCO2(g).
13.45 [PCl5]eqm=0.0198molL1
[PCl3]eqm=0.0232molL1
[Cl2]eqm=0.0404molL1
13.47 (a)81%
(b)Therewillbenetreactioninthereversedirection
13.49 (a)0.60
(b)0.50
(c)ThefractionsofSO2Cl2(g)dissociatedinpart(b)islessthanthatinpart(b),inagreementwith
LeChateliersprinciple.Therewasnetreactioninthereversedirectiontocountertheincrease
inchlorinegasconcentration.
Chapter14
14.1 (a) HCOOH aq + H 2 O(l) HCOO aq + H 3O + aq

acid base conj.base conj.Acid
(b) NH 3 aq + H 2S aq
NH 4 + aq + HS aq
base acid conj.acid conj.Base
(c) HSO 4 aq + OH aq
SO 4 2 aq + H 2 O(l)
acid base conj.baseconj.acid

14.3 HC2O4 (aq)actingasaBrnstedLowryacid:
HC2 O 4 aq + OH aq C2 O 4 2 aq + H 2 O(l)

HC2O4(aq)actingasaBrnstedLowrybase:
HC2 O 4 aq + H 3O aq
H 2 C 2 O 4 aq + H 2 O(l)
14.5 [H3O+]=4.0103molL1
[OH]=2.5x1012molL1
14.7 (a)pOH=2.9;pH=11.1
(b)[H3O+]=4.79105molL1;[OH]=2.09x1010molL1
(c))pOH=3.54;[OH]=2.88x104molL1
14.9 (a)pKa=4.2
(b)aquatedchloroaceticacidisastrongeracidthanaquatedbenzoicacid
14.10 ItfitsbetweenbenzoicandaceticacidsinTable14.5.
14.12 Kb=7.1x1011
ItfitsbetweendihydrogenphosphateandfluorideinTable14.5.
14.13 (a)AnaqueoussolutionofKBrhasapHof7.
(b)AnaqueoussolutionofNH4NO3hasapH<7
(c)AnaqueoussolutionofAlCl3hasapH<7
(d)AnaqueoussolutionofNa2HPO4haspH>7
14.15 (a)TheHattachedtoNhasthegreatestconcentrationofpositivecharge.Assuch,thisisthe
mostacidichydrogenatom.
(b)Theunprotonatedringnitrogenhasthegreatestconcentrationofnegativecharge.Itisthe
mostbasicnitrogenatominimidazole.
14.16 COaLewisbase.
14.17
(a) H (b) H H
N H
C H C C
H
C O H
H H
H H
H
H LewisBase

LewisBase
(c) (d) H H
C
Br H H
H
B
LewisBase C C
H H
H H

LewisAcid

(e) (f) H H
H
Cl C
H
C P H
C H
H C
H
H H H
H
Lewisbase,throughClatoms
LewisBase
14.19 Ka=6.87x105
14.22 [CH3COO]=[H3O+]=0.0013molL1
[CH3COOH]=0.0987molL1
pH=2.89
%aceticacidionized=1.3%

14.24 TheresultsshowninTable14.7arecorrect.
14.25 TheresultsshowninTable14.8arecorrect.
14.27 (a)0.30molL1aqueoussolutionofformicacid
pH=2.14;%ionisation=2.4%
0.10molL1aqueoussolutionofformicacid
pH=3.27;%ionisation=0.18%
(b)0.18%

14.28 [HOCl]=[OH]=6.6106molL1
pH=8.82

14.30 [oxalate]=[H3O+]=0.053molL1
pH=1.28
14.31 (a)Accordingtoincreasingacidity(i.e.decreasingpH)wehave
C<A<B
(b)accordingtoamountofNaOHthatcanbeconsumed,wehave
B(0.001molL1)<A(0.005molL1)<C(0.006molL1)
14.34 (a)2.88x103
(b)2.88
(c)2.88x103
14.35 (a)AtpH6.0
(i)1.33x104
(ii)16
(iii)2.78x106
AtpH=6.0,thedominantspeciesisH2PO4
(b)AtpH=9.0
(i)1.33x107
(ii)1.6x102
(iii)2.78x103
AtpH=9.0,thedominantspeciesisHPO42
14.36 (a)phenylalanine
[H 2 Phe+ ] [H 3O + ] 107.40
= = = 105.57 = 2.7 106
[HPhe] K a1 101.83
[HPhe] [H 3O + ] 107.40
= = = 101.73 = 54
[Phe ] Ka 2 109.13

ThedominantspeciesatpH=7.40isHPhe.
O
-
O
+
NH3

(b)glutamicacid
[H 3Glu + ] [H 3O + ] 107.40
= = 2.19
= 105.21 = 6.2 106
[H 2 Glu] K a1 10
[H 2 Glu] [H 3O + ] 107.40

= = 4.25
= 103.15 = 7.1104
[HGlu ] Ka 2 10
[HGlu ] [H 3O + ] 107.40
2
= = 9.67
= 102.27 = 190
[Glu ] K a3 10
ThedominantspeciesatpH=7.40isHGlu
O O
- -
O O
+
NH3
(c)lysine
[H 3 Lys 2+ ] [H 3O + ] 107.40
= = = 105.22 = 6.0 106
[H 2 Lys + ] K a1 102.18
[H 2 Lys + ] [H 3O + ] 107.40
= = 8.95
= 101.55 = 35
[HLys] Ka 2 10
[HLys] [H 3O + ] 107.40

= = 10.53
= 103.13 = 1350
[Lys ] K a3 10

ThedominantspeciesatpH=7.40isH2Lys+
O
+
H3N -
O
+
NH3
14.40 pH=4.13
14.42 (b)NH3andNH4ClwouldmakeabuffersolutionnearpH=9
14.43 Ifwepreparea(nottoodilute)solutionwitha2.0to1ratio(onamolesbasis)ofNa2HPO4(s)to
NaH2PO4(s),itwillfunctionasabuffersolutionwithpH=7.5.
14.45 (a)pH=3.89
(b)pH=3.86
14.46 (a)(i)pH=10.02
(ii)pH=10.2610.02=0.24
(b)(i)11.02
(ii)pH=11.3011.02=0.28
14.47 concentrationoftheaceticacidinvinegarsample=1.08molL1
massofaceticacidinvinegarsample=1.62g
14.49 0.119molL1
14.51 (a)4.47
(b)8.72
14.52 (a)4.19
(b)6.38
(c)9.19
(d)10.32
(e)11.13
14.53 1.049107molL1
REVIEWQUESTIONS
14.55 pH=2.12
[OH]=1.31012molL1
14.56 Kb=6.31x105
14.57 [H3O+]=10pH=103.75=1.78104molL1
Thesolutionisacidic(pH<7).
14.59
1
[ CH 3 3 NH + ][OH ] [ CH 3 3 N][H 3O ] 1
K b CH 3 3 N aq = =
[ CH 3 3 N] [ CH 3 NH ] [H 3O ][OH ]
+
3
1
1
= K a CH 3 3 NH +
Kw
=
Kw K a CH 3 3 NH +
1014 1014
= pK a
= 9.80
= 104.20 = 6.31 105
10 10
14.61
HPO42(aq)ionsactingasanacid:
HPO 4 2 aq + H 2 O l
PO 43 aq + H 3O (aq)
HPO42(aq)ionsactingasabase:
HPO 4 2 aq + H 2 O(l)
H 2 PO 4 aq + OH aq
14.63 (b)ClC6H4COOH(pKa2.88)isthestrongeracid,strongerthanbenzoicacid(pKa4.20).The
acidwiththelowestpKavalueisthestrongest.
14.65 (a)HCOOH(aq)(formicacid)isthestrongestacid.
C6H5OH(aq)(phenol)istheweakestacid.
(b)HCOOH(aq)(formicacid)hastheweakestconjugatebase.
(c)C6H5OH(aq)(phenol)hasthestrongestconjugatebase.
14.69 The0.10molL1solutionof(a)Na2S(s)hasthehighestpH.
The0.10molL1solutionof(f)AlCl3(s)hasthelowestpH.
14.71
(a)
trimethylphosphine,(CH3)3P,plusH3O+issimilartodimethylamine,(CH3)2NH,plusH3O+
(b)
BrdoesnotbehaveasaLewisacid
14.73 [H3O+]=1.58104molL1
(b)Ka=1.1x105(moderatelyweakacid)
14.75 (a)decreasespH
(b)increasespH
(c)NoaffectonthepH
14.77 [NH4+]=[OH]=1.6103molL1
[NH3]=0.015molL1
[H3O+]=6.25x1012molL1
pH=11.20
%NH3ionized=1.1%
11.79 (i)0.054%
(ii)0.17%
(iii)5.4%
14.81 (a)[OH]=9.2105molL1
[N2H5+]=9.2105molL1
[N2H62+]=9.01016molL1

(b)pH=9.96
14.83 AtpH=3.00,[CH3NH2]/[CH3NH3+]=0.42
AtpH=7.00,[CH3NH2]/[CH3NH3+]=4200
AtpH=11.00,[CH3NH2]/[CH3NH3+]=4.2x107
WhenpH=pKa=3.38,[CH3NH2]=[CH3NH3+]
14.85 (a)At
(i)pH=6,H2A(aq)hasthehighestconcentration
(ii)pH=8,HA(aq)hasthehighestconcentration
(iii)pH=10,HA(aq)stillhasthehighestconcentrationbutnotbyaswideamargin

(b)pKa1andpKa2canbeseenintheplot.
[H2A(aq)]=[HA(aq)]whenpH=pKa1
So,pKa1=about6.4
[HA(aq)]=[A2(aq)]whenpH=pKa2
So,pKa1=about10.3

(c)SincepKa1=6.38andpKa2=10.32forcarbonicacid,theacidisverylikelycarbonicacid.
14.87
(a)
H3Glu+
O O
HO OH
+
NH3
(b)
H2Glu
O O
-
HO O
+
NH3

(c)
HGlu
O O
- -
O O
+
NH3
(d)
Glu2
O O
- -
O O
NH2
14.89 3.89
14.91 (a)3.59
(b)2.24
14.93 Thebuffersolutionispreparedbyadding0.479molofNa2CO3forevery1.000molofNaHCO3
addedtowatertogiveanottoodiluteconcentration(sowehaveabufferwithsomecapacity).
14.95 (a)4.95
(b)5.05
14.99 0.167molL1
14.101 (a)7.46
(b)7.28
14.103 (a)0.180molL1
(b)[H3O+]=2.1103molL1
[C6H5NH3 +]=0.178molL1
[OH]=6.761012molL1
(c)2.68
14.105 (a)5.35
(b)9.40
(c)10.12
(d)16.7mL
(e)10.93
(f)WeneedanindicatorwithpKaneartheequivalencepointpHi.e.pKa10.93.
IndicatorswhichchangecolourintheneighborhoodofpH=11include
alizarineyellowR.
0.0014
0.0012
0.001
amount / mol
0.0008 HCN
0.0006 CN-
0.0004
0.0002
0
0 5 10 15
pH
14.107 (a)10H3O+ions.
(b)1H3O+ion
(c)IfthepHwere4,thentherewouldlikelynotbeanyhydroniumionsinthecube.Tovisualize
pH=4,youwouldhavetoimaginethecubeasasnapshottakenfromalargerquantityofwater.
Ifmanysuchsnapshotswereconsidered,thenabout1in10ofthemwouldhaveasingle
hydroniumion.
(d)IftheH3O+iontowatermoleculeratiois100:55000=1:550whenpH=1.0,thenthisratiois
1:55000000whenpH=6.0(i.e.ahydroniumconcentration105timessmaller).
14.109 Abuffersolutioncontainsanottoodilutesolutionofbothaweakacidandaweakbase.When
astrongbaseisadded,theweakacidreactswithitandconsumesmostofit.Inthecaseofa
carbonate/hydrogencarbonatebuffer,thehydrogencarbonatereactswiththeaddedbase.
HCO3(aq)+OH(aq)CO32(aq)+H2O()
14.111 (a)ThefractionofaceticaciddeclinesandthatofacetateionincreasesasthepHincreases,in
accordwiththebufferequation(seethe14.107above).WecanunderstandthisusingLe
Chateliersprinciple.
CH3COO(aq)+H3O+(aq)
CH3COOH(aq)+H2O()
IncreasingpHmeansdecreasingH3O+which,accordingtoLeChateliersprinciple,causesashift
intheequilibriumtotherighti.e.depletedaceticacidandincreasedacetate.
(b)Fromthebufferequation,
[CH3COOH]
[H 3O + ] =
1.8 105 = 104
[CH 3COO ]
atpH=4.Here,weseethat[CH3COOH]/[CH3COO]mustbegreaterthan1i.e.aceticacid
predominates.
AtpH=6,therightsideoftheaboveequationis106and[CH3COOH]/[CH3COO]mustbeless
than1i.e.acetatepredominates.
(c)Fromthebufferequation,weseethat[H3O+]=Ka=1.8105,whentheaceticacidand
acetateconcentrationsareequali.e.pH=log10(1.8105)=4.74.
14.113 (a)0.00135
(b)12.0%
(c)pHathalfway=2.86
pHatequivalencepoint=7.32
Chapter15
15.1 (a)
Ag + (aq) + I (aq)
AgI(s)
Q [Ag + ][I ] K sp 1.5 1016 atequilibrium
(b)
Ba 2+ (aq) + 2 F (aq)
BaF2 (s)
Q [Ba 2+ ][F ]2 K sp 1.7 106 atequilibrium

(c)
2 Ag + (aq) + CO32 (aq)
Ag 2 CO3 (s)
Q [Ag + ]2 [CO32 ] K sp 8.1 1012 atequilibrium
15.4 Ksp=1.9x107
15.6 (a)1.3x102molL1
(b)9.6101gL1
15.8 (a)AgCl
(b)Ca(OH)2
(c)Ca(OH)2
15.10 ThesolubilityofAg3PO4islargerthanthatpredictedusingKspofthesaltbecausethephosphate
ion,PO43,reactswithwatertoformHPO42(H2PO4andH3PO4uponfurtherreactionwith
water).TheconcentrationofPO43isconsequentlysignificantlyreduced,andthereaction
quotientfordissolutionofAg3PO4remainslessthanthesolubilityproductforlargerinitial
concentrationsofAg3PO4thanpredictedusingKsp.
15.13 (a)1.0 105 mol L1

(b)1.1108molL1
15.15 (a)PbS(s)
(b)Ag2CO3(s)
(c)Al(OH)3(s)
15.16 Q=5.3x109<Ksp=9.8x109
Thesolutionisnotsaturated.MorePbI2candissolve.

15.19 Q=6.3x108<Ksp=3.4x107
Themixtureisnotsaturated.SrSO4(s)willnotprecipitate.
15.20 [I]=4.4x109mol L1
[Pb2+] = 4.4 x 10-3 mol L1
15.22 [OH]=5.3106molL1
15.24 Knet= 1.1106

15.25 AtpH=1,thecyanideappearsonlyashydrogencyanide,HCN(aq).Silverappearsonlyas
Ag+(aq).AspHincreasespastpKa=log10(3.5104)=3.5,thecyanideion,CN,concentration
increases.Dependingontherelativeamountsofcyanideandsilver,someorallofthecyanide
complexessilvertheAg+(aq)concentrationdecreasesandthe[Ag(CN)2]increases.
TheconcentrationsremainconstantforpHfromabout5(i.e.whenverylittlehydrogencyanide
remains)allthewayto13.
REVIEWQUESTIONS
15.25 (a) PbSO 4 s

Pb 2+ (aq) + SO 4 2 (aq)
Q [Pb 2+ ][SO 4 2 ] K sp 1.8 108 atequilibrium.
(b) NiCO3 s
Ni 2+ (aq) + CO32 (aq)
Q [Ni 2+ ][CO32 ] Ksp 1.4 107 atequilibrium.
(c)
3Ag + (aq) + PO 43 (aq)
Ag 3 PO 4 (s)
Q [Ag + ]3 [PO 43 ] K sp 1.3 1020 atequilibrium.
Sr 2+ (aq) + 2 F (aq)
15.27 SrF2 (s)
Ksp=4.0x109
15.29 51mgofPbSO4remainsundissolved
15.31 (a)PbCl2(s)
(b)FeS(s)
(c)Fe(OH)2(s)
15.33 Q=1.1x106>Ksp=1.8x108
AgClwillprecipitateoutofsolution
15.35 (a)Q=2.4x109<Ksp=6.6x109
NiCO3willnotprecipitate
(b)Q=2.4x107>Ksp=6.6x109
NiCO3willprecipitate
15.37 Fe(OH)3(s)precipitatesfirst,followedbyAl(OH)3(s).Pb(OH)2(s)islasttoprecipitate
15.39
Au (aq) + Cl (aq)
AuCl(s)

Au (aq) + 2 CN (aq) [Au(CN) 2 ] (aq)
[Au(CN) 2 ] (aq) + Cl (aq)
AuCl(s) + 2 CN (aq)

Knet=4.0x1025
15.41 5.51x105
15.43 1.4104molL1
Chapter16
16.2 (a)+3
(b)+6
(c)+4
(d)+5
16.4 CH3CH2OHisoxidized.CH3CH2OHisthereducingagent.Cr2O72isreduced.Cr2O72isthe
oxidizingagent.
16.6 AsilverelectrodeimmersedinanaqueoussolutionofAgNO3providesthecathode.Anickel
electrodeimmersedinanNi2+solutionprovidestheanode.
Theoverallcellreactionis:2Ag+(aq)+Ni(s)2Ag(s)+Ni2+(aq)
ElectronsflowfromtheNi(s)totheAg(s).NO3inthesaltbridgeflowstowardstheanode
compartmentandNa+inthesaltbridgeflowstowardthecathodecompartment.
16.7
(a) V
direction of electron flow
anion flow
cation flow
(b)
V
anion flow
Zn(s) anode Zn 2+ (aq) Ni 2+ (aq) Ni(s) cathode
cation flow
(c)
V
C(s) anode Ag(s) cathode
Ag + (aq)
Fe 2+ (aq), Fe 3+ (aq)
anion flow
cation flow
a drop of Br 2 (l)
on the cathode
Mg(s) anode Mg 2+ (aq) Pt(s) cathode

Br (aq)

16.8 (a)E[Ni2+(aq)|Ni(s)]=0.25V
(b)E[Cl2(g)|Cl(aq)|Pt(s)]=1.36V
16.9 SeeaboveExercise16.8(b).
16.13
Zn(s) Zn 2 (aq) 2 e at the anode
2 (Ag (aq) e Ag(s)) at the cathode
Zn(s) 2 Ag (aq) Zn 2 (aq) 2 Ag(s)
Ecell =1.56V
16.14 (a)Ecell=1.298V(cellreactionisnotwritteninthespontaneousdirection)
(b)Ecell=0.51V(cellreactionisnotwritteninthespontaneousdirection)
(c)Ecell=1.023 V(cellreactionisnotwritteninthespontaneousdirection)
(d)Ecell=0.028V(cellreactioniswritteninthespontaneousdirection)
16.17 (a)Aluminum
(b)Aluminumandzinc
(c)Fe2+(aq)+Sn(s)Fe(s)+Sn2+(aq).ThisisNOTthedirectionofspontaneousreaction.
(d)Zn2+(aq)+Sn(s)Zn(s)+Sn2+(aq).ThisisNOTthedirectionofspontaneousreaction.
16.20 Ecell=+1.24V
16.22 0.041molL1
16.23 (a)AtpH=0,Ecell=+1.51V
(b)At pH = 5.0, Ecell=+1.04V
ThecellpotentialisgreateratpH=0.Thismeanspermanganateisastrongeroxidizingagent
underacidicconditions.
16.25 K=1.2x1019
16.27 2 H 2 O(l) + 2 e
H 2 (g) + 2 OH (aq) (Cathodereaction)
4 OH (aq)
O 2 (g) + 2 H 2 O(l) + 4 e (Anodereaction)
Ecell = 1.23 V
16.28 Thebrassfittingsprovidecathodeswhereoxygenisreducedtowater.Thesteelprovidesthe
anodewhereironisoxidizedtoFe2+.Ofcourse,thesteelcanprovideitsowncathodeandcan
corrodewithoutbrassfittings.However,becausecopper(theprincipalcomponentofbrass)isa
morenoblemetalthaniron,whenitisincontactwithironthereisaslightpolarizationatthe
junction,withironbecomingslightlypositivelycharged.Thismakestheoxidationprocessatthe
surfaceofironmorefavorable.Atthesametime,theslightnegativechargeonthebrassmakes
thereductionofoxygenmorefavorable.
Therateofcorrosionvariesfromcitytocitybecauseitdependsupontheionicstrengththe
totalconcentrationofionsofthecitywater.Ionsinthewatercarrycurrentfromtheanodeto
cathodetocompletethecircuit.Theconductivityofthewaterincreaseswithion
concentration.
16.29 Thecorrosionofironrequireswatertocarrythecurrentthatcompletesthecircuitandto
providetheaqueousenvironmentoftheproductFe2+ions.Italsorequiresoxygenfromtheair
thereactantatthecathode.Theserequirementsaremetbestattheairwaterpier
interface.Corrosionbelowthesurfacecantakeplaceduetodissolvedoxygen,butthe
concentrationislessthantheoxygenconcentrationinair.Corrosionabovethesurfaceoccurs
whenthesteelgetswet,throughwatersplashingontoitorwhenitrains.Thiswaterisnot
alwaysavailable.
16.30 (i)Tinimpedescorrosionofironbycoatingit,preventingoxygenfromcontactingtheiron.If
thetincoatinggetsscratched,theironwillcorrodequicklyatthescratchbecausethemore
noblemetaltinprovidesapreferredcathodeforreductionofoxygen.
(ii)Zincimpedescorrosionofironbyprovidingasacrificialanode.Becausezincisalessnoble
metal,itprovidesapreferredanode.Thezincisoxidized,consumingtheoxygen,inpreference
totheoxidationofiron.Scratchingthezinccoatingwillnotimpactitsabilitytoprotecttheiron.
(iii)Paintimpedescorrosionsimplybyprovidingacoating,keepingtheoxygenawayfromthe
iron.Ifitisscratched,theironwillcorrodeatthescratch,butonlyatitsnormalrateof
corrosion.Thenonconductingpaintdoesnotprovideanelectrodeforcorrosion.
REVIEWQUESTIONS
16.31 (a)OS(f)=1 OS(P)=+5

(b)OS(h)=+1&OS(O)=2 OS(As)=+5
(c)OS(O)=2 OS(U)=+4
(d)OS(O)=2OS(N)=+5
(e)OS(Cl)=1&OS(O)=2OS(P)=+5
(f)OS(O)=2 OS(Xe)=+6
16.33 (a)isnotanoxidationreductionreaction
(b)isanoxidationreductionreaction
(c)isnotanoxidationreductionreaction
(d)isanoxidationreductionreaction
16.35 (a) Sn s + 2 H + aq
Sn 2+ aq + H 2 g
(b) Cr2 O7 2- aq + 6 Fe 2+ aq + 14 H + (aq)
2 Cr 3+ aq + 6 Fe3+ aq + 7 H 2 O(l)
(c) MnO 2 s 2 Cl aq + 4 H + (aq)
Mn 2 aq Cl2 g + 2 H 2 O(l)
(d) HCHO aq + 2 Ag + aq + H 2 O(l) HCOOH aq + 2 Ag s + 2 H + (aq)
16.37 Electrons in the external circuit flow from the chromium electrode (the anode) to the iron
electrode (the cathode). Negative ions move in the salt bridge from the Fe2+|Fe half-cell (the
reduction half-cell) to the Cr|Cr3+ half-cell (the oxidation half-cell). The half-reaction at the
anode is Cr(s) Cr3+(aq) + 3 e and that at the cathode is Fe2+(aq) + 2 e Fe(s).
16.39
(a)+(c)
V
NO3
Na+
Ag(s) cathode
Mg(s) anode Mg2+(aq) Ag+(aq)

(b) Mg s
Mg 2 aq 2 e (oxidationhalfreactionthatoccursattheanode).
Ag aq e
Ag s (reductionhalfreactionthatoccursatthecathode)
Mg(s)+2Ag (aq)Mg2+(aq)+2Ag(s) (netreactioninthecell)
+
16.41 (a)+0.78V
(b)=0.32V
16.43 (a)when
p (NO)
Q 1.00
[NO3 ][H ]4
(b)E[NO3(aq)|NO(g)]=0.96V
16.45 (a)Tomakeacellwithpotentialcloseto1.1V,usingtheZn2+(aq)Zn(s)halfcell,wecoulduse
theCu2+(aq)Cu(s)halfcellasthecathodeandtheZn2+(aq)Zn(s)halfcellastheanode.
Ecell = E[Cu2+(aq)| Cu(s)] E[Zn2+(aq)|Zn(s)] = 0.337 V (0.763 V) = 1.10 V
(b)Tomakeacellwithpotentialcloseto0.5V,usingtheZn2+(aq)Zn(s)halfcell,wecoulduse
theNi2+(aq)Ni(s)halfcellasthecathodeandtheZn2+(aq)Zn(s)halfcellastheanode.
Ecell = E[ Ni2+(aq)Ni(s) ] E[Zn2+(aq)|Zn(s)] = 0.25 V (0.763 V) = 0.51 V
16.47 (a)Se(s)
(b)F(aq)
(c)F2(g),Cl2(g)
(d)F2(g),Cl2(g),Br2(),I2(s),O2(g)
(e)Yes
(f)No
(g)No
(h)Yes
16.49 (a)isNOTthedirectionofspontaneousreaction
(b)isthedirectionofspontaneousreaction
(c)isNOTthedirectionofspontaneousreaction
(d)isthedirectionofspontaneousreaction
16.53 (a)isthedirectionofspontaneousreaction
(b)isNOTthedirectionofspontaneousreaction
(c)isNOTthedirectionofspontaneousreaction
(d)isthedirectionofspontaneousreaction
16.55 AddingaKIsolutiontoastandardacidicsolutionofCu(NO3)2causesabrowncolouranda
precipitatetoformbecausethenitrateionoxidizesiodideundertheseconditions.TheI2thatis
formedfirstreactswithiodidetoformthebrownI3(aq)ion.Asiodidegetsconsumedthe
excessinsolubleiodineprecipitates.AsimilarresponseisnotobservedwhenKClorKBr
solutionsareaddedbecausenitratecannotoxidizechlorideorbromideunderstandard
conditionsthereisnoreaction.
6I(aq)+2NO3(aq)+8H+(aq)3I2(s)+2NO(g)+4H2O()(Balancedequation)
16.57 Ecell=+1.585V
16.59 (a)
V
salt bridge
Ni(s) cathode
Cd(s) anode Cd2+(aq) Ni2+(aq)

(b)
Ni 2+ (aq) + 2e
Ni(s)
Cd 2+ (aq) + 2e
Cd(s)
Ni (aq) + Cd(s)
2+
Ni(s) + Cd (aq) 2+
(c)TheNi(s)electrodeisthecathodeitislabeled+.Thecadmiumanodeislabeled.
(d) Ecell =+0.15V
(e)fromanodetocathode
(f)TheNa+(aq)ionsinthesaltbridgemovefromtheanodecompartmenttothecathode
compartment.TheNO3(aq)ionsmovefromthecathodecompartmenttotheanode
compartment.
(g)K=1.2x105
(h) Ecell =+0.21V
SinceEcellisstillpositive,thenetreactionisinthesamedirectiongiveninpart(b).
16.61 (a)Ecell = +0.236 V, K = 9.5 x 107

(b)Ecell = 0.531 V, K = 1.1 x 10-18
16.65 Kf=2.3x1025
16.67
Na+
Cl
Cl2(g) formed at anode

anode cathode
-oxidation of Cl to Cl2(g) -reduction of Na+ to Na(s)
takes place here takes place here
- sodium metal plates
onto cathode

16.69 Fluorinehasthelargestreductionpotentialofallspecies.Oxygengaswillformattheanodein
theelectrolysisofanaqueousKFsolution.
16.71Thebumperonanoffroadvehicleislikelytogetscratched.Thechromeplatedsteelwillcorrode
atthescratchfasterthanitwouldwithouttheplating.Thisisbecausechromiumisa(slightly)
morenoblemetalthaniron.Thegalvanizedsteelstaysprotected,evenwithscratches,untilallof
thezincplatingisoxidizedbycorrosion.Notethatcorrosionofzincisslowerthanthatforiron
becausezincoxidecoatsthezincprotectingitfromatmosphericoxygen.Whenironoxidizes,its
oxidedoesnotcoatthemetal.Thisisthetroublewithironitisvulnerabletocorrosion.
16.73
electron flow electron flow
inert
Fe(s) cathode
electrode
pipeline serves as cathode
serves as
in this electrolytic cell
anode
O2(g) + 4 H+(aq) + 2 e 2 H2O(l)
2 H2O(l) O2(g) + 4 H+(aq) + 2 e
Cl flow
Na+ and Mg2+ flow
By keeping the pipeline at a higher

potential than the inert electrode, the
pipeline behaves like a metal even
more noble - it does not corrode.

16.75 (a)Inthiscase,theironscrewsincontactwiththemorenoblecopperalloycorroderapidly.
Theycrumble,leavingholesinthecopperalloysheetswherewaterleaksin.
(b)Inthiscase,theironwrenchisthemorenoblemetal.Itacceleratesthecorrosionofthe
aluminumincontactwithitbypolarizingthealuminum,makingitslightlypositive.The
aluminumcorrodesrapidlyleavingawrenchshapedholeinthehull.
16.77 Iftheemfisappliedinthewrongdirection,thecorrosionofthepipelinewillbeaccelerated.
Thepotentialofthepipelineislowereditischargedpositivelyandtheoxidation(ofFe(s))
halfreactionismademorefavourable.
Chapter17
17.1 Thechangeinentropyforareversibleprocess(i.e.addtheheatveryslowly)isjustheatflow
intothesystemdividedbytemperature.Therefore,theentropyofthewaterandhexane
changebythesameamountitdependsonlyonthetemperatureofthesystemandthe
amountofheatadded.
S=q/T=106J/323.15K=3095J/K,forboththewaterandhexane.
17.3 121J/K
17.5 (a)1molofO3(g)
(b)1molofSnCl4(g)
(c)3molofO2(g)
17.8 (a)+160.59JK1
(b)198.76JK1
17.10 Sosys=134.23JK1
Hosys=657.01kJ
Souniv=+2071JK1
Sincethechangeinentropyfortheuniverseuponforwardreactionispositive,thereactionis
spontaneous.
17.12 (a)Type2
(b)Type3
(c)Type1
(d)Type2
17.14 rSo=198.76JK1
rHo=91.8kJ
rGo=32.6kJ
1 3
17.15 (a) 2 N2(g)+ 2 H2(g)NH3(g)
3
(b)2Fe(s)+ 2 O2(g)Fe2O3(s)
(c)3C(s)+3H2(g)+O2(g)CH3CH2COOH()
(d)Ni(s)istheelementinitsstandardstate.ItsfG=0.
17.17 rGo=70.87kJ
17.18 rGo=142.12kJ
Thereactionisspontaneousintheforwarddirection
17.19 T=838.7K
17.21 (a)rS<0.rGincreaseswithincreasingT.
(b)rS>0.rGdecreaseswithincreasingT.
(c)rS<0.rGincreaseswithincreasingT.
(d)rS>0.rGdecreaseswithincreasingT.
17.22 rGo=1.13kJ
17.25 rGo=+120.023kJ
K=9.18x1022

17.26 41kJ
17.27 +147kJ.Thereversereactionisspontaneous.
17.28 (a)Eo=0.236V
rGo=45.5kJ
K=9.46x107

(b)Eo=0.531V
rGo=102kJ
K=7.58x1017
17.30 (a)rGo=141.73kJ
(b)1.43x1025
(c)6.67x105
17.32 (a)p40C=1.37103bar
(b)p100C=6.20102bar
(c)62.5kJ
REVIEWQUESTIONS
17.33 22.0 J K1 mol1
17.35 (a) NaCl(g)

(b) H2S(g)
(c) C2H4(g)
(d) H2SO4()
17.37
r S = 1 S o (C 2 H 6 ,g) [2 S o (C,graphite) + 3 S o (H 2 , g)]
= 229.60 J K 1 mol1 [2 5.740 J K 1 mol1 + 3 130.684 J K 1 mol1 ]
= 173.93 J K 1 mol1
17.41 1. C(s) = C(graphite)

rS1=S[CH4(g)](S[C(s)]+2S[H2(g)])
=186.3JK1mol1(5.74JK1mol1+2130.7JK1mol1)=80.8JK1mol1
2. rS2 = S[CH3OH()] (S[CH4(g)] + S[O2(g)])

=126.8JK1mol1(186.3JK1mol1+205.1JK1mol1)=162.1JK1mol1
3. rS3 = S[CH3OH()] (S[C(s)] + 2 S[H2(g)] + S[O2(g)])

=126.8JK1mol1(5.74JK1mol1+2130.7JK1mol1+205.1JK1mol1)
=242.9JK1mol1
Justasreactions1&2addtogivereaction3,therSvaluesaddinthesamefashion.

rS1+rS2=80.8JK1mol1162.1JK1mol1=242.9JK1mol1=rS3

ThisisanexampleofHesssLawappliedtoentropy,whichcanonlybethecaseifSisastate
function.
17.43
S o univ = S o sys S o surr = 20.0 J K 1 mol1 619.5 J K 1 mol1
= 639.5 J K 1 mol1
This reaction is spontaneous in the forward direction, under the reaction mixture conditions
specified.
17.45 H 2 O(l) H 2 (g) + 12 O 2 (g)

Ssys=(S[H2(g)]+S[O2(g)])S[H2O()]
=(130.7JK1mol1+205.1JK1mol1)69.91JK1mol1=163.3JK1mol1
Hsys=(fH[H2(g)]+fH[O2(g)])fH[H2O()]
=285.8kJmol100=285.8kJmol1
H o sys 285.8 103 J mol1
S surr =
o
= = 959.1 J K 1 mol1
T 298K
S o univ = S o sys S o surr = 163.3 J K 1 mol1 959.1 J K 1 mol1
= 795.8 J K 1 mol1
This reaction is NOT spontaneous. There is no danger of water spontaneously decomposing into
its elements. On the contrary, reaction in the opposite direction is spontaneous (but very slow) if
in the reaction mixture at 25 C, p(H2) = p(O2) = 1 bar.
17.47 At sufficiently high T, the system change in entropy will be the dominant term and the reaction
will be spontaneous.
17.49 (a)=1258.1kJmol1
Thisreactionisspontaneous.Itisenthalpydriven.
(b)=124.6kJmol1
ThisreactionisNOTspontaneous.Bothenthalpyandentropytermsdisfavourthisprocess.
17.51 This problem is answered using thermochemical data from the NIST webbook
(webbook.nist.gov).
Thisvalueagreeswiththetabulatedfreeenergyofformation(fG)foraceticacid,aslongas
thesamedatabaseisusedtobeconsistent(thesedataarenotalwaysaccuratelydetermined,
ortabulated).Thisshouldnotbesurprisingbecausethereactionofinterestistheoneforwhich
rG=fG,bydefinition.
17.53 = 1139.2 kJ mol1
17.55 = 106 C.
17.57 = 1441.61 kJ mol1 This is in accord with experience.
17.59 K is very small, in accord with a positive standard free energy changethe forward reaction is
NOT favoured in a reaction mixture at 25 C and all reactants and products in their standard
states (i.e., the conditions that apply for specification of the standard free energy change of
reaction).
17.61 = 4.73 kJ mol1

17.63 =166.27kJmol1

17.65 =92.4C
17.67 (a)rS=2S[Hg()]+S[O2(g)]2S[HgO(s)]
=276.02JK1mol1+205.138JK1mol1270.29JK1mol1=
216.60JK1mol1
rH=0+02fH[HgO(s)]=2(90.83kJmol1)=181.66kJmol1

ApositiverHcorrespondstoanegativeHsurrandanegativeSsurr.
rG=vapHTvapS
=181.66kJmol1298.15K216.60JK1mol1/(1000J/kJ)=117kJmol1
We have rG at 25 C, so we can calculate K at 25 C (298 K) from rG -RT lnK
117 000 J mol-1 = (-8.314 J K-1 mol-1)(298 K) lnK
lnK = (117 000 J mol1)/(-8.314 J K1 mol1)(298 K) = -47.22
K at 298 K = 3.1 1021
17.69 (a) rS = 128.133 J K1 mol1

(b) The reaction is NOT spontaneous at 25 C and under standard conditions.
(c) rH = rG + T rS
= 115.55 kJ mol1 298 K 128.133 J K1 mol1/ (1000 J /kJ) = 77.37 kJ mol1
The minimum temperature at which the reaction becomes spontaneous is such that
rG = rH Tspon rS = 0 (above Tspon , rG < 0)
Tspon = rH / rS = 77.37 103 J mol1 / 115.55 J K1 mol1 = 669.5 K
17.71 (a) = 0.141 kJ mol1

The rhombic form of S8 solid is more stable than the monoclinic form at 80 C.
rG = rH T rS = 3.213 kJ mol1 383.15 K (8.7 J K1 mol1) / (1000 J /kJ) =
0.120 kJ mol1
The monoclinic form of S8 solid is more stable than the rhombic form at 110 C.
(b) rG = rH Ttrans rS = 0
at temperature, Ttrans, the temperature at which rhombic sulfur transforms to monoclinic sulfur.
Ttrans = rH / rS = 3.213 103 J mol1/(8.7 J K1 mol1) = 369 K = 96 C.
17.73 (a)rH = 62.10 kJ mol1

rS 132.738 J K1 mol1
rG = 22.524 kJ mol1
(b) = 1.13 104 bar
(c) rG = rH T rS = 0
at T = rH / rS = 62.10 103 J mol1/ (132.738 J K1 mol1) = 468 K
At this temperature, the vapour pressure of oxygen is 1.00 bar.
17.75 Hg() Hg(g)
rH = fH[Hg(g)] = 61.38 kJ mol1
rS = S[Hg(g)] S[Hg()] = 174.97 J K1 mol1 76.02 J K1 mol1
= 98.95 J K1 mol1
rG = rH T rS = 61.38 kJ mol1 298.15 K (98.95 J K1 mol1) / (1000 J /kJ ) =
31.88 kJ mol1
(a) p(Hg) = 1.00 bar

K = 1.00
rG=RTln(K)=0
=rHTrS
So,
T=rH/rS=61.38103Jmol1/98.95JK1mol1=620K
(b) p(Hg) = 1.33 103 bar

K = 1.33 103
rG = RT ln(K) = rH T rS
Solve for T.
T = rH / (rS R ln(K))
= 61.38 103 J mol1/ (98.95 J K1 mol1 8.314 J K1 mol1 ln(1.33 103)) = 399 K
17.77 (a) Entropy of the system decreases in some spontaneous reactions. These reactions occur
because of the increase in the entropy of the surroundings caused by the heat liberatedthey are
enthalpy driven reactions. However it is correct that the entropy of the universe increases with
every spontaneous reaction.
(b) Reactions with a negative free energy change (rG 0) are product-favoured. However,
these reactions sometimes occur very slowly. rG tells us how far a reaction will go to attain a
condition of equilibrium, but does not tell us the speed of the reaction.
(c) Some spontaneous processes are endothermic. These reactions occur because the system
entropy increases sufficiently to exceed the entropy lost by surroundings due to heat absorbed by
the systemthey are entropy driven reactions.
(d) Endothermic processes are sometimes spontaneoussee answer to (c).
17.79 rSisusuallypositiveforthedissolutionofcondensedsubstances.Dissolvedspecieshave
morefreedomasasolutethanasapurecondensedphase.Thereisapositivecomponentto
theentropyofdissolutionsimplyduetothedisorderofhavingamixtureoftwospecies.Inthis
typicalcaseofpositiveentropyofdissolution,ifrH=0
rG=rHTrS<0
andthedissolutionisspontaneous.Suchdissolutionsaredrivenbyentropy.
Somecondensedsubstancese.g.,liquidhydrocarbonsactuallyhavenegativeentropyof
dissolutioninwater.Thehydrophobiceffectisactuallyattributabletothenegativechangein
entropyassociatedwiththewatermoleculessolvatingthehydrophobicmolecule.
17.81 C6H6(s) C6H6()
(a) rH > 0
It takes energy (enthalpy) to break the intermolecular bonds holding the benzene molecules
rigidly in their lattice positions.
(b) rS > 0
A liquid has more disordermore entropythan the corresponding solid.
(c) rG = 0 at 5.5 C, the melting point, where the solid and liquid co-exist.
(d) rG > 0 at 0.0 C < the melting point, where the solid is the more stable phase.
(e) rG < 0 at 25.0C > the melting point, where the liquid is the more stable phase.
17.83 rG < 0
This process is spontaneousiodine dissolves readily in CCl4.
rS = (rH rG) / T > 0 since rH = 0
This dissolution is an entropy-driven process.
17.85 (a) N2H4() + O2(g) N2(g) + 2 H2O()

This is an oxidation-reduction reactionoxygen is the oxidizing agent and hydrazine is the
reducing agent.
(b)rH = 622.29 kJ mol1

rS = 5.08 J K1 mol1
rG = 623.80 kJ mol1
Chapter18
18.2 Forevery2molesofNOClconsumed,thereare2molesofNOandonemoleofCl2produced.
TherelativerateofappearanceofCl2istherateofappearanceofNOwhichequalstherateof
disappearanceofNOCl.
18.3 Inthefirsttwohours:0.0085molL1h1
Inthelasttwohours:0.002molL1h1
Theinstantaneousrateofdecayatt=4.0h:0.0044molL1h1
18.4 (a)Rate=k[NO2][O3]
(b)Theratetriples.
(c)Therateishalved.
18.7 Rate=k[NO]2[O2]
k = 7100 mol2 L2 s1
18.9 0.0035molL1
18.11 0.00217molL1
18.13 Theplotofln([N2O5])versustimegivesastraightline.Thereactionisfirstorder.
18.15 (a)t1/2of241Am=430years
t1/2of125I=63years
(b)125I
(c)1.57x1015atoms
18.17 57.2kJmol1
18.19 Allthreeoftheseprocessesarebimolecular.
Therateequationforthethirdstep:Rate=k[N2O][H2]

2 NO
N 2O2
N 2 O 2 + H 2
N 2O + H 2O
N 2 O + H 2
N 2 + H 2O
2 NO + 2 H 2
N 2 + 2 H 2O
18.21 (a)2NH3(aq)+OCl(aq)N2H4(aq)+H2O()+Cl(aq)
(b)step2
(c)Rate=k[NH2Cl][NH3]
(d)NH2Cl,N2H5+andOH
18.22 (a)Rate=k[CH3(CH2)5CHBrCH3][OH]
(b)Therateofreactionwilldouble.
(c)Therateofreactionwilldouble.
(d)
H
-
O
CH3
H3C
Br H
(e) (R)-octan-2-ol
CH3
H3C
H OH
18.23 (a)Therateofsubstitutionwilldouble
(b)Therateofsubstitutionwillnotchange
(c)
CH3
+
C
CH3 CH3

(d)Whetherornotinversiontakesplaceisirrelevantherebecausetheproductisthesamein
bothcasesduetosymmetry.
(e)TheproportionofthisreactionthatproceedsbytheSN2mechanismisnegligiblebecausethe
rateoftheSN1mechanismisenhancedbytherelativelystablecarbocationintermediate,and
becausetherateoftheSN2mechanismisreducedbythepresenceofthethreemethylgroups
aboutthecarboncenter.Theportionofcollisionsbetweeniodideandtertbutylchloridewhich
canleadtoreactionismuchsmallerthanthevalueformethylchloride(forexample).Thethree
methylgroupspresentanobstaclelimitingtherateoftheSN2reaction.TheSN1mechanism
presentsnosuchobstacletheiodidereactswithareactiveplanarintermediate.
REVIEWQUESTIONS
18.25 3.0104molL1min1
18.27 ThereactionissecondorderinAandfirstorderinB.Thetotalorderofthereactionisthree.
18.29 1.8103molL1h1.TherateofreactionistherateofchangeofCl,forthisreaction.
18.31 (a)secondorderinNOandfirstorderinO2
(b) Rate = k [NO]2 [O 2 ]
(c)25mol2L2s1
(d)2.8105molL1s1
(e)O2(g)reactsatrate=5.0105molL1s1;i.e.onehalftherateofNO.NO2(g)formsatthesame
rateasNO,1.0104molL1s1.
18.33 (a)ThereactionissecondorderinNOandfirstorderinH2
(b) Rate = k [NO]2 [H 2 ]
(c)6.32mol2L2s1
(d)0.159molL1s1
18.35 (a) Rate = k [CO]2 [O 2 ]

(b)secondorderin[CO]andfirstorderin[O2]
(c)4.6mol2L2min1
18.37 (a)0.58
(b)1280s
18.39 495min1
18.43 105min
18.45 Theln[phenylacetate]dataisbestfitbyastraightline.Thehydrolysisofphenylacetateisafirst
reaction.
k=0.021s1
18.47 Rate=k[NO2]2
k=1.1Lmol1s1
18.49 (a)23min
(b)77min
18.51 36s
18.53 84.9kJmol1
18.55
H--H--F
H2(g) + F(g)
Ea = 8 kJ mol1
H = 133 kJ mol1
HF(g) + H(g)
18.57 (a)Rate=k[Cl][ICl]
(b)Rate=k[O][O3]
(c)Rate=k[NO2]2
18.59 (a)Step2
(b)Rate=k2[O3][O]
18.61 (a)
Step 1 Slow H 2 O 2 aq + I aq
H 2 O l + OI aq
Step 2 Fast H + aq + OI aq
HOI aq
Step 3 Fast HOI aq + H + aq + I aq
I 2 aq + H 2 O l
H 2 O 2 aq + 2 I aq + 2 H + aq
2 H 2 O l + I 2 aq
(b)Thefirsttwostepsarebimolecular,whilethelastisternary.
(c)Rate=k2[H2O2][I]
18.63 (a)NO2(g)andCO(g)arereactants.
NO3(g)isanintermediate.
CO2(g)andNO(g)areproducts.

(b)
slow
fast
Ea1 Ea2
NO + NO3 + CO
2 NO2 + CO
1 NO2 appears as both reactant and

product - it cancels from the net reaction
NO2 + NO + CO2

18.65 Noanswerprovided.Theywillbederivedfromexplorationofthisactivity.
18.67 (a)False
Whiletheobservedratelawisconsistentwithasinglestepprocess,theremaybeothermulti
stepmechanismsalsoconsistentwiththeobservedratelaw.
(b)True
(c)False
Increasingtemperaturemeansmorefrequentandmoreenergeticcollisions(thataremore
frequentlysuccessful)i.e.therateincreaseswithtemperature.

(d) False
Theactivationenergyisfixedbythereaction.Itdoesnotvarywithtemperature.
(e)False
Theratewillincreasefourfoldifbothconcentrationsaredoubled.
(f)True
18.69 (a)True
(b)True
(c)False
Therategenerallyvarieswithtimee.g.infirstandsecondorderreactions.Onlyforzeroorder
reactionsdoestherateremainconstant.Zeroorderreactionsarisewhenthereisalimited
amountofacatalystandthereactantsarepresentinabundance.Inanycase,reactionsareonly
zeroorderforatime.Eventually,reactantsdepletesufficientlythattheamountofcatalystisno
longerratelimiting,andthereactionisnolongerzeroorder.
(d)False
Itispossiblethatthereactionproceedsviaasingleternaryprocess.Ternaryprocessesare
infrequent,buttheycanplayimportantroles.
Chapter19
19.2
(a)
(b)
(c)
(d)
19.4 (a)CH3CH=CH2
Nocistransisomers.

(b)(CH3)2C=CHCH3
Nocistransisomers.

(c)
(d)

(e)
(f)
19.6 (a)Br
(b)Br
(c)CH2CH3
(d)OH
(e)CH2OH
(f)CH=O
19.7 (a)
Cl
O
H3C CH3
H
(b)
O O
CH3
H3C
O
H CH3
19.8 ThisistheZisomer.
19.9 Thetwodownfieldlines,atabout139and113ppm,arethetwoalkenecarbonpeaks.
19.10
H H
H H
H H
H H
H H
19.11 (a)substitution
(b)elimination
(c)addition
19.13
(a) H (b) R
O O
R
R
(c) R (d)
R MgBr
O
19.14 (a)NH4+
Ammoniumisanelectrophile.Itisattractedtoconcentrationsofnegativecharge,andwill
donateaprotontoprotonacceptorsi.e.nucleophiles.
(b)CN
Cyanideisanucleophile.Itisattractedtoconcentrationsofpositivecharge(i.e.regionsof
depletedelectrondensity)suchasacidicprotonsandcarbonylcarbons.
(c)Br
Bromideisanucleophile.Itisattractedtoconcentrationsofpositivecharge(i.e.regionsof
depletedelectrondensity).

(d)CH3NH2
TheamineNatomisanucleophile.Itisattractedtoconcentrationsofpositivecharge(i.e.
regionsofdepletedelectrondensity).

(e)HC CH
Acetyleneisanucleophile.Ithasarelativelylooselyheldcloudofelectronswhich
electrophilesareattractedtoandviceversa.
19.15 BF3iselectrondeficientatthelowelectronegativityboronatom.IntheLewisstructureofBF3,
theboronatomhasonly6electronsinitsvalenceshell.BF3iselectrophilicattheboroncenter.
19.16
19.17 (a)CH3CH2CHClCH3
(b)(CH3)2CICH2CH2CH3
(c)chlorocyclohexane
Cl

19.18 (a)BromocyclopentanecanbepreparedfromcyclopenteneandHBr.
(b)3Bromohexanecanbepreparedfromhex2eneandHBr.
(c)1Iodo1isopropylcyclohexanecanbepreparedfromdimethylmethylenecyclohexane,
CH3
CH3
(d)
CH2 HBr CH3
H Br
19.19
(a)
(b)
19.20
19.21 (a)Additionofwaterto3methylhex3enegives3methylhexan3ol,

(b)Additionofwaterto1methylcyclopentenegives1methylcyclopentanol

(c)Additionofwaterto2,5dimethylhept2enegives2,5dimethylheptan2ol
19.22 (a)Butan2olcanbemadebyadditionofwatertobut1eneorbut2ene.
(b)3Methylpentan3olcanbemadebyadditionofwaterto3methylpent2eneor2
ethylbut1ene.
(c)1,2Dimethylcyclohexanolcanbemadebyadditionofwaterto1,2dimethylcyclohexeneor
1,6dimethylcyclohexene.
19.23 Ifthesecondbromineaddedtotheothercarbontheoneontheleft,thentheenantiomeric
productwouldbeformed.Bysymmetry,thispathwayisjustaslikelyastheoneshowninFigure
19.30ofthetext.Thetwoenantiomericproductswouldbeformedinequalamounts.
19.24
Thetwoenantiomersof1,2dibromo1,2dimethylcyclohexaneareexpecteduponbromination
of1,2dimethylcyclohexene.
19.25 SeeExercise19.24above
19.26 (a)Catalytichydrogenationof(CH3)2C=CHCH2CH3produces(CH3)2CHCH2CH2CH3.
(b)Catalytichydrogenationof3,3dimethylcyclopentenegives3,3dimethylcyclopentane.

19.27 (a)

(b)
19.28(a)(CH3)2C=O+CO2istheproductupontreating(CH3)2C=CH2withacidicKMnO4.
(b)2equivCH3CH2CO2HistheproductupontreatingoneequivalentofCH3CH2CH=CHCH2CH3with
acidicKMnO4.
19.29 (a)6methylhept3yne
(b)3,3dimethylbut1yne
(c)5methylhex2yne
(d)hept2en5yne
19.30 Thepeakjustabove3300cm1lookslikeanalkyneCHstretch,whilethepeakjustabove2100
cm1lookslikeanasymmetricalkyneCCstretch.TherealsoappeartobealkylCHstretch
peaksjustbelow3000cm1.ThecompoundlikelyhasalkylHsinadditiontothealkynylH.
19.31 Thetwodownfieldpeaks,~68and~85ppm,arecharacteristicofanalkyne.Alkene13Cchemical
shiftsoccurfurtherdownfield.
19.32 TheunknowncompoundiseitherCH3CH2CH2CH2CCHor(CH3CH2)CH3CHCCH.
19.33
H3C
H3C
H2SO4+ HgSO4
CH3
CH3
OH
H3C
CH3
19.34 (a)Tomake2pentanoneyoucouldhydrate1pentyne,CH3CH2CH2CCH.
(b)Tomake3hexanoneyoucouldhydrate2hexyne,CH3CH2CH2CCCH3.
19.35 (a)Tomake5methylhex1yne,(CH3)2CHCH2CH2CCHyoucouldstartwith
ethyne(acetylene),HCCH,treatitwithNaNH2tomakesodiumacetylide
addto3methylbutylbromide,(CH3)2CHCH2CH2Br
(b)Tomake2hexyne,CH3CH2CH2CCCH3youcouldstartwith
propyne,HCCCH3,treatitwithNaNH2tomakesodiumpropynylide
addtopropylbromide,CH3CH2CH2Br
Alternatively,youcouldtreat
pentyne,CH3CH2CH2CCH,withNaNH2tomakesodiumpentynylide
addtomethylbromide,CH3Br
(c)Tomake4methylpent2yne,(CH3)2CHCCCH3youcouldstartwith
propyne,HCCCH3,treatitwithNaNH2tomakesodiumpropynylide
addtoisopropylbromide,(CH3)2CHBr
Alternatively,youcouldtreat
3methylbut1yne,(CH3)2CHCCH,withNaNH2tomakesodium3methylbutynylide
addtomethylbromide,CH3Br
REVIEWQUESTIONS
19.37 -carotene is added to commercial food for ornamental fish to make the colour of the fish
(specifically the red-orange component of the colour) brighter and richer. -carotene is a red-
orange pigment, used in nature along with other pigments to make colours.
19.39 (a)Alkylandnitrile(orcyano)groupsarepresentinpropanenitrile(a.k.a.cyanoethane).
(b)Alkylandethergroupsarepresentincyclopentylmethylether.
(c)Alkyl,ketoneandestergroupsarepresentinmethyl3ketobutanoate(a.k.a.methyl
ethanoylethanoateormethylacetylacetate).
(d)Alkeneandketonegroupsarepresentin1,4benzoquinone.
(e)Alkeneandamidegroupsarepresentin2butenamide.
(f) Phenylandcarboxylgroupsarepresentinbenzoicacid.
19.41 Thedoublebondswithintheringsattheendsofcarotenearebetweencarbon1(thecarbon
connectedtothechain)andcarbon2,whereastheringdoublebondsincaroteneare
betweencarbon2andcarbon3.Otherwise,thetwomoleculesareidentical.
TheHOMOLUMOgapforcaroteneislargerthanthatforlycopene.Whereascarotene
absorbsbluelightandappearsorange,lycopeneabsorbsgreenlight(lowerfrequencyandlower
energythanbluelight)andappearsred.
19.43
(a)
H3C CH3
H H
(b)
H3C CH3
H3C CH 3

19.45 (a)4methylpent1ene
(b)3heptene
(c)1,5heptadiene
(d)2methylhex3ene
19.47 (a+b+c)Allthreeofthesemoleculeshavecistransisomers.
19.49 Methylcarboxylate,COOCH3,hashigherpriorotythancarboxyl,COOH.
19.51 (a)Z
(b)Z
19.53 (a)substitution
(b)elimination
(c)addition
(d)substitution
19.55
tr a n s itio n s ta t e
s lo w
E a2
tr a n s itio n s ta t e
fa s t
E a1
in te r m e d ia te
r e a c ta n ts
p r o d u c ts

19.57 CH3CH2CH=CHCH3 + HCl CH3CH2CHClCH2CH3 or CH3CH2CH2CHClCH3

Cl H
-
H CH3 Cl
H H Cl H
+ H
H3C H C CH3 CH3
H3C H H3C H
H Cl
-
H CH3 Cl
H H Cl
CH3
+ H
H3C H H C CH3
H3C H H3C H
19.59
H H
+ H
H3C C
H3C +
CH3 C H
H
Thecarbocationontheleftisthemorestable.
19.61
(a)
CH2 H2 & Pd CH3
H Br
(b) H
H H
Br2
H
H Br
H Br
(c) H
H H
HBr
H
H H
H OH
(d) H OH
H
KMnO4 NaOH H2O
H
H H

19.63
Oxidativecleavageof

yieldsasingleproduct,
O O
OH OH
becauseofsymmetry.
Oxidativecleavageof

givestwodistinctproducts,
O O O
O
+ OH
HO OH
HO
19.65
CH3 CH3 CH3 CH3
O O O O O O O O
CH3 CH3 CH3 CH3
n

19.67(a)6
(b)6
(c)3
19.69
CH Br
1 equiv HBr
H3C CH2
H3C
CH Cl
1 equiv Cl2
H3C
H3C Cl
H
CH
H2 + Lindlar catalyst
H
H3C
H3C H
19.71
NaNH2
- +
H3C CH H3C C Na
H H
CH3Br H2 + Lindlar catalyst
H3C CH3
H3C CH3
19.73 (a)

H3C H3C CH3 H3C CH3
CH2 CH3 H3C CH3

1-hexene, 2-methylpent-2-ene 2,3-dimethylbut-2-ene
(b)
H3C H
H3C CH3

(c)
H3C CH3
19.75
- H3C OH
H3C O
H H
H H
H H
Br H H -
H Br
AnOHbondisformed,aCHbondisbroken,aCCbondisformed(tomakeadoublebond)
andaCBrbondisbroken.
19.77
H H H H
+
H C H
H H
+
C
H H H H
H H
H H H H
+
H C H
H H
+
C
H H H H
H H
Becauseofthesethreeadditionalresonancestructures,the+chargeofthecarbocationis
spreadoutdelocalizedoverfourcarbonatoms.Thismakesthebenzylcarbocationespecially
stableforacarbocation.
19.79
O O
O H -
H
S O
O S
H3C H O
O O
CH2 H3C
+
H3C C CH3
H3C
H
O CH3 H
+ CH3
H3C O
+
C CH3
H3C CH3
H3C
CH3
H
O H
O O
S O
- S
O O H
O
O
H
+ CH3
O CH3
O
CH3
H3C CH3
CH3 H3C
CH3
19.81
A B
3 H2 Pd catalyst CH3
CH
KMnO4 - suppose acidic conditions
O O OH
+ + CO2
HO O
NaNH2 - followed by iodomethane
CH3
C

19.83 TreatacetylenewithNaNH2togetacetylide,HCC.Addto1bromotridecane,CH3(CH2)12Brto
getCH3(CH2)12CCH.TreatwithNaNH2togetpentadecynylide.Addto1bromooctane,
CH3(CH2)7BrtogetCH3(CH2)12CC(CH2)7CH3.
19.85
much slower
fast
H H
+
C
slow
Br H
H3C
fast
Ea1 Ea2
H H
+ H
C
H
H3C
H H
H
H3C
H H
H
H
H Br
H3C
H H
H
Br H
H3C


19.87
H
H
+ O
O H
H H
H H H
+
C H H
H
H H H
H H
Chapter20
20.1 236kJ/mol
20.2 (a)Cyclobutadieneismonocyclic,planarandfullyconjugated.Cyclobutadieneisantiaromatic.
(b)Cyclohepta1,3,5trieneismonocyclicandplanar,butnotfullyconjugated.
(c)Cyclopenta1,3dieneismonocyclicandplanar,butnotfullyconjugated.
(d)Cyclooctatetraeneismonocyclic,planarandfullyconjugated.Cyclobutadieneisanti
aromatic.
20.3 (a)Benzenehasjustone13CNMRabsorptionpeak.
(b)Chlorobenzenehasfour13CNMRabsorptionpeaks.
Cl
(c)Naphthalenehasthree13CNMRabsorptionpeaks.

(d)1,3dichlorobenzenehasfour13CNMRabsorptionpeaks.

Cl Cl
20.4
CH3

(a)ThereisanarylCHstretchingbandwiththreepeaksat3100,3070and3030cm1.The
alkylCHstretchingbandwithprincipalpeaksat2925and2850cm1.
(b)TheoutofplaneCHbendingvibrationsgiverisetotwopeaksat740and700cm1.
(c)TheinplaneCHbendingvibrationsproducepeaksat1090and1030cm1.ThearylCC
stretchesproduceabandwithprincipalpeaksat1610,1510and1470cm1.
20.5 Furanhas6electronsinitssystem.Itisaromatic,with1HNMRshiftsareat6.4and7.4ppm.
20.6 (a)Aromatic
(b)Antiaromatic
(c)Aromatic
20.8 (a)meta
(b)para
(c)ortho
20.9 (a)1bromo3chlorobenzene,ormbromochlorobenzene
(b)2methylpropylbenzene,or2methyl1phenylpropane
(c)1amino4bromobenzene,orpaminobromobenzeneorpbromoaniline
20.10
Br
CH3 Br CH3 CH3
Br
0bromotoluene mbromotoluene pbromotoluene
20.11 D2SO4sulfonatesthebenzeneringreversibly.Onsulfonation,anH+islosttothesolvent
(D2SO4).Ondesulfonation,D+addstothering.Sincethesolventfaroutnumbersthebenzene,
theHsarelostinaseaofDs.ThebenzeneendsupwithallHsreplacedbyDs.
20.12 (a)Nitrobenzene<toluene<phenol(hydroxybenzene)
(b)Benzoicacid<chlorobenzene<benzene<phenol
(c)Benzaldehyde<bromobenzene<benzene<aniline(aminobenzene)
20.13 Theproductsofelectrophilicbrominationofnitrobenzene,benzoicacid,benzaldehyde,
bromobenzene,chlorobenzene,benzene,toluene,phenolandaniline,respectively,are

20.14
(a) - (b) Br
O + O
N
O
O S
OH
S O
OH
O
(c) CH3 O CH3 (d) O OH

OH
S
O
+
O
O S O S
OH
OH O
(e) N N
O
OH
S
O +
O S O
OH

20.15 OxidizingmchloroethylbenzenewithKMnO4producesmchlorobenzoicacid,
O OH
Cl
OxidizingtetralinwithKMnO4produces1,2bezenedicarboxylicacida.k.a.phthalicacid,

O OH
O
OH
20.16 (a)BrominatetolueneusingBr2+FeBr3
Separatetheorthoproduct,2bromotoluene
Nitrateusingnitricandsulfuricacidstoobtainthe2bromo4nitroand2bromo6nitro
products:

-
CH3 O CH3
+
Br N Br
O
+
+
- N
O O

Separatethedesired2bromo4nitroproducte.g.usingdistillationorchromatography,or
maybeevenamolecularsieve.

(b)Nitratebenzenewith3equivalentsofNO2.

(c)Firstmakeanilinefrombenzene.
Nitratebenzeneusingnitricandsulfuricacidswith1equivalentofNO2
Reducethenitrobenzeneproductusinghydrogentogetaniline
Brominatetheanilinewith3equivalentsofbrominetogetthefullybrominatedproduct,
2,4,6tribromoaniline
REVIEWQUESTIONS
20.17 ManyskilledHuguenotsilkweaversanddyersemigratedfromFrancetoGermanyfollowingthe
revocationoftheEdictofNantes.Coaltarwasavailable,atthetime,asasourceofstarting
materials.TheRhineRiverprovidedthewaterneededtodothechemistry.
20.19 Nitratesareneededtomaketrinitrotoluene(TNT),animportantexplosive,fromtoluene.They
arealsousedtomakeotherexplosives(e.g.nitroglycerin)andasfertilizers.Duringtheleadup
toWorldWarII,theBritishcontrolledtheworldssupplyofnaturallyoccurringnitratesin
massiveguanodepositsinChile.TheGermansneededasyntheticsupplyofnitrates.Fritz
HaberandCarlBoschdevelopedaneffectivemeansofproducingammoniafromnitrogen(from
theair)andhydrogen.Theammoniacouldthenbeoxidizedtoproducethedesirednitrate.
20.21 Theplanararrangementof1,3,5,7tetramethylcyclooctatraeneproducesanantiaromatic
electronconfiguration.Itisdestabilizedwithrespecttosimplyhavingfourlocalizeddouble
bonds,asitdoesinthetubconformation.Thetubconformation,therefore,providesthe
observedlowestenergyconformation.
20.23
20.25 TherearethreenonequivalentHsinanthacenethecentralverticalpair,andtwopairs
(relatedviareflectionthroughtheverticalaxis)ofverticalpairsofHs.Thechemicalshiftsare
expectedtobeinthe6.5to8ppmrangetypicalofaromatics.
20.27 Phenanthrenehas14=43+2electrons.Althoughitisnotmonocyclic,itcertainlyqualifiesas
aromatic.Theouterringofatomsprovidestheprincipalpathoverwhich43+2electronsare
delocalizedinaccordwithHckelsrule.
20.29
9
10
Theshortestbondshavethehighestorderlookforthebondswhicharedoublemoreoften
thantheothers.TheshortestCCbondistheC9C10bond(labeledinthefirststructure).Itisa
4
doublebondin4ofthe5structures.Itsbondorderis1 5 .
20.31 C8H9Brhas4degreesofunsaturation,consistentwithasinglephenylring(aringand3double
bonds).Thecompoundisoorpbromoethylbenzene,
CH3 CH3
Br
or
Br
20.33 The1,3,5,7tetramethylcyclooctatetraenedianionshouldbeplanar,asHckelsruleissatisfied
andtheplanarstructureshouldhaveaspecialstability.
20.35

Indolehas10=42+2electrons.Itisaromatic.
20.37 1,3,5,7cyclononatetraeneisexpectedtobeunusuallyacidicbecauseofthestabilizationofthe
anion.ItcanbeconvertedtoasaltbytreatmentwithastrongbasesuchasNaNH2.Thesodium
saltofthearomaticcationwouldbeformed.
20.39

CH3
HO
CH3
2(3hydroxyphenyl)propaneorm(1methylethyl)phenola.k.a.misopropylphenol
HO O
OH

1,2benzenedicarboxlyicacida.k.aphthalicacid
20.41 (a)odinitrobenzene,mdinitrobenzeneandpdinitrobenzene
- - -
O + O O + O O + O
N O N N
+
N -
O
+ O
N
- +
O - N
O O

(b)1bromo2,3dimethylbenzene,1bromo2,4dimethylbenzene,1bromo2,5
dimethylbenzene,1bromo2,6dimethylbenzene,1bromo3,4dimethylbenzeneand1bromo
3,5dimethylbenzene
Br Br
Br Br
CH3 CH3 CH3 H3C CH3
CH3 H3C
CH3
Br Br
CH3 H3C CH3
CH3
20.43
Cl Cl Cl
-
Al Cl Cl Al
Cl Cl
H
H
H Cl
+
C
H H H
H
+ H
H C H H
+ H
H H C
H
H
Cl
Cl Cl Al Cl
-
Cl Al Cl
H Cl H
+ CH3 HCl
C CH3
H
20.47

(a)
O Br2 with FeBr3 O

CH3 O
CH3 CH3
+ HBr
Br Br
O CH3COCl with AlCl3 O

CH3 O
CH3 CH3
O + HCl
O
CH3 CH3

(b)
Theproductsofbrominationareobromomethoxybenzeneandpbromomethoxybenzene.The
productsofacylationareoacetylmethoxybenzeneandpacetylmethoxybenzene.

(b)

CH3 CH3
Br
Br2 with FeBr3
+ HBr
O O
CH3 CH3 O
CH3COCl with AlCl3 CH3

+ HCl
O O

Theproductofbrominationis4acyl2bromotoluene.Whilethemethylsubstituentiso,p
directing,theacylsubstituentismdirectingonlyoneproductisformed.Theproductof
acylationis2acetyl4acyltoluene.
20.49
ortho addition
O CH3 O CH3 O CH3
+ Br Br Br
C
H H +
H
+ C
C
H H
meta addition
O CH3 O CH3 O CH3
+ H H H
C + H
C
Br Br
+
Br
H C
H H
H
para addition
O CH3 O CH3 O CH3
+
C
+ +
C C
H H
Br H Br H Br H
Inthecaseoftheorthoandparaadditionintermediates,oneoftheresonancestructureshas
thepositivechargeonacarbonatombondedtotheelectronwithdrawingacetylgroup.This
resonancestructureisdisfavored,makingthecarbocationintermediateslessstableinthecase
oforthoandparaaddition.Metaadditionisthefavoredpathway,bydefault.
20.51
O O
Br
Br
Thecarbonyliselectronwithdrawing.Itleadstothemetabromination.However,becauseof
therigidrelativeorientationofthetwophenylrings,thiscorrespondstotwoproducts.
20.53
20.55 Diphenyletheranddiethylphenylaminereactfasterthanbenzene,whilechlorobenzeneand
benzoicacidreactslower.
20.57 (a)oBromotoluenecanbesynthesizedfrombenzeneviaaFriedelCraftsmethylation(i.e.treat
with1equivalentCH3ClandAlCl3)tomaketoluene,followedbybromination(treattoluenewith
1equivalentBr2andFeBr3)andseparationoftheorthoandparaproducts.Thisseparation
mightbeachievedbydistillation.
(b)2Bromo1,4dimethylbenzeneisobtainedifweapplyanotherFriedelCraftsmethylationto
theproduct,obromotoluene,frompart(a).Becausethefirstmethylisanactivatingorthopara
directing,whereasbromineisadeactivatingorthoparadirecting,the1,4dimethyland16
dimethylproductsareobtained.Afinalseparationstepisrequiredtoobtainthedesired
compound.
20.59 MethylatebenzeneusingCH3ClandAlCl3.NitrateusingHNO3andH2SO4togetoandp
nitrobenzene.Separatetheparaproduct.OxidizeitusingKMnO4toobtainthedesiredp
nitrobenzoicacid.
20.61 (a)MethylatebenzeneusingCH3ClandAlCl3.
NitratethetolueneproductusingHNO3andH2SO4.Separatetheorthoproduct.
OxidizeusingKMnO4toconvertthemethylgrouptocarboxylicacid.

(b)MethylatebenzeneusingtwoequivalentsofCH3ClandAlCl3.Separatetheo
dimethylbenzenefromtheparaproduct.
20.63 Trimethylammoniumisadeactivatingsubstituent.Unliketheaminesubstituent,ammonium
hasnolonepairofelectronstoparticipateinthesystem,andprovideanadditionalresonance
structurestabilizingthecarbocationintermediatesassociatedwithorthoandparasubstitution.
Nitrogen,beingmoreelectronegativethancarbon,isotherwisesomewhatelectron
withdrawing.Moreimportantly,thepositivechargeontheammoniumsubstituentdestabilizes
thecarbocationintermediate.
20.65
(a)
CH3 O CH3
HO
Cl S Cl
+ O
O S O
OH
(b)
OH O OH
HO
S
+ O
Br Br
O S O
OH
(c)
O CH3
HO
S
O
+
- N
O O
20.67
Cl
AlCl3
O

20.69
Br Br
O
+ +
N -
O
+
- N
O O
20.71 AdditionofHBrto1phenylpropenewithBraddingtothe2positiononpropyl
H Br -
H Br
H H H
H
CH3 CH3 Br
+
C
CH3
H H H

AdditionofHBrto1phenylpropenewithBraddingtothe1positiononpropyl
-
Br
Br H
H H
H Br
+ H
CH3 C H
CH3
CH3
H H H
H H H H
H + H
C H
CH3 CH3
+ CH3
C H H +
H C H
H
Theextraresonancestructuresassociatedwiththecarbocationintermediate,inthecaseof
additionofBrtothe1position,stabilizetheintermediate,enhancingtherateoftheassociated
pathway,makingthe1bromopropylproducttheexclusiveproduct.
20.73 (a)Inthefirststep,tolueneischlorinatedatthemetaposition.
(b)Inthesecondstep,tertbutylisoxidizedtomakecarboxylicacid.
20.75
-
Br
Br H
H H
H Br
+ H H
H C
H H
- - -
O + H O + H O H
N +
N N
O O O
H H H
H
H H H
+
C
H H H
- + - +
O C H -
+ O + H O + C H
N N N H
O O O

Thecarbocationintermediateisdestabilizedbytheelectronwithdrawingnitrogroup.The
resonancestructurewiththe+chargenexttotheformally+chargednitroNatomisespecially
destabilized.

-
Br
Br H
H H H Br
+ H H
H C
H H
H3C H H3C H H
O O H3C O
H
H H H
H
+ H H
C
H
+ H H
H3C C H +
O H3C H H3C C H
O O H
H
H
H
H3C + H
O
Thecarbocationintermediateisstabilizedbyanextraresonancestructure.AdditionofHBrto
themethoxycompoundismuchfasterthanadditiontothenitrocompound.
20.77
Cl
-
Cl Al Cl
Cl
Al Cl Cl
CH3
Cl
Cl
+ CH3
O H3C O
H3C
+
C
H
CH3 CH3
H O
CH3 H3C
CH3
+
C
H CH3
H H O
+ CH3
H3C O
Cl H3C +
C
-
Al Cl
Cl
Cl
H O
H3C
CH3
CH3
HCl
H3C O
Cl
Al Cl
Cl
Theparaisthepredominantproduct
Chapter21
21.1 (a)2bromobutane
(b)3chloro2methylpentane
(c)1choro3methylbutane
(d)1,3dichloro3methylbutane
(e)1bromo4chlorobutane
(f)4bromo1chloropentane
21.3
(a) CH3 (b) CH3
Cl H3C
H3C H C CH3 H3C Cl

3 Cl
(c) CH3 (d) CH3

Br
H3C CH3 Cl
Br
H3C CH3

21.5
(a)
HO HCl Cl
H3C CH3 H3C CH3
H3C H3C

(b)
H3C
H3C
Br CH3
PBr3
HO CH3
H3C
H3C
(c)
CH3 CH3
PBr3
CH3 CH3
HO Br

(d)
HO Cl
CH3 CH3
SOCl2
CH3 CH3
H3C CH3 H3C CH3

21.6
(a)
CH3 CH3
PBr3
CH3 CH3
H3C OH H3C Br

(b)
OH Cl
CH3 HCl
CH3

(c)
H3C H3C
OH SOCl2 Cl
H3C H3C

21.8
(a)
H H3C H
H3C
Br LiI
CH3
I
CH3
(b)
Cl H HS H
CH3 HS CH3
CH3 CH3

(c)
NaCN
Br
N
21.9
(a)
H3C H3C
NaOH
Br OH

(b)
H3C H3C
NaN3
+ -
H3C Br H3C N N N

21.10 (a)Theratetriples.
(b)Therateincreasesbyafactorof4.
21.11
H3C O
Br H H O
H3C NaCH3COO H3C
CH3 CH3
(S)-2-bromohexane
(R)-2-hexyl acetate

21.12
H CH3 H CH3
-
H3C H HS H3C H
Br CH3
CH3 SH
(R)-2-bromo-4-methylpentane 4-methylpentane-(S)-2-thiol

21.14 (a)CN(cyanideion)reactsfasterwithCH3CH2CH2Br
(b)ReactionofIwith(CH3)2CHCH2Clisfaster.
21.15 CH3I>CH3Br>CH3F
21.16 (a)Noeffect
(b)HalvingtheHBrconcentrationhasnoeffect.However,doublingthetertbutylalcohol
concentrationdoublestherateofreaction.
21.17
H3C
CH3 (S)-3-bromo-3-methyloctane
H3C
HBr H3C Br
CH3
H3C OH
+
H3C
(S)-3-methyloctan-3-ol CH3 (R)-3-bromo-3-methyloctane
Br CH3
21.18
HO CH3
CH3
Br CH3 (S)-2-phenylbutan-2-ol
CH3 H2O
+
H3C OH
CH3
(S)-2-bromo-2-phenylbutane
(R)-2-phenylbutan-2-ol
21.19
(a)
H CH3 CH3
elimination
H3C CH3 H3C CH3
Br H
H
(b)
CH3 CH3
elimination
H3C H3C
CH3 CH3
CH3 Cl CH3 CH3 CH3

(c)
H
H H
elimination
Br
CH3
CH3
21.20
(a)
CH3 CH3
elimination
Br
H3C H3C CH2
CH3 H3C

(b)
CH3
CH3
elimination
Cl
CH3
CH3
21.21 Rateoftheeliminationreactiontriples.
21.22 (a)SN2
(b)E2
(c)SN1
21.23
Br
Br
Mg
Mg + ether
CH3
H3C CH3
H3C
Grignard reagent
Br
Mg
D2O D
CH3
H3C CH3
H3C
21.24
CH3 CH3
PBr3
OH Br
H3C H3C
CH3 CH3
Mg + ether
Br Mg
H3C H3C Br
CH3 H2O CH3

Mg
H3C Br H3C CH3

REVIEWQUESTIONS
21.25 Methylbromideismanufacturedfrombromidesaltsrecoveredfromseawaterandmethane
theprincipalcomponentofnaturalgas.Itisalsonaturallyoccurringintheoceans,plantsand
soil.Methylbromidehasbeenusedasapesticide,orfumigant,intheagriculturalindustry.
Becauseitisapotentozonedepletingsubstance,itsusehasbeenphasedout.Alargenumber
ofalternativepesticidesareinuse,orarebeingdeveloped.Forexample,phosphineisusedto
fumigatefoodstorage,transportationandprocessingfacilities.Sulfurylfluorideand1,3
dichloropropenearetwootheralternativefumigantsusedtotreatfoodsandforestseedlings.
21.27
F H Cl
F F Br
2-bromo-2-chloro-1,1,1-trifluoroethane

Halothanehasalkylandalkylfluoride,chlorideandbromidefunctionality.
21.29 Morethan3800differentorganohalogencompoundsproducednaturallybylivingorganismsor
byforestfires,volcanoesorothergeothermalprocesses.Thesinglelargestbiogenicsourceof
thesecompoundsistheoceans.
21.31 (a)SubstratestructureplaysanimportantroleindeterminingwhetheranSN1orSN2
substitutionreactionwilloccur.SN2reactionsareinhibitedbybulkysubstituentscompletely
sointhecaseofattackatatertiarycarbonatom.Thisisbecauseofthesterichindrancecaused
bythesubstituents.TheSN2pathwayismostfavouredinthecaseofprimarycarbons.SN1
reactionsarefavouredbysubstituents(unlesstheyareelectronwithdrawing)becausethey
stabilizethecarbocationintermediateofthismechanism.
(b)AbetterleavinggroupincreasestherateofbothSN1andSN2reactions.
21.33 (a)Br
(b)Cl
(c)I
21.35

H3C
H3C O
H3C
H CH3COO O
Br H
CH3 3 CH

21.37 (a)Therateincreasesbythefactor3/2.
(b)Therateincreasesbythefactor3/2.
(c)Therateincreasesbythefactor6.
(d)Therateincreases
(e)Theconcentrationofallspeciesishalved.Therateofreactiondecreases4fold.
21.39
(a)
Cl Cl H3C Cl
H3C > H3C >
CH3 H3C CH3
(b)
CH3 CH3
H3C Br > Br > CH3
H3C H3C
Br
21.41 (a)ThisisanSN2reactionatatertiarycarbonatom.Itisstronglyhinderedandwouldsimplybe
tooslow.
(b)ThisisanSN2reactionataprimarycarbonthisisgood.Theonlytroubleisthathydroxide
isabadleavinggroup.
(c)Thisisaneliminationreactionatatertiarycarbonthisisgood.However,becauseHBris
theacidusedtodehydratethealcohol,thealkeneproductissubjecttoadditionofHBr.
21.43

CH3
CH3
H3C H2C CH3
CH3 NaOH
CH3
Cl
H3C CH3
CH3
H3C CH3
21.45 (a)Theratestaysthesame.
(b)Therateincreasesbyafactorof9.
21.47 (a)E2
(b)SN1
21.49
Cl
NaOH CH3
CH3 H2C
H3C
CH3
H3C H3C CH3

21.51 Theoceanshavehighconcentrationsofhalideions.Theoceansarealsothelikelyoriginofall
life,andarestillnowbrimmingwithlife.Itisnaturalthatorganohalogencompoundswouldbe
formedthere,andformedtherefirst.Moreoverandthisislikelywhytheoceanshavebeenso
crucialtolifetheoceansprovideasolventsupportingvastlymorechemistrythanispossibleof
thelandsurface.
21.53
(a) HCl
Cl
(b) OH
dilute H2SO4(aq)
(c) HCl
Mg & ether
Cl Mg
Cl
(d)
H2 & Pd catalyst
21.55 (a)1iodopropane
(b)butanenitrile
(c)1propanol
(d)UponreactionwithMginether,wegetpropylmagnesiumbromide.Subsequentreaction
withwaterproducespropane.
(e)methylpropylether
21.57
CH3 Br H3C Br
H3C Br > Br H3C >
> H3C
H3C CH3 CH3
1-bromobutane 2-bromobutane 2-bromo-2-methylpropane

1-bromo-2-methylpropane

21.59
-
H3C OH NaNH2 H3C O
PBr3 H3C Br
H3C OH
-
H3C O CH3
H3C O
+ H3C Br

21.61 E2eliminationreactionsyieldnonZaitsevproductsbecauseeliminationisfavouredattheleast
hinderedprotonvicinaltobromine(onthecarbonnexttothebromocarbon).E2elimination
followsaconcertedmechanismrequiringabasetoabstracttheprotonasthebromideleaves.
21.63 ReactionofHBrwith(R)3methylhexan3olyields()3bromo3methylhexane,becauseitis
anSN1substitution.Oncethecarbocationisformed,thestereochemistryofthestarting
materialislost.The(R)and(S)productsareequallylikely.
21.65
A Br B
NaOH
Br
C O
HO O
KMnO4 & acid OH
+
O OH
H2 & Pd
Chapter22
22.2 (a)tertiaryalcohol.
(b)containsprimaryandsecondaryalcoholfunctionalgroups.
(c)primaryalcohol.
(d)secondaryalcohol.
(e)phenol
(f)phenol
22.3
(a) OH (b) OH
CH3
H3C
H3C OH
CH3
(c) (d) OH
H3C OH
H3C

(e) OH (f) -
O
O OH
Br + +
N N -
O O

+
- N
O O
22.4 (a)di(2propyl)ethera.k.a.diisopropylether
(b)cyclopentylpropylether
(c)4bromophenylmethylether
(d)ethyl2methyl1propylether
22.5 OHstretch:3320cm1(strong,broad)
aromaticCHstretches:3090,3070and3010cm1(sharppeaks).
alkylCHstretches:2950and2890cm1(broad).
COstretches:1020cm1(strong,somewhatbroad).
CCstretchesofthebenzenering:1500to1370cm1(threesharpones)
benzeneCHinplane:peaksat1080and1040cm1
benzeneCHoutofplanebends:730and700cm1
22.6 TheIRspectrumoftheproductshouldnotshowthestrong,broadalcoholOHpeakaround
3300cm1,orthestrongCOpeaknear1000cm1.Instead,itshouldshowastrongC=O
stretchingpeaknear1750cm1.
22.7
O OH
NaBH4
O O
H3C CH3 H3C CH3
O O
O OH
LiAlH4
O OH
H3C CH3 H3C
22.8
OH - +
O Na
NaNH2
-
O O
H
H CH3
H3C
I
Wecannotmakecyclohexylethyletherbyfirstformingsodiumethoxide,thenreactingitwith
cyclohexyliodide.
22.9 bromoethane>chloroethane>2bromopropane>2chloro2methylpropane
22.10
(a)
CH3
H CH3
H2SO4
H3C CH3
H3C CH3
HO CH3
H3C
(b)
CH3
HO CH3
H2SO4
H3C CH3 H3C CH3
H H H

22.11
(a)
HO CH3 O CH3
CrO3
(b)
CH3 CH3
H3C NaOCl H3C
H
H H
O
OH
(c)
OH CrO3 O
22.12
(a) OH O
CrO3
(b)
H CrO3 O
OH
H3C
H3C OH
H
(c)
CrO3
H3C CH3 CH3
H3C
HO H O

22.13 OxidationofthealcoholsinExercise22.12withpyridiniumchlorochromate(PCC)givesthesame
productsinparts(a)and(b),andthealdehydeinpart(b).
22.14
OH
O S O OH
SO3 + H2SO4 NaOH high T
OH OH OH
CH3Cl + AlCl3 CH3
CH3
22.15
O O
-
- O
O
- HO
- H O - -
O O O O
+ +
N N
O O
H3C
Br
CH3
H
H H
- -
O O
+
N O H
O -
O
+
N
O
22.16
(a)
HI
H3C O CH3 H3C I H3C OH
+
(b)
O CH3 HI
OH H3C I
+
(c)
H3C HI H3C
O CH3 OH
H3C H3C I
H3C +
CH3 CH3

22.17
+
H
H
+
O O
H H H H
H3C CH3 H3C CH3
H
+ HO H HO H
O
H H CH3 H CH3
H
+
H3C CH3 O H3C O
H3C
H
O H H
H H O
H H
22.18 (a)2butanthiol
(b)2,6,6trimethylheptan4thiol
(c)3cyclopentenethiol
22.19 (a)ethylmethylsulfide
(b)tertbutylethylsulfide
(c)omethylthiophenylmethylsulfide
22.20 Tomake2butene1thiolfrom2butene1ol:
Youcouldtreat2buten1olwithPBr3tomake1bromobut2ene.
1bromobut2eneisthentreatedwithNaSHtomake2butene1thiol.

Tomake2butene1thiolfrommethylbut2enoate:
Firstreducemethylbut2enoatewithLiAlH4togetmethanoland2butene1ol.
2butene1olcanthenbeprocessedasabove.
REVIEWQUESTIONS
22.21 Thehydroxylgroupsontheoutsideofcyclodextrinsmakesthemsolubleinwater,allowingthe
drugencapsulatedbythecyclodextrintobedeliveredthroughoutthebody.
22.23 Thearticledescribestheuseofcyclodextrinstoformaggregatesandgiverisetodispersed
systems(i.e.notsolutions)withmorecomplexstructuresfordisperseddrugdelivery.Such
dispersedstructureincludeemulsions,microandnanocapsulesandspheres,aswellas
liposomesandniosomes.
Sublingualliterallymeansunderthetongue,referringtotheadministrationofadrugthrough
dissolutionandabsorptionofatabletheldunderthetongue.Inthecontextofthiscasestudy,
sublingualmightbeusedasametaphormeaningundertheabilitytodetect(i.e.taste)bythe
tongue.

22.25 Sometypesofwoundsproduceunpleasantodours.Cyclodextrinshavebeenusedtotreatthis
problembyencapsulatingodourmolecules.Thisisinadditiontotheiruseinincreasing
bioavailabilityofantibioticstothewound.
22.27
(a) H3C CH3 (b) O OH
O
CH3
O
O CH3
H3C
(c) H3C OH (d) HO
H
H3C CH3 H
OH
CH3
(e) OH
O
CH3
CH2
22.29
OH H3C OH
H3C
CH3
1-pentanol 3-methyl-1-butanol
or 3-methylbutan-1-ol
CH3 CH3
H3C
H3C OH OH
H3C
2-methyl-1-butanol 2,2-dimethyl-1-propanol
or 2-methylbutan-1-ol or 2,2-dimethylpropan-1-ol
CH3
OH
H3C OH H3C
CH3
CH3
3-methyl-2-butanol
2-pentanol
CH3
OH H3C CH3
H3C
OH
CH3
2-methyl-2-butanol 3-pentanol

22.31
CH3 H3C CH3
H3C O O
CH3
1-butyl methyl ether 2-methylpropyl methyl ether
CH3 CH3
H3C
H3C CH3 CH3
O H3C O
2-butyl methyl ether tert-butyl methyl ether
CH3
H3C
O CH3 H3C O CH3
1-propyl ethyl ether isopropyl ethyl ether

22.35 (a)singlet
(b)doublet
(c)triplet
(d)doublet
(e)doublet
(f)singlet

22.37
H3C
H3C OH
H3C CH3
OH
22.39 (a)
H
H3C CH3
OH
(b)
H
HO CH3

22.41
H3C O H3C OH
CH3 LiAlH4 CH3
CH3 CH3
CH3
NaNH2 CH3CH2I H3C O

CH3
CH3
22.43
(a)
OCl in acetic acid
OH O
(b)
OH O
OCl in acetic acid
H3C CH3 H3C CH3
(c)
OH O
OCl in acetic acid
H3C CH3 H3C CH3
24.45
CH3 HI
H3C O H3C I
H3C OH +
H3C CH3 HI
O H3C
H3C I
CH3
OH
+
CH3
CH3
HI CH3
H3C CH3
H3C I
O
H3C +
OH
CH3 CH3
HI
H3C H3C I
O
CH3 H3C
+
HO HO OH
H3C
OH + H3C I
H3C HI
O CH3
and
H3C
H3C OH + I
CH3 CH3
HI
H3C O CH3 H3C OH
+ H3C I

22.47
H OH H O
(a)
H
PCC
(b)
Br CH3
O CH3 HBr OH +
CH3
CH3
(c) 1. LiAlH4
O OH
H2C
H2C 2. H2O + H3C OH
CH3 O CH3
CH3
(c)
O H H H OH
H HBr
CH3 CH3
H Br
H
22.49
(a)
PCC
H3C
H3C
OH O
H
H
H

(b)
H3C CrO3 H3C

OH O
H
HO
H
(c)
H3C H3C +
- Na
OH NaNH2 O
H H
H H

(d)
H3C PCl3 H3C

OH Cl
H H
H H
22.51
(a) KMnO4 & H2SO4
strongly oxidizing conditions

O
+ CO2
H OH HO
H
oxidation takes place at the benzyl

position - in addition to the alcohol
intermediates are stabilized by the
neighboring phenyl ring
H
(b) H H2SO4 H
H H2 & catalyst
H
H H
H OH H H H
H
(c) PBr3
H OH Br
H
(d)
CrO3
H OH HO
H O
(e)
PCC
OH H
H
O
H
22.53
(a)
H3C H3C
PBr3
OH Br
(b)
H3C H3C OH
CrO3
OH O
(c)
H3C H3C
NaNH2
- +
OH O Na
(d)
H3C
PCC H3C H
OH
O
22.55
(a)
OH O
CrO3
(b) H OH H O
H PCC
(c)
CrO3 CH3
CH3
H3C
H3C
H O
H HO
HO
22.57
(a)
OH O
Na2CrO7
OH O
(b)
H3C H3C
SH-
H3C H3C
Br SH

(c)
SH
Br2
S
S

22.59 Aceticacid,pentane2,4dioneandphenolwillallreact,essentiallytocompletion,withNaOH.
22.61 OnlyaceticacidwillreactwithNaHCO3.
22.63 TheOatomsofthecrownetherwillcoordinateacation,holdingitatoneendofthemolecule
(thecrown).TobindCs+,onecouldpreparealargercrownetherbyaddingOCH2CH2Ounits.
22.65
CH3
H OH
H H
22.67 Williamsonethersynthesiscannotbeusedtopreparediphenyletherbecauseoneofthetwo
reagentsinWilliamsonethersynthesisisahalidewhichundergoesSN2substitutionby(inthis
case)phenoxide.ThetroubleisthatphenylhalidesarenotamenabletoSN2substitution.
Nucleophilicattackwillnotoccuratanaromaticcarbonatom.
22.69
H HO
H3C H3C
OH H
H3C H3C
H3C H H3C H
trans cis

ThecisisomerwilloxidizefasterwithCrO3thehydroxylgroupisaxialinthisisomer.
22.71
-
O H H2O
Cl O -
Cl O
H
Cl Cl Cl Cl
Cl O
H O
- H -
O Cl O
H
-
Cl O H neutralize
Cl O
Cl Cl Cl

22.73 Dehydrationreaction
O F
O F
-
O F
F
H O F
F H
H3C H3C +
O O
R R
H3C H3C
CH3 CH3
H
H
+
O R
H3C O
R CH3
H3C
O F
H H3C CH2 O F
H
H
-
O F
F H O F
F
22.75
OH CH3 CH3
H2SO4 m-chloroperoxylbenzoic
CH3 acid
O
1. NaNH2 dilute HCl
2. CH3Br
OH
O CH3
CH3
CH3
OH

22.77
+
Li
H - +
O O Li
H H3C I
H
-
I
22.79
CH3
OH
Chapter23
23.2 (a)2methylpentan3one
(b)3phenylpropanal
(c)2,6octandione
(d)trans2methylcyclohexanecarbaldehyde
(e)1,5pentanedial
(f)cis2,5dimethylcyclohexanone
23.3
(a) CH3 H (b) CH3 H
H3C O H2C O
(c) Cl O
(d) H
H3C CH3
O

(e) O (f) O
H
CH3
O
CH3
23.4
(a) O
OH PCC
H3C
H3C H
H
(b) O
OH
H3C LiAlH4 PCC
OH H3C
H
(c)
CH3
H3C
O
KMnO4 & H3O+ LiAlH4 PCC
H3C
OH
23.5
(a) O
OH PCC
H3C
H3C CH3
CH3
(b) O
CH
H3C H2SO4 & HgSO4
H3C
CH3
CH3 O
(c) KMnO4 & H3O+
H3C
CH2
H3C
CH3
+ CO2

23.6
N
OH
H3C
CH3
23.7
OH
O
CH3

23.8
Cl H OH
Cl Cl OH
23.9
H
+
H O + H
O O
H
R1 R2 R1 R2
+ H H H
O H
O O +
O
H
R1 R2 H R1
R2
H H H H
H O +
H O +
O O O H O
H
R1 H R1 H
R2 R2

23.10

H3C
CH3
CH3
O O
HO O
(1equivalentofethanol) (2equivalentsof
ethanol)

23.11
O
23.12
protection step
HO OH
O O
acid catalyzed H
H CH3 CH3
O O O
O
O
OH
O LiAlH4 H
H
CH3
O H
O O
H
O
O
deprotection step
OH OH
H
acid catalyzed H
O H H
H H
O
O

23.13
(a) CH3 (b)
N CH3
HO O
(c) OH
23.14
CH3
O N
H3C H3C
+ H2N CH3
CH3 CH3 CH3 CH3

23.15
23.16
O O CH3
O H3C
+ CH3
CH3
HO H3C
H3C
23.17
(a)
Ag+(aq) & NH3(aq) OH
H
H3C H3C
O O
(b) H3C CH3 H3C CH3

Ag+(aq) & NH3(aq)
H3C H H3C OH
O O
O
(c) Ag+(aq) & NH3(aq)
no reaction
REVIEWQUESTIONS
23.19 Functionalitiesexhibitedbypheromonesincludealkylchainsandrings,alcohol,aldehyde,ester
especiallyacetate,alkene,ketone,andetherespeciallyepoxidegroups.
23.21 (a)alkyl&amide(specifically,acetamide)
(b)alkyl&ester(specifically,acetate)
(c)alkyl,aromatic,aldehyde&carboxylicacid
23.23
23.25
CH3 CH3
H3C
O H3C O O
H3C H3C O
H3C
H CH3 H H
H
pentanal 2-methylbutanal 2,2-dimethylpropanal
3-methylbutanal
O
O O
H3C
CH3 H3C CH3
H3C CH3
CH3
2-pentanone 3-pentanone
3-methylbutanone

23.27 (a)3methylcyclohex3enone
(b)2,3dihydroxypropanal
(c)5isopropyl2methylcyclohex2enone
(d)2methylpentan3one
(e)3hydroxybutanal
(f)1,4benzenedicarbaldehyde
23.29
23.31
O
H
CH3
H3C
CH3
23.33
(a)
O OH
NaBH4 , then H3O+
H H H
(b)
O O
Tollens: AgNO3(aq) & NH3(aq)
H OH

(c)
O N
NH2OH
OH
H H

(d)
H3C Mg
O H3O+ OH
Br
CH3
H H
(e)
O CH3OH, H+ catalyst OH
O
H H
CH3
23.35
(a)
O HO H
NaBH4 , then H3O+
H3C CH3 H3C CH3

nucleophile is H
H3C
(b)
Mg HO
O
CH3
Br
H3C CH3 H3C CH3
nucleophile is CH3CH2
(c)
CH3
O NH2CH3 N
H3C CH3 nucleophile is NH2CH3 H3C CH3
it adds to the electron deficient carbonyl carbon

water is eliminated in a subsequent step

(d)
O H3C OH
CH3SH
H3C S
H3C CH3
nucleophile is CH3SH CH3
attacking with an S
lone pair

23.37 Thereactionofphenylmagnesiumbromidewithbutan2oneproducesaracemicmixtureof2
phenylbutan2ol.
23.39
H3C CH3
(a) O
HO O
OH
CH3 H3C H3O+ & catalyst CH3
+ CH3
a hemiacetal
H3C CH3
H3C CH3
HO CH3
O
OH
H3O+ & catalyst O O
CH3 H3C
H3C
+ CH3
CH3
an acetal
(b)
O OH
H3C CH3 + H3O+ & catalyst HO O
H3C CH3
a hemiacetal
OH
HO O + H3O+ & catalyst O O

H3C CH3
H3C CH3
an acetal

23.41
O H H
-
O + H2O
R1 R2 N N
H H H H
R1 R2 R1
N N
H H
H H
H H
R1 N R1 N
+
N N
R2 H R2
-
O H H
O H
add another ketone with
the same steps
R1
R1 N
N R2
R2
23.43
(a)
O
CH3MgBr HO CH3
H3C CH3
H3C CH3
(b) O HO CH3
CH3MgBr
(c)
O
CH3MgBr HO CH3
H3C CH3
H3C CH3

23.45
(a) O
HO CH3
CH3MgBr
H3C H
H3C H
Mg
(b) Br
O
HO
H3C
CH3 H3C
CH3
(c) O HO
CH3
CH3CH2MgBr
(d)
Mg
Br
O HO
H H
23.47
(a)
H3C Mg CH3
O Br H
CH3 CH3
H H HO
H
(b)
O
H3C Mg OH
Br
H
CH3
Mg
O Br
HO
H3C H H3C H
(c)
Mg
O H3C Br OH
H3C H3C
H H
CH3
H3C
O HO
Mg CH3
H3C H Br
H3C H
+
H3C H3C
OH O
H3C H H3C H
this choice leads to an additional aldehyde product

which could then react with the Grignard reagent to
form yet additional products

23.49
(a)
OH O
O
add H2O
OH OH
(b)
O
O
add NH3
NH2
(c)
O
O
add CH3OH
O
H3C
(d)
O
O
add CH3CH2SH
CH3
23.51
(a)
1,4 addition product
O + OH
NaBH4 then H
separation is necessary
+ chromatography is the likely choice
distillation would be difficult on
account of the similarity of the two
products
concentrated acid
(b)
O CH3
O
H2 & Pd OH
CH3MgBr
(c)
O O
H2 & Pd OH
NaBH4 then H+
(d)
Mg
O Br there may be a conjugate addition
product in addition to this one
OH the conjugate addtion product can
add another equivalent of
phenylmagnesium bromide

23.53
(a)
H3C CH3 NH2OH H3C CH3
O N
HO
(b)
NH NH2
H3C CH3 H3C CH3
-
O + + O
N N
O N
-
O O N
H
-
O + + O
N N
-
O O

(c)
H3C CH3 CH3CH2OH & H+

H3C CH3
O O
HO
CH3
H3C CH3
CH3CH2OH & H+
O
O
H3C CH3

23.55 Thioacetalformationisanalogoustoacetalformation.Inthiscase,itisthioalsaddingtoa
ketoneratherthanalcoholsaddingtoaketone.
+
H
+ H
O O
R1 R2 R1 R2
solvent
+
H H
H
R3 S + H H H H + H
+
O R3 S O R3 S O R3 S O
R1 R2 R1 R2 R1 R2 R1 R2
R3 S
H
R3
S R3
S
R1 R2
+ R1 R2
S
R3 H S
R3
solvent
25.57
Mg
Br
(a) O H3C
H
H3C H
H3C
CH3
HO
(b)
NaOCl O
H3C
CH3
O
(c)
Br2 & FeBr3 Br
H3C
CH3
CH3
(d) O O CH3
+
CH3OH & H Br
H3C
CH3

23.59
(a)
1,4 addition products
OH
H3C OH
H3C
CH3 OH
CH3 OH
CH3
CH3 H CH3
HO H3C CH3 H
HO H3C
H OH
H OH
HO
H HO
O H
O

1,2 addition products
OH
H3C
OH
H3C
CH3 OH
CH3 OH
CH3
CH3
HO H3C CH3
CH3
HO H3C
H OH
H OH
HO
H HO
HO H H
H OH
(b) The 1,4 addition products are enantiomers. The 1,2 addition products are a separate pair of
enantiomers.
(c)Iwouldnotexpectthe1,4or1,2additionproductstoyieldinequalamounts.Althoughtheaddition
cantakeplacefrombeloworabovetheringstructure,thestereochemistryofthesubstrateatexisting
stereocenterscanaffecttherateofthesetwopathways.The1,4additionrequiresattackbyhydride
(carriedbyBH4)atacarbonwithtwoadjacentstereocenters.Theenantiomericexcessislikelygreater
forthe1,4additionproducts.
Chapter24
24.2
(a) (b)
CH3 O O
H3C
H3C OH OH
CH3 CH3
O O
(c) (d)
OH OH
H H
OH
HO O
24.3
(a) (b)
O O
H3C
H3C Cl NH
H3C H3C
(c) (d) H3C O

H3C CH3
N H3C
O CH3
H3C
H3C
(e) CH3 O (f) O O
NH2 O
H3C CH3
24.4 (a)acarbonylstretchmostlikelyanesteroranaldehyde.
(b)C=Ostretchingband(therearetwo)ofananhydride.
(c)carboxylicacids.
(d)aketone(unlessthereisalsoabroadOHstretch24003300cm1)C=Ostretch.
24.5
(a) O
H3C CH3
O
1735 cm1 - an ester C=O stretch
(b) O
H3C CH3
N
H
1650 cm1 - an amide C=O stretch
(c)
O
H3C Cl
1735 cm1 - an acid chloride C=O stretch

24.6 In13CNMRspectroscopy,thecarboxylicacidcarbonylcarbonwillabsorbaround180185ppm
andtheketonecarbonylrangeisfrom180220ppm.Also,4hydroxycyclohexanonehasa
hydroxylfunctionalityandwillhaveaCOcarbonabsorptioninthe5090ppmrange.Theother
alkylcarbonswillmostlyabsorbinthe1030ppmrangethoughthecarbonnexttothe
carbonyl(inbothmolecules)canbeasfaras50ppmdownfield.Inthe1HNMRspectra,the
moleculesaredistinguishedbypossiblesplittingofthehydroxylHpeakinthecaseof4
hydroxycyclohexanone,and(moreimportantly)bytheextradownfieldpeakduetothemethine
HCO.
24.8
(a)
O
O
CH3
OH NaOCH3
O
(b)
H3C O H3C O
KOH
H3C H3C
- +
OH O K
H3C H3C

24.9 methanol<phenol<pnitrophenol<aceticacid<sulfuricacid
24.10 (a)CH3CH2CO2H<BrCH2CH2CO2H<BrCH2CO2H
(b)ethanol<benzoicacid<pcyanobenzoicacid
24.11 (a)CH3COCl>CH3CO2CH3 (b)CH3CH2CO2CH3>(CH3)2CHCONH2

(c) CH3CO2COCH3 > CH3CO2CH3 (d) CH3CO2CH3 > CH3CHO
24.12 ThefluorinesubstituentsinCF3CO2CH3areelectronwithdrawing,makingthecarbonylcarbon
moreelectrondeficient(attractingnucleophiles)andstabilizingthefourcoordinate
intermediatewhichhasadditionalelectrondensityduetothebondednucleophile.
24.13
(a)
O
O
CH3OH H3C CH3
H3C
O
Cl
(b)
O O
CH3CH2OH
H3C Cl H3C O CH3
(c)
OH
O
O
H3C O
H3C Cl

24.14
-
O O
H3C H3C
Cl Cl
+
N
H3C H3C
H H
N
H N
H H
H H
H
H
-
O O -
H3C Cl
H3C H
Cl N
N
H3C CH3 H
H H H
+
N
H H
H
24.15
(a)
O
O
NH3 H3C
H3C
NH2
Cl
(b)
CH3 O CH3NH2 CH3 O
CH3
H3C Cl H3C NH
(c)
H3C
O NH CH3 O
H3C H3C CH3
Cl N
CH3
(d) H3C
O
O NH
CH3 N CH3
Cl
H3C
24.16
OH
OH
-
+ O O
H N
H N O O
H
O CH3
H H3C
H3C O CH3
OH OH
+
H N O
H N O H
- O
O H CH3
CH3
O CH3
O CH3
24.17
O O
H3C OH CH3
O
O
OH
O
O
24.18
(a)
O H3C O H3C
NaOH(aq)
H3C O CH3 H3C OH HO CH3
(b) O
O
NaOH(aq)
O
OH
H3C OH
CH3

24.19
(a)
O
H3C CH3 LiAlH4
O H3C
CH3
OH
+
CH3
H3C OH
(b)
O
O LiAlH4 OH

+ HO
24.20
(a) O OH
CH3
2 CH3MgBr CH3
O
CH3
Mg
(b) Br
O 2 H3C OH
CH3
H3C O
(c) CH3
H3C
O CH3
Mg Br
H3C CH3 H3C
O OH

24.21
(a)
O
O
+
NH CH3 H3O (aq) & heat
OH
(b) O
LiAlH4
OH OH
from (a)
(c)
O
NH CH3 LiAlH4
NH CH3
24.22
O
H
N
O
O
H N
N H
H O
N
24.23 (a)CH3CH2CHOhasnoacidicHs
(b)(CH3)3CCOCH3isessentiallynonacidic.However,the3Hsonthemethylnexttothe
carbonylareslightlyacidic.
(c)TheHbondedtoOisacidicinaceticacid,CH3CO2H.
(d)ThemethyleneHsbetweenthetwocarbonylCsareacidicin1,3Cyclohexanedione.
24.24
(a)
H O -
H H+ O H O
H
-
C
H3C H H3C H H3C H
(b)
H O + -
H H O H O
H
-
C
H3C CH3 H3C CH3 H3C CH3
-
O O
-
H3C CH2 H3C CH2
(c)
-
O O O
H+
-
C
CH3 CH3 CH3
- -
CH O O
CH3 CH3
24.25
-
O O O O O O
+
CH3 H - CH3 CH3
H3C O H3C C O H3C O
H H H H
-
O O
CH3
H3C O
24.26
(a)
O O O O
H3C CH3 NaCH3CH2O H3C CH3
-
O O O C O
H H H
O O H3C
O O
Br
H3C - CH3 H3C CH3
O C O O O
H H CH3
O O
H3C CH3 O
O O HCl(aq) & heat
H CH3 H3C OH
(b)
Br O
OH
CH3
(c)
H3C
CH3
Br H3C
O
OH
REVIEWQUESTIONS
24.27
O O CH3 O
H3C H3C
H3C OH OH OH
CH3
hexanoic acid 4-methylpentanoic acid 3-methylpentanoic acid

chiral at C3
CH3 O
O CH3 O
H3C
H3C H3C OH
OH H3C OH
CH3
CH3
2-methylpentanoic acid 3,3-dimethylbutanoic acid 2,3-dimethylbutanoic acid

chiral at C2 chiral at C2
O O
H3C OH H3C OH
H3C CH3
H3C
2,2-dimethylbutanoic acid 2-ethylbutanoic acid

24.29 (a)pmethylbenzamide
(b)4ethylhex2enenitrile
(c)dimethylbutanedioate
(d)isopropyl3phenylpropanoate
(e)phenylbenzoate
(f)Nmethyl3bromobutanamide
(g)3,5dibromobenzoylchloride
(h)1cyanocyclopentene
24.31
(a)
Cl Cl
O
H3C O H3C O
Cl
cyclopentanecarbonyl chloride hex-2-enoyl chloride hex-4-enoyl chloride
(b)
O
NH2 NH2
NH2 H3C H3C
O O
cyclohex-1-enecarboxamide hept-2,4-dienamide hept-2,5-dienamide

(c)
N H3C H3C
N N
pent-2-enenitrile pent-3-enenitrile
cyclopentanecarbonitrile
(d) O O
O
H2C H3C
CH3 O CH3 O CH2
H3C O
methyl but-2-enoate ethyl propenoate ethenyl propanoate

24.33 (a)
O
H3C Cl
(b)
O
CH3
H3C O
CH3
24.35 (a)aceticacid<chloroaceticacid<trifluoroaceticacid
(b)benzoicacid<pbromobenzoicacid<pnitrobenzoicacid
(c)cyclohexanol<phenol<aceticacid
24.37
24.39 (c)CH3CONH2<(a)CH3CO2CH3<(d)CH3CO2COCH3<(b)CH3COCl
24.41
OH
H3O+ O
HO O
O
24.43
-
Cl Cl
Cl
O
- O
O
H3C H
H3C H3C H
H
- H
Al H -
H H Al H
H H Al H H
H
-
O
H OH
H3C H3O+
H H
H3C
H
H H
Al
24.45
(a)
-
Cl Cl
Cl
-
O
O O
R1 R2
R1
R1 R2
R2 Mg +
Mg
Br
Br R2 Mg
Br
-
O
OH
H3O+
R1 R2
R1 R2
R2
R2
+
Mg
Br
(b)
(a)
Cl
CH3 H3C
CH3MgBr then H3O+ CH3
O
OH
H3C H3C CH3
O
OH
(b) CH3
Cl CH3MgBr then H3O+
CH3 CH3
CH3
24.47
(a)
excess CH3MgBr in ether
Cl
then H3O+ H3C CH3
O
H3C OH
H3C
(b)
-
Cl O
NaOH(aq)
O O
H3C H3C
(c)
CH3
Cl HN
CH3NH2
O O
H3C H3C
(d)
Cl
LiAlH4 then H3O+
O OH
H3C H3C
(e)
OH
Cl O
O O
H3C H3C
(f) H3C
O
O
Cl H3C
- O
O
O
O
H3C
H3C
24.49
(a)
CH3 excess CH3MgBr in ether
O
then H3O+ H3C CH3
O
OH
H3C
H3C
Alternatively,startingwithmethylacetate,wecouldadd1equivalentofpropylmagnesium
bromide,then1equivalentofmethylmagnesiumbromide.

(b)
excess
Mg
Br
CH3
HO CH3
O
O
H3C

Thealternativeistostartwithmethylbenzoateandsuccessivelyadd1equivalentof
phenylmagnesiumbromideand1equivalentofmethylmagnesiumbromide.
24.51
O
O LiAlH4 then H3O+
OH
HO
24.53
O O O OH
HO O HO O
O OH

Thefirsttwoenolsshownarethemoststablebecausethe2carbonHsaremoreacidicthey
aretotwocarbonyls.
24.55
(a)
- -
O O O O O O
-
H3C C CH3 H3C CH3 H3C CH3
H H H
(b)
- -
H2C N H2C N
(c)
-
O O O
H3C - H3C H3C -
C CH3 CH3 CH CH3
H H H
(d)
O CH3 O CH3 -
O CH3
O O
-
O
N CH -
N N

24.57 Anenolateisabaseoranucleophileitisastabilizedcarbanion.Itcanreactbydonatinga
lonepairofelectronsthroughtheOatomorthroughthecarbon.Itreactswithelectrophiles.
TheneutralenolistheresultoftheenolatedonatingitselectronstoaprotonattheOatom.
Whileitisanacid,whenitdonatesitsprotonbacktoabase,itotherwisereactsthesameway
astheenolatei.e.donatingalonepairofelectronsthroughtheOatomorthecarbon.
Becauseitisneutral,whenitreactsinthisway,ittypicallyacquiresapositivecharge.In
contrast,theenolateisananiontypicallyreactingtoformaneutralspecies.Thereactionsof
theenolateareconsequentlymorefavourable(itismorefavourabletoformaneutralspecies
fromanion,thananionfromaneutralspecies)itismorereactive.
24.59
CH3
H3C
Br
O O
H3C CH3 O O
-
O C O
H3C CH3
O O
H
H3C
CH3
O O O O
H3C Br
H3C - CH3 H3C CH3
O C O O O
CH3
H3C H3C
CH3 CH3
O
HCl(aq) & heat H3C
OH
CH3 CH3
24.61
(a)
Br O
Br O
SOCl2
OH
Cl
-
O
H3C Br O
CH3
O
H3C CH3
(b) SOCl2
OH Cl
O O
NH3
NH2
24.63 Thisorderfollowsbecauseoftheincreasingbulkofthealkoxidesubstituentatthecarbonyl
carbon.Hydroxideaddstothecarbonylcarboninthefirststepofsaponification.Alarge
alkoxidesubstituentreducestheaccessibilityoftheelectrophiliccarbonylcarbontohydroxide.
24.65
(a)
Br Br O
Mg O
Mg in ether CH3
H3C O
CH3
O O
(b) H3C Mg
CH3
O Br CH3
O
O
(c) H3C Cl
CH3
AlCl3

24.67
(a) O
LiAlH4
OH
OH
H3C then H2O
H3C
(b)
O
O
CH3OH & HCl
OH CH3
O
H3C
H3C
(c)
O
O
SOCl2
OH
Cl
H3C
H3C
(d)
O O
NaOH
CH3
OH O
H3C then CH3I H3C

24.69
(a)
N
I NH2
LiAlH4
H3C NaCN
H3C H3C
CH3 then H2O
CH3 CH3
(b)
Br
Br Mg in ether Mg
O
H3C CH3
Br O
Mg
H3C
O

24.71

CH3 +
O CH3 -
Na
O
H3C H3C
O Cl O Cl
H3C H3C
- +
+ N Na + N
- N - N
N N
CH3 O +
H3C Na
-
H3C
O N + Cl
+
N
-
N
24.73
Br
Br CH3
Mg CH3
Mg in ether
O
1 equiv O
Cl N CH3
H3C
N CH3
CH3
CH3
24.75
Firststep
-
H O
H
H H
O O -
+ O
O
H
NH
NH
O
H NH2
O
Polymerizationstep
Theaminegroupattacksthecarboxylicacidonanothermolecule,extendingthechainby
anothermonomer.Thisprocessrepeatsmanytimes.
O
O
O N CH3
O N H
N H
H3C N
H
H
24.77
O O O O
H3C > H3C

OH H3C OH > HC CH3 >
3 OH
H H
24.79
O
CH3 O
O
OH H3C OH
CH3 H3O+
N CH3
O N
OH
O HO
24.81
(a)
H
O O
N
CH3
H
N
H
(b)
H
O O
N H3C
CH3
H + NH
CH3
N
H
-
O O
N H3C
CH3
H + +
NH2
CH3
N
H

(c)
O O O
CH3
N
CH3
H
N
H
(d)AtwofoldexcessofdiethylamineisrequiredbecausebothLSDanddiethylacetamideareproduced.
24.83
Firststep

Hydrolysisofacetylatedenzyme:
24.85
(a)
1. H3C O
O O -
O
CH3
H3C O CH3
Br
2.
+
3. H3O
(b)
1. H3C
O O O
-
O
H3C
H3C O CH3 CH3
CH3
CH3
2. Br
H3C
+
3. H3O
(c)
1. H3C
O O O
-
O
H3C
H3C O CH3 CH3
CH3 CH3
2. Br
H3C
+
3. H3O

Chapter25
25.2 (a)primaryamine
(b)secondaryamine
(c)tertiaryamine
(d)quaternaryammoniumsalt
25.3 TheintegralscorrespondtotheHscominginequivalentgroupsof2,2,2,2and3from
downfieldtoupfieldaccountingforthe11Hsinpethoxyaniline.Thetwodownfielddoublets
at6.7and6.6ppmareconsistentwithphenylHs.Moreover,thedoubletspointtoeach
otheri.e.thepeaksclosesttotheotherdoubletarelargerindicatingthattheyarecoupling
toeachother(coupleddoubletswellseparatedinchemicalshiftshowtwopairsofequal
intensitypeaks).ThisisconsistentwiththeexpectedcouplingoftheC2andC3(C1isthe
aminecarbon)phenylHsandtheequivalentC6andC5phenylHs(togiveintegralsof2,while
splittingtheneighboringpeakintoadoublet,ratherthanatriplet).AsOismore
electronegativethanN,thefurthestdownfielddoublet(i.e.at6.7ppm)likelycorrespondstothe
C3andC5Hs.Thequartetat3.9ppm(integratingto2)andthetripletat1.3ppm(integrating
to3)areconsistentwiththeethylgroupanalkylmethyleneandmethylgroup,withthe
methyleneHsdownfieldbecausetheircarbonisbondedtooxygen.Theremainingbroadpeak,
integratingto2,correspondstotheamineHs.Theirpeakisbroadenedduetohydrogen
bonding.
25.4 6peaks.ThemethylCpeak(CbondedtoanotheralkylC)shouldappearinthe1030ppmrange.
ThemethyleneCpeak(CbondedtoO)shouldappearinthe5070ppm.ThephenylCpeakswill
beinthe110150ppmrange,withtheCsbondeddirectlytoOandNfurthestdownfield.
25.5 (a)CH3CH2NH2
(b)NaOH
(c)CH3NHCH3
(d)(CH3)3N
25.6
CH3 CH3
+ -
N + HBr N Br
H H
H
25.7
(a)
H3C
H3C N
3
Cl
+ NH3
H3C CH3
(b)
H3C
+ -
H3C N CH3 Br
4
Br
+ NH3
H3C
CH3
25.8
Br CH3
N
+ H2N CH3
Br
25.9
(a) (b)
CH3 CH3 CH3
CH3
N Br2 N N CH3Cl & AlCl3
Br N
CH3
(c)
CH3 CH3
O
N CH3COCl & AlCl3 N
CH3

25.10
25.11
H
..
. N.
. .
N
H

25.12 ThepyridinelikeNismorebasicweseethenegativechargedensityappearingasaredpatch
intheelectrostaticpotentialmap.
REVIEWQUESTIONS
25.13 (a)Nmethylisopropylamineitisasecondaryamine
(b)(2methylcyclopentyl)amineitisaprimaryamine
(c)Nisopropylanilineitisasecondaryamine
25.15
(a) H3C O CH3

(b) tertiary amine
H3C N
O N CH3 N
O N N
tertiary amine CH3

N
CH3 an imine
H
N
H secondary amine

25.17
(a) (b) (c)

H3C CH3 NH H3C CH3
CH3 +
N N
H3C H3C CH3
(d)
(e)
NH2 H3C CH3
N
Br
25.19
CH3
O O CH3
H3C
O
NH2
25.21
(a) (b)
NH H3C NH2
CH3
OH
CH3
(c) (d)
H
N
H3C
+
N CH3
H3C
H3C
25.23
1
N
3
CH3
N
CH3
H2N O
2

3>1>2
25.25 Trimethylaminehasalowerboilingpointthandimethylamineeventhoughithasahigher
molecularweightbecauseithasnohydrogenbondingHs.DimethylaminehasonesuchH.
25.27
CH3 CH3
N H2SO4 then neutralize N
OH
tropine tropidine
note that the other position for the
hydroxyl corresponds to an
optically active alcohol
CH3 HO O
HO O CH3
N
OH N
HO
O
OH +
H
H
atropine

25.29
25.31 Nitrationatthe2position:
H O + O
N H H O
N O + N
H H N O N N O
H H +
H C H
H H
H H H H
H O
N N O
H
H
+
C
H H
H O H
O
+ N
N O N
H N
H O
- H H
A

Nitrationatthe3position:
H H H
+
N N N
H H + H
C
H H
O + H N
N N
O O O
O O
H H
+
N N
H H
-
H A
N N O
O O
O
Thecarbocationintermediateinthecaseofsubstitutionatthe2positionhasthreeresonance
structures.Thecarbocationmorestableandthecorrespondingreactionpathwaymore
favourable.
25.33
25.35 CH3CH2NH2ismorebasicthanCF3CH2NH2.Thefluorosubstituentsareelectronwithdrawing
theyreducetheavailabilityofelectronsatthenitrogenatom.
25.37 Triethylamineismorebasicthananiline.Thereactiondoesnotgointhedirectionindicated.
25.39
(a)
Br
H3C NH2 H3C NH2
Br2 (1 equivalent) H3C NH2
+
Br
H3C NH2
Br
(b)
CH3
H3C NH2 H3C + -
CH3I (excess) H3C N I
CH3
(c)
H3C NH2
CH3COCl & pyridine H3C NH O
CH3

25.41 Diphenylamineislessbasicthananilinebecausethenitrogenlonepairispartiallydelocalized
overtwobenzenerings,ratherthanjustone.
25.43 pmethoxyanilineismorebasicthananilinebecausethemethoxygroupiselectrondonating.
25.45
H
O H
H H +
- H
H O
H3C N H H3C
H + H
N
H3C CH3 CH3
H3C
H
H
H OH
H3C + H
N
CH3
H3C
choline

25.47 Stereocentersaremarkedwitharrowsbelow.Therearefourstereocenters,andassuchthere
are24=16stereoisomers.
O NH2
O
O
H CH3
H2N O H
H3C N NH
O H

25.49 Theaziridinegroup,liketheepoxidegroup,isveryreactivebecausethebondsarestrainedby
thetightthreememberedringarrangement.
25.51 DEETisanamidethatcanbepreparedbyreactionofanamine,diethylamine,withacarboxylic
acid,mmethylbenzoicacid,liberatingwaterintheprocess.Inpractice,thisreactionislikely
bestcarriedoutbyfirstpreparingtheacidchloridefromthecarboxylicacid.
Chapter26
26.1 Be2+ismorepolarizingthanBa2+becauseitissmaller.
26.2 (a)Chromium(VI)oxidehasaverypolarizing+6chargedmetalcation,producingachromium
oxygenbondswithastrongcovalentcharacter.
(b)Becausechromium(VI)issostronglypolarizing,itisacidicoxide,dissolvinginwaterto
producechromicacid.Themoreweaklypolarizingchromium(iii)formstheinsolubleoxide,
Cr2O3whichisamphoteric.
26.3 2H2(g)+O2(g)2H2O()
H2(g)+Cl2(g)2HCl(g)
3H2(g)+N2(g)2NH3(g)
26.4 2K(s)+H2(g)2KH(s)
Theproductofthisreactionispotassiumhydride.Itisanionicsolid(atroomtemperature).Itis
averystrongbaseconsistingofK+andHions.Itissostronglyreactivethatisgenerally
distributedasaslurryinmineraloil.
26.5 2Na(s)+Cl2(g)2NaCl(s)(exothermicreaction)
NaClisacolourlessionicwithhighmeltingpoint.Itissolubleinwater.
26.6 (a)2Cl(aq)Cl2(aq)+2e(reactionatanode,Clisoxidized)
2H2O()+2e2OH(aq)+H2(g)(reactionatcathode,H2Oisreduced)

(b)2I(aq)l2(aq)+2e(reactionatanode,lisoxidized)
Samereductionreactionasinpart(a)
26.7 2Ba(s)+O2(g)2BaO(s)(exothermicreaction)
BaOisacolourlessionicsolidwithhighmeltingpoint.Itissomewhatsolubleinwater.
26.8 Wewouldnotexpecttofindcalciumoccurringnaturallyintheearthscrustasafreeelement
becauseitistooelectropositiveittooreadilylosesitsvalenceelectrons.Itoccursonlyinthe
+2oxidationstate.
26.9 (a)Ga(OH)3(s)+3HCl(aq)GaCl3(aq)+3H2O()
Ga(OH)3(s)+3NaOH(aq)Na3GaO3(aq)+3H2O()
(b)Ga3(aq)isastrongeracidthanAl3
(c)2.77L
3
26.10 Al(s)+3HCl(aq)AlCl3(aq)+ 2 H2(g)
3
Al(s)+ 2 Cl2(g)AlCl3(s)
3 1
Al(s)+ 4 O2(g) 2 Al2O3(s)
26.11 InSiO2,siliconformsanetworkofsinglebondswithoxygeni.e.wegetacovalentlybonded
networksolid.ThemeltingpointofSiO2isthereforeveryhigh.ThebondinginCO2isalso
covalent,butCO2ismolecular.Theintermolecularforcesofattraction(dispersionforces)
betweenCO2moleculesareweakandareeasilybroken.Carbondioxideisgasatordinary
temperatures.
26.12 PbCl4
26.13 (a)
+ +
N N O N N O

(b)exothermic
26.14
+
N N N

26.15

S S

26.16 (a)F2canoxidizeCl(X=F,Y=Cl)forexample,whereas(b)Cl2cannotoxidizeF(X=Cl,Y=F).
26.17 (a)Z*(Ar)=+6.75;Z*(K)=+2.2;Z*(Cl)=+6.1
ThevalenceelectronsofArareheldverytightly.Incontrast,thevalenceelectronofK
experiencesamuchsmallereffectivenuclearcharge.Althoughthevalenceelectronsof
neighbouringClarealsoheldtightly,theeffectivenuclearchargeinthiscaseisnotquiteas
large.

(b)Z*(Ar)=+1.2;Z*(K)=+1.85;Z*(Cl)=+5.75
ThevalenceelectronofArisheldquiteweakly.Incontrast,thevalenceelectronsofCl
experienceamuchlargereffectivenuclearcharge.EventheKionsvalenceelectronsareheld
moretightly.
26.18 Theratioofthedensityofnitrogentohelium=7.00.
26.19 Whilexenonandkryptonhaveclosedvalencesandpsubshells,theydohaveopendsubshells
intheirvalenceshells.Theycanthereforeexpandtheirvalenceshellstoformbonds.
Nevertheless,thereisasizeableenergygaptothedsubshellsandsuchbondsarenotvery
stablebutcanbeformed.Inthecaseofneon,thevalenceshellhasn=2.Toformbonds,
neonwouldneedtousen=3shellorbitals.Thereisaverylargeenergygaptosuchorbitals,and
whileonecouldenvisionsuchbondstheywouldbeextremelyunstable,andnosuchbondshave
everbeenformed.
REVIEWQUESTIONS
26.21 (a)ThepropertiesofBeCl2,BCl3,AlCl3,TiCl4andFeCl3aretypicallycovalent,becauseofthe
smallsizeofandhighchargeofthecationswhichmakethemhighlypolarizing.Incontrast,K+
andAg+,whicharesinglychargedandnotsosmall,arenotnearlyaspolarizing.Thechloride
anionretainsitsindependentanionicformnexttothesecationstheassociatedcompounds
areionic.
(b)Al3+ishighlypolarizing,givingcovalentcharactertobondswithhalides.However,sincethe
smallfluorideionisrathernonpolarizable,AlF3isessentiallyanioniccompoundthebonding
hasverylittlecovalentcharacter.Itcontrast,chlorideandespeciallybromidearemuchmore
polarizable.BondsinAlCl3,andAlBr3havesignificantlymorecovalentcharacter.These
compoundsmorereadilymelttoformliquidsofmobileAlCl3,andAlBr3molecules.

(c)Singlychargedcations,K+,Ag+andNH4+,arenotverypolarizing.Theydonotattractwater
moleculesstronglyenoughtoholdthemascoordinatingligandsintheioniccrystallatticesof
KCl,AgNO3andNH4NO3.Incontrast,thepolarizingdoublyandtriplychargedcations,Mg2+,Fe3+
andCr3+,retaincoordinatedwaterligandswhentheirsaltsareprecipitatedfromaqueous
solutioni.e.theycrystallizeashydratedcompounds.

(d)ThesmallerLi+ionismorepolarizingthanthelargerRb+ion.Consequently,Li+holdswater
ligandsaboutitrathertightly,anditsmobilityinwateristhatof[Li(H2O)4]+ratherthanthatof
freelithiumions.Arubidiumionisinsufficientlypolarizingtodragwatermoleculesalongwith
it.Itsmobilityisthatofthefreecation.
26.23 (a)ThemolarenthalpychangeofhydrationofBe2+(2455kJmol1)isgreaterthanthatofBa2+
(1275kJmol1)becausetheformerismuchsmaller.
(b)ThemolarenthalpychangeofhydrationofFe3+(4340kJmol1)isgreaterthanthatofFe2+
(1890kJmol1)becausetheformerhasagreaterchargeitissmallertoosincethereisoneless
electrontoarrangearoundtheironnucleus.
26.25 Pb4+polarizesthechloridestosuchanextentthatthebondsinlead(IV)chloridehavesignificant
covalentcharacterandlead(IV)chloridecanexistasindividualneutralmoleculesinanonpolar
solvent.
26.27 224kJ.
Thereactionisendothermic.
26.29 rH=131.30kJ
rS=134.0J/K
rG=91.3kJ
1
26.31 Na(s)+ 2 F2(g)NaF(s)
1
Na(s)+ 2 Cl2(g)NaCl(s)
1
Na(s)+ 2 Br2()NaBr(s)
1
Na(s)+ 2 I2(s)NaI(s)
Allalkalimetalhalidesareionicsolids.Theyarecrystalline,brittle,dissolveinwaterandare
colourless(M+andXareclosedshellspecies).
1
26.33 Mg(s)+ 2 O2(g)MgO(s)
3Mg(s)+N2(g)Mg3N2(s)
26.35 Limestone,CaCO3,isusedinagriculture.Itisaddedtofieldstoneutralizeacidicsoil,toprovide
asourceofCa2+,anessentialnutrientforplants(andanimals).Sincethereisgenerallya
magnesiumimpurity,italsoprovidesasourceofMg2+,anotheressentialnutrient.Limestoneis
alsousedtomakelime,CaO,whichisusedtomakebricksandmortar.
26.37 1.3103kg
26.39 Becausetheequilibriumconstantfortheabovereactionissolarge,~107,itcanbeusedto
obtainmagnesiumhydroxidesolid(whereinmagnesiumionsareconcentratedinanionicsolid)
fromseawaterwithverysmallconcentrations.
26.41 Berylliumandberylliumalloysareusedinairplane(especiallyhighspeedplanes),missileand
spacecraftconstruction.Itisalsousedinhighenergyphysicsexperimentstomakewindows
andfilters.BecauseofitslowdensityitisrelativelytransparenttoXrays,forexample,yethas
thehighstrengthandstiffnessofmuchheaviermetals.Berylliumdustgeneratedin
manufacturingprocessesisverytoxic.Peoplebreathingthisdustoveraperiodoftimecan
developberylliosisaninflammatorydiseaseofthelungswhereinsufferersexperience
coughing,shortnessofbreath,feverandweightloss.
26.43 Iodinegetsreducedandborohydride,BH4,getsoxidized.
26.45
Cl

Al Cl
Cl
Cl
AlCl4istetrahedral
26.47 (a)BCl3(g)+3H2O()B(OH)3(s)+3HCl(aq)
(b)110.5kJ
26.49 SiO2(s)+2C(s)Si()+2CO(g)
Si(s)+2Cl2(g)SiCl4()(TheSiCl4()ispurifiedbydistillation)
SiCl4(g)+2Mg(s)2MgCl2+Si(s)

Inthelaststep,themagnesiumchloridebyproductiswashedawaywithwater.Thesiliconleft
behindinthiswayisfurtherpurifiedbyzonerefiningwhereinanarrowcylinderofsiliconis
heatedandmeltedinonesegmentalongthecylinder.Theheatingslowlytraversesthelength
ofthecylinder.Impuritiesconcentrateinthemeltedsegment,leavinghigherpuritysilicon
behind.
26.51 (a)Si+2CH3Cl(CH3)2SiCl2
(b)83.5kPa
(c)12.2g
26.53 Ca(OH)2(s)+H3PO4(aq)CaHPO4(s)+2H2O()
26.55 rH=58.02 kJ
rG = 5.40 kJ
Thereactionisexothermicandslightlyproductfavouredunderstandardconditions.
26.57 5N2H5+(aq)+4IO3(aq)5N2(g)+H+(aq)+2I2(s)+12H2O()
E = 1.43 V
26.59 (a)
O O O O

N N N N
O O

Twoalmostequivalentresonancestructurescanbedrawn,givingthetwoNObondsonthe
rightbondordersofabout1.ResonancestructuresshowingtheNObondontheleftas
anythingbutadoublebondarenotatalldominant.Thislatterbondisthusmoreofadouble
bond.Thisisconsistentwithitsobservedshorterlength.

(b)rS=141JK1
K = 141
(c)fH[N2O3(g)]=83.71kJ
26.61 rH==884kJ
rG=841 kJ
ThisreactionisproductfavouredrG<0anditisexothermicwhichmeansthatitisless
productfavouredathighertemperature.
26.63
F F
S F
S S S F
F F F
F
ON(S) = +1 ON(S) = +2 ON(S) = +4
F F F
F F F
F S F F S S F
F F F
F F F
ON(S) = +6 ON(S) = +5

26.65 Anyspecieswithreductionpotentialgreaterthanthatofchlorine(i.e.>1.36V)canbeused.
Forexample,
F2(g)+2Cl(aq)2F(aq)+Cl2(g)
H2O2(aq)+2H+(aq)+2Cl(aq)2H2O()+Cl2(g)
PbO2(s)+SO42(aq)+4H+(aq)+2Cl(aq)PbSO4(s)+2H2O()+Cl2(g)
2 MnO4(aq) + 16 H+(aq) + 10 Cl(aq) 2 Mn2+(aq) + 8 H2O() + 5 Cl2(g)
26.67 ThereductionpotentialofMnO4(aq)is1.51Vunderstandardconditions.Sincethisisgreater
than1.44V,itisNOTpossibletooxidizeMn2+(aq)withBrO3(aq).
26.69
F
Br F
26.70 190kJ
26.71 1.6 kg
26.73 P4O10(s) and SO3(g) are acidic oxidespotassium and sulfur are non-metals.
P4(s) + 5 O2(g) P4O10(s)
S8(s) + 12 O2(g) 8 SO3(g)
The acidic oxides react with water to form acidic solutions:
P4O10(s) + 6 H2O() 4 H3PO4(aq) phosphoric acid, which ionizes in aqueous
solution to form H3O+(aq).
SO3(g) + H2O() HSO4-(aq) aquated hydrogensulfate ions, which ionize in aqueous
solution to form H3O+(aq).
26.75 S2, Cl, K+ and Ca2+ ions are monatomic ions with the same electron configuration as argon.
26.77 In order of increasing basicity, we have CO2 < SiO2 < SnO2
26.79 (a) 2 Na(s) + Br2() 2 NaBr(s)

(b) 2 Mg(s) + O2(g) 2 MgO(s)
(c) 2 Al(s) + 3 F2(g) 2 AlF3(s)
(d) C(s) + O2(g) CO2(g)
26.81 (a) Electrolysis of aqueous sodium chloride:

2 Na+(aq) + 2 Cl(aq) + 2 H2O() 2 Na+(aq) + 2 OH(aq) + Cl2(g) + H2(g)
(b) Electrolysis of aqueous sodium chloride is not the only source of sodium hydroxide, or of
hydrogen. It is, however, the principle source of chlorine.
26.83 (a) Li(s) and Be(s) are metals

B(s) is a metalloid
C(s), N2(g), O2(g), F2(g) and Ne(g) are non-metallic substances.
(b) + (c) Li(s), Be(s) and B(s) are silver-white shiny, with metallic appearance. C is a black
solid (graphite) or a lustrous tansparent very hard crystalline material (diamond). N2(g), O2(g),
F2(g) and Ne(g) are all gases, colourless except for a yellow tinge in the case of fluorine.
26.85 (a) 2 KClO3(s) + heat 2 KCl + 3 O2(g)

(b) 2 H2S(g) + 3 O2(g) 2 H2O() + 2 SO2(g)
(c) 2 Na(s) + O2(g) Na2O2(s)
(d) P4(s) + 3 OH-(aq) + 3 H2O() PH3(g) + 3 H2PO4-(aq)
(e) 2 NH4NO3(s) + heat N2O(g) + 2 H2O(g)
(f) 2 In(s) + 3 Br2() 2 InBr3(s)
(g) SnCl4() + 4 H2O() Sn(OH)4(aq) + 4 H+(aq)
26.87 Dry, inert powders are used to extinguish sodium fires. A class D fire extinguisher is required.
The worst thing you can do is put water on the fire, as the sodium will react violently with water.
26.89 The amount of gas produced by heating 1.00 g A is
pV (27.86 kPa)(0.450 L)
n(gas) = = 0.00506 mol
RT (8.314 L kPa K 1 mol1 )(298 K)
Bubbling this gas through Ca(OH)2(aq) gives a white solid, C. This suggests the gas is carbon
dioxide. Carbon dioxide reacts in aqueous calcium hydroxide to form insoluble calcium
carbonate, CaCO3(s). CO2(g) is also a typical product in the thermal decomposition of
carbonates, suggesting A is a carbonate. The other decomposition product, B, would then be an
oxide. This is consistent with it forming a basic aqueous solution. If the gas were CO2, then the
mass of 0.00506 mol would be
0.00506 mol 44.01 g mol1 = 0.223 g
This leaves 1.00 0.223 = 0.777 g as the mass of the oxide. If we take the decomposition
reaction to be (M is replaced by M2 in case of a univalent metal, etc.)
MCO3(s) + heat MO(s) + CO2(g),
then the molar mass of MO(s) is determined to be
0.777 g / 0.00506 mol = 154 g mol1
Subtracting the molar mass of O leaves the molar mass of M,
154 g mol1 16 g mol1 = 138 g mol1
This is pretty close to the molar mass of barium. This identification is verified by the green
coloured flame, characteristic of barium. Also, the sulfate precipitate is characteristic of barium.
A = BaCO3(s)
B = BaO(s)
C = CaCO3(s)
D = BaCl2(s)
E = BaSO4(s)
Chapter27
27.1 (a)methylamine,CH3NH2,(b)methylnitrile,CH3CN,(c)azide,N3and(e)bromide,Brare
monodentateligands.
(d)enethylenediamine,H2NCH2CH2NH2and(f)phenphenanthroline,C12H8N2are
bidentate(specialcaseofpolydentate)ligands
27.2 NH4hasnolonepairsanddoesnotserveasaligand.
27.3 (a)[Co(NH3)3Cl3]
(b)(i)oxidationnumber:+3.coorinationnumber:6
(ii)oxidationnumber:+2.coorinationnumber:6
27.4 (a)2.0106M
(b)4.0106M
(c)5.0x104
27.5 (i)rG=67.2kJmol1

Theentropytermaccountsforthebetterpartofthisnegativechangeinfreeenergy.Thelarge
positiveentropyofthisprocessresultsbecause6ligandsarefreedwithonly3bidentateligands
takingtheirplace.
(ii)K=6.021011
27.6 Only1.0molofAgCl(s)willprecipitate.
27.7
H
H H H
N H
N
H
H H - -
3+ O O
H N Co N H S
H H O O
-
Br
N
H H
H
dark violet isomer (A)
H
H H H
N H
N
H
H H
3+ -
H N Co N H Br
H H
- -
O O
S
O O N
H H
H
violet-red isomer (B)

[Co(NH3)5Br]SO4(aq)+BaCl2(aq)[Co(NH3)5Br]Cl2(aq)+BaSO4(s)
27.8
(a)
H H
H H H H
H N
N H -
Cl
N
H
H H H H
2+ 2+
H N Fe N H H N Fe N H
H H H
H
- -
Cl Cl
- N
Cl H H
H
(b)
H H
H H H H
N N
H
- 2+ - 2+ -
Br Pt N H Br Pt S N
H
-
S N
H H
H
N
(c)
H H
H H H H
N O H
N
- H
N O N
H
H H H O
2+ 2+
H N Co N H H N Co N
H H -
H O
- -
O N O N
O N O N
- -
O O O O
(d)
H
H
N
-
Cl
2+ -
H N Co Cl
H
-
Cl
-
Cl
27.9 (a)cisandtransisomers
(b)noisomers
(c)noisomers
(d)twoenantiomers
(e)noisomers
(f)noisomers
27.10 (a)[Fe(en)3]2hasastereocenteratFe2givingrisetotwoenantiomers.
(b)Thecobaltionintrans[Co(en)2Br2]isastereocenter,givingrisetotwoisomersthecisand
transspecies.
(c)Thecobaltioninfac[Co(en)(H2O)Cl3]isastereocenter,givingrisetotwoisomersthefac
andmerspecies
(d)Theplatinumionin[Pt(NH3)(H2O)(Cl)(NO2)]isastereocenter.Forexample,theNH3ligand
canbetranstoanyoftheotherthreeligands.
27.11 [Ti(OH2)6]3+<[Ti(NH3)6]3+<[Ti(CN)6]3
27.12 (a)In[Ru(H2O)6]2,Ru2isinthe+2oxidationstate.
dx2 - y2 dz2 dx2 - y2 dz2
dxy dxz dyz dxy dxz dyz
low spin high spin

diamagnetic paramagnetic
(b)In[Ni(NH3)6]2,Ni2isinthe+2oxidationstate.

dx2 - y2 dz2
dxy dxz dyz
low spin
paramagnetic
27.13
(a) (c)
paramagnetic paramagnetic
[Mn(CN)6]45 d electrons [Fe(H2O)6]3+5 d electrons
(b) (d)
diamagnetic paramagnetic
[Co(NH3)6]3+6 d electrons [Cr(en)3]2+ d electrons

REVIEWQUESTIONS
27.15 (a)[Ar]3d6 Fe2andCo3

(b)[Ar]3d10 CuandZn2
(c)[Ar]3d5 Mn2andFe3
(d)[Ar]3d8 CoandNi2
27.17 (a) Cr2 O3 s + 2 Al s

Al2 O3 s + 2 Cr s
(b) TiCl4 (l) + 2 Mg(s)
Ti(s) + 2 MgCl2 (s)
2
(c) 2 Ag CN 2 aq + Zn s
2 Ag s + Zn CN 4 aq
(d) 3 Mn 3O 4 s + 8 Al s 9 Mn s + 4 Al2 O3 s
27.19 [Cr(en)2(NH3)2]3+
27.21 First,dissolveaknownamountofCrCl3inaknownvolumeofwater.Thisprocessisrepeated
severaltimes,exceptthatsodiumchlorideisalsoaddedtothesolution.Theresultingsolutions
allhavethesame(known)totalconcentrationofCr3+,anddifferent(known)total
concentrationsofchloride.ExcessAgNO3(aq)isthenaddedtoeachofthesesolutions.There
willbeaprecipitateofsilverchloride.Afterfiltering,dryingandweighingtheprecipitate,we
candeterminehowmuchchloridewasavailableforprecipitationineachsolution.Sincethe
totalamountofchlorideisknownforeachsolution,wecandeterminetheamountofchloride
thatwasnotavailableforprecipitationineachcase.Thisistheamountofchloridethatwas
partofthecomplex.Sincethetotalconcentrationofchromiumisknownineachcase,wenow
knowtheratioofchromiumtocomplexboundchlorideforeachsolution.Thesevaluesarethen
plottedagainstfreechlorideconcentrationdeterminedbytheamountofprecipitate.Thisplot
shouldshowwholenumberplateausinrangesofchlorideconcentrationsdeterminedbythe
successiveformationconstantsforthevariousspecies.Weshouldbeabletoidentifytheranges
thatcorrespondto[Cr(H2O)6]3+,[Cr(H2O)5Cl]2+and[Cr(H2O)4Cl2]+.Thesecorrespondto0,1and2
boundchlorideperchromium.Accordingtotheinformationgiven,weneedtoadddiethylether
toobtain[Cr(H2O)3Cl3].Thus,anadditionalexperimentwhereindiethyletherisaddedtoa
solutionfromtheexperimentdescribedbeforetheprecipitationreactioninordertoobtain
theneutralcomplexspecies.Theneutralcompoundwillpartitionintothediethyletherlayer.It
canbeseparatedoff,andtheneutralcomplexcanbeobtainedbyevaporatingtheether.Also,
oncethesolutionswithspecificchargedspeciesareidentified,wecanevaporatethewaterand
crystallizethedistinctionicsolidcompounds.
27.23 (a)5.0x1011
(b)250
(c)3.1105M
27.25
Complex Co2 Ni2 Cu2 Zn2
Kf also known 7.7 104 5.6 108 6.8 1012 2.9 109
as

HereweseetheorderCo2+<Ni2+<Cu2+>Zn2+forthestabilityoftheamminecomplexes.
ThisisconsistentwiththeIrvingWilliamsseries.
27.27 Twostereoisomerscisandtrans.
27.29
H
H H H H
N H H
O H H
N
N
H 2+ H
O Co N 2+
H H H N Co N
- H H H
Cl H
N
H
N -
H H H H Cl
H
H H
H H H H
N H H N H H
N N
H 2+
H
2+
H N Co N H N Co N
H H H H
- H H
Cl O
H -
O H Cl
H H
enantiomers

27.31
(a)
H
H
N -
H Cl H
N
N
- 2+ H
Cr N 2+
Cl N Cr N H
H H
- H -
Cl Cl H
- -
Cl Cl
fac mer

(b)
-
Br H
-
Cl H
N
N
H
2+ H
N Cr N H 2+
N Cr N H
H
- H
Cl H -
Br H
-
Cl -
Cl
cis-mer trans-mer

(c)
H H
H H
N H N H
N HN
H H
H H
2+ 2+
N Cr N N Cr N
H
N H H
N
H N H N
H H
H H
trans-fac cis-fac
H H
N H
N
H
2+
N Cr N H
H
N H
H N
H
H
mer

27.33 AtransisomerwouldrequiretheNatomstobeonoppositesidesoftheplatinum.The
CH2CH2linkbetweentheNatomsisnotlongenoughtoallowthis.
27.35 (a)False
(b)False
(c)True
(d)False
27.37
d2 d2
x - y2 z
dx2 - y2 dz2
[Cr(CN)6]44 d electrons [Cr(SCN)6]44 d electrons

low spin complex high spin complex

SCNislowerinthespectrochemicalseriesthanCN.Itdoesnotsplitthedorbitalenergiesas
muchascyanide.
27.39
(a) (c)
[FeCl4]26 d electrons [MnCl4]25 d electrons
4 unpaired electrons 5 unpaired electrons
(b) (d)
[CoCl4]27 d electrons [ZnCl4]210 d electrons
3 unpaired electrons 0 unpaired electrons

27.41 (a)6
(b)Octahedral
(c)+3
(d)0
(e)diamagnetic
(f)
H
H H
N H H -
Cl
H H
N
N
- 3+ H
Cl Co N 3+
H H N Co N
- H H H
Cl H
H N
N -
H H H H Cl
H
H H
H H H H
N H H N H H
N N
H 3+ - 3+
H N Co N Cl Co N
H - H H
Cl H H
- H N -
Cl Cl
H H
enantiomers

27.43 Hexaaquairon(II)isparamagneticbecauseitisahighspincomplexwith4unpairedelectrons.
WhenNH3isaddedtothesolutiontheammmoniacomplexisformed.Thiscomplexis
diamagneticitisthelowspincomplexwithnounpairedelectrons.
27.45 Lowspin:nounpairedelectrons.
Highspin:4unpairedelectrons.
27.47
- -
Cl H Cl H
H H H H
N N
- -
Cl Cl
H H H
3+ - 3+
H N Co Cl H N Co N H
H H H
-
H N Cl
H N
H N
H H H H
H H
cis-tetraamminedichlorocobalt(III) chloride trans-tetraamminedichlorocobalt(III) chloride

27.49 (a)+2
(b)6
(c)1
(d)Paramagnetic
27.51 (a)K=5.792106
(b)productfavoured
(c)Becausethereactionisexothermic(rH==160.8kJ),itislessproductfavouredathigher
temperatures.Consequently,itispossibletousethisreactiontopurifynickelmetal.
Specifically,onewouldreactimpurenickelwithcarbonmonoxideatordinaryorevenlow
temperature,wheretheproductishighlyfavoured.Thegaseousproductiscollected,then
raisedintemperaturetoreversethereactionanddepositpurenickel.
Chapter28
Therearenoinchapteranswersnecessaryforthischapter.
REVIEWQUESTIONS
28.1 EachMgatomhas12sand32pvalenceshellorbitals.Thus,thereare4Nmolecularorbitals
formedfromthevalenceorbitalsofNMgatoms.EachMgatomcontributes2valence
electrons,whileeachmolecularorbitalcanaccommodate2electrons.Thus,oftheavailable
molecularorbitalsarefilledwithelectrons.
28.3 (a)Metalatomsthatcanformasolidsolutioniniron,asinterstitialatoms,mustbesmallerthan
ironatoms.Ironatomshavearadiusof156pm.Aluminumatomshavearadiusof118pm.
TheseareconsiderablysmallerthanFeatoms,andmightoccupyinterstitialsitesinasolid
solutionwithiron.
(b)Metalatomsthatcanformasolidsolutioniniron,assubstitutionalatoms,mustbesimilar
insizetoironatoms,andhavesimilarelectronegativity.Neighbouringelementsinthesame
periodasironhavesimilarsizeandsimilarelectronicproperties.Thus,Mn(radius=161pm)or
Co(radius=152pm)mightbeexpectedtoformsuchsolidsolutions.
28.5 The band gap of GaAs is 140 kJ mol1. The energy gap for an individual electron is this energy
divided by Avagadros numberi.e., 140 kJ mol1 / 6.022 1023 = 2.32 1022 kJ =
2.32 1019 J (per photon)
The maximum wavelength of light that can excite a transition across the band corresponds to the
minimum frequency that can do so. This corresponds to photon energy equal to the band gap.
Eg = h = h c /
So,
= h c / Eg = 6.626 1034 J s 2.998 108 m s1 / 2.32 1019 J = 8.54 107 m =
854 nm
This corresponds to light in the near infrared region of the electromagnetic spectrum.
28.7 Pyrex,orborosilicateglass,ismadebyaddingboronoxidetothemelt.Theglassthatresults
uponrapidcooling(slowcoolingproducesopaqueceramicmaterials)hasalowerthermal
expansioncoefficient(i.e.,foragivenincreaseintemperatureitsdegreeofexpansionisless)
thanordinaryglass.Thermalexpansion(orcontractionuponcooling)causesstrainsinordinary
glassthatcancauseittobreak.Thisisaproblemforglassthatisheatedinanoven.
28.9 (a)Hydroplasticityisthepropertyofmaterialsthatbecomeplasticwhenwaterisaddedto
them.Clayshavethisproperty.Whenwet,theyarereadilydeformedintoalmostanydesired
shape.Theyretainthisshapeafterdeformation,allowingthewetclaytobeheatedinan
oveni.e.,firedtomaketheshapefirmandrigid.

(b)Arefractorymaterialcanwithstandveryhightemperatureswithoutdeformation.Theyalso
havelowthermalconductivities,makingthemusefulforthermalinsulationespeciallyunder
hightemperatureconditions.Forexample,thespaceshuttleusesrefractoryceramictilesinits
heatshieldtoprotectagainsttheextremetemperatureconditionsofreentry.TheColumbia
spaceshuttledisasterresultedfromamissingheatshieldtile.
28.11 To operate a 700 W microwave oven, we would need N cells of the type described in 28.10,
where
700 W = N 0.0925 0.25 W = N 0.0231 W,
accounting for the 25% efficiency, i.e.,
N = 700 / 0.0231 = 30300 cells required.
The total area of the solar panel = 30300 cm2 = 3.03 m2.
28.13 In Table 28.1 of the text, the composition of pewter is given as 91% Sn, 7.5% Sb, 1.5% Cu. To
get the density of pewter requires knowing the arrangement of the atoms and appropriate values
for the atomic radii. Here, we will assume that the atoms are arranged pretty much the way they
are in the bulk elements. We will calculate the density of pewter as a weighted average of the
densities of the constituent elements. From www.webelements.com we get the bulk element
densities:
Sn 7310 kg m3
Sb 6697 kg m3
Cu 8920 kg m3
From these densities, we get
0.91 7310 + 0.075 6697 + 0.015 8920 kg m3 = 7288 kg m3
as the approximate density of pewter.
28.15 Whilehydrogenbondingisusuallystrongerthandispersionforces(locally),wecannotmakea
blanketstatementthathydrogenbondingisalwaysstronger.Dispersionforcesincreasewith
thesizeofthemoleculesinvolvedand,morespecifically,withthenumberofelectrons.Thisis
whyiodine,anonpolardiatomicmolecule,isasolidatnormaltemperature.Iodineatomshave
manymoreelectronsthanOatomsandespeciallyHatoms,andtheyaremuchfurtherfromthe
nucleussoaremuchmorepolarizable.Thedispersionforcesbetweeniodinemoleculesare
consequentlysubstantialeven,basedontheevidenceoftheirphasesatambienttemperature,
moreeffectivethanthehydrogenbondingnetworksinwater.
Chapter29
29.1 (a)Threoseisanaldobutose
(b)Ribuloseisaketopentose
(c)Tagatoseisaketohexose
(d)2deoxyriboseisanaldopentose
29.2
HO H
OH
29.3
CH3
H Cl CH3
H H Cl H
CH3 H H
(S)-2-chlorobutane CH3
(R)-2-chlorobutane

29.4
(a) (b) (c) O
H NH2 HO H H
H
H3C H3C H3C

OH H CH3
O O
29.5
(a) O (b) O (c) OH
HO H H OH O
HO H HO H HO H
H OH H OH
OH
OH OH
L-sugar
D-sugar D-sugar

29.6
(a) O (b) O (c) OH
H OH HO H O
H OH H OH H OH
HO H HO H
OH
OH OH
D-sugar
L-sugar L-sugar

29.7
OH
HO OH
H
OH H
H OH
H OH
29.9
HO OH HO
O OH
O
H HO H HO
H OH H
OH
OH H OH H
-D-fructofuranose -D-fructofuranose
H H
OH
H O H O OH
H H OH H H OH
HO OH HO
OH H OH
OH H
-D-fructopyranose -D-fructopyranose

29.11
OH HO
H O
H
HO H O CH3
HO
H H
29.13
NH2
N
HO N
O
P N
O O N
OH
O
HO
O
P N
NH
O
O
O N N NH2
HO
29.15 DNAsequence3CCGATTAGGCA5iscomplementarytoGGCTAATCCGT(bydefaultthis
is5to3).Arranged5to3,thissequenceisACGGATTAGCC.
29.17 RNAsequence3CUAAUGGCAU5orUACGGUAAUCiscomplementarytoDNA
sequenceGATTACCGTA.
29.19 (a)Ala,alanine,iscodedbyGCU,GCC,GCAorGCG
(b)Phe,phenylalanine,iscodedbyUUUorUUC.
(c)Leu,leucine,iscodedbyUUA,UUG,CUU,CUC,CUAorCUG
(d)Tyr,tyrosine,iscodedbyUAUorUAC.
29.21 mRNAbasesequenceAUCGGUgivesrisetotRNAsequence,ACCGAU.
REVIEWQUESTIONS
29.23 (a)
O
H OH
H OH
HO H
HO H
OH
(b)ThisisanLsugarsocalledbecausethehydroxylonthebottomcarbon
stereocenterisontheleftinthisFischerprojection.

(c)
H OH
O
H H
H
OH
OH OH OH

29.25
O
H H
H OH
HO H
HO H
OH
29.27 AscorbicacidhastheLconfigurationatthecarbonnexttotheprimaryalcohol.
29.29 (a)Amonosaccharideisasimplecarbohydrateconsistingofasinglechainpolyhydroxyl
ketoneoraldehyde.(e.gDmannose)

O
HO H
HO H
H OH
H OH
OH
(b)
OH
OH
O OH
OH HO
H H
H H
e.g.Dmannofuranosetheanomericcenterisindicatedbythearrow
(c)TomakeaFischerprojection,weconstructtheconformationofthecarbonchain
arrangedverticallysuchthatallCCbondspointintothepaper.Todothis,weimagine
thatthecarbonchainwhichotherwisecurlsintoaspiralisflattenedontotheplaneof
thepapertheothersubstituentsonthechainpointabovetheplaneofthepaper.
Thesebondsaredrawnashorizontallines.Theexactstereochemistryispreservedin
theFischerprojection.
H OH
H OH
H OH
OH
(d)Aglycosideistheacetalformedfromamonosaccharideandanalcohol.Thealcohol
isfrequentlyanothermonosaccharide.
OH
OH
O H
OH HO
H O
H H OH
O OH
OH HO
H H
H H
(e)ReducingsugarsaresugarsthatcanbereducedbyTollensreagentabasicaqueous
solutionofAgNO3.Suchsugarsarealdosesintheiropenchainform.Theringformis
alsoreducingbecauseitcanopenupunderbasicconditions.

(f)Pyranoseformisthesixmemberedringformofanaldohexoseanaldehydewith6
carbons.
OH
H O H
H
H H
HO OH
OH OH e.g. - D-allopyranose
(g)A1,4linkisaglycosidiclinkagebetweenC1ofonesaccharideandC4ofanother
saccharide.

(h)ADsugarhastheDconfigurationatthecarbonnexttotheprimaryalcohol.
O
HO H
HO H
H OH
H OH
OH
e.g.Dmannose.
29.31 DalloseandLalloseareenantiomers.Intheirpureforms,theyhavethesamevaluesof
allphysicalpropertiesexceptspecificrotation.Thus,theyhavethesame(a)melting
point,(b)solubilityinwater,and(d)density.
(c)Thespecificrotationsareequalinmagnitudebutoppositeinsign.
29.33
Br
(a)
H3C
H O CH3
H3C CH3
(b)
H NH2
29.35 28%Dgalactopyranoseand72%Dgalactopyranose
29.37 Weseethatalanine,leucine,andphenylalaninehavenonpolarRgroups.Serineandaspartic
acidhavepolarRgroups.TheRgroupoflysineisanonpolarchainwithapolarend.
29.39 Tripeptide serine-leucine-valine:
29.41 (a) The amino acid sequence in the protein is its primary structure.
(b) The way different peptide chains in the overall protein are arranged with respect to one
another is the quaternary structure.
(c) The way the polypeptide chain is folded, including how amino acids which are far apart in the
sequence end up in the overall molecule, is the tertiary structure.
(d) The way the amino acids near one another in the sequence arrange themselves is the
secondary structure.
29.43 (a) Sugar ribose: (b) Nucleoside adenosine:
(c) Nucleotide adenosine 5-monophosphate:
29.45 ATGC and CGTA are not the same molecule. The nucleosides are differently arranged when
connected at the 5 and 3 positions to phosphate.
29.47 (a) Transcription is the process wherein mRNA is produced complementary to a strand of DNA.
The first step is the unwinding of the DNA double helix. An RNA strand complementary to a
DNA strand is synthesized, next to the DNA strand. The RNA strand is then unwound from the
DNA. It goes on to protein synthesis. The DNA returns to its double helix form.
(b) Translation is the process wherein the codons of the mRNA are read and used to synthesize
the specific coded protein. A process of sequentially reading the codons is coordinated with the
process that makes a peptide linkage to the next amino acid in the specified sequence.
29.49 Raffinoseisnotareducingsugar.Theglycosidiclinkagescannotbehydrolyzedunderbasic
conditions.
29.51 (a)Glucocerebrosidehashydroxyl,acetal,amide,alkeneandalkylfunctionalgroups.

(b)Hydrolysisofglycosidiclinkage:
Hydrolysisofamide

(c)
29.53 (a) The complementary strand of DNA is (5)GAATCGCGT(3)

(b) The complementary strand of mRNA is (5)GAAUCGCGU(3)
(c) The three anticodons are (5)UUC(3), (5)CGA(3), and (5)ACG(3). They are
complementary to the three codons of the mRNA, (5)GAA(3), (5)UCG(3), and
(5)CGU(3).
(d) (5)GAA(3) codes for Glu, glutamic acid, (5)UCG(3) codes for Ser, serine, and
(5)CGU(3) codes for Arg, arginine.
Chapter30
Inthesesolutions,thesymbols 01 e and 10 canbeusedinterchangeably,ascan 42 He and 24 .
86 Rn 84 Po 2 He
(a) 222 218 4
30.1
84 Po
(b) 218 At 01 e
218
85
30.2 Ephoton=9.91014J
E=60GJmol1
30.3 (a) 23290Th 208

82 Pb 6 42 He 4 0
1 e
(b)
232
90 Th 228
88 Ra 24 He
228
88 Ra 228
89 Ac 01 e
228
89 Ac 228
90 Th 01 e
30.4 (a) 137 N 136 C 10
41
(b) 20 Ca 19
0
1
41
K
38 Sr
(c) 90 Y 10
90
39
11 Na 12 Mg 1
(d) 22 22 0

30.5 14 Si
(a) 32 32
15 P+ 0
1
Ti Sc +
(b) 45
22
45
21
0
1
239
(c) 94 Pu 235
92 U + 42 He
K Ca +
(d) 42
19
42
20
0
1
30.6 3.087x109KJmol1
5.145108kJmol1nucleons
30.7 (a)0.094mg
(b)36.9years
(c)81.7years
30.8 26.9days
30.9 6200years
30.10 Thesampleist=3010yearsold.
Theringdatagivetheageofthetreetobe285352years
30.11 Theisolatedsampleconsistsofthefraction,20/50=0.40,oftheoriginalthreonine.Sincethe
isolatedsampleweighs60.0mg,theremusthavebeen60.0mg/0.40=150.0mgofthreonine
intheoriginalsample.
REVIEWQUESTIONS
30.13 (a) 54
26 Fe 42 He
2 01 n 56
28 Ni
(b) 27
13 Al He
4
2 P n 30
15
1
0
(c) 32
16S 01 n
11 H 32
15 P
(d) 96
42 Mo 21 H
01 n 9743Tc
(e) 98
42 Mo 01 n
9943Tc 0
1
(f) 18
9 O
F 18
8
0
1
30.15 (a) 111

47 Ag
111
48 Cd
0
1
(b) 87
36
Kr 1
0 87
37 Rb
(c) 231
91 Pa
227
89 Ac 24 He
(d) 230
90 Th
He 4
2
226
88 Ra
(e) 82
35 Br
Kr 82
36
0
1
(f) 24
11 Mg
Na 24
12
0
1
30.17
235
92 U
231
90Th 2 He
4
231
90 Th
231
91 Pa
0
1
231
91 Pa
227
89 Ac 2 He
4
227
89 Ac
22790Th 0
1
227
90 Th
223
88 Ra 2 He
4
223
88 Ra
219
86 Rn 2 He
4
219
86 Rn
215
84 Po 2 He
4
215
84 Po
211
82 Pb 2 He
4
211
82 Pb
211
83 Bi
0
1
211
83 Bi
211
84 Po
0
1
211
84 Po
207
82 Pb 2 He
4
30.19 (a) Gold-198 decays to mercury-198.
79 Au 19880 Hg 1
198 0
The atomic number increases by 1, while the mass number does not change. This is beta decay.
(b) Radon-222 decays to polonium-218.
86 Rn 21884 Po 2 He
222 4
The atomic number decreases by 2, while the mass number decreases by 4. This is alpha decay.
(c) Cesium-137 decays to barium-137.
55 Cs
13756 Ba 1
137 0
This is beta decay.

(d) Indium-110 decays to cadmium-110.
49 In 48 Cd 1
110
110 0
This is positron emission.
30.21 (a) Bromine-80m is a metastable state of bromine. It most likely decays by gamma emission to
form bromine-80.
35 Br 35 Br + n
80m 80
n is the number of gamma photons emitted.

(b) Californium-240 is beyondin mass and atomic numberthe band of stability. However,
its neutron to proton ratio is very low. It most likely decays by positron emission.
98 Cf 97 Bk + 1
240 240 0
Alternatively: 24098 Cf 96 Cm + 2 He
236 4
(c) Cobalt-61 has a high neutron to proton ratio. It most likely decays by beta emission.
27 Co 28 Ni + 1
61 61 0
(d) Carbon-11 has a low neutron to proton ratio. It most likely decays by positron emission.
6C 5 B + 1
11 11 0
3 16 20 13
30.23 (a) Of the nuclei H O F and N
3 20
H and F have high neutron to proton ratios and are likely to decay by beta emission.
238 19 22 24
(b) Of the nuclei U F Na and Na
22
Na has a low neutron to proton ratio and is likely to decay by positron emission.
30.25 For 10B,
m = 5 1.00783 + 5 1.00867 10.01294 g mol1 = 0.069510 g mol1 =
6.9510105 kg mol1
Eb = m c2
= 6.9510105 kg mol1 (2.998108 m s1)2
= 6.2481012 J mol1 = 6.248109 kJ mol1
Per nucleon,
Eb / n = 6.248109 kJ mol1 / 10 = 6.248108 kJ mol1 nucleons
For 11B,
m = 5 1.00783 + 6 1.00867 11.00931 g mol1 = 0.081805 g mol1 =
8. 1805105 kg mol1
Eb = m c2
= 8. 1805105 kg mol1 (2.998108 m s1)2
= 7.3531012 J mol1 = 7.353109 kJ mol1
Per nucleon,
Eb / n = 7.353109 kJ mol1 / 11 = 6.684108 kJ mol1 nucleons
We see that 11B is the more stable nucleusit has a higher binding energy per nucleon.
30.31 64 h corresponds to 64 h / 12.7 h = 5.04 half-lives. At this time, the mass of 64Cu is
25.0 g (1/2)5.04 = 0.760 g
53 I 54 Xe + 1
(a) 131 131 0
30.33
(b) 40.2 days corresponds to 40.2 days / 8.04 days = 5.00 half-lives. At this time, the mass of
198
Au is
2.4 g (1/2)5 = 0.075 g
30.35 13 days corresponds to 13 days / (78.25 / 24) days = 4.0 half-lives. At this time, the mass of
67
Ga is
0.015 mg (1/2)4.0 = 9.4 104 mg
86 Rn 84 Po + 2 He
(a) 222 218 4
30.37
222
(b) 20.0% of Rn remains after n half-lives.
0.200 = (1/2)n
n = ln(0.200) / ln(1/2) = 2.32
2.32 half-lives corresponds to 2.32 3.82 days = 8.87 days
30.39 0.72 of the 14C remains after n half-lives.

0.72 = (1/2)n
n = ln(0.72) / ln(1/2) = 0.47
0.47 half-lives corresponds to 0.17 5.73 103 years = 2700 years
This is the age of the bone fragment.
30.41 (a) A cobalt-60 source will drop to 1/8 of its original activity after n half-lives.
0.125 = (1/2)n
n = ln(0.125) / ln(1/2) = 3
3 half-lives corresponds to 3 27 years = 15.81 years
(b) 1 year corresponds to 1 / 5.27 = 0.190 half-lives. At this time, the fraction of 60Co
remaining is
(1/2)0.190 = 0.877
30.43 (a)
11 Na + 0 n
23 1 24
11 Na
24
11Na 24
12 Mg + 0
1
(b)
Na-24 decay
450
400
350
300
Activity/Bq
250
200
150 y = 421.9e-0.046t
100
50
0
0 5 10 15 20 25
time/h
The data is clearly well fit by a simple exponential decay, 421.9 e0.046 t. The parameters of this fit
are well approximated using just the first and last data. k = 0.046 corresponds to t1/2 = ln 2 / k
= ln 2 / 0.046 h = 15 h
30.45
239
94 Pu + 2 01 n 241
94 Pu
241
94 Pu 241
95 Am + 0
1
30.47 238
92U + 126 C 246 1
98 Cf + 4 0 n
It must be carbon-12.
30.49 (a) 114

48 Cd 21 H
115
48 Cd 1 H
1
(b) 6
3 Li 21 H
74 Be 01 n
(c) 40
20 Ca 21 H
19
38
K 42 He
(d) 63
29 Cu 21 H
30
65
Zn
30.51 10
5 B 01 n
73 Li 24 He
30.53 6
3 Li 01 n 31 H 24 He
30.55 Carbon-14 levels in the atmosphere are in steady statedetermined by the flux of cosmic rays
that produce it in the upper atmosphere. Plants take up carbon-14 (via carbon dioxide) in
proportion to its concentration in the atmosphere. When they die, no more carbon-14 is absorbed.
The relative amount of carbon-14 (to carbon-12) decays exponentially with the known half-life of
carbon-14. Measuring this isotope ratio allows the age of the sample to be determinedvia the
logarithm of the isotope ratio divided by its initial value (the atmospheric level). The method, as
described here, assumes the atmospheric level has remained constant. This level is known to
have varied by up to 10% in the past. The method can be corrected for this variation, however.
Nevertheless, the method is limited to objects between 100 and 40,000 years old. There has not
been enough carbon-14 decay in objects less than 100 years old, while the level of carbon-14 is
too small to give an accurate age measurement beyond 40,000 years.
30.57 Radiation can cause transmutation of elements within cells, or can simply ionize or otherwise
disrupt cellular molecules. The resulting chemical reactions can significantly affect cellular
function and even damage DNA molecules. This can lead to cell death, if the cell is unable to
repair the damage at the rate it occurs. Thus, exposure of humans to radiation can cause radiation
sickness and even death, at sufficiently exposure levels. The killing of tissue by radiation can be
used to treat diseases such as cancer, however. By focusing radiation on a tumour, we can kill the
cancer tissue and possibly cure the patient.
30.59 The amount of 87Rb is decreased by the factor,

0.951 = (1/2)n
n = ln(0.951) / ln(1/2) = 0.072 half-lives
This corresponds to 0.072 4.8 1010 years = 3.5 109 years.
30.61 The amount of 235U decreases by the factor

0.72 / 3.0 = 0.24 = (1/2)n
n = ln(0.75) / ln(1/2) = 2.06 half-lives
This corresponds to 2.06 7.04 108 years = 1.45 109 years.
30.63 Amount of 235U = 1000 g / 235.0439 g mol1 = 4.255 mol

Amount of energy released by fission of uranium 235 = 4.255 mol 2.1 1010 kJ mol1 =
8.9 1010 kJ
To obtain the same amount of energy from coal requires
8.9 1010 kJ / 2.9 107 kJ t1 = 3100 t of coal
30.65 The time between the sample injection and the taking of the blood sample is negligible compared
to the half-life of tritium. This is a sample dilution problem. A 1.0 mL sample was injected, and
a 1.0 mL blood sample was taken. The activities measured are proportional to the sample
concentrations. The ratio of the activities equals the ratio of the blood volume to 1.0 mL. The
blood volume is just
2.0 106 Bq / 1.5 104 Bq 1.0 mL = 130 mL
30.67 We could label the methanol with the radioactive isotope, 15O, carry out the reaction, and then
sample the water and look for 15O that could only have come from methanol. The same
experiment could be carried out with labelled acetic acid to see if acid 15O ends up in the water
product.
30.69 The number of atoms in 1.0 mg of 238U is
6.022 1023 mol 1.0 103 g / 238.050782 g mol1 = 2.530 1018
From N/ t kN
we get (note that 1 Bq = 1 s1)
k = ( N/ t) / N
= 12 s1 / 2.530 1018 = 4.74 1018 s1
= 4.74 1018 s1 (606024365) s y1 = 1.50 1010 y1
t1/2 = ln(2) / k = 4.6 109 y
This is close to the literature value, and consistent with the uncertainty expected with a
measurement of only 12 events.

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Answers to SelectedTextbook Questions

H3C CH3 CH3

5.23 (a) H 2 O(g)

6.32 (a) HBr(g) + H 2 O(l)

6.36 (a) Cu 2+ (s) + CO32 (aq) CuCO3 (s)

(b) H 2 CO3 (aq) + OH (aq)

(c) H 3O + (aq) + CH 3 NH 2 (aq)

(d) H 3Citrate(aq) + OH (aq)

2 N2(g) + 6 H2(g) + 5 O2(g)

8.7 (c) Li<Si<C<Ne

50% isosurface of 1s orbital

90% isosurface of 1s orbital

s obital 90% isosurface

CH3 H CH3 H CH3 CH3

9.21 (a) Br>CH2CH2OH>CH2CH3>H

CH3CHCH2 CH2 CH3

(b) 1 SO3H 2 SH 3 OCH2CH2OH 4NH2

10.47 (1) 120

11.17 TakingHeasthereference,RateofeffusionofSF6 =0.166

11.101 (a) O 2 < B2 H 6 < H 2 O i.e.indescendingorderaccordingtomolarmass

13.6 (a) [NH 3 ] 6.2 10-4 mol L1

13.11 (b) K 2 = K12

13.13 (a) K 2 ( K 2 ) 2 = (2.5 1029 ) 2 = 6.3 1058

13.14 K 3 K1 K 2 8.12 0.771 13.7

14.1 (a) HCOOH aq + H 2 O(l) HCOO aq + H 3O + aq

15.13 (a)1.0 105 mol L1

15.24 Knet= 1.1106

15.25 (a) PbSO 4 s

direction of electron flow

direction of electron flow

Mg(s) anode Mg 2+ (aq) Pt(s) cathode

16.31 (a)OS(f)=1 OS(P)=+5

direction of electron flow

direction of electron flow

16.61 (a)Ecell = +0.236 V, K = 9.5 x 107

direction of electron flow

Cl2(g) formed at anode

electron flow electron flow

2 H2O(l) O2(g) + 4 H+(aq) + 2 e

Na+ and Mg2+ flow

By keeping the pipeline at a higher

17.33 22.0 J K1 mol1

17.35 (a) NaCl(g)

17.41 1. C(s) = C(graphite)

2. rS2 = S[CH3OH()] (S[CH4(g)] + S[O2(g)])

3. rS3 = S[CH3OH()] (S[C(s)] + 2 S[H2(g)] + S[O2(g)])

17.45 H 2 O(l) H 2 (g) + 12 O 2 (g)

17.53 = 1139.2 kJ mol1

17.57 = 1441.61 kJ mol1 This is in accord with experience.

17.61 = 4.73 kJ mol1

17.69 (a) rS = 128.133 J K1 mol1

17.71 (a) = 0.141 kJ mol1

17.73 (a)rH = 62.10 kJ mol1

(a) p(Hg) = 1.00 bar

(b) p(Hg) = 1.33 103 bar

17.85 (a) N2H4() + O2(g) N2(g) + 2 H2O()

(b)rH = 622.29 kJ mol1

18.35 (a) Rate = k [CO]2 [O 2 ]

1 NO2 appears as both reactant and

19.57 CH3CH2CH=CHCH3 + HCl CH3CH2CHClCH2CH3 or CH3CH2CH2CHClCH3

CH3 CH3 CH3 CH3

CH2 CH3 H3C CH3

KMnO4 - suppose acidic conditions