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PREFACE

ThesecondeditionofChemistrycontinuesthesubstantialcommitmentofJohnWileyandSons
Australiatolocalchemistryeducation.Studentstodayrequirevariousmultimediaactivities,online
resourcesandtestingtomaintainengagement.Withthisedition,theauthorsandWileyhavecontinued
toexpandthediverseancillaryresourcesavailablethroughWileyPLUSwhichcomplementthetext.In
additiontothetextitself,WileyhasdevelopedextensivenewmediacontentforChemistry,2ndedition.
Writtenincloseconsultationwiththeauthorsandspecificallydesignedforthenewversion5of
WileyPLUS,thetextandresourcesprovidelecturersandstudentsthecompleteandintegratedtoolsto
helpteachersteach,andstudentslearn.

Chemistry,2ndeditioncontinuestoprovidetheappropriateamountoforganic,inorganicandphysical
chemistryforthemajorityofAustralasianfirstyearChemistrycourses.Inthiseditionanewchapterhas
beenaddedtothetext,chapter14Thepblockelements,forthosecoursesthatincludemoreofthis
inorganicchemistrytopic.TheauthorswouldliketoacknowledgetheassistanceofTonyWeddfrom
theUniversityofMelbourneinthepreparationofthischapter.

Additionallymorethanhalfofthechaptershavesignificantnewcontent,andallchaptershavebeen
revised.Chapter8Chemicalthermodynamicshasbeenbrokenintosmallersectionsallowing
mathematicalcontenttobeignoredifnotrequired,andthethermodynamicsmaterialhasbeenrewritten.
Newendofchapterquestionshavealsobeenaddedthroughout,includinganumberofvisual
problems,whileallfiguresandartworkhavebeencloselyscrutinisedandfurtherenhanced.

Thefirsteditionintroducedtwofeatures,ChemicalConnectionsandChemistryResearch,that
provedpopularandhavebeenretained.TheChemicalConnectionsfeatureshighlighttheconnections
betweenthechemicalconceptswithinthechapterandapplicationsofthatchemistryintheworldaround
youchemistrydoesnotstopatthelaboratorydoor.Inadditiontotheapplicationsdiscussedthroughthe
bodyofthetext,theseseparatepagesgivemoreindepthdescriptionsofapplicationsandcovermany
diversesubjects,includingDNAprofiling,desalinationandnanotechnology.Complementingthis,
ChemistryResearchshowcasesinspirationalworkperformedinresearchlaboratoriesinAustraliaand
NewZealandrelatedtotopicsineachchapter.NewcontributionstoChemistryResearchinChemistry,
2ndeditionincludeproteinrecognition,computationalchemistryandphotoelectronspectroscopy.

Ourthanksgoestothefollowingresearchersandcontributors,whohaveprovidedinformationand/or
materialsfortheChemicalConnectionsandChemistryResearchfeatures.
PaulVBernhardt,UniversityofQueensland
MargaretBrimble,UniversityofAuckland
SallyBrooker,UniversityofOtago
MarkBuntine,CurtinUniversity
SamCarroll,CSIRO
JohnCarver,UniversityofAdelaide
MichelleCoote,AustralianNationalUniversity
DeannaD'Allessandro,UniversityofSydney
JamesDeVoss,UniversityofQueensland
ChrisEaston,AustralianNationalUniversity
EmilioGhisalberti,UniversityofWesternAustralia
PaulHaddad,UniversityofTasmania
TrevorHambley,UniversityofSydney
JasonHarper,UniversityofNewSouthWales
RichardHartshorn,UniversityofCanterbury
CraigHawker,UniversityofCalifornia,SantaBarbara
TesseHoekstra,CSIRO
FrancaJones,CurtinUniversity
ScottKable,UniversityofSydney
CameronKepert,UniversityofSydney
SimonWLewis,CurtinUniversity
MaxLu,UniversityofQueensland
MarcelMaeder,UniversityofNewcastle
KathrynMcGrath,VictoriaUniversityofWellington
MarkOgden,CurtinUniversity
RogerRead,UniversityofNewSouthWales
CarlHSchiesser,UniversityofMelbourne
TimSchmidt,UniversityofSydney
FrancesSeparovic,UniversityofMelbourne
DanielSoutham,CurtinUniversity
ClaudineStirling,UniversityofOtago
JeffTallon,MacDiarmidInstituteandIndustrialResearchLtd
JohnTsanaktsidis,CSIRO
MarkvonItzstein,GriffithUniversity
GordonWallace,UniversityofWollongong
JacquelineAnneWilce,MonashUniversity
(Richard)MingWahWong,UniversityofSingapore
ZhiPing(Gordon)Xu,UniversityofQueensland

Muchofthepopularityofthefirsteditioncanbeattributedtotheconsultativenatureoftheauthorial
process.Thesecondeditionhasalsobeenthroughanextensive,thoroughandrigorousreview.
UndertakenbyacademicsteachingundergraduateChemistryinAustraliaandNewZealand,morethan
50contributedtheirtimeincarefullyreviewingdraftchaptersandmakingsuggestionstotheauthors.In
thiscontexttheauthorsandpublisherswouldliketoacknowledgetheimportanceofthecontributions
madeby:
BelindaAbbott,LaTrobeUniversity
PhilAndrews,MonashUniversity
StuartBailey,CurtinUniversity
StephenBest,UniversityofMelbourne
JoanneBlanchfield,UniversityofQueensland
SuzanneBoniface,VictoriaUniversityofWellington
DavidBrown,CurtinUniversity
RonClarke,SydneyUniversity
JamesCrowley,UniversityofOtago
MurrayDavies,JamesCookUniversity
GregDicinoski,UniversityofTasmania
PeterFredericks,QueenslandUniversityofTechnology
LawrieGahan,UniversityofQueensland
BobGilbert,UniversityofQueensland
LisbethGrondhal,UniversityofQueensland
JasonHarper,UniversityofNewSouthWales
HughHarris,UniversityofAdelaide
TobyHudson,SydneyUniversity
GeoffJameson,MasseyUniversity
LynneJones,CurtinUniversity
RichardKeene,JamesCookUniversity
TrevorKitson,MasseyUniversity
GeraldLaurence,UniversityofAdelaide
KieranLim,DeakinUniversity
MaxMassi,CurtinUniversity
RossMcGeary,UniversityofQueensland
CarlaMeledandri,UniversityofOtago
JulieNiere,RMITUniversity
AlanPayne,CurtinUniversity
SbastienPerrier,SydneyUniversity
StephenRalph,UniversityofWollongong
MarkRiley,UniversityofQueensland
TrevorRook,RMITUniversity
DavidSalter,UniversityofAuckland
GarySchenk,UniversityofQueensland
TimSchmidt,SydneyUniversity
MadeleineSchultz,QueenslandUniversityofTechnology
TrevorSmith,UniversityofMelbourne
DanielSoutham,CurtinUniversity
ChrisSumby,UniversityofAdelaide
MattheusTimmer,VictoriaUniversityofWellington
MarkWaterland,MasseyUniversity
TonyWedd,UniversityofMelbourne
NatalieWilliamson,UniversityofAdelaide
DavidWilson,LaTrobeUniversity
DannyWong,MacquarieUniversity
AllanBlackman,SteveBottle,SiggiSchmid,MauroMocerino,andUtaWilleaddthefollowing:
WewouldliketothanktheteamatWiley,especiallyJasonGray,whohaveallworkedsotirelessly
inthedevelopmentofthistext.Wewouldalsoliketogiveparticularthankstothemanyfriendsand
professionalcolleagueswhosenamesappearinthisprefacewhohavealsomadesignificant
contributionstothisproject.Ourgoaltocreateatextthatisrichinlocalcontextsandexamplesand
whichmatchestheneedsandexpectationsofchemistsinAustraliaandNewZealandwouldnothave
beenpossiblewithoutthiscrucialinputandforthatwethankyouandlookforwardtoyourfurther
feedbackandfuturesupport.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.

RESOURCES
WileyPLUS
WileyPLUSisaresearchbased,onlineenvironmentforeffectiveteachingandlearning.Throughareviseddesign,itenables
students'confidencesotheyknowwhattodo,howtodoit,andthattheyhavedoneitcorrectly.Ithasbeendevelopedasaresult
ofsignificanteducationalresearchandfocusgroupinputtodeliverasolutionthatoffersbothstudentsandlecturersasuperior
onlinelearning,homeworkandassessmentsystem.

ResearchbasedDesign
WileyPLUSprovidesanonlineenvironmentthatintegratesrelevantresources,includingtheentiredigitaltextbook,inaneasyto
navigateframeworkthathelpsstudentsstudymoreeffectivelyandsobuildconfidence.
WileyPLUSaddsstructurebyorganisingthetextbookcontentintosmaller,moremanageablechunks.
Innovativefeaturessuchascalendars,visualprogresstrackingandselfevaluationtoolsimprovetimemanagementand
strengthenareasofweakness.
Relatedmedia,examplesandsamplepracticeitemsreinforcethelearningobjectives.

OneononeEngagement
WithWileyPLUSforChemistry,2ndeditionstudentsreceive24/7accesstoresourcesthatpromotepositivelearningoutcomesand
engagement.
IneachchapterwithinWileyPLUS,conceptmodulesarewrittenaroundaclearlearningobjective,andstartwithaConcept
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Thereisalsoscaffoldedpractice.Thescaffoldingvariouslytakestheformofhints,linkstothetext,guidedonline(GO)
tutorialshelpingthestudentstepthroughasimilarproblem,solutionsshowinghowtheanswerisreached,andtheanswer.
Thesehelpthestudentunderstand'howtodoit'.WhenthelecturercomestoteststudentswithinWileyPLUS,theycanchoose
whatscaffoldinghelpcanbemadeavailabletothestudentsforeveryquestion.
Newlywrittenvisualisationsgivestudentsanengagingformattogainbothvisualandconceptualunderstandingofkeytopics.
MeasurableOutcomes
Throughouteachstudysession,studentscanassesstheirprogressandgainimmediatefeedback.WileyPLUSprovidesprecise
reportingofstrengthsandweaknesses,aswellasindividualisedquizzes,sothatstudentsareconfidenttheyarespendingtheirtime
ontherightthings.WithWileyPLUS,studentsalwaysknowtheexactoutcomeoftheirefforts.

InstructorResources
WileyPLUSprovidesreliable,customisableresourcesthatreinforcecoursegoalsinsideandoutsideoftheclassroomaswellas
visibilityintoindividualstudentprogress.Precreatedmaterialsandactivitieshelpinstructorsoptimisetheirtime:

Customisablecourseplan:WileyPLUScomeswithaprecreatedcourseplandesignedbyasubjectmatterexpertuniquelyforthis
course.Simpledraganddroptoolsmakeiteasytoassignthecourseplanasisormodifyittoreflectyourcoursesyllabus.

Precreatedactivitytypesinclude:
Questions
Readingsandresources
ConceptMasteryassignmentstestkeyconceptsfrommultiplepointsofview(visual,symbolic,graphical,quantitative).
Additionally,manyorganicquestionsincludethosewhichrequirestudentstodrawusingMarvinSketch.
ReactionExplorerisaninteractivesystemforlearningandpractisingreactions,synthesesandmechanismsinorganic
chemistry,withadvancedsupportfortheautomaticgenerationofrandomproblemsandcurvedarrowmechanismdiagrams.
WileyPLUSgradebook:WileyPLUSprovidesinstantaccesstoreportsontrendsinclassperformance,studentuseofcourse
materialsandprogresstowardslearningobjectives,helpinginformdecisionsanddriveclassroomdiscussions.

CourseMaterialsandAssessmentContent
MostproblemsintheWileyPLUSQuestionAssignmentsarecodedalgorithmicallywithhints,linkstotext,whiteboard/show
workfeatureandinstructorcontrolledproblemsolvinghelp.
WileyPLUSAlgorithmicquestionsareavailableforeverychapter.
PowerPointslideshavebeencompletelyrewritten.
TheInstructors'SolutionsManualcontainsworkedsolutionstotheendofchapterproblemsinthetext.
TheTestBankisavailableinWord,Blackboard,WebCTandMoodle.Thisisaseparatetestbankfromthatfoundin
WileyPLUS.
TheComputerisedTestBankallowslecturerstoproducehardcopytestsfromthetestbank.
TheArtFilesprovidesallimagesfromthetextinaformatthatallowseasyintegrationintothelecturers'ownresources.

ContributorstoChemistry,2ndEditionResources
TheauthorsandpublisherswouldliketothankJohnHill,LaTrobeUniversity,forhissubstantialcontributioninprovidingthe
WileyPLUSconceptmodulesandConceptBasics.

Theywouldalsoliketothankthefollowingfortheirtimeandcontributiontotheinstructorresources:
SolutionsManual:JohnHill,LaTrobeUniversity
PowerPoint:MelissaLatter,UniversityofWesternAustralia
TestBank:JohnHill,LaTrobeUniversityFlorenceLaibe,MonashUniversityJosephLane,WaikatoUniversityMelissa
Latter,UniversityofWesternAustraliaShannanMaisey,UniversityofWesternAustralia.
www.wileyplus.com

Poweredbyproventechnologyandbuiltonafoundationofcognitiveresearch,WileyPLUShasenrichedtheeducationofmillions
ofstudentsinover20countriesaroundtheworld.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.

ACKNOWLEDGEMENTS
Theauthorsandpublisherwouldliketothankthefollowingcopyrightholders,organisationsand
individualsfortheirpermissiontoreproducecopyrightmaterialinthisbook.

Images
AAP:/AndreaRobinson/UnderlicenseofAAPONEImages489/AFP/GenyaSavilov1167
(bottom)/APPhoto/STR286(bottom)ReprintedwithpermissionfromJournaloftheAmerican
ChemicalSociety,RCoulstonetal.,Harnessingtheenergyofmolecularrecognitioninananomachine
havingaphotochemicalon/offswitch,Vol.128,No.46,20062011AmericanChemicalSociety
1035,1036(bottom),1037CourtesyofANSTO12(2images)ANTPhoto.com.au:/DaveWatts
1080(top)/FredyMercay1080(bottom)/KelvinAitken1081(bottom)AssociateProfessor
TrevorAppleton747(right3images)ArmfieldLimited,www.armfield.co.uk234Australian
Synchrotron114(top)BBarnsley,AustralianNationalBotanicGardens839(top)Reproduced
withpermission.FromAllanMTorresetal.,1999,JournalofBiochemistry,341,78594.
BiochemicalSociety1081(top)BIPM.ReproducedwithpermissionoftheBIPM(Bureau
internationaldespoidsetmesures)35(top)AllanBlackman75(top),90(right),93(left),246,257,
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SallyBrooker577(2images)CengageLearningInc.:/FromBettleheim,Brown,Campbell,Farr,
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14.142007byBrooks/Cole,Reproducedbypermission,www.cengage.com/permissions1079/
(quaternary)/Fig.12.8,p.578,fromZumdahl&Zumdahl,Chemistry6E,2003byBrooks/Cole,
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JohnCarnemolla362/JonathanBlair226/Bettmann5(left),1167(top)/Construction
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380DigitalVision92(left)Elsevier:/ThismaterialwaspublishedinJournalofMolecular
Biology,340,Rekasetal,InteractionofthemolecularchaperoneaBcystallinwithasynuclein:effects
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BiophysicalResearchCommunications,Vol.335(2),HastingsAF,OttingG,FolmerRH,DugginIG,
WakeRG,WilceMC,WilceJA1098,1099LarsOliverEssen672FairfaxPhotoLibrary:/James
Davies809/JasonSouth824(bottom)/RobertPearce370FundamentalPhotographs:/Larry
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PaulHaddad157DavidAHardy,www.astroart.org1173(bottom)HughesMedicalInstitute.
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Research,AlmadenResearchCenter.Unauthorizedusenotpermitted.125(right)Image1001149
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Inc.283,1074,1075/AdaptedfromMcCann,MC,Roberts,K,1991,Architectureoftheprimarycell
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Washnik98,254(top),275(2images),395,432,475(4images),513,547/DHallidayandRResnick,
FundamentalsofPhysics,2nded.,Revised1986,JohnWiley&Sons,Inc.Usedbypermission1163
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Inc.1102/WileyRegistryofMassSpectralData,8thedition,April2006,JohnWiley&Sons,Inc.
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DrLawrenceKobilinsky1110LawrenceBerkeleyNationalLaboratory613(2images)Simon
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WilceMC,WilceJA,InteractionofthereplicationterminatorproteinofBacillussubtiliswithDNA
probedbyNMRspectroscopy,3616,September23,2005,withpermissionfromElsevier1100
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Nature,466,Atomicallyprecisebottomupfabricationofgraphenenanoribbons,byCaietal.2010
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Text
AustralianSynchrotron11415Table12.6,p.577,fromZumdahl&Zumdahl,Chemistry6E,
2003byBrooks/Cole,apartofCengageLearning,Inc.,Reproducedbypermission.
www.cengage.com/permissions651FromWeiser,ME,Atomicweightsoftheelements2005,Pure
Appl.Chem.,Vol.78,No.11,pp.205166,IUPAC2006,andWieser,ME&Berglund,M,Atomic
weightsoftheelements2007,PureAppl.Chem.,Vol.81,No.11,pp.213156IUPAC2009front
endpapersTimSchmidtandScottKable907

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PROLOGUE
Itislikelythatyouarereadingthesewordsbecauseyouhaveenrolledinafirstyearchemistrycourseat
university.Itmaybethatyouarestartingonacareerinchemistry,oryoumaybeplanningtostudy
anothersubjectforwhichchemistryisaprerequisite.Someofyouwillhavestudiedchemistry
throughouthighschool,while,forothersamongyou,thismaywellbethefirsttimeyouhave
encounteredchemistry.Butregardlessofyourbackgroundinchemistry,orthereasonsyouarestudying
thesubject,youareallgoingtohavetolearnsomechemistryoverthecomingmonths,andwesincerely
hopethatreadingthisbookwillmakethattaskeasier.Eachmemberoftheauthorteamhasbeenexactly
whereyouarenowweallsurvivedfirstyearchemistryandweallknowwhichteachingandlearning
approachesworkedforus.Itisouraimtobringthoseapproachestothisbooksothattheymayassist
youinyourstudies.
Thoseofyouwithyoursightssetonacareerinchemistrywillalreadyknowtheimportanceofthe
subjectandthekindofworkthatchemistsdo.Chemistsarepeopletrainedinthescienceofchemistry,
andtheyareinterestedinmanydifferentaspectsofmatter.Somechemistsareprimarilyconcernedwith
chemicalsynthesis,thepreparationofnewtypesofmatterthathavenotpreviouslyexisted.Examples
includenewdrugsforthetreatmentofdiseasenewstrong,lightweightmaterialsforuseinconstructing
everythingfromyachtstoskyscrapersandplasticsthatcanconductelectricityoremitlight.Other
chemistsareprimarilyinterestedinmeasuringthepropertiesandamountsofmatterforexample,how
muchheataparticularmaterialcanholdorhowmuchcarbondioxideisintheatmosphere.Agrowing
numberofchemistsneverevenventureintothechemicallaboratory,preferringtousecomputersto
predict,withgreataccuracy,propertiesofmatterthathasyettobemade.Theseexamplesserveto
illustratethefactthatchemistryisanexpandingsubject.Inthenottoodistantpast,chemistrywas
viewedasanarrowlydefinedsciencecarriedoutbymen(alwaysmen)inwhitecoats(alwayswhite
coats)whoinhabitedlabsfilledwithflaskscontainingallkindsofnoxiouschemicals.Thankfully,thisis
nolongerthecasenowadays,therearelikelytobemorewomenthanmeninafirstyearchemistry
class,andthescopeofchemistryhasincreasedenormously.Indeed,chemistrynowoverlapswithmany
othersciencestothepointwherethemarginsbetweenthedifferentdisciplineshavebecome
significantlyblurred.Thisisshownbythefollowingstatisticsconcerningthemostprestigiousawardin
chemistry,theNobelPrize.Ofthe25awardeesovertheperiod20002009,fewerthanhalfofthemhad
aPhDinchemistry.ManyhadamedicaldegreeorPhDinthebiologicalsciences,onehadaPhDin
physics,while,remarkably,twohadnoPhDatall.Theprizeswereawardedfortopicsasdiverseas
discoveriesabouthowwaterandothersmallmoleculescanpassthroughthewallsofcells,howproteins
aredegradedincells,thestructureandfunctionoftheribosome,thediscoveryanddevelopmentofa
proteininjellyfishthatglowsgreen,andthedevelopmentofmethodstodeterminethestructureoflarge
molecules.Manyofthesesubjectswouldusuallybethoughtofasthedomainofbiologicalscientists,
buttheirbasisisundeniablychemistry.Andhereinliesthereasonthatchemistryisaprerequisitefora
largenumberofsciencecourses.

Considermedicine,forexample.Ifyouaretrainingtobeadoctor,aknowledgeofchemistryiscrucial
weare,afterall,madeupofatoms.Thehumanbodyplayshosttoadizzyingvarietyofchemical
reactions,allofwhichplayaparticularroleinaqualitythatwecalllife.Weareabletosee,thanksin
parttoamoleculecalledretinal,whichundergoesachemicalreactionwhenitisexposedtolight.We
maintainabodytemperatureofapproximately37Cprimarilyduetoamoleculecalledadenosine
triphosphate,whichundergoesachemicalreactioninthebodythatreleasesenergy.Ournervesfunction
astheydobecauseoftheverydelicatebalanceofsodiumandpotassiumionsinthebody.Current
medicalresearchisnotjustaboutbettersurgicaltechniquesitaimstofindcuresfordiseasessuchas
cancer,HIV/AIDSandAlzheimer'sthroughanunderstandingofthemolecularbasisofsuchdiseases.
Medicalstudentsmustlearnaboutthemyriadprocessesthatenablethehumanbodytofunctionand
appreciatetherolethatchemistryplaysinmanyofthem.
Ifyouarehopingtobecomeadentist,youwillneedtobefamiliarwiththechemistryofcalcium
hydroxyapatite,animportantcomponentoftoothenamel.Dentistsneedtoappreciatetheusesand
possibledangersofmercuryfillingsmoreandmorepeoplearechoosingtohavemercuryfillings
replacedwithwhitefillingsbecauseofthepossiblehealthrisk,andanydentistmustbeabletoadvise
patientsonthissubject.Alsoofcurrentinterestisthequestionoffluoridationofwatersuppliestoreduce
theincidenceoftoothdecay,particularlyinyoungchildren.Whataretherisksandwhatarethe
benefits?Whatistheroleoffluorideinreducingtoothdecay?Whatformoffluorideisaddedtocity
watersupplies?Again,dentistsneedtohaveanunderstandingofthisveryemotiveissue.Asadentist,
youwillencounteralargenumberofnewpolymericmaterialsusedinfillings,implantsandprostheses,
andyouwillhavetounderstandthechemistryofthesetomakeappropriatechoicesofmaterialfor
particularapplications.

Thoseofyoustudyingtobepharmacistsandpharmacologistswillencountersignificantamountsof
chemistryinyourcourses.Obviously,drugsandthewayinwhichtheyaremanufacturedareimportant
inthesedisciplines,buthowthesedrugsinteractwithmoleculesinthebodyalsoconstitutesa
significantportionofyourstudy,andyouwillcertainlyrequireanappreciationofchemicalkineticsto
understandthedifferentratesatwhichparticulardrugsact.

BiochemistryandgeneticsareconcernedmainlywithhugemoleculessuchasDNA,RNAandproteins,
andtheimportanceofchemistryinthesedisciplinesisselfevident.Tounderstandhowthesemolecules
function,biochemistsandgeneticistsneedaknowledgeofchemicalprinciplessuchasacidbase
chemistry,hydrogenbondingandmolecularrecognition,aswellasanappreciationofthebasicsbehind
themethodsusedforstructuraldeterminationofthesemolecules.Biochemicalapplicationsinforensics,
mostnotablyDNAfingerprinting,havesignificantchemistrycomponentssamplesmustbekept
scrupulouslycleantoavoidcontamination,andhighlypurereagentsandstringentlycontrolled
techniquesmustbeusedtoobtainusableevidence.People'slivesdependontheskillandunderstanding
ofthepersoncarryingouttheseanalyses.

Thechemistryoftheenvironmentcontinuestoincreaseinimportanceaswegrowtoappreciatethe
significantimpactsthatmankindishavingontheEarth.Recognitionandconfirmationofthedamaging
consequencesofgreenhousegasesintheatmosphere,forexample,areduetothecarefuland
painstakingmeasurementsbyscientistsallaroundtheglobe.Becauseofthis,wenowusetermssuchas
carbonfootprintandfoodmiles,whichwereunheardofonlytwodecadesago.Likewise,
chlorofluorocarbons(CFCs)havenowbeenallbutbannedbecauseoftheircapacitytodestroythe
ozonelayer,afactrecognisedasaresultofexperimentsinthechemistrylaboratory.Itisbecauseofthis
workthattheozoneholeinthevicinityofAustraliaandNewZealandhassloweditsgrowthandis
showingsomesignsofrecovery.
Itiscertainthatwewillrunoutofaccessiblefossilfuelsatsomestage,possiblyinyourlifetimewhat
weurgentlyneedisnotmoreefficientuseofthisdwindlingresourcebutanentirelynewsourceof
energy.BothAustraliaandNewZealandareperfectlysituatedtoexploitsolarpower.Chemistsareat
theforefrontofresearchinthisareaandaredevelopingnewmaterialsthatcancleanlyandefficiently
convertsunlighttoelectricity.Again,thoseofyoustudyingenvironmentalscienceorecologywilllearn
aboutthesesubjectsandthechemistrybehindthem.

Inshort,themajorityofscienceshavesomechemistrycomponentindeed,youwillfindchemical
names,chemicalformulaeandchemicaldiagramsinmostscientifictextbooks.Butchemistryalsocrops
upinquiteunexpectedplaceslaw,forexample.Scientificdiscoverieswithanycommercialpotential
areusuallyimmediatelypatented,andthisprocessiscarriedoutbypatentattorneys.Giventhatmanyof
themostvaluablepatentsconcerndrugs,itisobviouslyvitalthatthepatentattorneysinvolvedhavean
appreciationofchemistry,andgraduateswhotrainedinbothpatentlawandchemistryarecurrentlyin
greatdemand.Similarly,anunderstandingofbothchemistryandcommerceisamajoradvantagein
manufacturingindustries,andasignificantnumberofcommercestudentsnowopttoincludesome
scienceunitsintheirdegrees.Giventheimportanceofchemistryinourmodernworld,wewouldhope
thatourleaderswouldhaveatleastsomeappreciationofthesubject.Thesubjectofclimatechange,for
example,mustbeaddressedonthebasisofscience,ratherthaneconomics,and,inanidealworld,
politicianswouldbesufficientlyversedinthechemistryofclimatechangetobeabletomakeinformed
decisions.Afterall,thefutureoftheplanetisatstake.

Butwhatofchemistryasadisciplineinitself?Whydopeoplechoosetobechemists?Thereisno
simpleanswertothisquestion,butitisprobablytruetosaythatmostchemistsarefascinatedbythe
natureofmatterandseekanunderstandingofitusingchemicalprinciples,suchasthesynthesisofnew
molecules,determinationofthestructuresofchemicalspeciesandstudiesofthereactivityofa
particularmolecule.Trainedchemistsgoontoaremarkablevarietyofjobs,notnecessarilyinchemistry
labs,andthedemandforchemistrygraduatesisalwaysstrong.

Sonowthatyouhaveanappreciationofjustwhatchemistryis,itistimetobeginourstudy.Wewill
startwithafundamentalconceptwhichunderpinsallofchemistrytheatom.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

1 TheAtom
Chemistryisthescienceconcernedwiththestudyofmatter.Matterisanythingthattakesup
spaceandhasmasseverythingyoucansee,smell,touchortaste.Centraltotheworkof
chemistsisthestructureofmatterinotherwords,thewaysinwhichmatterisconstructed
fromthefundamentalbuildingblock,theatom.

Althoughatomsaretrulytiny,andcannotbeseenusingconventionalmeansof
magnification,moderntechnologyallowsvisualisationofindividualatoms.Forexample,the
electronmicroscopeimageatrightshowsasheetofgraphene,amaterialcomposedentirely
ofcarbonatoms.Eachhexagoncomprisessixcarbonatomsandthewholesheetisjusta
singleatomthick,asshownintheaccompanyingballandstickmodel.Suchatomicscale
imagescanaidunderstandingofthepropertiesofgraphene,includingitsunusualstrength
andconductivity.
NASAOzoneHoleWatch,http://ozonewatch.gsfc.nasa.gov

IncontrasttoAndreGeimandKonstantinNovoselov,whowereawardedtheNobelPrizein
physicsin2010fortheirworkongraphene,theearlytwentiethcenturypioneersdidnothave
recoursetoourmodernhitechmethods.Ourunderstandingofthestructureoftheatom,and
thewayinwhichatomspacktogetherinthreedimensionalspace,owesmuchtoexperiments
carriedoutbytwoAustralasianbornscientists,ErnestRutherford(18711937,NobelPrize
inchemistry1908)andWilliamLawrenceBragg(18901971,NobelPrizeinphysics1915),
usingequipmentthatwouldnowbeconsideredprimitive.TheNewZealandbornRutherford
wasthefirsttoshowthattheatomconsistsofapositivelychargednucleussurroundedby
tinynegativelychargedelectrons,whileBragg(borninAustralia),togetherwithhisBritish
bornfatherWilliamHenryBragg,developedthetechniqueofXraycrystallography,in
whichXraysareusedtodeterminethethreedimensionalstructureofsolidmatteronthe
atomicscale.ThecontributionoftheBraggswillbeoutlinedfurtherinchapter7.This
chapterisprimarilyconcernedwiththeatom.ItwillexaminethecontributionofRutherford
andotherstothedeterminationofthestructureoftheatom,andwillshowhowaparticular
structuralfeatureoftheatomformsthebasisoftheperiodictableoftheelements.

KEYTOPICS

1.1Atoms,molecules,ions,elementsandcompounds
1.2Theatomictheory
1.3Thestructureoftheatom
1.4Theperiodictableoftheelements
1.5Electronsinatoms

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.1Atoms,Molecules,Ions,Elementsand
Compounds
Chemistryisthestudyofmatter.Chemistsviewmatterasbeingcomposedofvariouschemicalentities.
Beforeweembarkonourstudyofchemistry,wewillbrieflydefinesometermsusedtodescribethese
entities.Thiswillaidourunderstandingofthematerialinthischapterwewilllookattheseconcepts
again,ingreaterdetail,insubsequentchapters.Atomsarediscretechemicalspeciescomprisinga
centralpositivelychargednucleussurroundedbyoneormorenegativelychargedelectrons.Atomsare
alwayselectricallyneutral,meaningthatthenumberofelectronsisequaltothenumberofprotonsinthe
nucleus.Chemistsregardtheatomasthefundamentalbuildingblockofallmatter,soitmaysurprise
youtolearnthatindividualatomsarerarelyofchemicalinterestfreeatoms(withtheexceptionofthe
elementshelium,neon,argon,krypton,xenonandradon)areusuallyunstable.Ofmuchgreaterinterest
tochemistsaremolecules,whicharecollectionsofatomswithadefinitestructureheldtogetherby
chemicalbonds.Thesmallestmoleculescontainjusttwoatoms,whilethelargestcanconsistofliterally
millions.Mostgasesandliquidsconsistofmolecules,andmostsolidsbasedoncarbon(organicsolids)
arealsomolecular.Likeatoms,moleculesareelectricallyneutralandare,therefore,uncharged.
Moleculesareheldtogetherbycovalentbonds,whichinvolvethesharingofelectronsbetween
neighbouringatoms.

Ionsarechemicalspeciesthathaveeitherapositiveornegativeelectriccharge.Thosewithapositive
chargearecalledcationsthosewithanegativechargearecalledanions(respectivelydesignatedbya+
or).Ionscanbeformallyderivedfromeitheratomsormoleculesbytheadditionorremovalofoneor
moreelectrons.Forexample,removinganelectron(e)fromasodium,Na,atomgivestheNa+cation.

Addinganelectrontoanoxygenmolecule,whichconsistsoftwooxygenatomsbondedtogetherandis
designatedO2,givesthesuperoxideanion.

Elementsarecollectionsofonetypeofatomonly,andthe118elementsknownatthetimeofwriting
arelistedintheperiodictableontheinsidefrontcover.Compoundsaresimplysubstancescontaining
twoormoreelementsinadefiniteandunchangingproportion.Compoundsmaybecomposedof
molecules,ionsorcovalentlybondednetworksofatoms.Notethatwedonothaveindividual
moleculesofanioniccompoundsuchassodiumchloride.Thechemicalformulaofsodiumchloride,
NaCl,simplyrepresentsthesmallestrepeatingunitinanenormousthreedimensionalarrayofNa+ions
andClions.Thesameappliestocertaincovalentlybondedstructures.Forexample,quartz,whichis
composedofaninfinitethreedimensionalnetworkofcovalentlyboundSiandOatoms,hasthe
chemicalformulaSiO2,whichrefersnottoindividualSiO2moleculesbuttothesmallestrepeatingunit
inthenetwork.

Alloftheabovechemicalentities(atoms,molecules,ions,elementsandcompounds)maybeinvolved
asreactantsinchemicalreactions,processesinwhichtheyundergotransformationsgenerally
involvingthemakingand/orbreakingofchemicalbonds,andwhichusuallyresultintheformationof
differentchemicalspeciescalledproducts.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.2TheAtomicTheory
Today,wetaketheexistenceofatomsforgranted.Wecanexplainmanyaspectsofthestructureofthe
atomand,infact,currenttechnologyallowsustoseeandevenmanipulateindividualatoms.
However,scientificevidencefortheexistenceofatomsisrelativelyrecent,andchemistrydidnot
progressveryfaruntilthatevidencewasfound.

Theconceptofatomsbegannearly2500yearsagowhentheGreekphilosopherLeucippusandhis
studentDemocritusexpressedthebeliefthatmatterisultimatelycomposedoftinyindivisibleparticles
thewordatomisderivedfromtheGreekwordatomos,meaningnotcut.Thephilosophers'
conclusions,however,werenotsupportedbyanyscientificevidencetheywerederivedsimplyfrom
philosophicalreasoning.Theconceptofatomsremainedaphilosophicalbelief,havinglimitedscientific
usefulness,untilthediscoveryoftwolawsofchemicalcombinationinthelateeighteenthcenturythe
lawofconservationofmassandthelawofdefiniteproportions.Thesemaybestatedasfollows:
thelawofconservationofmass:Nodetectablegainorlossofmassoccursinchemicalreactions.
Massisconserved.
thelawofdefiniteproportions:Inagivenchemicalcompound,theelementsarealwayscombined
inthesameproportionsbymass.
TheFrenchchemistAntoineLavoisier(17431794)proposedthelawofconservationofmassasa
resultofhisexperimentsinvolvingtheindividualreactionsoftheelementsphosphorus,sulfur,tinand
leadwithoxygen.HeusedalargelenstofocustheSun'sraysonasampleofeachelementcontainedin
aclosedjar,andtheheatcausedachemicalreactiontotakeplace.Heweighedtheclosedjarandits
contentsbeforeandafterthechemicalreactionandfoundnodifferenceinmass,leadinghimtopropose
thelaw.(LavoisierwasbeheadedfollowingtheFrenchRevolution,thejudgeathistrialreputedly
sayingtheRepublichasnoneedofscientists.)Thelawofconservationofmasscanbealternatively
statedasmassisneithercreatednordestroyedinchemicalreactions.

AnotherFrenchchemist,JosephLouisProust(17541826),wasresponsibleforthelawofdefinite
proportions,followingexperimentsthatshowedthatcoppercarbonatepreparedinthelaboratorywas
identicalincompositiontocoppercarbonatethatoccursinnatureasthemineralmalachite.Healso
showedthatthetwooxidesoftin,SnOandSnO2,andthetwosulfidesofiron,FeSandFeS2,always
containfixedrelativemassesoftheirconstituentelements.Thelawstatesthatchemicalelementsalways
combineinadefinitefixedproportionbymasstoformchemicalcompounds.Thus,ifweanalyseany
sampleofwater(acompound),wealwaysfindthattheratioofoxygentohydrogen(theelementsthat
makeupwater)is8to1bymass.Similarly,ifweformwaterfromoxygenandhydrogen,themassof
oxygenconsumedwillalwaysbe8timesthemassofhydrogenthatreacts.Thisistrueevenifthereisa
largeexcessofoneofthem.Forinstance,if100gofoxygenismixedwith1gofhydrogenandthe
reactiontoformwaterisinitiated,allthehydrogenwouldreactbutonly8gofoxygenwouldbe
consumedtherewouldbe92gofoxygenleftover.Nomatterhowwetry,wecannotalterthechemical
compositionofthewaterformedinthereaction.

WORKEDEXAMPLE1.1

ApplyingtheLawofDefiniteProportions
Theelementmolybdenum,Mo,combineswithsulfur,S,toformacompoundcommonly
calledmolybdenumdisulfidethatisusefulasadrylubricant,similartographite.Itisalso
usedinspecialisedlithiumbatteries.Asampleofthiscompoundcontains1.50gofMofor
each1.00gofS.Ifadifferentsampleofthecompoundcontains2.50gofS,whatmassof
Modoesitcontain?

Analysis

ThelawofdefiniteproportionsstatesthattheproportionsofMoandSbymassmustbethe
sameinbothsamples.Tosolvetheproblem,wewillsetupthemassratiosforthetwo
samples.Intheratioforthesecondsamplethemassofmolybdenumwillbeanunknown
quantity.Wewillequatethetworatiosandsolvefortheunknownquantity.

Solution

ThefirstsamplehasaMotoSmassratioof:

WeknowthemassofSinthesecondsample,butthemassofMoisunknown.Wedoknow,
however,thattheMotoSmassratioisthesameasthatinthefirstsample.Wesetuptheratio
forthesecondsampleusingxfortheunknownmassofMo.Therefore,fromthelawof
definiteproportions,wecanwrite:

Wecansolveforxbymultiplyingbothsidesoftheequationby2.50gS,togive:

Isouranswerreasonable?

Toavoiderrors,itisalwayswisetodoaroughcheckoftheanswer.Usually,somesimple
reasoningisallweneedtoseeiftheanswermakessense.Thisishowwemightdosucha
checkhere:Noticethatthemassofsulfurinthesecondsampleismorethantwicethemass
inthefirstsample.Therefore,weshouldexpectthemassofMointhesecondsampletobe
somewhatmorethantwicewhatitisinthefirst.Theanswerweobtained,3.75gMo,ismore
thantwice1.50gMo,soouranswerseemstobereasonable.

PRACTICEEXERCISE1.1
Cadmiumsulfideisayellowcompoundthat
isusedasapigmentinartists'oilcolours.A
sampleofthiscompoundiscomposedof
1.25gofcadmium,Cd,and0.357gof
sulfur,S.Ifasecondsampleofthesame
compoundcontains3.50gofsulfur,what
massofcadmiumdoesitcontain?

Thelawsofconservationofmassanddefiniteproportionsservedastheexperimentalfoundationforthe
atomictheory.Theypromptedthequestion,Whatmustbetrueaboutthenatureofmatter,giventhe
truthoftheselaws?Inotherwords,Whatismattermadeof?Atthebeginningofthenineteenth
century,JohnDalton(17661844),anEnglishscientist,usedtheGreekconceptofatomstomakesense
ofthelawsofconservationofmassanddefiniteproportions.Daltonreasonedthat,ifatomsreallyexist,
theymusthavecertainpropertiestoaccountfortheselaws.Hedescribedsuchproperties,andthe
followinglistconstituteswhatwenowcallDalton'satomictheory.
1.Matterconsistsoftinyparticlescalledatoms.
2.Atomsareindestructible.Inchemicalreactions,theatomsrearrangebuttheydonotthemselves
breakapart.
3.Inanysampleofapureelement,alltheatomsareidenticalinmassandotherproperties.
4.Theatomsofdifferentelementsdifferinmassandotherproperties.
5.Whenatomsofdifferentelementscombinetoformagivencompound,theconstituentatomsin
thecompoundarealwayspresentinthesamefixednumericalratio.

Dalton'stheoryeasilyexplainedthelawofconservationofmass.Accordingtothetheory,achemical
reactionissimplyareorderingofatomsfromonecombinationtoanother.Ifnoatomsaregainedorlost,
andifthemassesoftheatomscan'tchange,themassafterthereactionmustbethesameasthemass
before.Thisexplanationofthelawofconservationofmassallowsustouseanotationsystemof
chemicalequationstodescribechemicalreactions.Achemicalequationcontainsthereactantsonthe
lefthandsideandtheproductsontherighthandside,separatedbyaforwardarrow,asdemonstratedin
thefollowingchemicalequationfortheformationofliquidwaterfromitsgaseouselements.

Thelawofconservationofmassrequiresustohavethesamenumberofeachtypeofatomoneachside
ofthearrowthisbeingthecase,thechemicalequationaboveisdescribedasbalanced.Wewilldiscuss
thisconceptindetailinchapter3.Notethatthischemicalequationalsospecifiesthephysicalstatesof
thereactantsandproduct.Gases,liquidsandsolidsareabbreviatedas(g),(l)and(s),respectively,after
eachreactantandproduct.

ThelawofdefiniteproportionscanalsobeexplainedbyDalton'stheory.Accordingtothetheory,a
givencompoundisalwayscomposedofatomsofthesameelementsinthesamenumericalratio.
Suppose,forexample,thatelementsXandYcombinetoformacompoundinwhichthenumberof
atomsofXequalsthenumberofatomsofY(i.e.theatomratiois1to1).IfthemassofaYatomistwice
thatofanXatom,theneverytimeweencounterasampleofthiscompound,themassratio(XtoY)
wouldbe1to2.Thissamemassratiowouldexistregardlessofthesizeofthesampleso,insamplesof
thiscompound,elementsXandYarealwayspresentinthesameproportionbymass.

StrongsupportforDalton'stheorycamewhenDaltonandotherscientistsstudiedelementsthatcan
combinetogiveatleasttwocompounds.Forexample,sulfurandoxygencancombinetoformboth
sulfurdioxide,SO2,andsulfurtrioxide,SO3.Theformercontainsoneatomofsulfurandtwoatomsof
oxygen,whilethelattercontainsoneatomofsulfurandthreeatomsofoxygen.Althoughtheyhave
similarchemicalformulae,theyaredifferentchemicallyforexample,atroomtemperature,SO2isa
colourlessgaswhileSO3,whichmeltsat16.8C,isasolidorliquid,dependingonthetemperatureof
theroom.IfweanalysesamplesofSO2andSO3inwhichthemassesofsulfurarethesame,weobtain
theresultsshownintable1.1.
TABLE1.1 MassCompositionofSulfurDioxideandSulfurTrioxide
Compound Massofsulfur Massofoxygen
SO2 1.00g 1.00g

SO3 1.00g 1.50g


Notethattheratioofthemassesofoxygeninthetwosamplesisoneofsmallwholenumbers.

Similarobservationsaremadewhenwestudyotherelementsthatformmorethanonecompoundwith
eachother.Theseobservationsformthebasisofthelawofmultipleproportions,whichstatesthat:
Whenevertwoelementsformmorethanonecompound,thedifferentmassesofoneelementthat
combinewiththesamemassoftheotherelementareintheratioofsmallwholenumbers.

Dalton'stheoryexplainsthelawofmultipleproportionsinaverysimpleway.Supposeamoleculeof
sulfurtrioxidecontains1sulfurand3oxygenatoms,andamoleculeofsulfurdioxidecontains1sulfur
and2oxygenatoms(figure1.1).Ifwehadjustonemoleculeofeach,oursampleswouldeachhave1
sulfuratomand,therefore,thesamemassofsulfur.Then,comparingtheoxygenatoms,wefindthey
areinanumericalratioof3to2.Butbecauseoxygenatomsallhavethesamemass,themassratiomust
alsobe3to2.ThelawofmultipleproportionswasnotknownbeforeDaltonpresentedhistheory,and
itsdiscoverydemonstratesscienceinaction.ExperimentaldatasuggestedtoDaltontheexistenceof
atoms,andtheatomictheorysuggestedtherelationshipsthatwenowcallthelawofmultiple
proportions.Whenfoundbyexperiment,theexistenceofthelawofmultipleproportionsaddedgreat
supporttotheatomictheory.Infact,formanyyears,itwasoneofthestrongestargumentsinfavourof
theexistenceofatoms.

FIGURE1.1Compoundscontainingoxygenandsulfurdemonstratethelawofmultipleproportions.
Representedherearemoleculesofsulfurtrioxide,SO3 ,andsulfurdioxide,SO2 .Eachhasone
sulfuratom,andthereforethesamemassofsulfur.Theoxygenratiois3to2,bothbyatomsand
bymass.

AsoutlinedintheChemicalConnectionsfeatureonthenextpage,wearenowabletoseeandeven
manipulateindividualatoms,therebyprovidingproofoftheatomicnatureofmatter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.3TheStructureoftheAtom
Eventhoughabsoluteproofoftheexistenceofatomswasnotavailablearoundtheturnofthetwentieth
century,scientistswereinterestedinthestructureoftheatom.WhileDalton'stheorysaidthatatoms
wereindestructibleandcouldnotbebrokenapart,experimentsaroundthistimeshowedthiswasnot
necessarilytrue.Inparticular,thediscoveryofradiationintheformofXraysbyWilhelmRntgen
(18451923)in1895(seefigure1.2)andradioactivitybyAntoineHenriBecquerel(18521908,
picturedinfigure1.3)in1896ledscientiststobelievethattheatomwascomposedofdiscreteparticles,
asbothformsofradiationinvolvethereleaseofparticlesfromatoms,thoughtatthattimetobe
indivisible.

FIGURE1.2AreproductionofoneofthefirsteverXrayimages,takenbyWilhelmRntgen(NobelPrizein
physics,1901)on22December1895.Thehandisthatofhiswife.
FIGURE1.3AntoineHenriBecquerel(NobelPrizeinphysics,1903)discoveredradioactivity.

ChemicalConnections

Nanotechnology:ControllingStructureattheMolecularLevel

Nanotechnologyisawordthatisfindingincreasinguse,especiallyinthepopularmedia.As
weshallseeinchapter2,theprefixnanomeans10 9,andnanotechnologycanthereforebe
broadlydefinedasthescienceofobjectshavingdimensionsonthenanometre(10 9m)scale.
Individualatomshavediametersoftheorderof10 10minotherwords,fractionsofa
nanometre.Nanoscaleobjectsthereforehavedimensionsofperhapstenstohundredsof
atoms.

Nanotechnologydealswithusingsuchsmallscaleobjectstoaccomplishusefultasks.Oneof
thegoalsofnanotechnologyistobuildmaterialsfromtheatomup.Thereareseveralreasons
forthegreatinterestinnanotechnology.Forone,thepropertiesofmaterialsarerelatedto
theirstructures.Bycontrollingstructuresattheatomicandmolecularlevel,wecan(in
principle)tailormaterialstohavespecificproperties.Drivingmuchoftheresearchinthisarea
arethecontinuingeffortsbycomputerandelectronicsdesignerstoproduceeversmaller
circuits.Thereductionsinsizeachievedthroughtraditionalmethodsareneartheirlimit,so
newwaystoachievesmallercircuitsandsmallerelectricaldevicesarebeingsought.

Anotherareaofresearchofmuchinteresttodayisthefieldofmolecularselfassembly,in
whichcertainmolecules,whenbroughttogether,spontaneouslyarrangethemselvesinto
desirablestructures.Biologicalsystemsemploythisstrategyinconstructingstructuressuchas
cellularmembranes.Thegoalofscientistsistomimicbiologybydesigningmoleculesthat
willselfassembleintospecificarrangements.

Visualisingandmanipulatingnanoscaleobjects
Wecannotuseopticalmicroscopestoobservenanoscaleobjects,becausetheirdimensions
aresmallerthanthewavelengthofvisiblelight.However,theinventionofboththescanning
tunnellingmicroscope(STM)andtheatomicforcemicroscope(AFM)inthelatetwentieth
centuryhasallowedustoseeand,moreremarkably,manipulateindividualatoms.TheSTM
andAFMoperateusingthesamebasicprinciplemovingthetipofanextremelyfinestylus
acrossasurfaceatadistanceofatomicdimensions.InthecaseoftheSTM,thesurfacemust
beelectricallyconducting,andthiscausesacurrenttoflowbetweenthesurfaceandthetip.
Themagnitudeofthiscurrentdependsonthedistancebetweenthetipandthesurface,soas
thetipismovedacrossthesurface,computercontrolofthecurrentataconstantvaluewill
causethetiptomoveupanddown,therebygivingamapofthesurface.Becauseofitstiny
size,thetipcanalsobeusedtomoveindividualatoms.Oneofthefirstdemonstrationsof
nanotechnologycamein1989whenDonEigler,ascientistatIBM,manipulated35atomsof
xenononanickelsurfaceusinganSTMtospellthenameofhisemployer(figure1.4).

FIGURE1.4IndividualXeatoms(bluedots)onanickelsurfacemanipulatedbyanSTMtip.

AnAFM(illustratedinfigure1.5)isusedtostudynonconductingsamples.Thestylusis
movedacrossthesurfaceofthesampleunderstudy.Forcesbetweenthetipoftheprobeand
thesurfacecausetheprobetoflexasitfollowstheupsanddownsofthebumpsthatarethe
individualmoleculesandatoms.Amirroredsurfaceattachedtotheprobereflectsalaser
beamatanglesproportionaltotheamountofdeflectionoftheprobe.Asensorpicksupthe
signalfromthelaserandtranslatesitintodatathatcanbeanalysedbyacomputertogive
threedimensionalimagesofthesample'ssurface.

FIGURE1.5InanAFM,asharpstylusattachedtotheendofacantileverproberidesupand
downoverthesurfacefeaturesofthesample.Alaserbeam,reflectedoffamirrored
surfaceattheendoftheprobe,changesangleastheprobemovesupanddown.A
photodetectorreadsthesechangesandsendstheinformationtoacomputer,which
translatesthedataintoanimage.

AtypicalAFMimageisshowninfigure1.6.Itinvolvesmanipulatingsingleatomstogive
whatisprobablythesmallestknownwriting.

FIGURE1.6Theworld'ssmallestwriting?Theelementsymbolforsilicon,Si,isspelledoutwith
individualsiliconatoms(dark)amongtinatoms(light).Thesiliconatomswere
manipulatedwiththetipofanAFM.

Furtherevidenceforthepresenceofdiscreteparticlesinatomscamefromexperimentswithgas
dischargetubes,suchasthatshowninfigure1.7.Whenthetubewasfilledwithalowpressuregasand
ahighvoltagewasappliedbetweentheelectrodes,negativelychargedparticlesflowedfromthe
negativeelectrode(cathode)tothepositiveelectrode(anode).

FIGURE1.7Diagramofagasdischargetube.

Becausetheyemanatedfromthecathode,theparticleswerecalledcathoderays.In1897,theBritish
physicistJJThomsonpassedcathoderaysthroughamagneticfieldusingthemodifieddischargetube
showninfigure1.8.Themagneticfieldcausedthepathofthecathoderaystobend.Analysisofthis
effectallowedThomsontodeterminethechargetomassratioofthecomponentsofcathoderays,what
wenowknowaselectrons.
FIGURE1.8DiagramoftheapparatususedbyJJThomsontodeterminethechargetomassratioofthe
electron.Thecathoderaybeampassesbetweenthepolesofamagnetandbetweenapairof
metalelectrodesthatcanbegivenelectriccharges.Themagneticfieldtendstobendthebeam
inonedirection(topoint2)whilethechargedelectrodesbendthebeamintheoppositedirection
(topoint3).Byadjustingthechargeontheelectrodes,thetwoeffectscanbemadetocancel
eachother(point1).Theamountofchargeontheelectrodesrequiredtobalancetheeffectofthe
magneticfieldcanbeusedtocalculatethechargetomassratio.

In1909,theAmericanchemistRobertMillikandeterminedthechargeonanindividualelectronby
measuringtheratesatwhichchargedoildropsfellbetweenelectricallychargedplates.This,combined
withThomson'sresults,allowedcalculationofthemassofanelectronas9.0910 31kg.The
knowledgethatatomswereelectricallyneutralmeantthattheelectronmusthaveapositivelycharged
counterpart,butitsexactnaturewasnotknownbytheearlyyearsofthetwentiethcentury.Itwasthe
workoftheNewZealandbornscientistErnestRutherford(18711937)thatshedlightnotonlyonthe
positivelychargedcomponentoftheatom,butalsoonthestructureoftheatomitself.Around1909,
Rutherford,whohadalreadywontheNobelPrizeinchemistryin1908forhisworkonthetheoryof
radioactivity,devisedhisfamousgoldfoilexperimentdepictedinfigure1.9.Rutherfordtookan
incrediblythinsheetofgold(onlyafewatomsthick)andbombardeditwithastreamofpositively
chargedparticlescalledalphaparticles.
FIGURE1.9SchematicviewofRutherford'sgoldfoilexperiment.Whenabeamofpositivelychargedalpha
particleswasshotatathingoldfoil,mostofthempassedstraightthroughthefoil.Some,
however,weredeflectedstraightbacktowardsthesource.

Mostoftheparticleswentstraightthroughthefoilessentiallyundisturbed,someweredeflectedthrough
variousangles,andabout1in8000wasdeflectedalmoststraightbacktowardsthesource.Ofthis
amazingobservation,Rutherfordsaid,Itwasalmostasincredibleasifyouhadfiredafifteeninch
[38.1centimetre]shellatapieceoftissuepaperanditcamebackandhityou.Toexplainhis
observations,Rutherfordproposedanewmodeloftheatom.Hesuggestedthateveryatomhasatiny
positivelychargedcentralcore,whichhecalledthenucleus,thatconstitutesmostofthemassofthe
atom.Thepositivechargeinthenucleusisduetoparticles,whichhecalledprotons,andthenumberof
theseinthenucleusdeterminestheidentityoftheatom.Theelectricalneutralityoftheatomrequires
thatthereisthesamenumberofelectronsinanatomasthereareprotonsinthenucleus,andthese
surroundthecentralcore,asshownschematicallyinfigure1.10.

FIGURE1.10Diagram(nottoscale)showingthenucleusandthevolumeoccupiedbythesurrounding
electrons.Ifthisweredrawntoscale,thenucleuswouldbeinvisible.
Electronsoccupyavolumethatishugecomparedwiththesizeofthenucleus,buteachelectronhas
suchasmallmassthatalphaparticlesarenotdeflectedbytheelectrons.Consequently,analphaparticle
isdeflectedonlywhenitpassesverynearanucleus,anditbouncesstraightbackonlywhenitcollides
headonwithanucleus.Becausemostofthevolumeofanatomisessentiallyemptyspace,mostalpha
particlespassthroughthefoilwithoutbeingaffected.Fromthenumberofparticlesdeflectedandthe
patternofdeflection,Rutherfordcalculatedthatthepositivenucleusoccupieslessthan0.1%ofthetotal
atomicvolume.Togiveyouanideaofwhatthatmeans,anatomthesizeofarugbystadiumwould
haveanucleusthesizeofapea.WhenRutherfordcalculatedthenuclearmassbasedonthenumberof
protonsinthenucleus,thevaluealwaysfellshortoftheactualmass.Infact,Rutherfordfoundthatonly
abouthalfofthenuclearmasscouldbeaccountedforbyprotons.Thisledhimtosuggestthattherewas
anotherparticleinthenucleusthathadamassclosetoorequaltothatofaproton,butwithnoelectric
charge.Thissuggestioninitiatedasearchthatfinallyendedin1932withthediscoveryoftheneutron
byJamesChadwick(18911974),aBritishphysicist.Becausetheyarefoundinthenucleus,protons
andneutronsaresometimescallednucleons.Table1.2summarisesthesubatomicparticlespresentin
thismodeloftheatom.
TABLE1.2 PhysicalDatafortheElectron,ProtonandNeutron
Particle Symbol Charge(C) Mass(kg) Mass(u)
electron e 1.602210 19 9.109410 31 5.485810 4
proton p +1.602210 19 1.672610 27 1.0073
neutron n 0 1.674910 27 1.0087

Note:Thechargeismeasuredincoulombs(C).Thefinalcolumngivesthemassinatomicmass
units(u)1u=1.6605410 27kg( themassofthe12Catom)(p.10).

Overtheinterveningyears,ithasbeenshownthatprotonsandneutronsarethemselvescomposedof
stillsmallerparticlescalledquarks.Theexistenceofquarkshashelpedusunderstandhowtheatomic
nucleuscanstaytogetherdespitethepresenceofpositivelychargedprotonsincloseproximity.
However,quarksareveryunstableoutsidetheconfinesoftheatomicnucleusandareofmoreinterestto
physiciststhanchemists.

Toexaminehowatomsareconstructed,wewillconsiderthesimplestpossibleatom,hydrogen,withthe
chemicalsymbolH.Ahydrogenatomconsistsofasingleprotoninthenucleus,andasingleelectron.
Wedesignatethisas .WeusethisterminologyforanychemicalelementXasfollows:

whereAisthemassnumber,ZistheatomicnumberandXisthechemicalsymbolofthechemical
element.Theatomicnumber(Z)isthenumberofprotonsinthenucleus.Themassnumber(A)isthe
numberofprotonsinthenucleusplusthenumberofneutrons(N)inthenucleus.

Notethattheatomicnumberisalsoequaltothenumberofelectronsinaneutralatom(i.e.oneinwhich
thenumberofprotonsandthenumberofelectronsisthesame).Achemicalelementisdefinedbyits
atomicnumberallatomshavingthesameatomicnumberareatomsofthesameelement.Therefore,the
symbol tellsusthatanatomofhydrogencontains1proton(Z=1),1electronand0neutrons(A=
1).

Ifweweretoanalyseasampleofhydrogenatoms,wewouldfindthatroughly1atominevery6600
wouldhaveapproximatelytwicethemassofa atom.Theseheavieratomsbelongtoanisotopeof
hydrogencalleddeuterium.Isotopesareatomsofanelementwiththesamenumberofprotons(i.e.the
samevalueofZ)butdifferentnumbersofneutrons(i.e.differentvaluesofA).Deuteriumatomsare
symbolisedas ,meaningthatthereis1proton(Z=1)and1neutron(A=2)inthenucleus.The
atomissometimescalledprotiumtodistinguishitfromdeuterium.Inchemicalterms,deuteriumatoms
behaveessentiallyidenticallytohydrogenatoms,buttherearesomeimportantdifferencesinreactivity
whentheyarebondedtootheratoms.Inaddition,hydrogenalsohasathirdisotopecalledtritium, ,
whichhas1protonand2neutronsinthenucleus.Itistheleastabundantisotopeofhydrogen,withonly
1to10atomsoftritiuminevery10 18atomsofhydrogen.Tritiumisradioactive,meaningthatthe
nucleusisunstableandundergoesspontaneousdecaytogiveanatomofhelium,He,aprocesswewill
lookatingreaterdetailinchapter27.Heliumatomsarecharacterisedbyhaving2protonsinthe
nucleus(Z=2).Heliumhastwostableisotopes, and ,with1and2neutrons,respectively,in
thenucleus.Theelementwith3protonsinthenucleus,lithium(Z=3),hasthestableisotopes and
with3and4neutrons,respectively.AnyatomofaspecifiedAandZiscalledanuclide.A
radionuclideisaradioactivenuclide.

WORKEDEXAMPLE1.2

TheCompositionofAtoms
Thefollowingradioactiveisotopeshavemedicalapplications.Determinethenumberof
protons,neutronsandelectronsineachisotope.
(a) Dy(usedinthetreatmentofarthritis)
(b) (usedtoimagethethyroidgland)
(c) (usedinstudiesofironmetabolism)

Analysis

Thenumberofprotonsisequaltotheatomicnumber(Z),thenumberofneutronsisfound
fromZandthemassnumber(A),andthenumberofelectronsinaneutralatommustequal
thenumberofprotons.

Solution
(a)Dyisthechemicalsymbolfordysprosium.Thesubscript66isZ,whichisthenumber
ofprotonsinthenucleus.Thesuperscript165isA.Wefindthenumberofneutrons
bysubtractingZfromA:AZ=16566=99neutrons.Becausethisisaneutral
atom,thenumberofelectronsmustequalthenumberofprotons. has66
protons,99neutronsand66electrons.
(b)Iisthesymbolforiodine.Z=53andA=131.Ztellsusthatthenucleuscontains53
protons.SubtractingZfromA,wefindthatthereare78neutronsinthisisotope.
Finally,theatomisneutral,sothereare53electrons.
(c) Iron,Fe,hasZ=26.Aneutralatomof has26protons,26electrons,and5926
=33neutrons.

Isouranswerreasonable?

Inallcases,thenumberofprotonsisequaltothenumberofelectrons,asrequiredforneutral
atoms.Wehavefollowedtherulesforcalculatingthenumberofneutronsandhavecarried
outthecalculationsproperly.Ouranswersshouldthereforebecorrect.

PRACTICEEXERCISE1.2
Thefollowingradioactiveisotopeshave
medicalapplications.Determinethenumber
ofprotonsandneutronsineach.
(a) (usedasanimagingand
therapeuticagent)
(b) (usedinstudiesofthelungs)
(c) (usedintheformofawirefor
internalcancertreatment)

Inclusionoftheatomicnumberinthisterminologyisalmostredundantwhenthechemicalsymbolis
included,soitiscommontoseeashorthandversionthatexcludesthis.Thus,weoftenwrite as
simply1H,asweknowthatallatomsofhydrogenhaveZ=1.Usingthesameshorthandversion,
deuteriumwouldbewrittenas2Handtritiumas3H.

AtomicMass

Wesawintable1.2thatthe12Cisotopeisusedasthebasisbywhichatomicmassismeasured.The
atomicmassunit(u)isthemass(1.6605410 27kg)equalto themassofoneatomof12C,and
themassesofallatomsaremeasuredrelativetothis.TheatomicmassunitisalsoknownastheDalton
(Da),particularlyinbiochemistry.Usingthisscale,wefindthatthemassofasingle19Fatomis18.998
4032uandthatofasingle31Patomis30.973762u.Becausebothfluorineandphosphorushaveonly
onenaturallyoccurringisotope,wecanbesurethatanyfluorineatomwechosefromamacroscopic
sampleoffluorinewouldhaveamassof18.9984032u,whileanyphosphorusatomchosenfroma
macroscopicsampleofphosphoruswouldhaveamassof30.973762u.Wethereforesaythatthe
atomicmassoffluorineis18.9984032uandtheatomicmassofphosphorusis30.973762u.
However,themajorityofelementsintheperiodictablecomprisetwoormoreisotopes,andthemassof
asingleatomchosenatrandomfromamacroscopicsampleoftheseelementswouldnotbeconstant
itwoulddependonwhichisotopewaschosen.Wethereforedefinetheatomicmassoftheseelementsas
theaveragemassperatomofanaturallyoccurringsampleofatomsoftheelement.Consider,for
example,bromine,Br.TherearetwonaturallyoccurringisotopesofBr,namely and ,eachof
whichcontains35protonsinthenucleus.Nucleioftheformercontain44neutronswhilethoseofthe
lattercontain46.Anynaturallyoccurringsampleofbrominewillbecomposedof50.69%ofthe
isotopeand49.31%ofthe isotope.Giventheatomicmassesoftheseisotopes( ,
)wecancalculatetheaverageatomicmassofBrbytakingthesumoftheatomicmass
ofeachisotopemultipliedbyitsabundanceasfollows.

TheaverageatomicmassofBr,79.90u,isjustlessthantheaverageofthemassesofthetwoisotopes
(79.9173u)becausethelighter isotopeisslightlymoreabundantthantheheavier isotope.
Figure1.11illustratestherangeofisotopiccompositionsfoundinfourelements,oneofwhichistin,the
elementwiththelargestnumberofstableisotopes.

FIGURE1.11Thenaturalabundancesoftheisotopesofchlorine,Cl,chromium,Cr,germanium,Ge,andtin,
Sn,illustratethediversityofisotopicdistributions.Themassnumberandrelativeabundanceof
eachisotopeareindicated.

Whilethedistributionofisotopesinsamplesofmostelementsisessentiallyconstant,thereareten
elements(H,Li,B,C,N,O,Si,S,ClandTl)whichshowsubstantialvariationintheirisotopic
compositions,dependingonthesourceoftheelement.Consider,forexample,hydrogen.Aswehave
seen,thiselementhasthreeisotopes,1H,2Hand3H,thelastofwhichwewillneglectinthisdiscussion
becauseofitsnegligibleabundance.Ifweanalysedsamplesofatmosphericmethaneandnaturalgas,
wewouldfindthattheproportionofthe2Hisotopeinthehydrogenatomsoftheformerwouldbe
greaterthanthatinthelatter,andhencetheaverageatomicmassofHinthetwosampleswouldbe
different.Therefore,insteadofquotingasinglevaluefortheaverageatomicmassofhydrogen,arange
ofvaluesofatomicmassisgiven[1.00784u1.00811u],whichcorrespondstothelowestandhighest
valuesmeasuredinnaturalsamples.Table1.3givestherangeofatomicmassvaluesfortheseten
elements,togetherwiththeconventionalatomicmasseswhichcanbeusedwhenthesourceofthe
sampleisunknown.
TABLE1.3 AtomicMassRangesandConventionalAtomicMassesforH,Li,B,C,N,O,Si,S,ClandTl
Element Atomic Atomicmassrange Conventionalatomicmass
name Symbol number (u) (u)
hydrogen H 1 [1.007841.00811] 1.008
lithium Li 3 [6.9386.997] 6.94
boron B 5 [10.80610.821] 10.81
carbon C 6 [12.009612.0116] 12.011
nitrogen N 7 [14.0064314.007 14.007
28]
oxygen O 8 [15.9990315.999 15.999
77]
silicon Si 14 [28.08428.086] 28.085
sulfur S 16 [32.05932.076] 32.06
chlorine Cl 17 [35.44635.457] 35.45
thallium Tl 81 [204.382204.385] 204.38

Inthisbook,wewillusetheconventionalatomicmasseslistedintable1.3inanycalculationsinvolving
thesetenelements.

WORKEDEXAMPLE1.3

CalculatingAverageAtomicMassesfromIsotopic
Abundances
Naturallyoccurringtitanium,Ti,isamixtureoffiveisotopesandhasthefollowingisotopic
composition:

Theatomicmassesoftheisotopesareasfollows:

Usethisinformationtocalculatetheaverageatomicmassoftitanium.

Analysis

Inasamplecontainingmanyatomsoftitanium,8.25%ofthetotalmassiscontributedby
atomsof46Ti,7.44%byatomsof47Ti,73.72%byatomsof48Ti,5.41%byatomsof49Ti
and5.18%byatomsof50Ti.Thismeansthat,whenwecalculatethemassofthehypothetical
averageatomofTi,wehavetoweightitaccordingtoboththemassesoftheisotopesand
theirrelativeabundance.(Keepinmind,ofcourse,thatsuchanatomdoesnotreallyexist.
Thisisjustasimplewaytoseehowwecancalculatetheaverageatomicmassofthis
element.)

Solution
Wewillcalculate8.25%ofthemassofanatomof46Ti,7.44%ofanatomof47Ti,73.72%of
anatomof48Ti,5.41%ofanatomof49Tiand5.18%ofanatomof50Ti.Addingthese
contributionsgivesthetotalmassoftheaverageatom.Therefore:

Isouranswerreasonable?

Byfarthemostabundantisotopeis48Ti,sowewouldexpecttheaverageatomicmasstobe
closetothemassofthisisotope.Ourcalculatedaverageatomicmass,47.867u,isindeedjust
lessthanthemassofthe48Tiisotope(47.9479463u),becausethelighter46Tiand47Ti
isotopesareslightlymoreabundantthantheheavier49Tiand50Tiisotopes.Hence,wecan
feelconfidentouransweriscorrect.

ChemistryResearch

TheOpenPoolAustralianLightWaterReactor

Aswehaveseeninthischapter,someatomicnucleiareradioactiveanddecayspontaneously
togivelighternuclei.Theenergyproducedinsuchradioactivedecayprocessescanbe
harnessedinnuclearreactorstogenerateelectricity.However,theOpenPoolAustralianLight
WaterReactor(OPAL)inSydney,theonlynuclearreactorinAustralasia,producesno
electricityandisusedonlyforscientificapplicationsundertheauspicesoftheAustralian
NuclearScienceandTechnologyOrganisation(ANSTO).Someoftheseapplicationsare
outlinedbelow.

TheOPALreactor,picturedinfigures1.12and1.13,usesuraniumenrichedintheisotope
asitsnuclearfuel,andconsumesabout30kgofuraniumperyear.Whena
nucleusundergoesradioactivedecay,freeneutronsareproduced.Neutronsinteractwith
matterinspecificways,andanalysisoftheresultsoftheseinteractionscanprovideextensive
informationaboutthematterbeingstudied.BeamsofneutronsfromtheOPALreactorare
usedastheradiationsourceinanumberofinstrumentsdesignedtoinvestigateavarietyof
propertiesofmatter.Theseinstrumentsincludediffractometersdesignedtoinvestigatethe
threedimensionalarrangementofatoms(particularlyhydrogenatoms)insolids,measure
stressinmaterials,studythemagneticpropertiesofsubstances,andrecordthemotionsof
atomsinchemicalreactionsonthemillisecondtimescale.
FIGURE1.12TheblueglowduetoCherenkovradiation.Thisradiationisemittedwhencharged
particlessuchashighenergyelectronstravelataspeedfasterthanthespeedof
lightinthemediumthroughwhichtheytravel(inthiscase,water).

FIGURE1.13AviewoftheOPALreactor.Thereactorcoreliesatthebottomofthecircular
section.

Neutronscanalsobeusedtopreparemacroscopicamountsofspecificisotopes.Aswehave
seeninworkedexample1.2,someradioactiveisotopesareusefulinmedicaldiagnosisand
treatment.However,theseoftendonotoccurnaturallyinusablequantitiesowingtotheir
shortlifetimes.Forexample,the (Tc=technetium,m=metastable)isotope,whichis
usedinover80%ofnuclearmedicineimagingprocedures,mustbepreparedviathedecayof
the (Mo=molybdenum)isotope,whichisitselfradioactiveandhasahalflifeof66
hours.ThelatterispreparedintheOPALreactorbytheirradiationofauraniumtargetwith
neutronsand,followingpurification,isthenshippedtohospitalsthroughoutAustralasia.
OthermedicalisotopesproducedbytheOPALreactorare , , and .

InadditiontotheOPALreactor,ANSTOisalsoequippedwithparticleacceleratorsand
cyclotrons,bothofwhichinvolveelementaryparticlestravellingatveryhighspeeds.The
ANTARES(AustralianNationalTandemAcceleratorforAppliedResearch)particle
acceleratorhasbeenusedtodetermine,amongotherthings,theageofanimportantEuropean
historicalartefact.AcrownmadeofironandgoldatthecathedralinMonza,Italywas
thoughttobethatofCharlemagne(c.742814),thefirstHolyRomanEmperor,buthistorical
documentscouldonlydateittosometimebetweenthelateRomanandtheMiddleAges,a
timespanofseveralhundredyears.Fortunately,thepreciousstonesinthecrownwere
attachedusingamixtureofbeeswaxandclay,andthisallowedtheuseofradiocarbondating,
aprocesswheretheamountoftheradioactiveisotope inthebeeswaxcouldbemeasured.
Analysisoflessthan1mgofthemixtureusingANTARESplacedthedateofthecrown's
manufacturebetweentheyears700and780,atimeperiodthatcoincideswiththelifeof
Charlemagne.

PRACTICEEXERCISE1.3
Aluminiumatomshaveamassthatis2.248
45timesthatofanatomof12C.Whatisthe
atomicmassofaluminium?

PRACTICEEXERCISE1.4
Naturallyoccurringcopperiscomposedof
69.15%63Cuand30.85%65Cu.Atomsof
63Cuhaveamassof62.9296uandthoseof
65Cuhaveamassof64.9278u.Calculate
theaverageatomicmassofcopper.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
1.4ThePeriodicTableoftheElements
WehavealreadyseenthattheelementsH,HeandLicanbeorderedonthebasisofincreasingatomic
number(Z=1,2and3,respectively).Ifwecontinuesuchanordering,weobtaintheperiodictableofthe
elements.TheperiodictableweusetodayisbasedprimarilyontheeffortsofaRussianchemist,Dmitri
IvanovichMendeleev(18341907,picturedinfigure1.14),andaGermanphysicist,JuliusLotharMeyer
(18301895).Workingindependently,thesescientistsdevelopedsimilarperiodictablesonlyafewmonths
apartin1869.Mendeleevisusuallygiventhecredit,however,becausehepublishedhisversionfirst.

FIGURE1.14DmitriIvanovichMendeleevdevelopedtheperiodictable./SPL/RussellKightley

TheextraordinarythingabouttheworkofMendeleevandMeyerwasthattheyknewnothingofthe
structureoftheatom,sowereunawareoftheconceptofatomicnumber,whichisthebasisofthemodern
periodictable.Whattheydidknow,however,weretheatomicmassesofmanyoftheelements.Bearin
mindalsothatnotalloftheelementshadbeendiscoveredatthistime.Mendeleevwaspreparingachemistry
textbookforhisstudentsattheUniversityofStPetersburgand,lookingforsomepatternamongthe
propertiesoftheelements,hefoundthat,whenhearrangedtheminorderofincreasingatomicmass,similar
chemicalpropertieswererepeatedoverandoveratregularintervals.Forinstance,theelementslithium,Li,
sodium,Na,potassium,K,rubidium,Rb,andcaesium,Cs,aresoftmetalsthatreactvigorouslywithwater.
Similarly,theelementsthatimmediatelyfolloweachofthesealsoconstituteasetwithsimilarchemical
properties.Thus,beryllium,Be,followslithiummagnesium,Mg,followssodiumcalcium,Ca,follows
potassiumstrontium,Sr,followsrubidiumandbarium,Ba,followscaesium.Alloftheseelementsform
compoundswithoxygenhavinga1:1metaltooxygenratio.Mendeleevusedsuchobservationsto
constructhisperiodictable,whichisillustratedinfigure1.15.
FIGURE1.15Mendeleev'soriginalperiodictable,takenfromtheGermanchemistryjournalZeitschriftfrChemie,
1869,12,4056.

Atfirstglance,Mendeleev'soriginaltablelookslittlelikethemoderntablegiveninfigure1.16.However,
acloserlookrevealsthattherowsandcolumnshavebeeninterchanged.TheelementsinMendeleev'stable
arearrangedinorderofincreasingatomicmass.Whenthesequenceisbrokenattherightplacesand
stacked,theelementsfallnaturallyintocolumns.
FIGURE1.16Theperiodictableoftheelements.Atthetimeofwriting,118elementswereknown.

Mendeleevplacedelementswithsimilarpropertiesinthesamerowevenwhenthisleftoccasionalgapsin
thetable.Forexample,heplacedarsenic,As,inthesamerowasphosphorusbecausetheyhadsimilar
chemicalproperties,eventhoughthisleftgapsinotherrows.Inastrokeofgenius,Mendeleevreasoned,
correctly,thattheelementsthatbelongedinthesegapshadsimplynotyetbeendiscovered.Infact,onthe
basisofthelocationofthesegaps,Mendeleevcouldpredict,withastonishingaccuracy,thepropertiesofthe
yettobefoundelements,andhispredictionshelpedserveasaguideinthesearchforthem.

Theelementstellurium,Te,andiodine,I(notethattheGermanforiodineisjod,whichhasthe
abbreviationJinMendeleev'soriginaltable),causedMendeleevsomeproblems.Accordingtothebest
estimatesatthattime,theatomicmassoftelluriumwasgreaterthanthatofiodine.Yet,iftheseelements
wereplacedinthetableaccordingtotheiratomicmasses,theywouldnotfallintotheproperrowsrequired
bytheirproperties.Therefore,Mendeleevswitchedtheirorder,believingthattheatomicmassoftellurium
hadbeenincorrectlymeasured(ithadnot),andinsodoingviolatedhisorderingsequencebasedonatomic
mass.

ThetablethatMendeleevdevelopedisthebasisoftheoneweusetoday,butoneofthemaindifferencesis
thatMendeleev'stablelackstheelementshelium,He,neon,Ne,argon,Ar,krypton,Kr,xenon,Xe,and
radon,Rn.InMendeleev'stime,noneoftheseelementshadyetbeendiscoveredbecausetheyarerelatively
rareandbecausetheyhavevirtuallynotendencytoundergochemicalreactions.Whentheseelementswere
finallydiscovered,beginningin1894,anotherproblemarose.Twomoreelements,argon,Ar,and
potassium,K,didnotfallintotherowsrequiredbytheirpropertiesiftheywereplacedinthetableinthe
orderrequiredbytheiratomicmasses.Anotherswitchwasnecessaryandanotherexceptionhadbeenfound.
Itbecameapparentthatatomicmasswasnotthetruebasisfortheperiodicrepetitionofthepropertiesofthe
elements.WithRutherford'sdiscoveryofthestructureoftheatom,itbecameapparentthattheelementsin
theperiodictablewerearrangedinorderofincreasingatomicnumber,notatomicmass,andwhenthiswas
realiseditbecameobviousthatTeandI,andArandK,wereinfactinthecorrectpositions.

TheModernPeriodicTable
Theperiodictableinusetodayisshowninfigure1.16,andalsoontheinsidefrontcoverofthisbook.The
horizontalrowsarecalledperiodsandarenumbered1to7,whiletheverticalcolumnsarecalledgroups
andarenumbered1to18.Theelementsarearrangedinorderofincreasingatomicnumberacrosseach
period,andanewperiodbeginsaftereachgroup18element.Theatomicmassesaregiven(generallyto
foursignificantfigures)beloweachchemicalsymbol.Whiletheatomicmassusuallyincreaseswithatomic
number,youcanseetheexceptionswementionedpreviously(TeandI,andArandK)aswellasCoand
Ni.Whiletheisotopiccompositionand,therefore,theatomicmassesofmostelementsarewellestablished,
therearesomeunstableelementsthatundergospontaneousradioactivedecay(seechapter27).Giventhat
theisotopiccompositionofsuchelementscannotbeknown,itisusualtosimplyquotethemassnumberof
thelongestlivedisotopeoftheelement,andthesearegiveninparenthesesintheperiodictable.Notethat
therearediscontinuitiesintheperiodictablebetweenelements56and72,andbetweenelements88and
104,andthesetwosetsofelementsaregivenbelowthetableitself.Theelementsfrom57to71arecalled
thelanthanoids(or,lesscommonly,therareearthelements).Elements89to103arecalledtheactinoids.
Thelanthanoidsandactinoidsaregenerallysituatedbelowtherestoftheperiodictable,simplytosave
spaceandtomakethetableeasiertoreadnotethatthelanthanoidandactinoidelementsarechemically
distinctfromtherestoftheelementsintheperiodictable,anddonotbelongtoanyofthegroups1to18.
Thelanthanoidsandactinoidsaresometimescalledthefblockelements,andasimilarterminologyisalso
usedelsewhereinthetableelementsingroups1and2arecalledthesblockelements,elementsingroups
3to12arecalledthedblockelements,andelementsingroups13to18arecalledthepblockelements.As
wewillsee,s,p,dandfrefertoorbitals,particularregionsinspaceintheatomwhereelectronshaveahigh
probabilityofbeingfound.Thedblockelementsarealsocalledtransitionmetals.

Individualgroupswithintheperiodictablearealsoknownbyparticularnames,althoughthispracticeisless
prevalentthaninthepast.Group1elementsarecalledalkalimetals,group2elementsarecalledalkaline
earthmetals,group15elementsarecalledpnictogens,group16elementsarecalledchalcogens,group17
elementsarecalledhalogensandgroup18elementsarecallednoblegases.Ofthese,onlytheterms
halogensandnoblegasesareincommonusage.

Allelementsontheperiodictablebelongtooneofthreecategoriesmetals,nonmetalsandmetalloids
andthegroupingsareshownbythedifferentshadingsontheperiodictableinfigure1.16.Metalsare
generallygoodconductorsofheatandelectricity,aremalleable(canbebeatenintoathinsheet)andductile
(canbedrawnoutintoawire),andhavetheusualmetalliclustre.Elementsthatdonothavethese
characteristicsarecallednonmetals,andthemajorityofthesearegasesatroomtemperatureandpressure.
Thepropertiesofmetalloidsliesomewherebetweenthemetalsandnonmetals.Themostnotablepropertyof
theseelementsisthefactthattheytendtobesemiconductors,andmetalloidssuchassilicon,Si,and
germanium,Ge,havethereforefoundwideuseinsiliconchipsandtransistors.Notethattheclassificationof
therecentlypreparedelements116,117and118issomewhatarbitrary,asweighablequantitiesofthese
havenotyetbeenobtained.

NamingtheElements
Alloftheelementsintheperiodictablehaveone,twoorthreeletterabbreviationsoftheirnames.The
abbreviationsofmanyelementsaresimplythefirstoneortwolettersoftheirnames(e.g.carbon,C,oxygen,
O,lithium,Li)buttherearequiteanumberofelementsforwhichthederivationoftheabbreviationisnot
quitesoobvious:forexample,potassium,K,tin,Sn,lead,Pb,andiron,Fe.Suchapparentanomaliesoccur
becauseofthewaythattheelementswereoriginallynamed.Whenanewelementisdiscovered,the
discovererusuallygetstosuggestanamefortheelement,whichisthenratifiedbyIUPAC,theInternational
UnionofPureandAppliedChemistry.

Ofalltheelementsontheperiodictable,C,S,Fe,Cu,As,Ag,Sn,Sb,Au,Hg,PbandBiwereknownto
ancientcivilisationssothedateoftheirdiscoveryisnotknown.Ofthese,Fe,Cu,Ag,Sn,Sb,Au,Hgand
PbareabbreviationsfortheLatinnamesferrum,cuprum,argentum,stannum,stibium,aurum,hydrargyrum
andplumbum.Theearliestknowndiscoveryofanelementwasthatofphosphorus,P.Itwasisolatedin1669
byHennigBrandfromthedistillationofurine(hewasapparentlytryingtomakesilverorgold
unsuccessfully,ofcourse!)andwasnamedaftertheGreekwordphosphoros,meaningbringeroflight,as
theelementglowsinthedark.Elementshavebeennamedaftercountries(germanium,francium,americium,
polonium)andevenaftertheplacestheywerefirstdiscoveredtheSwedishtownofYtterbyhasthe
distinctionofhavingfourelements(erbium,Er,ytterbium,Yb,yttrium,Y,andterbium,Tb)namedafterit,
asthesewerefirstfoundindepositsclosetothetown.Surprisinglyfewelementshavebeennamedafter
peopleatpresent,only15peoplehavebeenimmortalisedontheperiodictable,andtheyarelistedintable
1.4.Itisinterestingtonotethatnoneofthepeoplelisteddiscoveredtheelementnamedafterthem.
TABLE1.4 Peopleafterwhomelementshavebeennamed
Element
Name Briefbiography named
VasiliiYefrafovich ChiefofstaffoftheRussianCorpsofMiningEngineers samarium,Sm
vonSamarski (element62)
Bykhovets(1803
1870)
JohanGadolin(1760 Finnishchemistfirstpersontoisolatealanthanoid gadolinium,
1852) element Gd(element
64)
Pierre(18591906) HusbandandwifescientificteamPierreFrenchandMarie curium,Cm
andMarie(1867 PolishbybirthjointlywontheNobelPrizeinphysicsin (element96)
1934)Curie 1903
AlbertEinstein(1879 Mostfamousscientistofthetwentiethcentury,ifnotall einsteinium,
1955) timeGermanbybirthwontheNobelPrizeinphysicsin Es(element
1921 99)
EnricoFermi(1901 Italianphysicistmadegreatadvancesinthestudyof fermium,Fm
1954) nuclearreactionswontheNobelPrizeinphysicsin1938 (element100)
DmitriMendeleev Russianchemistrenownedforthedevelopmentofthe mendelevium,
(18341907) periodictable Md(element
101)
AlfredNobel(1833 SwedishinventorofdynamiteandpatronoftheNobel nobelium,No
1896) Prizes (element102)
ErnestLawrence AmericaninventorofthecyclotronwontheNobelPrize lawrencium,
(19011958) inphysicsin1939 Lr(element
103)
ErnestRutherford NewZealandphysicist/chemistmadeseminal rutherfordium,
(18711937) contributionstounderstandingthestructureoftheatom Rf(element
wontheNobelPrizeinchemistryin1908 104)
GlennSeaborg(1912 Americanchemistfirstpreparedmanyoftheelements seaborgium,
1999) beyonduraniumintheperiodictablewontheNobelPrize Sg(element
inchemistryin1951 106)
NielsBohr(1885 Danishphysiciststudiedelectronicenergylevelswithin bohrium,Bh
1962) atoms,whichaidedourunderstandingoftheatomwon (element107)
theNobelPrizeinphysicsin1922
LiseMeitner(1878 Austrianphysicistmadefundamentaldiscoveries meitnerium,
1968) concerningnuclearfissioncontroversiallyneverawarded Mt(element
aNobelPrize 109)
WilhelmRntgen GermanphysicistdiscovererofXrayswinnerofthe rntgenium,
(18451923) inauguralNobelPrizeinphysicsin1901 Rg(element
111)
NicolausCopernicus PolishastronomerproposedthattheSun,ratherthanthe copernicium,
(14731543) Earth,wasthecentreofthesolarsystem Cn(element
112)

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1.5ElectronsinAtoms
Whilewehavetouchedbrieflyontheconceptofelectrons,wehavetothispointconcentratedprimarily
onthenucleusoftheatomandthewayinwhichthenumberofprotonsinthenucleusdeterminesthe
chemicalidentityoftheatom.However,manyofthechemicalpropertiesofanatomand,most
importantly,itschemicalreactivityaredeterminednotbythenucleusbutbytheelectrons.

Oneofthemostinterestingthingsaboutelectronsisthatwecannotreallysayexactlywheretheyareat
anyparticulartime,soweusuallytalkabouttheirmostprobablelocations.Electronsoccupyregionsof
spacecalledorbitalsinatoms.Eachorbitalhasacharacteristicelectrondistributionandenergy.For
example,thelowestenergysituationforahydrogenatom,thegroundstate,occurswhenthesingle
electronoccupiesanorbitalinwhichitsmostprobabledistancefromthenucleusis5.291011m.
Thisorbitalhasasphericalelectrondistribution.Ifthegroundstatehydrogenatomabsorbsaspecific
amountofenergy,theelectroncanbepromotedtoahigherenergyorbitaltoformanexcitedstatein
whichtheelectronlies,onaverage,furtherfromthenucleus.Suchaprocessiscalledanelectronic
transition,andtheelectrondistributioninthehigherenergyorbitalisdumbbellshaped.Similarly,the
electroninanexcitedstatehydrogenatomcanmovetoalowerenergyorbitalthroughtheemissionof
energy,oftenintheformoflight.Indeed,aswewillseeinchapter4,suchprocessesarethebasis
behindbothneonandsodiumvapourlights.Orbitalshavedefiniteenergies,sotheenergyofany
electronisdictatedbytheenergyoftheorbitalitoccupiestherefore,anelectroninanatomcanhave
onlycertainwelldefinedenergies.Thisisafundamentalprincipleofthescienceofquantummechanics
calledquantisation,aphenomenonfirstproposedbytheGermanphysicistMaxPlanck(18581947,
NobelPrizeinphysics,1918)in1900.Wewilllearnmoreaboutthequantisationofenergyinchapter4.

Electronshaveasinglenegativecharge,andtheoverallchargeonanychemicalspeciesisdetermined
bythenumberofelectronsrelativetothenumberofprotonsforexample,theperoxideion,O22,hasa
2chargebecausetherearetwomoreelectronsthanprotonsintheion.Similarly,theLi+ioncontains
threeprotonsandtwoelectrons,soithasasinglepositivecharge.Inadditiontotheirnegativecharge,
allelectronshaveanintrinsicpropertycalledspin.Thiscanhaveoneoftwovalues,whichare
commonlycalledspinupandspindownandareoftendepictedasfollows:

Eachorbitalwithinanatomcancontainamaximumoftwoelectrons,oneofwhichmustbespinupand
theotherspindown.

Chemistsareinterestedinelectronsbecausetheyconstitutethechemicalbondsthatholdatomstogether
inmolecules.Covalentchemicalbondsusuallyconsistofone,twoorthreepairsofelectronsshared
betweenatoms,eachpaircontainingelectronsofoppositespin.Foramoleculetoundergoachemical
reaction,thesebondsmustusuallybebrokenandnewonesmadethisrequiresareorganisationofthe
electronpairsbetweenthereactantandproductmolecules,andtheeasewithwhichthiscanbedone
determineshowfastthereactionoccurs.Reactionsinwhichoneormoreelectronsaretransferred
betweenchemicalspeciesarealsoknownsuchreactions,knownasredoxreactions,areimportantina
hugenumberofchemicalandbiochemicalprocessesinfact,asyouarereadingthis,ironionsand
oxygenmoleculesarebusyexchangingelectronsinyourbloodtotransportoxygenaroundyourbody.

Becauseoftheirimportanceinbothchemicalstructureandchemicalreactivity,electronsoccupya
centralplaceinchemistry.Intheremainingchaptersofthisbook,wewilllearnmoreofthepropertiesof
atomsandmoleculesthatarepredominantlydictatedbyelectrons.

WehavelearnedmuchabouttheatomintheyearssinceRutherford'sseminalexperiment.Indeed,we
havedetailedonlytheverybasicsofatomicstructureintheprecedingpageslaterchapterswilloutline
someoftheamazingcomplexityoftheatom.Forthemoment,itissufficientforyoutoappreciatethat
theatomiscomposedofapositivelychargedcentralnucleuscontainingprotonsandneutrons,whichis
surroundedbynegativelychargedelectronsthatcanundergotransitionsonlybetweenwelldefined
energylevels.Andwithonly118differenttypesofthesebuildingblocks,wecanconstructthe
universe.

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SUMMARY
Atoms,Molecules,Ions,ElementsandCompounds
Atomsareafundamentalbuildingblockofallmatter.Unchargedcollectionsofatomsbondedtogether
inadefinitestructurearecalledmolecules.Theseareheldtogetherbycovalentbondsthatshare
electronsbetweenadjacentatoms.Ionsarechargedchemicalspeciesthatmaybederivedfromboth
atomsandmolecules.Cationsarepositivelycharged,whileanionsarenegativelycharged.Elements
compriseonlyasingletypeofatom,whilecompoundsaremadeupoftwoormorechemicalelements.
Allofthesedifferentchemicalentitiescanbeinvolvedasreactantsinchemicalreactions,inwhichthey
aretransformedtoproducts.

TheAtomicTheory
Allmatteriscomposedofatoms.Theexistenceofatomswasproposedonthebasisof:
thelawofconservationofmass.Massisconservedinchemicalreactions.
thelawofdefiniteproportions.Elementsarecombinedinthesameproportionsbymassinany
particularcompound.
thelawofmultipleproportions.Whentwoelementsformmorethanonecompound,thedifferent
massesofoneelementthatcombinewiththesamemassoftheotherelementareintheratioof
smallwholenumbers.

Dalton'satomictheorywasthefirsttoproposetheexistenceofatomsonthebasisofscientific
observations.Thebasictenetsofhistheoryare:
1.Matterconsistsoftinyparticlescalledatoms.
2.Atomsareindestructible.Inchemicalreactions,theatomsrearrangebuttheydonotthemselves
breakapart.
3.Inanysampleofapureelement,alltheatomsareidenticalinmassandotherproperties.
4.Theatomsofdifferentelementsdifferinmassandotherproperties.
5.Whenatomsofdifferentelementscombinetoformagivencompound,theconstituentatomsin
thecompoundarealwayspresentinthesamefixednumericalratio.

Dalton'stheoryallowsustousechemicalequations,inwhichreactantsandproductsareseparatedbyan
arrow,todescribechemicalreactions.Suchequationsarebalancedwhentheycontainthesamenumber
ofeachtypeofatomoneachsideofthearrow.

Modernapparatusenablesustoseeindividualatoms,andatomictheoryisnowatomicfact.

TheStructureoftheAtom
AlthoughDaltonproposedtheatomtobeindivisible,experimentsinthelatenineteenthcenturyshowed
thiswasnotthecase.Thenegativelychargedelectronwasthefirstsubatomicparticletobediscovered,
whileRutherford'sgoldfoilexperiment,inwhichathingoldsheetwasbombardedwithalphaparticles,
gaveevidenceforasmall,positivelychargednucleus.Thepositivechargeisduetosubatomicparticles
calledprotons,andthenumberoftheseinthenucleusdeterminestheidentityoftheatominquestion.
Thethirdcomponentoftheatom,theneutron,waspredictedbyRutherfordandfoundbyChadwick.
Theatomthuscomprisesthreesubatomicparticles,theelectron,protonandneutron,thelattertwo
collectivelybeingcallednucleons.Eachtypeofatomisdesignatedbyachemicalsymbol,whichis
determinedbyitsatomicnumber(Z),thenumberofprotonsinthenucleus.Themassnumber(A)is
equaltothenumberofprotonsplusthenumberofneutronsinthenucleus.Theterminologyusedto
depictanatomofanyelementXis .AllatomswiththesameZareofthesameelementhowever,
atomsofthesameelementcandifferinthenumberofneutronsinthenucleus,andthisgivesriseto
isotopes.Isotopescanbeeitherradioactive(i.e.theydecayspontaneously)orstable.Aradioactive
nucleusiscalledaradionuclide,whileanuclideisthenamegiventoanyatomicnucleus.Wecan
measureatomicmassinatomicmassunits(u),where1u=1.6605410 27kg,andisequalto of
themassofoneatomof12C.Theatomicmassofanysampleofatomsistheweightedaverageofthe
massesoftheisotopespresentinthesample.

ThePeriodicTableoftheElements
Theperiodictableoftheelementscontainsthe118knownelementsarrangedinorderofincreasing
atomicnumber,andwasdevelopedbybothMendeleevandMeyer.Thehorizontalrowsarecalled
periodsandtheverticalcolumnsgroups.Elementsinthesamegrouptendtohavesimilarchemical
properties.Theperiodictableisdividedintosectionsaccordingtotheelectronconfigurationofthe
elements,namelythesblockelements,thepblockelements,thedblockelementsandthefblock
elements.Thefblockelementsaredividedintothelanthanoids(alsosometimescalledtherareearth
elements)andtheactinoids,whilethedblockelementsarealsocalledthetransitionmetals.The
elementsincertaingroupsintheperiodictablehavespecialnames:group1elementsarecalledalkali
metals,group2elementsarecalledalkalineearthmetals,group15elementsarecalledpnictogens,
group16elementsarecalledchalcogens,group17elementsarecalledhalogensandgroup18elements
arecallednoblegases.Theelementsoftheperiodictablecanbeclassifiedasmetals,nonmetals,or
metalloids.

ElectronsinAtoms
Electronsoccupyregionsofspacecalledorbitals.Thelowestenergyarrangementofelectronsinthe
orbitalsofanatomiscalledthegroundstate.Electronscanbepromotedtohigherenergyorbitalsby
absorptionofenergytogiveexcitedstatesconversely,electronsinhigherenergyorbitalscanmoveto
lowerenergyorbitalswiththeemissionofenergy,oftenaslight.Suchprocessesarecalledelectronic
transitions.Theenergiesofelectronsinatomsaredeterminedbytheenergiesoftheorbitalswithinthe
atom,soelectronsinatomscanhaveonlycertainwelldefinedenergies.Thisiscalledquantisation,a
fundamentalprincipleofquantummechanics.Electronshaveasinglenegativecharge,andoneoftwo
possiblespins.Anorbitalinanatomcanholdamaximumoftwoelectrons,whichmustbeofopposite
spin.Covalentbondscompriseone,twoorthreepairsofelectrons.Chemicalreactionsofteninvolve
reorganisingtheseelectronsinbondmakingandbondbreakingprocesses.Redoxreactionsinvolvethe
transferofoneormoreelectronsbetweenchemicalspecies.

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KEYCONCEPTSANDEQUATIONS
Thelawofconservationofmass(section1.2)
Thetotalmassofreactantspresentbeforeareactionstartsequalsthetotalmassofproductsafterthe
reactionisfinished.Wecanusethislawtocheckwhetherwehaveaccountedforallthesubstances
formedinareaction.

Thelawofdefiniteproportions(section1.2)
Ifweknowthemassratiooftheelementsinonesampleofacompound,theratiowillbethesameina
differentsampleofthesamecompound.

Thelawofmultipleproportions(section1.2)
Indifferentcompoundscontainingthesametwoelements,thedifferentmassesofoneelementthat
combinewiththesamemassoftheotherelementareinaratioofsmallwholenumbers.

Atomicmass(section1.3)
Thisisusedtodeterminethemassofanyatomrelativetothatofthe12Cisotope.

Periodictableoftheelements(section1.4)
Thisisatableofthechemicalelementsarrangedinorderofincreasingatomicnumber.Wecanusethe
periodictabletofigureoutwhetheraparticularelementisametal,nonmetalormetalloid,predictits
chemicalreactivity,calculateitsnumberofprotonsandelectrons,obtainitsatomicmassandsoon.In
fact,allofchemistryiscontainedwithintheperiodictable.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWQUESTIONS
Atoms,Molecules,Ions,ElementsandCompounds
1.1Definethefollowingterms:atom,covalentbond,ion,cation,anion,element,compound,reactant,
chemicalreaction,product.
TheAtomicTheory
1.2Nameandstatethethreelawsofchemicalcombinationdiscussedinthischapter.
1.3WhichpostulateofDalton'satomictheoryisbasedonthelawofconservationofmass?Whichis
basedonthelawofdefiniteproportions?
1.4Whichofthelawsofchemicalcombinationisusedtodefinethetermcompound?
1.5Inyourownwords,describehowDalton'satomictheoryexplainsthelawofconservationofmass
andthelawofdefiniteproportions.
TheStructureoftheAtom
1.6Writethesymbolfortheisotopethatformsthebasisoftheatomicmassscale.Whatisthemassof
thisatomexpressedinatomicmassunits?
1.7Whatarethenames,symbols,electricchargesandmasses(expressedinu)ofthethreechemically
importantsubatomicparticlesintroducedinthischapter?
1.8Whereinanatomisnearlyallofitsmassconcentrated?Explainyouranswerintermsofthe
particlesthatcontributetothismass.
1.9Whatisanucleon?Whichoneshavewestudiedinthischapter?
1.10Definethetermsatomicnumberandmassnumber.
1.11Intermsofthestructuresofatoms,howareisotopesofthesameelementalike?Howdothey
differ?
1.12Considerthesymbol ,whereXstandsforthechemicalsymbolforanelement.What
informationisgivenby(a)Aand(b)Z?
1.13Writethesymbolsoftheisotopesthatcontainthefollowing.(Usethetableofatomicnumbers
printedinsidethefrontcover,asneeded.)
(a)anisotopeofiodinehavingatomswith78neutrons
(b)anisotopeofstrontiumhavingatomswith52neutrons
(c)anisotopeofcaesiumhavingatomswith82neutrons
(d)anisotopeoffluorinehavingatomswith9neutrons
ThePeriodicTableoftheElements
1.14Whatisthechemicalsymbolforeachofthefollowingelements?
(a)chlorine,
(b)sulfur,
(c)iron,
(d)silver,
(e)sodium,
(f) phosphorus,
(g)iodine,
(h)copper,
(i) mercury,
(j) calcium
1.15Whatisthenameofeachofthefollowingelements?
(a)K,
(b)Zn,
(c)Si,
(d)Sn,
(e)Mn,
(f) Mg,
(g)Ni,(h)Al,
(h)C,
(i) N
1.16OnwhatbasisdidMendeleevconstructhisperiodictable?Onwhatbasisaretheelements
arrangedinthemodernperiodictable?
1.17Intheperiodictable,whatisaperiod?Whatisagroup?
1.18WhydidMendeleevleavegapsinhisperiodictable?
1.19Whichisbetterrelatedtothechemistryofanelement:itsmassnumberoritsatomicnumber?Give
abriefexplanationintermsofthebasisfortheperiodictable.
1.20Onthebasisoftheirpositionsintheperiodictable,whyisitnotsurprisingthat90Sr,adangerous
radioactiveisotopeofstrontium,replacescalciuminnewlyformedbones?
1.21Intherefiningofcopper,sizableamountsofsilverandgoldarerecovered.Whyisthisnot
surprising?
1.22Whywouldyoureasonablyexpectcadmiumtobeacontaminantinzincbutnotinsilver?
1.23Basedondiscussionsinthischapter,explainwhyitisunlikelythatscientistswilldiscoveranew
element,neverbeforeobserved,havinganatomicmassofapproximately73.
1.24Ineachofthefollowingsetsofelements,statewhichfitsthedescriptioninparentheses.
(a)Ce,Hg,Si,O,I(halogen)
(b)Pb,W,Ca,Cs,P(transitionmetal)
(c)Xe,Se,H,Sr,Zr(noblegas)
(d)Th,Sm,Ba,F,Sb(lanthanoidelement)
(e)Ho,Mn,Pu,At,Na(actinoidelement)
1.25Whichpropertyofmetalsallowsthemtobedrawnintowire?
1.26Goldcanbehammeredintosheetssothinthatsomelightcanpassthroughthem.Whichproperty
ofgoldallowssuchthinsheetstobemade?
1.27Whichnonmetalsoccurasmonatomicgases(gasesthatexistassingleatoms)?
1.28Whichtwoelementsexistasliquidsatroomtemperatureandpressure?
1.29Whichphysicalpropertyofmetalloidsdistinguishesthemfrommetalsandnonmetals?
1.30Sketchtheshapeoftheperiodictableandmarkoffthoseareaswherewefind
(a)metals,
(b)nonmetalsand
(c)metalloids.
ElectronsinAtoms
1.31Whatisanorbital?
1.32Whenelectronsofoppositespinsoccupyanorbital,wesaythattheirspinsarepaired.Molecules
withoddnumbersofelectrons,therefore,cannothavealloftheelectronspinspaired,andwesay
thattheyhaveunpairedspins.Whichofthefollowingmoleculesmusthaveunpairedspins:N2,F2,
CO,NO,NO2?
1.33Whatisthedifferencebetweenanatominitsgroundstateandanatominitsexcitedstate,given
thatthenumbersofprotons,neutronsandelectronsinbothsituationsarethesame?
1.34Quantisationisveryimportantontheatomicscalebut,inthelargescaleofoureverydaylives,we
barelynoticeit.Whydoyouthinkthismightbeso?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWPROBLEMS
1.35Laughinggasisacompoundformedfromnitrogenandoxygeninwhichthereis1.75gof
nitrogenforevery1.00gofoxygen.Thecompositionsofseveralnitrogenoxygencompounds
follow.Whichoftheseislaughinggas?
(a)6.35gnitrogen,7.26goxygen
(b)4.63gnitrogen,10.58goxygen
(c)8.84gnitrogen,5.05goxygen
(d)9.62gnitrogen,16.5goxygen
(e)14.3gnitrogen,40.9goxygen
1.36Oneofthesubstancesusedtomelticeonfootpathsandroadsincoldclimatesiscalciumchloride.
Inthiscompound,calciumandchlorinearecombinedinaratioof1.00gofcalciumto1.77gof
chlorine.Whichofthefollowingcalciumchlorinemixtureswillproducecalciumchloridewithno
calciumorchlorineleftoverafterthereactioniscomplete?
(a)3.65gcalcium,4.13gchlorine
(b)0.856gcalcium,1.56gchlorine
(c)2.45gcalcium,4.57gchlorine
(d)1.35gcalcium,2.39gchlorine
(e)5.64gcalcium,9.12gchlorine
1.37Ammoniaiscomposedofhydrogenandnitrogeninaratioof9.33gofnitrogento2.00gof
hydrogen.Ifasampleofammoniacontains6.28gofhydrogen,whatmassofnitrogendoesit
contain?
1.38Acompoundofphosphorusandchlorineusedinthemanufactureofaflameretardanttreatment
forfabricscontains1.20gofphosphorusforevery4.12gofchlorine.Supposeasampleofthis
compoundcontains6.22gofchlorine.Whatmassofphosphorusdoesitcontain?
1.39Refertothedataaboutammoniainquestion1.37.If4.56gofnitrogencombinedcompletelywith
hydrogentoformammonia,whatmassofammoniawouldbeformed?
1.40Refertothedataaboutthephosphoruschlorinecompoundinquestion1.38.If12.5gof
phosphoruscombinedcompletelywithchlorinetoformthiscompound,whatmassofthe
compoundwouldbeformed?
1.41MoleculesofacertaincompoundofnitrogenandoxygencontainoneatomeachofNandO.In
thiscompound,thereis1.143gofoxygenforeach1.000gofnitrogen.Moleculesofadifferent
compoundofnitrogenandoxygencontainoneatomofNandtwoatomsofO.Whatmassof
oxygenwouldbecombinedwitheach1.000gofnitrogeninthesecondcompound?
1.42Tinformstwocompoundswithchlorine.Inoneofthem(compound1),therearetwoClatomsfor
eachSnatomintheother(compound2),therearefourClatomsforeachSnatom.When
combinedwiththesamemassoftin,whatwouldbetheratioofthemassesofchlorineinthetwo
compounds?Incompound1,0.597gofchlorineiscombinedwitheach1.000goftin.Whatmass
ofchlorinewouldbecombinedwith1.000goftinincompound2?
1.43Themasscorrespondingto1atomicmassunitis1.6605410 24g.Usethisvaluetocalculate
themassingramsof1atomof12C.
1.44Usethemasscorrespondingtotheatomicmassunitgiveninquestion1.43tocalculatethemass
of1atomofsodium.
1.45Thechemicalsubstanceinnaturalgasisacompoundcalledmethane.Itsmoleculesarecomposed
ofcarbonandhydrogenandeachmoleculecontainsfouratomsofhydrogenandoneatomof
carbon.Inthiscompound,0.33597gofhydrogeniscombinedwith1.0000gof12C.Usethis
informationtocalculatetheatomicmassoftheelementhydrogen.
1.46ElementXformsacompoundwithoxygeninwhichtherearetwoatomsofXforeverythree
atomsofO.Inthiscompound,1.125gofXiscombinedwith1.000gofoxygen.Usetheaverage
atomicmassofoxygentocalculatetheaverageatomicmassofX.Useyourcalculatedatomic
masstoidentifyelementX.
1.47Ifanatomof12Chadbeenassignedarelativemassof24.0000u,determinetheaverageatomic
massofhydrogenrelativetothismass.
1.48Anatomof109Aghasamassthatis9.0754timesthatofa12Catom.Whatistheatomicmassof
thisisotopeofsilverexpressedinatomicmassunits?
1.49Naturallyoccurringmagnesiumiscomposedof78.99%of24Mg(withanatomicmassof23.9850
u),10.00%of25Mg(withanatomicmassof24.9858u)and11.01%of26Mg(withanatomic
massof25.9826u).Usethisinformationtocalculatetheaverageatomicmassofmagnesium.
1.50Givethenumbersofneutrons,protonsandelectronsintheatomsofeachofthefollowing
isotopes.(Usetheperiodictableprintedinsidethefrontcover,asneeded.)
(a) 226Ra
(b)14C
(c)
(d)
1.51Givethenumbersofelectrons,protonsandneutronsintheatomsofeachofthefollowing
isotopes.(Consulttheperiodictableprintedinsidethefrontcoverasnecessary.)
(a) 137Cs
(b)131I
(c)
(d)
1.52FromtheelementsNe,Cs,Sr,Br,Co,Pu,InandO,chooseonethatfitseachofthefollowing
descriptions.
(a)agroup2metal
(b)anelementwithpropertiessimilartothoseofaluminium
(c)atransitionmetal
(d)anoblegas
(e)anactinoid
1.53Writethenamesandchemicalsymbolsforthreeexamplesofeachofthefollowing:
(a)halogens,
(b)alkalimetals,
(c)actinoidsand
(d)noblegases.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
ADDITIONALEXERCISES
1.54Anatomofanelementhas25protonsinitsnucleus.
(a)Istheelementametal,anonmetalorametalloid?
(b)Onthebasisoftheaverageatomicmass,writethesymbolfortheelement'smostabundant
isotope.
(c)Howmanyneutronsareintheisotopeyoudescribedin(b)?
(d)Howmanyelectronsareinanatomofthiselement?
(e) Howmanytimesheavierthan12Cistheaverageatomofthiselement?
1.55ElementsXandYformacompoundinwhichthereisoneatomofXforeveryfouratomsofY.
Whentheseelementsreact,itisfoundthat1.00gofXcombineswith5.07gofY.When1.00gof
Xcombineswith1.14gofO,itformsacompoundcontainingtwoatomsofOforeachatomofX.
CalculatetheatomicmassofY.
1.56Anironnailiscomposedoffourisotopeswiththepercentageabundancesandatomicmasses
giveninthefollowingtable.Calculatetheaverageatomicmassofiron.

Isotope Percentageabundance Atomicmass(u)


54Fe 5.80 53.9396
56Fe 91.72 55.9349
57Fe 2.20 56.9354
58Fe 0.28 57.9333

1.57Rustcontainsanironoxygencompoundinwhichtherearethreeoxygenatomsforeachtwoiron
atoms.Inthiscompound,theirontooxygenmassratiois2.325:1.000.Anothercompoundof
ironandoxygencontainstheseelementsintheratioof2.616:1.000.Whatistheratioofironto
oxygenatomsinthesecondironoxygencompound?
1.58Oneatomicmassunitcorrespondstoamassof1.6605410 24g.Calculatethemass,ingrams,
ofoneatomofmagnesium.Whatisthemassofoneatomofiron,expressedingrams?Usethese
twoanswerstodeterminehowmanyatomsofMgarein24.305gofmagnesiumandhowmany
atomsofFearein55.847gofiron.Compareyouranswers.Whatconclusionscanyoudrawfrom
theresultsofthesecalculations?Withoutactuallyperforminganycalculations,howmanyatoms
doyouthinkwouldbein40.078gofcalcium?
1.59Thediameterofatypicalatomis10 10m,andthediameterofatypicalnucleusis10 15m.
Calculatethetypicalatomicandnuclearvolumesanddeterminewhatfractionofthevolumeofa
typicalatomisoccupiedbyitsnucleus.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYTERMS
actinoids element nucleon
alkalimetals excitedstate nucleus
alkalineearthmetals fblockelements nuclide
alphaparticle groundstate orbital
anion group pblockelements
atomicmass halogens periodictableoftheelements
atomicmassunit(u) ion period
atomicnumber(Z) isotopes pnictogens
atom lanthanoids product
cation lawofconservationofmass proton
chalcogens lawofdefiniteproportions quantisation
chemicalequation lawofmultipleproportions radioactive
chemicalreaction massnumber(A) radionuclide
chemicalsymbol matter rareearthelements
compound metalloids reactant
covalentbond metals redoxreaction
dblockelements molecule sblockelements
Dalton'satomictheory neutron spin
electronictransition noblegases subatomicparticles
electron nonmetals transitionmetals

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

2 TheLanguageof
Chemistry
Chemistry,likeanyspecialistdiscipline,hasalanguageallitsown.Thelanguageof
chemistryisnotmerelyaboutwordsitisalsoaboutsymbols,diagrams,formulae,
abbreviations,equationsandpictures.Aworkingknowledgeofthislanguageisneededtobe
abletodescribeanddepictchemicalelements,compoundsandprocesses,andto
communicateandappreciatemanyoftheimportantconceptsofthisscience.Inthischapter
wewillconcentrateonthreeimportantareaswithinthebroadfieldofthelanguageof
chemistry:
measurementandunits
representationsofmolecules
nomenclature,thewayinwhichwenamechemicalspecies.
KEYTOPICS

2.1Measurement
2.2Representationsofmolecules
2.3Nomenclature

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
2.1Measurement
Chemistryisascienceofmeasurement.Wheneverweweighacertainmassofaparticularsubstance,evaluatetherateofachemical
reactionordeterminethecellpotentialofanelectrochemicalcell,wearemakingmeasurements.Measurementsalwayshaveaunit
andalwayshaveanassociateduncertainty.Ameasurementthatismissingeitheroftheseismeaningless.

SIUnits
On23September1999,NASA,theNationalAeronauticsandSpaceAdministrationoftheUSA,lostcontactwithitsMarsClimate
Orbiterspacecraft(figure2.1)asitwasabouttoenterorbitaroundMars.Theorbitereventuallycrashedintotheplanet.Theloss
wasattributedtoanerrorthatresultedfromanincorrectuseofunitsoneteamofscientistsworkingontheprojectusedimperial
units(feet,pounds)whileothers,workinginadifferentlocation,usedSIunits(metres,kilograms)incalculatingthethrustnecessary
toplacethespacecraftintoorbitaroundMars.Similarly,on23July1983,AirCanadaflight143,aBoeing767with69peopleon
board,ranoutoffuelat12000mbecausethefuelhadbeenmeasuredinincorrectunits.Thankfully,thepilotswereabletoglideto
asuccessfullanding.

FIGURE2.1NASA'sMarsClimateOrbitercrashedintoMarsaftercalculationsweremadeusinginconsistentunits.

Thesetwoexamplesillustratethesignificanceofunitsinourmodernworld.Aunitisaspecificstandardquantityofaparticular
property,againstwhichallotherquantitiesofthatpropertycanbemeasured.Forexample,wecanmeasurealllengthswithrespect
tothelengthof1metre,andmetreisthereforeaunitoflength.Humanshaverecognisedtheimportanceofunitsofmeasurementfor
thousandsofyears.Oneoftheearliestdocumentedunitsofmeasurementwasthecubit,aunitoflengthusedinancientEgyptequal
tothedistancebetweenthetipofthemiddlefingerandtheelbow.Infact,manyunitsusedbytheancientEgyptianswerebasedon
partsofthehumanbody,suchasthedigit,thepalm,thehandandthespan.Obviouslypeoplecomeinalldifferentshapesandsizes,
sothissystemwasfarfromsatisfactory.Overtime,ajumbleofmeasuringsystemsandstandardsdeveloped.Forexample,itis
believedthatinaroundtheyear1100,England'sKingHenryIdefinedtheyardasthedistancefromtheendofhisnosetothetipof
histhumb,while200yearslaterKingEdwardIIdecreedthatthreebarleycornslaidendtoendconstitutedaninch.ItwasinFrance,
followingtheFrenchRevolutionin1789,thataseriousattemptwasfirstmadetodevelopaninternationalsystemofunits.On22
June1799,twopiecesofplatinum,oneweighingexactly1kilogramandtheotherexactly1metreinlength,weredepositedinthe
ArchivesdelaRpubliqueinParis,markingtheintroductionofwhatiscommonlyknownasthemetricsystemandwhatscientists
callSI(SystmeInternational)units.TheSIhasasetofbaseunitsforsevenmeasuredquantities.Thesearegivenintable2.1
alongwiththeirdefinitions(noticethatthedefinitionofthemetrehaschangedsince1799themetreisnowexpressedmore
precisely,intermsunimaginable200yearsago).
TABLE2.1 TheSevenSIBaseUnits
Measurement Unit Symbol Derivation
length metre m Themetreisthelengthofthepathtravelledbylightinavacuumduringatimeinterval
of ofasecond.

mass kilogram kg Thekilogramisequaltothemassoftheinternationalprototypeofthekilogram.


time second s Thesecondisthedurationof9192631770periodsoftheradiationcorrespondingto
thetransitionbetweenthetwohyperfinelevelsofthegroundstateofthe133Csatom.
temperature kelvin K Thekelvinisthefraction ofthethermodynamictemperatureofthetriplepoint
ofwater.
amountof mole mol Themoleistheamountofsubstanceofasystemwhichcontainsasmanyelementary
substance entitiesasthereareatomsin0.012kilogramsof12C.

Whenthemoleisused,theelementaryentitiesmustbespecifiedandmaybeatoms,
molecules,ions,electrons,otherparticlesorspecifiedgroupsofsuchparticles.
electric ampere A Theampereistheconstantcurrentwhich,ifmaintainedintwostraightparallel
current conductorsofinfinitelength,ofnegligiblecrosssectionandplaced1metreapartina
vacuum,wouldproduce,betweentheseconductors,aforceof210 7newtonsper
metreoflength.
luminous candela Cd Thecandelaistheluminousintensity,inagivendirection,ofamonochromatic
intensity radiationoffrequency54010 12hertzandthathasaradiantintensityinthatdirection
of wattpersteradian.

Aworkingknowledgeoftheunitsandsymbolsgivenintable2.1isessentialinchemistry.However,theprecisedefinitionsare
generallycomplicated,anditisnotnecessarytomemorisetheirderivations,whicharegivenforinterestonly.Itshouldbenoted
that,atthetimeofwriting,proposalshavebeenmadetoredefineboththemoleandthekilogram.Theinternationalprototypeofthe
kilogram(whichiskeptinavaultattheInternationalBureauofWeightsandMeasuresnearParis)hasbeenfoundtohavelostabout
50govertime,andadefinitionwhichdoesnotinvolveaphysicalobjectthatissubjecttochangeisthoughttobepreferable.
Similarly,adefinitionofthemolethatdoesnotinvolvemasshasbeenproposed.Suchredefinitionswillmakenodifferencetothe
useofSIunitsineverydaylife,andwillhaveonlyaminisculeimpactonallbutthemostprecisescientificmeasurements.

WeareallfamiliarwiththeSIunitsforlength(metre,m),mass(kilogram,kg)andtime(second,s).TheSIunitoftemperature
(kelvin,K)hasabsolutezero(273.15C),thecoldestpossibletemperature,asitszeropoint.Temperatureismorecommonly
measuredindegreesCelsiusatemperatureinCelsiusmaybeconvertedtodegreeskelvinbyadding273.15.Thismeansthatthe
freezingpointofwater,0C,isequalto273.15K,whiletheboilingpointofwater,100C,is373.15K.Notethatatemperature
differenceof1kelvin(wedonotsay1degreekelvin)isthesameasatemperaturedifferenceof1degreeCelsius.

TheSIunitofamountofsubstance,aconceptthatwillbediscussedinchapter3,isthemole(mol),whiletheunitofelectrical
current,theampere,willbediscussedwhenwestudyelectrochemistryinchapter12.TheSIunitofluminousintensity(the
brightnessoftheradiationemittedbyphosphorescentandfluorescentcompounds)isthecandela.

TheSIunitsforanyphysicalquantitycanbebuiltfromthesesevenbaseunits.Forexample,thereisnoSIbaseunitforarea,butwe
knowthattocalculatetheareaofarectangularroomwemultiplyitslengthbyitswidth(i.e.itslengthinonedimensionbyitslength
intheother).Therefore,theSIunitforareaisderivedbymultiplyingtheunitforlength(m)bytheunitforlength(m)togivem2
(metresquared,orsquaremetre).Table2.2listsseveralderivedSIunitsthatareimportantinchemistry.
TABLE2.2 SIDerivedUnitsCommonlyUsedinChemistry
Expressionintermsofsimpler ExpressionintermsofSIbase
Measurement quantities Unit units
area lengthwidth (a) squaremetre m2
volume lengthwidthheight(a) cubicmetre m3
speed,velocity distance(b)/time metrepersecond ms1
acceleration velocity/time metrepersecond ms2
squared
density mass/volume kilogrampercubicmetre kgm3
specificvolume volume/mass cubicmetreperkilogram m3kg 1
force massacceleration newton,N 1N=1kgms2
pressure force/area pascal,Pa

energy forcedistance(b) joule,J

power energy/time watt,W

electriccharge electriccurrenttime coulomb,C 1C=1As


electric energy/electriccharge volt,V
potential

(a)Widthandheightaresimplylengthindifferentdirections.
(b)Distanceisanothernameforlength.
Theunitsforareaandvolume,squaremetreandcubicmetre,respectively,areprobablyfamiliartoyou,asaretheirsymbols,m2
andm3.However,whileyouarealsoprobablyfamiliarwiththeunitofvelocity,metrepersecond,youmayperhapswonderhow
thesymbolms1isobtained.Toobtainavelocity,wedividelengthbytime,andweobtaintheunitforvelocitybydividingtheunit
oflength(m)bytheunitoftime(s).Wecanwritethesymbolfortheresultingunitintwoways:asm/s,or,asweshalldo
throughoutthisbook,asms1.Recallthatx1issimplyanotherwayofwriting ,andso,whenwewritems1,thisisthesameas
.Similarly,weobtainanaccelerationbydividingvelocitybytime,andtheunitisthenderivedfromtheunitofvelocity

(ms1)dividedbytheunitoftime(s).Theunitistherefore (metrepersecondsquared),wheres2isthesameas .
Thisillustratesaveryimportantconceptthatisusedthroughoutthisbookwhenweperformcalculations:unitsundergothesame
kindsofmathematicaloperationsasthenumberstowhichtheyareattached.Wedemonstratethisinworkedexample2.1.

WORKEDEXAMPLE2.1

DerivingSIunits
Heatcapacity,whichwewillmeetinchapter8,isameasureoftheheatrequiredtoraisethetemperatureofaparticular
substanceby1K.Wecanobtainheatcapacityvaluesbydividingtheheatprovidedbythetemperaturechangeobtained.
WhatisthederivedSIunitofheatcapacity?

Analysis

Asweobtainheatcapacityvaluesbydividingheatbytemperaturechange,wewillobtaintheunitforheatcapacityby
dividingtheunitsofheatbytheunitsoftemperaturechange.

Solution

TheSIunitofheatisthejoule(J)andtheSIunitoftemperature,andthereforetemperaturechange,isthekelvin(K).
Therefore,theunitofheatcapacityis:

PRACTICEEXERCISE2.1
Thekineticenergyofanobjectofmassmmovingat
velocityuis .WhatisthederivedSIunitofkinetic
energy?

SometimesitisinconvenienttouseSIbaseorderivedunits.Forexample,wewouldnotwanttousemetrestomeasurethetiny
lengthofanatomicradiusortheenormousdistancetotheneareststar.TheSIsystemaddressesthisproblembytheuseofprefixes
thatdivideormultiplytheunitbyaparticularpoweroften.Forexample,theprefixcentimeansthefollowingunitisdividedby
100,whiletheprefixkilosignifiesthatthefollowingunitismultipliedby1000.Table2.3liststhemostcommonprefixes.
TABLE2.3 CommonPrefixesforSIUnits
Prefix Symbol Factor
tera T 10 12
giga G 10 9
mega M 10 6
kilo k 10 3
deci d 10 1
centi c 10 2
milli m 10 3
micro 10 6
nano n 10 9
pico p 10 12
femto f 10 15

Eachprefixhasanassociatedsymbol,whichisplacedimmediatelybeforethebaseunit.Therefore,kmreferstokilometre,aunitof
10 3m,whilecm(centimetre)isaunitof10 2m.

WORKEDEXAMPLE2.2

UsingSIprefixes

Objectsthataresmallerthanabout210 7mcannotbeseenunderanopticalmicroscope.Couldweuseanoptical
microscopetoobserveavirusthatis20nmlong?

Analysis

Weneedtoconvert20nmtometres,andcompareitwith210 7m.TheSIsymbolnstandsfornanoandmeans10 9,
sowewillusethisconversionfactor.

Solution

Weknowfromtable2.3that1nm=110 9m,andtherefore20nm=2010 9m=210 8m.Thisislessthan2


10 7mandhencewewillnotbeabletoseethisvirususinganopticalmicroscope.

Isouranswerreasonable?

Wecancheckourresultbyconvertingthesizeofthesmallestvisibleobject(210 7m)tonanometressothatitcanbe
compareddirectlywiththesizeofthevirus210 7misequalto20010 9m,or200nm.Thevirusis20nmlongthe
smallestobjectthatcanbeseenunderthemicroscopeis200nm,soagainweconcludethattheviruswillnotbevisible.

PRACTICEEXERCISE2.2

1.Givetheabbreviationfor:
a.microgram
b.micrometre
c.nanosecond.
2.Howmanymetresarein:
a.1nm
b.1cm
c.1pm?
3.Whatsymbolisusedtorepresent:
a.10 2g
b.106m
c.10 6s?

NonSIunits
AlthoughSIunitshavebeenadoptedinnearlyallcountries(USA,MyanmarandLiberiabeingtheonlyexceptions),therearemany
nonSIunitsincommonusagethroughouttheworld.Forexample,wesawonp.25thattemperaturesaremuchmorelikelytobe
measuredindegreesCelsius(ordegreesFahrenheitintheUSA,MyanmarandLiberia)thanintheSIunitkelvin.Evenchemistsare
notimmunetothisweoftenusethelitre,aunitofvolumeequalto1000cm3,ratherthanthemorecorrect(butinconveniently
large)m3.Themillilitre(1cm3)isalsooftenused.VariousnonSIunitsofpressure(atmosphere,millimetreofmercury,torr,bar),
ratherthantheSIunitpascal,arestillregularlyseeninthechemicalliterature.AslongasuseofnonSIunitspersists,itwill
occasionallybenecessaryforyoutobeabletoconvertbetweennonSIandSIunits.Todothis,weneedtoknowtheconversion
factorbetweentheunits.Thenwecanobtainanequationtoconvertbetweenthetwo.Thisisillustratedinworkedexample2.3.

WORKEDEXAMPLE2.3

Unitconversions
Thelawsofcricketstatethatacricketpitchis22yardsinlength.Howlongisacricketpitchinmetresgiventhat1metre
=1.0936yards?

Analysis

Wearetoldthat1metrecorrespondsto1.0936yardsinotherwords,thereare1.0936yardsineverymetreor,toputit
yetanotherway,1.0936yardspermetre.Therefore,theconversionfactor,intermsofyardspermetre,is
.

However,weareaskedtoconvertfromyardtometre,andthereforeneedtheconversionfactorintermsofmetresper
yard(metreyard 1).Weobtainthisknowingthat:

Wecannowsolvetheproblembymultiplyingthisconversionfactorby22yards.

Solution

22yard0.9144metreyard 1=20.12metre

Isouranswerreasonable?

Weknowthat1metreisslightlylongerthan1yard,sowewouldexpectournumericalanswertobeslightlylessthan22,
whichitis.Noticealso,aswewillseeonpp.289,thattheunitsinoursolutionareconsistentyardmetreyard 1=
metre.

PRACTICEEXERCISE2.3
Usethegivenconversionfactorstocarryoutthefollowing
conversionsinvolvingpressureunits.
1.Convert0.3bartopascal(1pascal=110 5bar).
2.Convert451millimetresofmercurytopascal(1
pascal=7.5010 3millimetresofmercury).
3.Convert3.81atmospherestopascal(1pascal=9.87
10 6atmosphere).

Noticethatthemethodofunitconversiondescribedonp.27canalsobeusedforconversionbetweenSIunits.Forexample,
supposewewantedtoexpress418cm3inm3wewouldneedtheconversionfactorintermsofm3cm3.Fromtheunitprefixc,we
knowthat:
Theconversionfactoristherefore ,andwecarryouttheconversionasfollows:

DimensionalAnalysis
OneofthequestionsmostcommonlyaskedbystudentsisWhatequationsdoIneedtolearnforthefinalexam?Ifyoureadthis
bookfromcovertocover(orindeed,ifyoujustgototheglossaryofequationsattheendofthebook),youwillfindalargenumber
ofequations,allofwhichareimportanttothesubjectofchemistryinonesenseoranother,andyoumightthinkthatitisnecessary
foryoutolearnthemallbyheart.You'llbehappytoknowthatthisisnotthecase.

Dimensionalanalysisinvolvesusingtheunitsofaphysicalquantitytoderivetheequationusedtodetermineitsvalue.Wefirst
encounteredthisonp.26whenwestatedthatunitsundergothesamekindsofmathematicaloperationsasthenumberstowhich
theyareattached.Wethenwentontoillustratethisinworkedexample2.1(p.26)whenwedeterminedtheunitsofheatcapacity
(JK1)throughknowledgeofthefactthatheatcapacityisequaltoheat(J)dividedbytemperaturechange(K).Wewillnowlookat
thisprinciplemoreclosely,usingthestoichiometricequations and ,whichwillbeintroducedinchapter3.Theseare
twoofthemostusedequationsinchemistryand,withoutdoubt,theseequationsarethetwomostoftenwrittenincorrectly.Yet,all
youneedtoknowtodeterminethecorrectformsoftheseequationsaretheunitsofmolarmass(M),gmol1,andconcentration(c),
molL1.

Theunitofmolarmass,gmol1,isobtainedbydividingaphysicalquantityhavingtheunitgrambyaphysicalquantityhavingthe
unitmole.Thesephysicalquantitiesaremass(m)andamount(n),respectively.Knowingthisallowsustowritetheequationrelating
mass,amount,andmolarmassasfollows:

Therefore,

Andthereyouhaveittheequationisgivenbytheunits.Thecorrectunitsofmolarmass(gmol1)areobtainedonlyifwedivide
mass(g)byamount(mol).Noothercombinationofmassandamountwillgivethecorrectunitsofmolarmass.

Asimilarsituationoccursinthecaseofconcentration.TheunitofconcentrationismolL1,andisthereforeobtainedbydividinga
physicalquantityhavingtheunitmolebyaphysicalquantityhavingtheunitlitre.Weknowthatmoleistheunitofamount(n)and
litreistheunitofvolume(V).Therefore,wecanwrite:

Therefore,

Again,noothercombinationofamountandvolumewillgivethecorrectunitsofconcentration.

Dimensionalanalysisassistsyounotonlyinrememberingthecorrectformofanequation,butalsoinensuringyouhaverearranged
anequationcorrectly.Consider,forexample,rearrangingtheaboveequationforconcentration,tomakenthesubject.Thecorrect
rearrangement,obtainedbymultiplyingbothsidesoftheequationbyV,gives

andwecaneasilycheckthisbecauseweknowthattheunitsonbothsidesoftheequationmustbethesame.Onthelefthandside,
wehaveunitsofmolandontherighthandsidewehaveunitsofmolL1L=mol.Therefore,wecanbeconfidentthatwehave
rearrangedtheequationcorrectly.

Ifwehadarrangedthevariablesincorrectly,e.g. or ,wecouldquicklyseefromtheunitsthatwehadmadeamistake
givesunitsofmolL1/L=molL2,while givesunitsofL/molL1=L2mol1.Neithercanbecorrectastheydonotgivethe
unitsofmol.
Thisisalwaysagoodcheckwheneveryourearrangeanequationiftheunitsarenotthesameonbothsidesoftherearranged
equation,youhavemadeamistake.

Therearesituationswheredimensionalanalysismight,atfirstglance,appearnottowork.Consider,forexample,theidealgas
equation,pV=nRT,whichwewillencounterinchapter6.Giventhatpressure(p)ismeasuredinPa,volume(V)inm3,amount(n)
inmolandtemperature(T)inK,andthegasconstant(R)hasunitsofJmol1K1,wecanworkouttheunitsonbothsidesofthe
equation:
TheunitsofpV(lefthandside)arePam3=Pam3.
TheunitsofnRT(righthandside)aremolJmol1K1K=J.
Thisdoesnotappeartobecorrect,asitlooksasthoughwehavedifferentunitsoneachsideoftheequation.However,remember
thatbothPaandJarederivedunitsfromtable2.2(p.25)wecanseethat1J=1kgm2s2and1Pa=1kgm1s2.Therefore

andwecanseethattheunitsonbothsidesoftheequationare,infact,thesame.

Dimensionalanalysisisnotlimitedtotheserelativelysimpleequations.Itworksforanyequation.Thisisbecausethenumbersand
theunitsonbothsidesofanequationmustbethesame.Asworkedexample2.4shows,dimensionalanalysiscanalsobeusedto
determinethecorrectformofanequationifyouknowtheunitsofalltheconstituentcomponents.

WORKEDEXAMPLE2.4

DimensionalAnalysis
Anaqueoussugarsolutionwillboilatatemperatureslightlygreaterthan100C,dependingonhowmuchsugarthe
solutioncontains.Themagnitudeofthisboilingpointelevation(T)canbecalculatedfromsomecombinationofthe
molalboilingpointelevationconstant(Kb)andthemolality(b)ofthesolution.Giventhattheunitsofbaremolkg 1and
thoseofKbareKmol1kg,whatequationshouldbeusedtocalculateTwhenthisismeasuredinK?

Analysis

WeneedtocombinetheunitsofbandKbtogiveunitsofKinourfinalanswer.Therearethreepossibilities:

WeneedtodeterminethefinalunitsforTthatresultfromeachofthesethreepossibilities.Thecorrectequationwill
givefinalunitsofK.

Solution

Weinserttheappropriateunitsintoeachofthethreeexpressionsabove.

Therefore,thecorrectequationtocalculatetheboilingpointelevationisT=Kbb.

Isouranswerreasonable?

GiventhatthereisonlyonewayofcombiningtheunitsofKbandbtogiveunitsofK,wecanbeconfidentouransweris
correct.

Wewilllearnmoreaboutboilingpointelevationinchapter10.
PRACTICEEXERCISE2.4
Deducethecorrectformofeachofthefollowing
equationsbyconsideringtheunitsofallthecomponents
oftheequation.
(a)Obtainanequationformass(m,g)intermsof
molarmass(M,gmol1)andamount(n,mol).
(b)Obtainanequationforthegasconstant(R,Jmol1
K1)intermsofpressure(p,Pa),volume(V,m3),
amount(n,mol)andtemperature(T,K).
(c) Obtainanequationforthespeedoflight(c,ms1)
intermsofenergy(E,J),Planck'sconstant(h,Js)
andwavelength(,m).

UncertaintiesandSignificantFigures
Everymeasurementhasanassociateduncertainty,whichresultsfromthelimitationsofthemethodsweusetomakethe
measurement.Consider,forexample,aquantitythatyouprobablyknowwell:yourweight.Ifyouusedananaloguesetofbathroom
scaleswhichcanweightothenearestkilogramtoweighyourself,youmightfindthatyourweightliesalmostexactlyhalfway
betweenthedivisionscorrespondingto71kgand72kg.Doyouquoteyourweightas71kgor72kg?Thereisobviouslysome
uncertaintyoverthelastfigureinthemeasurement.Youthereforeinvestinamoreexpensivesetofdigitalscaleswhichcanweigh
tothenearest0.1kilogramusingthese,youfindyouweigh71.6kg.However,ifyouwaitlongenough,younoticethatthedisplay
fluctuatesbetween71.5kgand71.7kg.Again,thelastfigureintheanswerisuncertain.Youcouldkeepbuyingscalesthatweigh
toeversmallerfractionsofakilogram,butyouwouldalwaysfindthattherewouldbesomeuncertaintyinthefinalfigureofthe
measurement.Wecanillustratethisconceptfurtherbyconsideringthetwothermometersinfigure2.2,whichdisplaythesame
temperature.
FIGURE2.2Thermometerswithdifferentscalesgivereadingswithdifferentprecision.Thethermometeronthelefthasdivisionsthatare1C
apart,allowingthetemperaturetobeestimatedtothenearest0.1C.Thethermometerontherighthasdivisionsevery0.1C,
thereforepermittingestimationofthetemperatureto0.01C.

Thedivisionsontheleftthermometerare1Capartanditisthereforecertain,barringanyimperfectionsinthemanufactureofthe
thermometer,thatthetemperatureisgreaterthan24Candlessthan25C.Itcanbeestimatedthatthetopofthefluidcolumnfalls
about0.3ofthewaybetweenthedivisionsfor24Cand25C,sothemeasurementcanberecordedas24.3C.However,we
cannotsaythatthetemperatureisexactly24.3C,asthelastfigureisonlyanestimate,andtheleftthermometermightbereadas
24.2Cbyoneobserverand24.4Cbyanother.Thethermometerontherightisgraduatedindivisionsof0.1Candmaytherefore
bereadtoagreaterprecisionthantheotherthermometer.Readingthethermometerontheright,itisnowcertain,againassumingno
flawsinthethermometer,thatthetemperatureliesbetween24.3Cand24.4C,andanotherfigureinthemeasurementcanbe
estimatedbynotingthatthetopofthefluidliesabout0.2ofthewaybetweenthedivisions.Therefore,thetemperatureaccordingto
thethermometerontherightwouldbestatedas24.32C.Byconventioninscience,allfiguresinameasurementuptoand
includingthefirstestimatedfigurearerecorded.Thefiguresrecordedaccordingtothisconventionarecalledsignificantfigures.
Thethermometerontherightcanbereadtoagreaterprecision,andthemeasurementmadecontainsacorrespondinglylarger
number(4)ofsignificantfigures.Thenumberofsignificantfiguresinameasurementisequaltothenumberofdigitsknownfor
certain,plusonethatisestimated.Therefore,therewillalwaysbeuncertaintyinthelastsignificantfigureofanymeasurement.In
theaboveexample,thefinalfiguresofboth24.3Cand24.32Careuncertain.

Itisusuallyeasytodeterminethenumberofsignificantfiguresinanumbersimplycountthefigures.However,ambiguitiesmay
arisewhenzerosarepresentforexample,doesthenumber0.0023containtwo(23),four(0023)orfive(0.0023)significant
figures?Suchproblemscanbeavoidedbywritingnumbersinscientificnotation,whichimmediatelyshowshowmanysignificant
figuresarepresent.Scientificnotationexpressesnumbersintermsofpowersoftenforexample,thenumber15becomes1.510 1
inscientificnotation,362becomes3.6210 2,andsoon.Inscientificnotation,0.0023iswrittenas2.310 3,anditcanbeseen
thatthenumbercontainsonlytwosignificantfigures.Similarly,themoreprecisenumber0.00230wouldbewrittenas2.3010 3,
andthisthenhasthreesignificantfigures.Notethatthenumberofsignificantfiguresinameasurementisthesameregardlessofthe
units.Forexample,alengthof2.310 3mcanbeexpressedinmillimetres(2.3mm)ornanometres(2.310 6nm),butineach
casethevaluesmusthavethesamenumberofsignificantfigures,astheprecisionofthemeasurementdoesnotdependontheunits
inwhichitisexpressed.
WORKEDEXAMPLE2.5

SignificantFigures
Determinethenumberofsignificantfiguresinthefollowingnumbers.
(a)0.004136
(b)0.1060
(c)10.01

Analysis

Weneedtowritetheabovenumbersinscientificnotation.Wecanthendeterminethenumberofsignificantfiguresfrom
thenumberoffiguresinthescientificnotation.

Solution

Thenumberswritteninscientificnotationareasfollows.
(a) 4.13610 3
(b)1.06010 1
(c) 1.00110 1

Therefore,allthreenumbershavefoursignificantfigures.

Isouranswerreasonable?

Theambiguityinsignificantfigurescomeswithzeros.Aretheysignificant,oraretheyplaceholders?Inthenumber
0.004136,allthezerosareplaceholders,andwritingthisinscientificnotation(4.13610 3)makesthisclearnoneof
thezerosappearinthescientificnotationofthisnumber,sotheycannotbesignificant.Theothertwonumberscontain
zerosthataresignificant,becausetheyappearinthescientificnotation.Takingtheserulesintoaccount,ouransweris
reasonable.

PRACTICEEXERCISE2.5
Howmanysignificantfiguresdothefollowingnumbers
contain?
(a)1.000405
(b)0.001000
(c)1000010.0

Theuncertaintyinanymeasurementgenerallydependsontheprecisionoftheinstrumentusedtomakethatmeasurement.For
example,a20mLpipettemayhaveanuncertaintyof0.05mL(meansplusorminus).Wewouldthereforequotethepipetteas
measuring20.000.05mL(seefigure2.3).
FIGURE2.3The0.1mLgraduationsonthispipetteimplyanuncertaintyof0.05mL.

Thismeansthatthepipettedeliversbetween19.95mLand20.05mLwheneveritisused.Thistypeofuncertaintyiscalledan
absoluteuncertaintyinotherwords,theuncertaintyhasthesameunitsasthequantitybeingmeasured.Wecanalsoquotethe
percentageuncertaintyforaninstrument.Inthiscase,wewouldcalculatethepercentageuncertaintyforthepipetteasfollows:

Aswewillseebelow,percentageuncertaintiesareimportantwhenwearedoingcalculationsinvolvingeithermultiplicationor
division.

Itshouldbenotedthattherearetwotypesofuncertaintiesinanymeasurement.Randomuncertaintiesrefertothereproducibilityof
ameasurement,andaregenerallytakenaccountofinthequoteduncertaintyoftheapparatususedtomakethemeasurement.These
arewhatgiverisetothetotaluncertaintythatwereportattheendofacalculation(seebelow).Systematicuncertaintiesusually
resultfromdeficienciesinthemeasuringequipmentorfromhumanerror,forexample,whenusingapipettewhichdeliversonly
19.00mLratherthanthestated20.00mL,orusingapHmeterwhichhasbeenincorrectlycalibrated.Theseuncertaintiescanbe
eliminatedthroughcarefulexperimentaltechnique.

UncertaintiesandSignificantFiguresinCalculations
Wehaveshownabovehowtodeterminethenumberofsignificantfiguresinanindividualnumber.Butwhenweusenumbersina
calculation,howmanysignificantfiguresdoestheanswercontain?Andhowdouncertaintiesinnumericalmeasurementstranslate
toanuncertaintyinthefinalanswerwhenthesemeasurementsareusedincalculations?Moreoftenthannot,youwillberelyingon
yourcalculatortocarryoutcalculationsthiswillgenerallygiveananswercontainingmanymoresignificantfiguresthanare
justifiedandwilltellyounothingabouttheuncertaintyinthatanswer.Youthereforeneedtomakeuseofsomerulestoappreciate
whatsortofprecisionyoushouldgiveinyourfinalanswer.

Todeterminetheappropriatenumberofsignificantfiguresintheanswerofacalculation,thefollowingrulesapply:
Whenanumericalmeasurementismultipliedbyaconstant,thenumberofsignificantfiguresintheanswerwillbethesameas
thatinthenumericalmeasurement.
Whentwoormorenumericalmeasurementsaremultipliedordivided,thenumberofsignificantfiguresintheanswershould
notbegreaterthanthenumberofsignificantfiguresintheleastprecisemeasurement.
Whentwoormorenumericalmeasurementsareaddedorsubtracted,theanswershouldhavethesamenumberofdecimal
placesasthemeasurementwiththefewestnumberofdecimalplaces.

Wecanillustratetheserulesasfollows.Ifwecalculate:

onatendigitcalculator,theansweris13.49709375,anumberwithtenfigures.Buthowmanyofthesefiguresaresignificant?The
numbersinthenumerator(topline)containthreeandfoursignificantfiguresrespectively,whilethedenominator(bottomline)
containstwosignificantfigures(the0atthestartofthenumberisnotsignificant)andsoitmakesnosensetohaveananswerthatis
manyordersofmagnitudemoreprecisethananyofthenumbersfromwhichitisderived.Theruleatthebottomoftheprevious
pageformultiplicationanddivisionstatesthatwecanhaveonlyasmanysignificantfiguresinourfinalanswerasthereareinthe
leastprecisemeasurement.Therefore,inthisexample,wecanexpressouranswertoonlytwosignificantfigures,soourfinalanswer
becomes:
Ifwecalculatethesum:

acalculatorwillgivetheansweras169.807.However,lookingatthelayoutofthesumabove,weseethattherearenofigures
beneaththe7of3.247orthe6of41.36inotherwords,thefirstfigureafterthedecimalpointistheonlyonethatisknownforall
threenumbers.Addinganunknownfiguretothe6or7willgiveananswerthatisalsounknown,soforthissumwearenotjustified
inwritingfiguresinthesecondandthirdplacesafterthedecimalpoint.Thefirstfigureafterthedecimalpointistheonlyonethatis
knownforallthreenumbersand,therefore,weroundtheanswertothefirstdecimalplace,giving169.8.

Differentrulesapplywhenworkingwithlogarithms,aswewilldoextensivelyinchapter11whenconsideringpH.
Thelogarithmofanumbercanhavethesamenumberoffigurestotherighthandsideofthedecimalpointasthereare
significantfiguresinthenumber.

Forexample,thenumber0.00321hasthreesignificantfigures(thisbecomesmoreobviouswhenitiswritteninscientificnotation
as3.2110 3).Usingacalculatortodeterminethelogarithmgives2.4934949676.Thisshouldthenbequotedas2.493.

Thereverseisalsotruegivenalogarithm,youdeterminethecorrectnumberofsignificantfiguresintheantilogarithmfromthe
numberoffigurestotherightofthedecimalpoint.Hence,usingacalculator,wefindthattheantilogarithmof4.18is6.60693448
10 5.Thisshouldbequotedtotwosignificantfigures,namely6.610 5.

Theaboverulesforlogarithmsapplytobothcommon(log 10)andnatural(lnorlog e )logarithms.

Whilesignificantfiguresanduncertaintiesarerelated,therulesfordeterminingtheuncertaintyintheanswerofacalculationare
somewhatdifferentfromthoseforsignificantfiguresonthepreviouspage.Theyareasfollows:
Whentwoormorenumericalmeasurementsareaddedorsubtracted,theuncertaintyinthefinalansweristhesumofthe
absoluteuncertaintiesinthemeasurements.
Whentwoormorenumericalmeasurementsaremultipliedordivided,theuncertaintyinthefinalansweristhesumofthe
percentageuncertaintiesinthemeasurements.

Itisusualtoquotethefinaluncertaintyasanabsoluteuncertainty,soitisnecessarytobeabletoconvertfromapercentagetoan
absoluteuncertainty.

Wewillillustratetheserulesinworkedexample2.6.

WORKEDEXAMPLE2.6

Calculatinguncertainties
Aswewillseeinsection2.2,manysimplesaltsareobtainedashydratesfromaqueoussolutionthatis,theycrystallise
withadefinitenumberofwatermolecules(sometimescalledwaterofcrystallisation).Suchsaltshavethegeneralformula
MaXbcH2O,wherea,bandcaregenerallyintegers.Thewaterofcrystallisationcanoftenberemovedbyheating,togive
theanhydroussaltMaXb.

Inanexperiment,2.400gofCoSO47H2Owasheatedtoremovethewaterofcrystallisationuntilnofurthermasslosswas
observed.Atthispoint,themassofanhydrousCoSO4obtainedwas1.323g.Usethesefigurestocalculatethe
percentage,bymass,ofH2OinCoSO47H2O,andgivetheuncertaintyinyourfinalanswer.Notethatthebalanceusedto
weighthesampleshasanabsoluteuncertaintyof0.001g.

Analysis

Wearegiventhemassofthehydratedandanhydroussalts,sothemassdifferencebetweenthesemustcorrespondtothe
massofwaterinthehydratedsalt.Wethendividethisbythemassofthehydratedsaltandmultiplyby100toobtainthe
percentagebymassofwater.Wemustalsodeterminetheuncertaintyinthefinalanswer.Thiswillderivefromthe
uncertaintiesintheweighings.

Solution
Wewillfirstcalculatethepercentagebymassofwaterinthehydratedsalt,andthendeterminetheuncertaintyinthe
answer.

Notethat,becauseeachmasshasfoursignificantfigures,wecanquotetheansweratthisstagetofoursignificantfigures.

Nowwewillcarryouttheuncertaintyanalysis.Westatedonthepreviouspagethatthebalanceusedhasanabsolute
uncertaintyof0.001g,soyoumightthinkthateachmeasuredmasshasthisuncertainty.Infact,theuncertaintyineach
measuredmassis0.002g.Thisisbecauseeverymeasurementwemakeusingthebalanceisinfactthedifference
betweentworeadingsthefinalbalancereading,andtheinitial(zero)balancereading,bothofwhichhaveanabsolute
uncertaintyof0.001g.Becauseweareessentiallysubtractingtwovalues,wemustaddtheirabsoluteuncertainties,for
example:

Wecannowdeterminetheuncertaintyinthemassofwaterinthehydratedsalt.

Again,becausewearesubtractingtwomeasurements,weaddtheirabsoluteuncertainties.

Becausethenextstepinthecalculation,thedeterminationofthepercentagebymassofwaterinthehydratedsalt,
involvesadivision,wemustconverttheabsoluteuncertaintiesinboththemassofthehydratedsaltandthemassofwater
inthehydratedsalttopercentageuncertainties,andthenaddthemtogether.

Notethatwehaveretainedtwosignificantfiguresinthepercentageuncertaintyinthemassofwater.Itisoftenadvisable
tocarryextrafiguresintheuncertaintythroughoutthecalculationandthenroundtoasinglefigureattheend.

Nowwemustconvertourcalculatedpercentageuncertaintytoanabsoluteuncertainty.Wedothisasfollows.

Therefore,ourfinalanswerlooksasthoughitis(44.880.20)%.However,somethoughtwillshowusthatthisisnot
quitecorrect.Itisusualtoquoteuncertaintiestoasinglesignificantfigurethisisbecauseouranswerisgenerally
uncertainonlyinitsfinalfigure.Sowewouldthenamendouransweraboveto(44.880.2)%.However,thisstillposes
problemsastheuncertaintyrefersnottothefinalfigurebuttothefirstfigureafterthedecimalpoint.Aswehaveshown
that0.2istheminimumuncertaintyinouranswer,thisthendictatesthenumberofsignificantfigurestowhichthe
answercanbegiveninotherwords,thesecondfigureafterthedecimalpointintheanswerisnotsignificant,giventhe
magnitudeoftheuncertainty.

Thus,ourfinalanswer,includingtheuncertainty,is(44.90.2)%.

Isouranswerreasonable?

Themassloss(1.077g)ingoingfromCoSO47H2OtoCoSO4issolelyduetothewatermoleculesintheformer.This
massisalittleunderhalfthetotalmassofCoSO47H2Oandthuswewouldexpectthatwatershouldmakeupjustunder
50%ofthetotalmassofCoSO47H2O.Ournumericalanswer(44.9%)isthereforelikelytobecorrect.Checkingthatour
uncertaintyisreasonableissomewhatmoredifficult.However,weknowthatthetotaluncertaintyresultsfromtwo
weighings,andthateachofthesehasanuncertaintyofmuchlessthan1%.Therefore,ourfinaluncertaintyof0.2%
appearsreasonable.

PRACTICEEXERCISE2.6
Givetheanswersofthefollowingcalculationstothe
correctnumberofsignificantfigures.
(a)4.196+8.3492+14.73
(b)5.361.259
(c)6.38(2.514+5.4)
(d)thetotalmassoftwobeakersofwater,eachof
whichweighs37.50g
(e)log(2.1855.48)
(f)

PRACTICEEXERCISE2.7
Performthefollowingcalculationsinvolving
measurements.Givetheanswerstothecorrectnumberof
significantfigures,andusetheappropriateunits.
(a)21.0233g+21.0g
(b)32.02mL2.0mL
(c)54.183g0.0278g
(d)10.0g+1.03g+0.243g
(e)

(f) 1.03m2.074m3.9m

PRACTICEEXERCISE2.8

Astudentwantedtoprepare100mLofa1.000gL1
solutionofNaClanddevisedthefollowingmethod.The
studentweighed0.100gofsolidNaClonabalanceand
transferredthistoa100mLvolumetricflask.Sufficient
waterwasthenadded,withstirring,togiveafinalvolume
of100mLaccordingtothemarkonthevolumetricflask.

Giventhattheuncertaintiesinthebalanceandvolumetric
flaskwere0.001gand1mL,respectively,calculatethe
finaluncertaintyintheconcentrationoftheNaClsolution.
Didthestudentsucceedinpreparinga1.000gL1
solution?Ifnot,whatwastheconcentration,includingthe
uncertainty,ofthesolution?

Thewordprecisehasbeenusedinthissection,withoutbeingdefined.Itisimportanttoappreciatethedifferencebetween
accuracyandprecisionwhenmakingmeasurements.Ameasurement'saccuracyreferstohowclosethevalueistothecorrect
value,whileprecisionsignifieshowreproducibleaparticularmeasurementiswhenmadeanumberoftimesand,therefore,how
manysignificantfiguresitcanbequotedto.Thetwoconceptsareillustratedinfigure2.4.
FIGURE2.4Thedifferencebetweenprecisionandaccuracyinthegameofgolf.Golfer1hitsshotsthatareprecise(becausetheyaretightly
grouped),buttheaccuracyispoorastheballsarenotnearthetarget(thetruevalue).Golfer2needshelp.Theshotsareneither
precisenoraccurate.Golfer3winswithshotsthatareprecise(tightlygrouped)andaccurate(inthehole).

PRACTICEEXERCISE2.9
Fourworkersweigha10.000gmassthreetimeson
severaldifferentkitchenscalesandobtainthefollowing
results.
WorkerA:10.022g,9.976g,10.008g
WorkerB:9.836g,10.033g,9.723g
WorkerC:10.230g,10.231g,10.232g
WorkerD:9.632g,9.835g,9.926g
Whichsetofdatahasthebestprecision?Whichhasthe
bestaccuracy?

ChemicalConnections

TheNationalMeasurementInstitute

TheNationalMeasurementInstitute(NMI)istheorganisationresponsibleforprovidingunitandmeasurementstandards
andservicesinAustralia.Ithasfourmainsections:
legalmetrologyandbusinessservices
physicalmetrology
analyticalservices
chemicalandbiologicalmetrology.

Wementionedearlierinthischapterthattheprimarystandardofmassistheinternationalprototypeofthekilogram,
whichisaplatinumiridiumcylinderheldattheInternationalBureauofWeightsandMeasures.TheNMIholdsCopy
No.44(figure2.5)oftheinternationalprototypeofthekilogram.ItservesastheAustralianstandardofmassandthe
NMIusesittocalibrateasetof1kgstainlesssteelstandards.Thosestandardsarethenusedtocalibratestandardswith
massesfrom0.5mgto20kg,whichareusedforallcalibrationworkonmassandthemeasurementofvariousother
quantities.
FIGURE2.5Australia'sCopyNo.44oftheinternationalprototypeofthekilogram.Thisismadeofa90%platinum10%iridium
alloy.

Whilemeasurementmightseemasomewhatesotericfield,itisofgreatimportanceinmanydisciplines,including
chemistryandbusiness.Forexample,oneofthekeyaimsoftheNMIistopromoteuniformmeasurementpolicyand
practicetohelpinternationaltrade.OneareainwhichtheNMIhasbeenactiveisthewineindustry.

Australiaexportshundredsofmillionsoflitresofwineeachyear.Awineconnoisseurwilltellyouthattaste,bouquetand
colourarethequalitiesthatcharacteriseawine(figure2.6).Ametrologist(someonewhospecialisesinmeasurement)
mighttalkmoreaboutthelevelsofchemicalresidues,contaminantsandpreservatives.Inadditiontohealthandquality
concerns,manyinternationalmarketshavestrictregulationsonacceptablelevelsofethanol,sulfitesandheavymetalsin
wines.Exportersmustcomplywiththeseregulationstoensuretheycanselltheirwinesintothosemarkets.
FIGURE2.6Chemicalanalysiscanquantifywhatawineexpertdetectsusingthesenses.

NMIprovidesthewineindustrywithanalyticalchemistryservicestodeterminepesticide,insecticideandherbicide
residues,foreignmatter,alcoholcontentandotherimportantinformation.Thetechniquesusedhavebeenvalidated
againstthoseusedinothercountriestoensurethemeasurementsareacceptedbyexportmarkets.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
2.2RepresentationsofMolecules
Thelanguageofchemistryisnotonlyaboutthemeaningofwords,butalsoabouthowwecanrepresent
chemicalspeciesusingparticularcombinationsofletters,numbers,symbolsandpictures(seefigure2.7).In
thissectionwewilldescribesomeofthemanydifferentwaysinwhichwecandepictmolecules,aswellas
thebondmakingandbondbreakingprocessesthatoccurinchemicalreactions.

FIGURE2.7 Differentwaysofrepresentingthechemicalspeciesmethane:
(a)chemicalformula,
(b)structuralformula,
(c)3Dstructuralformula,
(d)ballandstickmodeland
(e)spacefillingmodel.

ChemicalFormulae
Thesimplestwaytodescribethecompositionofanysubstanceistowriteitschemicalformula.Thisshows
thenumberofeachtypeofatompresentinasubstance.Achemicalformulacontainselementalsymbolsto
representatomsandsubscriptednumberstoindicatethenumberofatomsofeachtype.Itmaybeassimple
aswater,H2O,orascomplicatedasC30H34AuBClF3N6O2P2PtW,thecompoundwhichcurrentlyholdsthe
recordforcontainingthemostelements.Aswehaveseeninchapter1,eachchemicalelementisdescribed
byaone,twoorthreelettersymbol,andtheseformthebasisforallchemicalformulae.Thesimplest
chemicalformulaedescribepureelementsandareusuallyjusttheirelementalsymbolsaslistedonthe
periodictableforexample,heliumisHe,siliconisSiandcopperisCu.Suchformulaeimplythatthebulk
elementsarecomposedofeitherindividualatomswhichdonotinteract(suchasHe)orinfinitethree
dimensionalarraysofbondedatoms(suchasSiandCu).However,thisisnotthecaseforsomeelements
andwemustwritemorecomplexchemicalformulaeforthese.Forexample,sevenelements(hydrogen,
nitrogen,oxygen,fluorine,chlorine,bromineandiodine)occurnaturallyneitherasindividualatomsnoras
threedimensionalarraysbutasmoleculescontainingtwoatoms(diatomicmolecules).Tosignifythis,their
chemicalformulaearewrittenasH2,N2,O2,F2,Cl2,Br2andI2respectively.Someotherelementsoccuras
largermoleculesaphosphorusmoleculecontainsfourPatomsandasulfurmoleculecontainseightSatoms
sotheirchemicalformulaeareP4andS8respectively.Achemicalformulathatreferstoadiscretemolecule
isoftencalledamolecularformulaasitdescribesthetypesandnumbersofatomspresentinthemolecule.
Notethatasubscriptednumeralreferseitheronlytotheatomimmediatelyprecedingit,or,ifitfollowsa
groupofatomsenclosedinparentheses,totheentiregroupofenclosedatoms.Forexample,thechemical
formulaB(OH)3showsthatthecompoundcontainsoneboronatom,threeoxygenatomsandthree
hydrogenatoms.

Chemicalcompoundscontainmorethanoneelement.Therefore,thereispotentiallymorethanonewayto
writetheformulaofanycompound.Forexample,hydrogenchlorideisadiatomicmoleculewithoneatom
eachofhydrogenandchlorine.ItschemicalformulamightthereforebewrittenasHClorClH.Toavoid
possibleconfusion,chemistshavestandardisedthewritingofchemicalformulae.Forbinarycompounds
(compoundscontainingonlytwoelements)thefollowingguidelinesapply:
1.Withtheexceptionofhydrogen,theelementfurthertotheleftintheperiodictableappearsfirst.
ExamplesareKCl,PCl3,Al2S3andFe3O4.
2.Ifhydrogenispresent,itappearslastexceptwhentheotherelementisfromgroup16or17ofthe
periodictable.Forexample,wewritehydrogenlastinLiH,NH3,B2H6andCH4,butfirstinH2O2,
H2S,HClandHI.
3.Ifbothelementsarefromthesamegroupoftheperiodictable,theloweroneappearsfirst,for
exampleSiCandBrF3.
4.Ifthecompoundisionic,wewritethecation(thepositivelychargedion)first,followedbytheanion
(thenegativelychargedion).ExamplesareNaBrandMgCl2.

Writingchemicalformulaeforcompoundscontainingmorethantwoelementsrequiressomeknowledgeof
thebondingwithinthecompound.Aswewilldiscussingreaterdetailinchapter5,chemicalcompounds
canbedividedbroadlyintotwoclassesioniccompoundsandcovalentcompoundswhichare
distinguishedbythetypeofbonding.Ioniccompoundsarecomposedsolelyofions,andtheattractive
forcesbetweenionsofoppositechargeresultintheformationofinfinitethreedimensionallattices.Onthe
otherhand,covalentcompoundsarecharacterisedbybondinginvolvingthesharingofelectronsbetween
adjacentatoms.Towritethechemicalformulaofanioniccompoundcontainingmorethantwoelements,we
againwritethecationfollowedbytheanion.Forexample,theformulaofsodiumnitrate,whichcontains
positivelychargedsodiumions,Na+,andnegativelychargednitrateions,NO3,isNaNO3.Notethatthe
orderingoftheelementsintheNO3ionconformstotherulesgivenabove.Notealsothatwemustalways
ensurethatthetotalchargeontheioniccompoundiszero,sothenumberofNa+andNO3ionsmustbethe
same,andweneverincludetheindividualionicchargesintheoverallformula.Writingthechemical
formulaforcalciumnitrateisalittlemorecomplicated.TheformulaofthecalciumionisCa2+,whilethatof
thenitrateionisNO3.Wecanseethat,toachieveanoverallchargeofzero,wewillrequireoneCa2+ion
andtwoNO3ions,anditiswiththelatterthatapotentialproblemarises.Wesignifythepresenceoftwo
NO3ions,aswedoforanyion,byusingasubscripted2immediatelyfollowingtheion.However,you
canseethat,ifwedothis,wewillhavetwosubscriptednumbersimmediatelyadjacenttoeachother,
therebyleadingtopossibleconfusion.Incasessuchasthis,weenclosetheioninparentheses,andplacethe
subscripted2outsidetheparentheses.Puttingthecationfirst,wethereforewritethechemicalformulaas
Ca(NO3)2.Asstatedonthepreviouspage,itisunderstoodthatthesubscripted2referstotheentiregroup
ofatomswithintheparenthesesthatis,thechemicalformulaimpliesoneCa2+ionandtwoNO3ions.

Toillustratethedifferencebetweentheuseofsubscriptednumbersandnumbersofnormalcase,consider
thefollowingchemicalreaction,whichdescribessolidCa(NO3)2dissolvinginwatertoformitsconstituent
ions.
Notethatsubscriptsareusedonlywhenwearereferringtothenumberofconstituentatomsorionswithin
anelementorcompoundinotherwords,theyappearinchemicalformulaeonly.Conversely,normalcase
numbersareusedascoefficientstodescribethenumberofatoms,ionsormoleculespresentinaparticular
chemicalreaction.Thiswillbecoveredinmuchgreaterdetailinchapter3.

PRACTICEEXERCISE2.10
Writethechemicalformulaeforthecompoundsresultingfromall
possiblecombinationsofthefollowingcationsandanions(16
compoundsintotal).

Ifcalciumnitrate,awhitecrystallinesolid,isexposedtomoistair,itabsorbswaterandformsahydrate.
ThishydrateisalsoawhitecrystallinesolidbutithasthechemicalformulaCa(NO3)24H2O.Thisprocess
canbereversedbyheatingthehydrateundervacuumtoremovethewatermolecules,whichresultsinthe
formationofanhydrousCa(NO3)2(anhydrousmeansthatthecompoundcontainsnowatermolecules).The
formationofhydratesisrelativelycommonamongioniccompounds,anditisusualtowritethewater
moleculesinsuchcompoundsattheendofthechemicalformula.

Themajorityofcovalentcompoundsarecarbonbasedorganiccompounds,thechemicalformulaeofwhich
areoftenwrittenwithcarbonfirst,followedbyhydrogenandthentheremainingelementsinalphabetical
order(e.g.C2H6O,C4H9BrO,CH3Cl).Themajorshortcomingofachemicalformulaisthatittellsuslittleor
nothingaboutthestructureofthecompoundinquestion.Toobtainthisinformation,werequirestructural
formulae.

StructuralFormulae
Chemistsareinterestedinthewayinwhichatomsarebondedtogethertoformmolecules.Whilemolecular
formulaeareusefulintellingusthechemicalmakeupofmolecules,theyonlyrarelygiveusanyideaof
whichatomisbondedtowhich.Forexample,themolecularformulaofwaterisalwayswrittenasH2O,but
thistellsusnothingabouthowtheatomsarearrangedinthemolecule.Wecannottellfromthemolecular
formulaalonewhichofthethreepossiblearrangementsofatomsbelowisthecorrectoneforH2O.

Structuralformulaeattempttoshowthewayinwhichtheatomsinamoleculearebondedtogether,
therebygivingussomestructuralinformation.Thechemicalsymbolsarestillusedforeachelementpresent,
butnowtheconstituentatomsareplacedintheorderinwhichtheyarebondedtogetherandthebonds
betweenneighbouringatomsarerepresentedaslines.Asinglelinerepresentsasinglebond,which,aswe
willseeinchapter5,consistsofapairofelectrons.Considerforexampletheammoniamolecule,NH3.We
canshowthewayinwhichthefouratomsarebondedtogetherinthismoleculebydrawingthestructural
formulaasfollows.
Fromthisdepiction,itisobviousthatthenitrogenatomisbondedtothreeHatomsbysinglebonds.Itis
alsocommontoseeammoniadepictedas:

whichgivesusthesamestructuralinformationasthepreviousdiagram(theNatomisbondedtothreeH
atomsbysinglebonds),butshowsthemoleculeapparentlyadoptingaslightlydifferentgeometry.This
illustratesanimportantpointaboutstructuralformulae:structuralformulaedonotnecessarilyshowthe
correctgeometryofacompound,simplybecauseitisdifficulttoaccuratelyrepresentthreedimensional
moleculesintwodimensions.Whilebothofthedepictionsonthepreviouspagecorrectlyshowallofthe
bondsinthemolecule,neitherisstrictlycorrectfromastructuralpointofviewastheydonotshowthe
actualthreedimensionalarrangementoftheatoms.Bothofthemalsoneglectthefactthatthereisapairof
electronsontheNatomwhichdoesnotparticipateinbonding.Thisistermedalonepairofelectrons.While
suchelectronsareoftenignoredindepictionsofmolecules(theirpresenceisusuallyimpliedbythe
chemicalformula),theycanhavesignificantstructuralconsequences.Wherenecessary,theycanbeshown
asfollows.

Inlaterchapters,youwillfinditcanbeimportanttoshowlonepairsonatoms,especiallywhenyoudraw
organicreactionmechanisms,whichshowthemovementofelectronsinbondmakingandbondbreaking
processes.Evenwiththeinclusionofthelonepair,thisisstillnotanaccuratedepictionoftheammonia
moleculeinathreedimensionalsense,butitshowsthecorrectconnectionsbetweentheconstituentatomsof
themolecule.Wewillseelaterhowtointroducethreedimensionalelementsintostructuralformulae.

Itisintheworldoforganicchemistrythatstructuralformulaeareparticularlyuseful.Whilemanycovalent
inorganiccompoundstendtobesmallmoleculesinwhichasinglecentralatomisjoinedto2,3,4,5or6
surroundingatoms,organicmoleculestendtoexistasringsandchains,andhaveahugevarietyofpossible
geometries.Thisisduetotheunusualpropensityofcarbonatomstobondtothemselves,apropertycalled
catenation,whichcanleadtotheformationofmassivemolecules.Eachcarbonatominamoleculecan
formbondstoasmanyasfourothercarbonatoms,whichmeansthatevenrelativelysmallorganic
moleculeshavemanydifferentpossiblewaysinwhichtheconstituentatomscanbebondedtogether.
Structuralformulaeallowustodepictthesepossibilities.

Carbonisatetravalentelement,meaningthatitpreferstoformatotaloffourbondswithinamolecule.
Thesebondsmaybesingle,doubleortriple.Thismeansthattherearefourdifferentwaysthatacarbon
atomcanformatotaloffourbonds:foursinglebonds,twodoublebonds,adoublebondandtwosingle
bonds,oratriplebondandasinglebond.Hydrogen,ontheotherhand,ismonovalent,meaningthatit
usuallyformsonlyonesinglebondtoanotheratomand,inanorganicmolecule,thisismostoftentoa
carbonatom.Thiscanbeillustratedbythepropanemolecule,whichhasthechemicalformulaC3H8.Given
thateachCatommustformfourbondsandeachhydrogenatommustformone,thereisonlyonepossible
wayofattachingalltheelementsthisisshowninastructuralformulabelow.

Wecanseefromthisthatthethreecarbonatomsofapropanemoleculelinktoformachaininwhicheach
carbonattheendofthechain(calledaterminalcarbon)issinglybondedtothreehydrogenatoms,andthe
innercarbonissinglybondedtotwohydrogenatoms.Noticethatthestructuralformulaofpropanecontains
moreinformationthanthechemicalformula.Bothformulaeidentifythenumberofatoms(threeCatoms
andeightHatoms),butthestructuralformulaalsoshowshowtheatomsareconnected.

ThepropanemoleculecontainsonlyCCandCHsinglebonds.Itisalsopossibletohavedoublebonds
andtriplebondsinorganicmolecules,whichwedesignatebytwoandthreelinesrespectively,asshownin
figure2.8.

FIGURE2.8Depictionsofsingle,doubleandtriplebondsbetweencarbonatoms.

Structuralformulaecanremoveambiguitiesinherentinchemicalformulae.Forexample,theethanoland
dimethylethermoleculeshavethesamechemicalformula,C2H6O.However,thestructuralformulae
depictedinfigure2.9clearlyshowthedifferencesinthewaytheatomsareconnectedwithinthemolecules.

FIGURE2.9Structuralformulaeofdimethyletherandethanol.Bothmoleculeshavethesamechemicalformula,
C2 H6 O.

Moleculessuchasthesethathavethesamechemicalformulabutdifferentchemicalstructuresarecalled
isomers.Structuralformulaeareaconvenientwaytodistinguishbetweenisomers.

Twotypesofshorthandstructuralformulaearecommonlyused.Theconstituentatomsincondensed
structuralformulaearearrangedinbondedgroups,andtheactualbondsarenotdrawn.Forexample,we
wouldwritethecondensedstructuralformulaeofdimethyletherandethanolasCH3OCH3andCH3CH2OH
respectively,whichessentiallygivesusthesamestructuralinformationasthestructuralformulae,butwitha
significantsavingofspace.Notethatthecondensedstructuralformulaeattempttoshowtheorderinwhich
theatomsarebondedtogether,anddifferfromthechemicalformula,whichisC2H6Oinbothcases.
Condensedstructuralformulaecanalsobedrawnformorecomplexmoleculessuchas2methylpropane,
C4H10.

ThecondensedstructuralformulaofthismoleculecanbewrittenasCH3CH(CH3)CH3,(CH3)2CHCH3or
(CH3)3CH,allofwhichareequivalent.Inthesecases,anyCH3groupinparenthesesisunderstoodtobe
bondedtothemiddlecarbonofthelongestcarbonchain.

Wecanalsouselinestructures,inwhichCatomsarenotdrawnexplicitly,todepictmolecules.Line
structuresareconstructedaccordingtothefollowingguidelines:
1.AllbondsexceptCHbondsareshownaslines.
2.CHbondsandHatomsattachedtocarbonarenotshowninthelinestructure.
3.Singlebondsareshownasonelinedoublebondsareshownastwolinestriplebondsareshownas
threelines.
4.Carbonatomsarenotlabelled.Allotheratomsarelabelledwiththeirelementalsymbols.Following
theseguidelines,wewouldthenwritethelinestructureofpropane,C3H8,as:

Inthisdiagramacarbonatomisimpliedateachendofthechainandatthekinkinthechain.Thecarbon
atomsaresinglybondedtoeachotherand,astherearenootherelementalsymbolsinthestructure,itis
assumedthateachcarbonatombondstotheappropriatenumberofhydrogenatomssothatitformsatotal
offourbonds.Thismeanstheterminalcarbonatomswillbondtothreehydrogenatomsandthecentral
carbonatomwillbondtotwohydrogenatoms.Weillustratehowtodrawlinestructuresfurtherinworked
example2.7.

WORKEDEXAMPLE2.7

Drawinglinestructures
Constructlinestructuresforcompoundswiththefollowingstructuralformulae.

Analysis

Weareaskedtoconvertthestructuralformulaeabovetolinestructures.Todothis,wesimply
applytheguidelinesgivenpreviously.

Solution

Usingguidelines1and2,weremoveallCHbondsandHatomsattachedtoCatomsfromthe
structure,therebyleavingthecarbonbasedframeworkofeachmolecule(rememberthatMe=
CH3).Guideline3statesthatdoublebondsremainastwolines.Thisgivesusthefollowing:

ThefinalguidelinetellsustoremovethelabelsforallCatoms.Thisgivestheanswer:

Isouranswerreasonable?
Tocheckthatthelinestructuresrepresentthecorrectsubstances,countthenumberof
intersectionsandlineends,whichshouldequalthenumberofCatomsinthecompound.Thefirst
linestructurehasfive,thesecondhasthreeandthethirdhasfive,matchingthechemical
formulae.Thereforeouranswersappearcorrect.

Youshouldbefamiliarwithlinestructures,andyoushouldbeabletoconvertfromastructuralformulatoa
linestructure,andfromalinestructuretoastructuralformula.Todothelatter,keepinmindthatcarbon
atomsarenotshowninalinestructure,sothefirststepistoplaceaCateverylineintersectionorkinkand
attheendofeveryline.Thenaddsinglybondedhydrogenatoms(H)untileverycarbonatomhasfour
bonds.

WORKEDEXAMPLE2.8

ConvertingLineStructures
Drawthestructuralformulaeanddeterminethechemicalformulaeofthemoleculesinthe
followinglinestructures.

Analysis

WeknowthatlinestructuresshowallstructuralfeaturesexceptcarbonatomsandCHbonds.
Wecanthereforeconvertalinestructureintoastructuralformulaintwosteps.First,placeaCat
anyunlabelledlineendandateachlineintersectionorkink.Second,addhydrogenatomsuntil
eachcarbonatomhasfourbonds.Thechemicalformulaisthenobtainedbycountingthenumber
ofatomsofeachelement.

Solution

BeginbyplacingaCateachintersection,kinkandlineend.

Nowaddhydrogenatomsuntileachcarbonatomhasatotaloffourbonds.Eachcarbonatomin
thefirststructurealreadyhastwobonds,soeachneedstwohydrogenatoms.Thisgivesthe
structuralformula:

andthechemicalformulaC2H4Cl2.

Thesecondstructurehasfourcarbonatoms.Thetwoterminalcarbonatomshavejustonebond,
soeachneedsthreehydrogenatoms.Thecarbonwiththedoublebondtooxygenalreadyhasits
completesetoffourbonds.TheotherinnercarbonatomhasabondtoCandabondtoO,soit
needstwohydrogenatoms.Thisgivesthestructuralformula:

andthechemicalformulaC4H8O2.

Thethirdstructurecontainsatriplebond.Theterminalcarbonatomneedsonehydrogenatom,
buttheothercarbonatomofthetriplebondalreadyhasfourbonds.Thenextcarbonatomhas
twobonds,onetocarbonandonetooxygen.Twohydrogenatomsareneededtogivethisatom
fourbonds,andthisgivesthestructuralformula:

andthechemicalformulaC3H4O.

Isouranswerreasonable?

Checktheconsistenciesofthestructuralformulaebycountingthenumberofbondsassociated
witheachcarbonatom.Ifyouhaveconvertedthelinestructurecorrectly,eachcarbonatomwill
havefourbonds.

PRACTICEEXERCISE2.11
Convertthefollowinglinestructureinto
structuralandchemicalformulae.

Whilelinestructuresarethebasisforthedepictionofmostmoleculesinthechemicalliterature,itis
commontoseevariationsontheruleswehaveoutlinedpreviously.Forexample,wemightseebutane,
C4H10,writtenasanyofthefollowing:

Alloftheseareacceptablealternativesforthestrictlycorrectdepictionshownbelow.

Noticealsothatinmoleculeswithnodoubleortriplebonds,thecarbonchaincanbedrawninany
orientation.Thefollowingequivalentlinestructurescanbedrawnforpentane,C5H12:
butthefirsttwoofthesewouldbemostcommonlyseen.

Thedepictionofmoleculesaslinestructurescangiverisetosomeveryinterestingshapes,andsomeof
thesehaveservedasinspirationsforthesynthesisofparticularmolecules.Consider,forexample,the
moleculesbelow,allofwhichhavebeensynthesised.

Probablythemostremarkableexampleofmolecularsynthesisinspiredbylinestructuresistheseriesof
moleculescalledNanoputians,whichwerereportedin2003byDrStephanieChanteauandProfessorJames
TourfromRiceUniversityintheUSA.Thesearemoleculesthat,whendrawnaslinestructures,resemblethe
humanform.TwoexamplesofNanoputians(namedaftertheLilliputiansinJonathanSwift'sGulliver's
Travels)areshowninfigure2.10.Hadwechosentodescribethesewiththeirchemicalformulae(C39H42O2
andC38H44O2forNanoKidandNanoBalletDancerrespectively)wewouldhavenoideaofthedelightful
shapesthatrepresentationsofthesemoleculesdisplay.
FIGURE2.10 Linestructuresof:
(a)NanoKid
(b)NanoBalletDancer.

ThreedimensionalStructures
Whilethestructuralformulaeencounteredsofargivemorestructuralinformationthanchemicalformulae,
theydonotnecessarilygiveacompleterepresentationofamolecule.Forexample,noneofthemolecules
shownpreviouslyareflat,butyouwouldnotknowthisfromlookingatthestructuralformulae.Wemust
thereforeattempttointroducesomeaspectsofthreedimensionalityinourrepresentations.Therearea
numberofwaysthiscanbedone.

ThreedimensionalStructuralFormulae
Thesimplestwayofdrawingathreedimensionalstructureintwodimensionsistouseastructuralformula
orlinestructureasabase,andthenaddsomeperspective.Thisisillustratedbelowusingthemolecule1,2
dimethylcyclopentane.Thisisacyclicmoleculeconsistingofapentagonofcarbonatoms,withCH3
groupsattachedtotwoadjacentcarbons.Wecandrawthelinestructureasfollows.

However,whenthismoleculeisviewedinthreedimensionsfromsideon,wecanimmediatelyseethatthe
flatlinestructureisnotanadequaterepresentationeachcarbonatomintheringhastwoattachedatoms,
eithertwoHatomsoraHatomandtheCatomofaCH3group,whichpointeitheraboveorbelowthe
planeofthering.ThisleadstotwopossiblerelativearrangementsoftheCH3groupswithinthemolecule
eitherbothonthesamesideofthering,oronoppositesidesandhencetwopossibleisomersnamed
usingtheprefixescisandtrans(seefigure2.11).

FIGURE2.11Representationsofthetwopossibleisomersof1,2dimethylcyclopentane.ThetwoCH3 groups
maybearrangedsothattheyareoneitherthesameoroppositesidesofthering.Inreality,the
cyclopentaneringsarenotflatbutslightlypuckered.

ThecisisomerhasbothCH3groupsonthesamesideofthering.(Notethatitdoesnotmatterwhether
theyarebothonthetoporbottomsideoftheringthesamecompoundresults.)TheCH3groupsareon
oppositesidesoftheringinthetransisomer.Wecanshowthisinourlinestructurebydrawingthebondsto
thesegroupsaswedges.Asolidwedge( )representsabondcomingoutofthepagetowardsthe
observer,whileahashedwedge( )representsabondgoingbackintothepage.Anormallineisusedfor
bondsintheplaneofthepage.Thereforethetwoisomerscanbedrawnaslinestructuresasfollows:
anditcanbeeasilyseenthattheyaredifferentcompounds.

Whencarbonisbondedtofouratoms,thoseatomsgenerallyadoptatetrahedralarrangementaroundthe
carbonatom,asthisarrangementplacesthemasfaraspossibleawayfromeachother.Itisconventionalto
drawthethreedimensionalnatureofthefourbondsaroundasinglecarbonatomasfollows:

whereXisanyatom.Inthisrepresentation,onebondgoesintotheplaneofthepage,onecomesoutofthe
planeofthepage,andtwolieintheplaneofthepage.Wecanshowthethreedimensionalityofmolecules
containingmorethanonecarbonatombyjoiningtheseindividualunitstogether.Suchthreedimensional
depictionsarenotlimitedtoorganiccompoundswewillseeinchapter13thattransitionmetalcomplexes
candisplayawidevarietyofgeometries,andwecanuseanalogousdiagramstoportraythese.Forexample,
itiscommontohavesixatomsboundtoatransitionmetaliontogiveacomplexofgeneralformulaML6.
EachLatomsitsatthecornerofanimaginaryoctahedroninwhatiscalledanoctahedralgeometry.We
woulddrawsuchanarrangementasfollows.

Inthiscasewehavethetwoverticalbondsintheplaneofthepage,whiletwobondsgointotheplaneand
twobondscomeoutoftheplane.Whileitispossibletomakeremarkablydetailedthreedimensional
drawingsusingonlyapenandpaper,itiseasiertousecomputerstodrawsomewhatmorerealistic
depictionsofmolecules.

BallandstickModels
Inaballandstickmodel,ballsofarbitrarysizerepresentatomsandsticksrepresentchemicalbonds.Figure
2.12showsaballandstickmodelofpropane.Theballsareusuallydrawnindifferentcolourstodistinguish
betweendifferentelementspresentinthemolecule(seefigure2.13).Suchmodelsgenerallyenabletheeasy
visualisationofthreedimensionalfeaturesofthemolecule.

FIGURE2.12Ballandstickmodelofpropane,C3 H8 .
FIGURE2.13Thecoloursandsizesofballsusedtorepresentatomsinthisbook.

SpacefillingModels
Whileballandstickmodelsareuseful,theyarefarremovedfromrealitychemicalbondsarenotsticks,
andthesizeofatomsisbynomeansarbitrary.Aspacefillingmodelrecognisesthatamoleculeisdefined
bythespaceoccupiedbyitselectrons,andattemptstorepresenttherelativesizeofatomswithinamolecule
byshowingthesizeofeachatom'selectroncloud.RecallfromRutherford'sgoldfoilexperiment(pp.78)
thatelectroncloudsmakeupnearlytheentirevolumeofanyatom.Eachatominaspacefillingmodelis
shownasadistortedsphererepresentingthevolumeoccupiedbyitselectrons.Thesespheresmergeintoone
anothertobuilduptheentiremolecule.Aspacefillingmodelcantellusataglancewhethertheelectron
cloudsofatomsinamoleculeoverlap,andthereforewhetherthoseatomsarebondedtogetherornot.Figure
2.14showsaspacefillingmodelofpropanenoticethatthespheresoftheneighbouringCatomsoverlapto
asignificantextent,implyingtheseatomsarebondedtogether.ThepresenceofCHbondsisalsoobvious
fromtheoverlapofthespheresrepresentingCandH.Figure2.15showsballandstickandspacefilling
modelsofseveralchemicalcompoundscommonineverydaylife.

FIGURE2.14Spacefillingmodelofpropane,C3 H8 .

FIGURE2.15Differentrepresentationsofsomecommoncompounds.
OtherRepresentations
Itisofteninconvenient,ifnotimpossible,toshoweveryatominalargemoleculesuchasaproteinor
nucleicacid,anditisusualtodrawcartoontypestructuresofsuchmolecules.Figure2.16showssucha
viewofhaemoglobin,theironcontainingproteinthatcarriesoxygeninhumanblood.Insteadofshowing
eachindividualatominthemolecule(C2952H4664N812O832S8Fe4isthemolecularformulaofoneformofthe
protein),theproteinchainsareshownasribbonswhichfoldinparticularwaysdependingontheir
chemicalenvironment.

FIGURE2.16Arepresentationofthestructureofhaemoglobinshowingfourhaemgroups(colouredspheres).The
differentcolouredribbonsdenotedifferentpartsoftheprotein.

Stereoviewsareoftenhelpfulinvisualisinglargemolecules,astheyallowtheimagetobeviewedinthree
dimensions,althoughviewingthemproperlyrequiressomepractice.AnexampleofastereoviewofDNAis
showninfigure2.17.
FIGURE2.17StereoviewofDNA.

Toviewstereoviews(whicharethreedimensionalimages),youmustbeabletogocrosseyed.Youwill
eventuallyfindthat,withlotsofpractice,athreedimensionalimageappearsinthemiddleofthetwo
structuresinfigure2.17.Ifyoudonotgetitthefirsttime,keeptrying!

Whichofourvariousdepictionsisthecorrectone?Theanswerisnoneofthem.Atomsarenotfinite
colouredspheresandbondsarenotsticksattachedtoatoms.Therepresentationsweuseinchemistryare
merelyattemptstovisualisethingsthat,inallprobability,areimpossibletodepict.However,thisisnotto
saythatourrepresentationsareuseless.Aswewillseethroughoutthisbook,wecanunderstandmany
importantfacetsofmolecularstructurethroughstudyingtheserepresentations.Butkeepinmindatalltimes
thattherepresentationsaremodelsnothingmoreandnothingless.

MechanisticArrowsinChemicalReactions
Inadditiontorepresentingthestructuresofmolecules,wealsowanttobeabletodepictthewayinwhich
chemicalbondsarebrokenandformedwithinandbetweenchemicalspeciesaschemicalreactionsoccur.
Wedothisbymeansofmechanisticarrows,whichshowthemovementofelectronsinbondbreakingand
bondmakingprocesses.

Atwoheadedmechanisticarrowshowsthemovementofapairofelectrons.Theelectronsmovefromthe
tailtotheheadofthearrow,resultinginanumberofpossiblechemicalprocesses,someofwhichare
detailedbelow.

BondBreaking
Considerthefollowingbondbreakingprocess:

Inthiscase,thearrowstartsatthemiddleofthebond.Thebondbreaksinaheterolyticfashion,withboth
electronsendingupontheClatom.ThisgivesrisetotheformationofanH+cation(proton)andaClanion.

BondMaking
Considerthefollowingbondmakingprocess:

Here,abondisformedbetweenthecarbonylOatomandtheH+ion,withthetwoelectronsinthebond
comingfromoneofthelonepairsofelectronsonthecarbonylOatom.Thisleavesaformalpositivecharge
ontheOatom.

ChargeNeutralisation
Considerthefollowingchargeneutralisationprocess:

ThepositivelychargedcarbonylOatomcanbeneutralisedbytakingtwoelectronsfromthedoublebond
andlocatingthemonthecarbonylOatom.ThearrowstartshalfwayalongthebondandfinishesattheO
atom.ThisprocessleavesthecarbonylCatompositivelycharged.

Inthefollowingchargeneutralisationprocess

protonlosstogiveaneutralcompoundoccursbytakingthetwoelectronsfromanNHbondandlocating
themontheNatom.ThetailofthearrowthereforeissituatedhalfwayalongtheNHbondandthehead
pointstotheNatom.
Theseexamplesillustratesomeimportantfactsaboutmechanisticarrows.Firstly,thetailofthearrowmust
besituatedatasourceofanelectronpair:thatis,eitherhalfwayalongabondoronalonepairofelectrons.
SomethoughtwillconvinceyouthatthismeansamechanisticarrowcanneverstartateitherH+oranH
atom(averycommonmistake!).Similarly,theheadofthearrowmustbesituatedinaregionabletoaccept
apairofelectrons.Thusitwouldbeunlikely,forexample,fortheheadofanarrowtobeatanegatively
chargedatomorion.Itisimportanttorememberthattotalchargemustbeconservedinanymechanistic
process.Thus,inalltheexamplesabove,bothsidesoftheequationshavethesametotalcharge.Itshould
alsobenotedthatwecanusemorethanonearrowtorepresentmultiplesimultaneousbondmakingand
bondbreakingprocesses.Thisisillustratedbelow.

Here,threeprocessesoccuressentiallysimultaneously.
1.OHremovesaprotonfromaCH group,resultingintheformationofH O.
3 2
2.ThepairofelectronswhichwereintheCHbondmovesoastogiveaC Cdoublebond.
3.TheCBrbondbreaksheterolytically,withbothelectronsinthebondmovingtotheBr,togiveaBr
ion.

Asingleheadedarrowshowsthemovementofasingleelectron.Sucharrowsareusuallyfoundonlyin
reactionsinvolvingradicals,chemicalspecieswhichcontainoneormoreunpairedelectrons.Anexampleis
givenbelow,inwhichtheBrBrsinglebondisbrokeninahomolyticfashion,suchthateachofthe
bondedatomsreceivesanelectron,givingtwobromineradicals.

Youwillmakeextensiveuseofmechanisticarrowsinthelaterchaptersofthisbook,especiallyinwriting
organicreactionmechanisms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
2.3Nomenclature
Representingmoleculesasimagesallowsustoimpartagreatdealofinformationconcerningmolecularstructure.
Butmoleculescanalsobenamed,andthereareoccasionswhenthisismoreconvenientthandrawingapicture.In
theearlydaysofchemistry,thelistofknowncompoundswasshort,andchemistscouldmemorisethenamesofall
ofthem.Newcompoundswereoftennamedbytheirdiscovereraftertheirplaceoforigin,physicalappearanceor
properties.Today,morethan50millioncompoundsareknownandmillionsmorearesynthesisedeachyear.
Chemistsconsequentlyneedsystematicproceduresfornamingchemicalcompounds.TheInternationalUnionof
PureandAppliedChemistry(IUPAC)hasestablisheduniformguidelinesfornamingvarioustypesofchemical
substances,andchemistsincreasinglyuseIUPACapprovednamesratherthantheircommoncounterparts.Inthis
sectionwewillintroducetherulesfornomenclature,thesystemforthenamingofcompounds.Youwillencounter
manychemicalnamesinsubsequentchapters,andthebasicsthatyoulearninthissectionwillaidyourinterpret
ationofthesenames.Wewillinvestigatethenamingoftransitionmetalcomplexesinchapter13.Youshouldbe
awarethattherearesomecompoundsthatarebetterknownbytheircommon,unsystematicname,andnottheir
systematicIUPACname.Thebestexampleofthisiswater,thesystematicnameofwhichisoxidane.Unsystematic
namesforasmallnumberofcommoncompoundsareacceptedbyIUPAC.

ChemistryResearch

IUPAC

AssociateProfessorRichardHartshorn,UniversityofCanterbury

TheInternationalUnionofPureandAppliedChemistry(IUPAC)istheorganisationresponsiblefor
helpingchemiststalktoeachotherabouttheirscience.Itdoesthisbydevelopingandsystematisingthe
nomenclature,symbolsandterminologythatarerequiredforchemistry.Thenamesandformulaeof
chemicalcompoundsarecentraltothelanguageofchemists,andrulesarerequiredtotellpeoplehowto
putthemtogetherandworkoutwhattheymean.Therulesareregularlyupdated,bothtomakethem
simpler,andtoprovidewaysofnamingnewkindsofmoleculesthatwerenotenvisagedwhentherules
werefirstwritten.

Differentsetsofrulesarerequiredfordifferentkindsofcompounds.Forexample,organiccompounds
andmetalcomplexesarenamedindifferentways.ThedifferentsetsofrulesappearinIUPAC'scolour
books,including:
theRedBook(NomenclatureofInorganicChemistry)(figure2.18)
FIGURE2.18TheRedBookisoneofIUPAC'srulebooksfornomenclature,symbolsandterminology.
theBlueBook(NomenclatureofOrganicChemistry)
theGreenBook(Quantities,UnitsandSymbolsinPhysicalChemistry)
thePurpleBook(CompendiumofMacromolecularNomenclature)
theGoldBook(CompendiumofChemicalTerminology).
RichardHartshorn,AssociateProfessorintheDepartmentofChemistryattheUniversityofCanterbury,
Christchurch,workswithIUPACtodevelopnomenclatureforinorganiccompoundsnomenclature
rulesarenotdevisedsolelybychemistsfromthenorthernhemisphere!

Hartshorndescribeshimselfasacoordinationchemistbyinclinationandbytraining.Hesayshelikes
makingnewcompounds(prettycolours!)andfindingoutwhatreactionscanbedoneonthem.Inhisown
words:

Ofcourse,oncecompoundshavebeenmade,wehavetonamethem.Asacoordination
chemist,thismeansknowinghowbothorganiccompoundsandinorganiccompoundsare
named.WorkingwithIUPACallowsmetohavesomeinputintotherecommendationsfor
namingcompounds.

Igotintonomenclaturethroughoneofmyresearchprojects,whichinvolvedpreparingand
studyingcomplexesofnewaminoacids.Itturnedoutthattheconventionalnomenclature
thatwasavailablewasnotparticularlyconvenienttohighlightthedifferencesandsimilarities
betweenthevariouscomplexesthatwehadmade.Thesimpleanswerwastoinvent
somethingnew,andwepublishedanarticleshowinghowthisnomenclaturecouldbeused
moregenerallyforanylinearorbranchedchainligandswrappedaroundanoctahedral
centre.ThearticlewasseenbysomeofthepeopledoingnomenclatureworkwithIUPAC.
Theywereonthelookoutforanyoneshowinganinterestinnomenclatureandits
development,andapproachedmetoseeifIwasinterestedinjoiningtheirgroup.

Verysoonafterthat,IfoundmyselfpartofthesmallteampreparingtherevisionoftheRed
Book.Ittookmorethanfiveyears'ofconsultation,andwritingandrevisingthetext,in
responsetocommentsfromnomenclatureexperts,beforethenewrecommendationswere
completedandreadyforpublication.Tofindit,lookupNomenclatureofInorganic
Chemistry,Recommendations2005byNGConnelly,TDamhus,RMHartshornandAT
Hutton,RoyalSocietyofChemistry,Cambridge,inyourlibrarycatalogue.Ifitisnotthere,
tellyourlibrarianthatitshouldbe!Isaythatbecauseitreallyshouldbe,notbecauseIhavea
vestedinterestIdon'tgetanyroyalties!

Youcanalsofinditonline,throughtheIUPACwebsite:
www.iupac.org/publications/books/rbook/Red_Book_2005.pdf.

Newnomenclatureisbeingdevelopedallthetimefornewcompounds,andsometimesevenforoldones.
IUPACiscurrentlydevelopingrecommendationsforpreferredIUPACnames(PINs).Mostcompounds
canbenamedinmorethanonesystematicway.ThePINsrecommendationsarebeingdevelopedtohelp
insituationswhereitisreallyimportantthateveryoneusesthesamename(suchasinhealthandsafety,
patentlaw,taxationandotherregulatoryareas).Chemistswillstillbefreetousethecurrentrangeof
systematicnomenclatures,butPINsmayberequiredforparticularsituations.

NamingInorganicCompounds
Thewayinwhichwenameinorganiccompounds(i.e.thosenotcomposedprimarilyofcarbonandhydrogen)
dependstosomeextentontheexactnatureofthecompoundinquestion.Wewillexaminethedifferentpossible
typesofinorganiccompoundsinthefollowingpages.Youshouldappreciatethatwhatfollowsis,ofnecessity,an
abbreviatedversionoftheIUPACrulesfornaminginorganiccompounds.Thefullversionmaybefoundatthe
IUPACwebsite(www.iupac.org).

NonmetallicBinaryCompounds
Thewrittennameofacompoundincludesthenamesoftheelementsitcontainsandinformationaboutthenumber
ofatomsofeachelementpresent.Theelementshavetooccurinsomeorder,andthisissetbythesameguidelines
asforthechemicalformula(seep.36).Namescancontainelementalnames,rootsderivedfromelementalnames
andprefixesindicatingthenumberofatomsofeachelement.Tables2.4and2.5listthemoreimportantrootsand
prefixesthatappearinthenamesofnonmetallicbinarycompounds,compoundsthatcontainonlytwoelements,
neitherofwhicharemetals.
TABLE2.4 CommonRootsforNamingCompounds
Element Fullname Root
As arsenic arsen
Br bromine brom
C carbon carb
Cl chlorine chlor
F fluorine fluor
H hydrogen hydr
I iodine iod
N nitrogen nitr
O oxygen ox
P phosphorus phosph
S sulfur sulf

TABLE2.5 NumberPrefixesforChemicalNames
Number Prefix Example Name
1 mono CO carbonmonoxide(a)
2 di SiO2 silicondioxide
3 tri NI3 nitrogentriiodide
4 tetra SnCl4 tintetrachloride
5 penta PCl5 phosphoruspentachloride
6 hexa SF6 sulfurhexafluoride
7 hepta IF7 iodineheptafluoride

(a)Thefinalooftheprefixisomittedinthiscase.

Wecansummarisetherulesfornamingnonmetallicbinarycompoundsinfourguidelines:
1.Theelementclosertotheleftoftheperiodictableappearsfirst.Ifbothelementsarefromthesamegroupof
theperiodictable,theloweroneappearsfirst.
2.Theelementthatappearsfirstretainsitselementalname.
3.Thesecondelementbeginswitharootderivedfromitselementalnameandendswiththesuffixide.Some
commonrootsarelistedintable2.4.
4.Whenthereismorethanoneatomofagivenelementintheformula,thenameoftheelementusuallycontains
aprefixthatspecifiesthenumberofatomspresent.Commonprefixesaregivenintable2.5.

Numericalprefixesareessentialinnamingsimilarbinarycompounds.Forexample,nitrogenandoxygenformthe
sixdifferentcompoundsshownasspacefillingmodelsinfigure2.19:NO,nitrogenmonoxideNO2,nitrogen
dioxideN2O,dinitrogenoxideN2O3,dinitrogentrioxideN2O4,dinitrogentetraoxideandN2O5,dinitrogen
pentaoxide.

FIGURE2.19Spacefillingmodelsofthesixcompoundsformedbetweennitrogenandoxygen.

WORKEDEXAMPLE2.9

Namingbinarycompounds
Namethefollowingbinarycompounds:SO2,CS2,BCl3andBrF5.

Analysis

Noneofthesecompoundscontainsametallicelement,soweapplytheguidelinesfornonmetallicbinary
compoundnomenclature.

Solution
Namethefirstelement,usearootplusideforthesecondelementandindicatethenumberofatomswith
prefixes.Therefore,weobtain:

SO2:sulfurdioxide

CS2:carbondisulfide

BCl3:borontrichloride

BrF5:brominepentafluoride.

PRACTICEEXERCISE2.12
Namethecompoundsthatcontain:
(a)Fouratomsofbromineandoneatomof
silicon
(b)Threeatomsofoxygenandoneatomof
sulfur
(c)Threeatomsoffluorineandoneatomof
chlorine.

BinaryCompoundsofHydrogen
Hydrogenrequiresspecialconsiderationbecause,aswesawearlier,itmayappearfirstorsecondinthechemical
formulaofacompoundand,asaresult,itmayappearfirstorsecondinthename.Thisisparticularlyevidentinthe
diatomicmoleculesthathydrogenformswithelementsfromgroups1and17,whicharenamedaccordingtothe
guidelinesonthepreviouspage.Forexample,LiHislithiumhydride,andHFishydrogenfluoride.Withelements
fromgroups2and16,hydrogenformscompoundscontainingtwoatomsofhydrogen.Exceptforoxygen,thereis
onlyonecommonlyoccurringbinarycompoundforeachoftheseelements,sotheprefixdiisomitted.Examples
areH2S,hydrogensulfide,andCaH2,calciumhydride.Oxygenformstwobinarycompoundswithhydrogen.These
haveunsystematicnames:oneiswater,H2O(systematicnameoxidane),andtheotherishydrogenperoxide,H2O2
(systematicnamedioxidane).Binarycompoundsofhydrogenwithelementsfromgroups13,14and15have
unsystematicnamesincommonuseB2H6isdiborane,CH4ismethane,SiH4issilane,NH3isammonia(systematic
nameazane)andPH3isphosphine(systematicnamephosphane).Infact,carbon,boronandsiliconformmany
differentbinarycompoundswithhydrogen,andonlythesimplestofthesearelistedhere.

IonicCompounds
Binarycompoundswhichcontainmetalionsareoftenionic,consistingofacationandananion(seechapter1,p.2).
Wenamebinaryioniccompoundswiththecationfirstandtheanion,whichtakesthesuffixide,last.Forexample,
NaClisnamedsodiumchloride,whileKIisnamedpotassiumiodide.CompoundssuchasCaF2,inwhichthe
numbersofcationsandanionsarenotthesame,donotrequiretheactualnumberofcationsandanionstobe
specified.ThusCaF2isnamedcalciumfluoride,notcalciumdifluoride.Thereasonforthisisthatcalciumisagroup
2element,andwillthereforeformonlya2+cation.Thiswillalwayscombinewithtwo1anionstoformaneutral
ioniccompound,andthereforeweneednotspecifydifluoride.Usingthesamereasoning,wecanseethatNa2Sand
MgI2arenamedsodiumsulfideandmagnesiumiodiderespectively.Ioniccompoundscontainingpolyatomicions
suchasNH4+,NO3andSO42areagainnamedwiththecationfollowedbytheanion,butyouwillneedtolearn
boththenamesandthechargesofthecommonpolyatomicionstobeabletoname,andwritechemicalformulaefor,
compoundscontainingtheseions.Table2.6liststhemorecommonpolyatomicions.
TABLE2.6 Namesandchemicalformulaeofsomecommonpolyatomicions
Formula Name
Cations
NH4+ ammonium

H3O+ hydronium(oxonium)

Hg 22+ dimercury(2+)

Diatomicanions
OH hydroxide

CN cyanide

Anionswithcarbon
CO32 carbonate

HCO3 hydrogencarbonate(bicarbonate)

CH3COO acetate

C2O42 oxalate

Oxoanions
SO42 sulfate

SO32 sulfite

NO3 nitrate

NO2 nitrite

PO43 phosphate

MnO4 permanganate

CrO42 chromate

Cr2O72 dichromate

ClO4 perchlorate

ClO3 chlorate

ClO2 chlorite

ClO hypochlorite

Youcanseefromthistablethatthereareasignificantnumberofanionscontainingacentralatomsurroundedby
oxygenatoms.Suchionsarecalledoxoanions,andtheirnamescanbededucedusingthefollowingrules:
1.Thenamehasaroottakenfromthenameofthecentralatom(forexample,carbonate,CO 2,andnitrite,
3
NO2).
2.Whenanelementformstwodifferentoxoanions,theonewithfeweroxygenatomsendsinite,andtheother
endsinate(forexample,SO32,sulfite,andSO42,sulfate).
3.Chlorine,bromineandiodineeachformfourdifferentoxoanionsthataredistinguishedbyprefixesand
suffixes.Thenomenclatureoftheseionsisillustratedforbromine,butitappliestochlorineandiodineaswell:
BrO,hypobromiteBrO2,bromiteBrO3,bromateandBrO4,perbromate.
4.Apolyatomicanionwithachargemorenegativethan1mayaddH+togiveanotheranion.Theseanionsare
namedfromtheparentanionbyaddingthewordhydrogen.Forexample,HCO3ishydrogencarbonate,
HPO42ishydrogenphosphateandH2PO4isdihydrogenphosphate.

NamingOrganicCompounds
Organiccompoundsarecomposedprimarilyofcarbonandhydrogenatoms,andthenamingsystemusedisbased
onthenumberofcarbonatomsintheparticularmolecule.Notsurprisingly,thereareanenormousnumberofrules
fornamingorganiccompoundsandatthisstagewewillrestrictourselvestothebasics.Indeed,computerprograms
arenowabletogeneratenamesfromnearlyanystructuraldiagram,providingahelpfulsupplementtoknowledgeof
therulesofIUPACnomenclature.

FunctionalGroups
Theconceptoffunctionalgroupsunderpinsalloforganicchemistryandmakesitthesystematicdisciplinethatitis.
Afunctionalgroupissimplyagroupofoneormoreatomswithinamolecule,bondedtogetherinaparticular
fashion,andisusuallythepointofreactionwithinamolecule.Organicmoleculesarealsonamedprimarily
accordingtothefunctionalgrouporgroupstheycontain.Thepowerofthefunctionalgroupconceptisthat
moleculescontainingthesamefunctionalgrouptendtobehaveinchemicallysimilarways,andthisallowsusto
predicttheirreactivitytowardsparticularreagentswithsomeconfidence.Forexample,althoughthetwomolecules
belowlookquitedifferent,theybothcontainthealdehydefunctionalgroup,CHO.

Wecanthereforepredictthatbothmoleculeswillundergoareactioncalledoxidation,inwhichtheCHOgroupis
convertedtoaCOOH(carboxylicacid)functionalgroup.Similarly,bothcompoundswillreactwithspeciescalled
reducingagents,whichwillconverttheCHOgrouptoaCH2OH(primaryalcohol)group.(Wewilllearnalot
moreaboutthespecificreactionsinvolvedlaterinthistextbook.)

Itthereforemakessensetonameorganiccompoundsaccordingtotheirfunctionalgroups,andwewilllearnhow
thisisdoneonthefollowingpages.Butfirst,thecommonfunctionalgroupsthatyouwillencounterareoutlinedin
table2.7.NotethatRisacommonlyusedsymboltodenoteeitheraHatom,oranalkylgroup(table2.9,p.55).
Youshouldbeabletoidentifythepresenceofeachofthesefunctionalgroupsinanymolecule.
TABLE2.7 CommonFunctionalGroups
Functionalgroup Nameofgroup Foundin R=

hydroxyl alcohols C

carbonyl aldehydes CorH

carbonyl ketones C
carboxyl carboxylicacids CorH

Alcohols

TheOH(hydroxyl)groupispresentinallalcohols.Itisattachedtoacarbonatom,whichitselfmaybeattachedto
one,twoorthreeothercarbonatoms(theexceptionismethanol,CH3OH,whichcontainsonlyonecarbonatom).
Alcoholsareclassifiedasprimary(1),secondary(2)ortertiary(3)accordingtothisnumber,asshowninfigure
2.20.

FIGURE2.20Structuralformulaeofprimary,secondaryandtertiaryalcohols.

Wecanalsoclassifycarbonatomswithinmoleculesaccordingtothisscheme.Thusacarbonatomattachedtoone
carbonatom(asinaprimaryalcohol)iscalledaprimarycarbonatom,acarbonatomattachedtotwocarbon
atoms(asinasecondaryalcohol)iscalledasecondarycarbonatom,andacarbonatomattachedtothreecarbon
atoms(asinatertiaryalcohol)iscalledatertiarycarbonatom.

WORKEDEXAMPLE2.10

Writingpossiblestructuresforalcohols
WritecondensedstructuralformulaeforthetwoalcoholswiththemolecularformulaC3H8O.Classify
eachasprimary,secondaryortertiary.

Analysis

WeknowthatalcoholscontaintheOHgroup.Wemustthereforedrawthetwopossiblestructuresof
theformulaC3H8OwhichcontainanOHgroup,rememberingthateachcarbonatominthemolecule
musthavefourbonds.Inproblemslikethis,itisgenerallyeasiesttodrawthestructuralformula,andthen
convertittothecondensedform.

Solution

Wehaveathreecarbonchaininthemolecule,andsotheOHgroupcanbeattachedonlytoeitherthe
terminalcarbon(itdoesnotmatterwhichonethesamecompoundresultsregardlessofwhichendwe
attachthefunctionalgroupto)orthecentralcarbon.Therefore,webeginbydrawingthecarbonchain,
thenattachtheOHgroupinthetwopossiblepositions,andfillinthehydrogenatoms.Doingthisgives
usthefollowingtwocompounds.
ThecompoundaboveisaprimaryalcoholastheOHgroupisattachedtoacarbonatomdirectly
bondedtoonlyoneothercarbon.

Incontrasttothefirststructure,theabovecompoundisasecondaryalcohol,thecentralcarboninthe
chainbeingbondedtotwoothercarbonatoms.

PRACTICEEXERCISE2.13
Writecondensedstructuralformulaeforthefour
alcoholswiththemolecularformulaC4H10O.
Classifyeachasprimary,secondaryortertiary.

AldehydesandKetones

Aldehydesandketonesbothcontainthesamefunctionalgroup,thecarbonylgroup(C O),buttheydifferinthe
waythatthecarbonylgroupisbondedtotherestofthemolecule.Aldehydesalwayshavethecarbonatomofthe
carbonylgroupbondedtoatleastonehydrogenatom,andthismeansthatthecarbonylgroupofanaldehydemust
alwaysbeattheendofacarbonchain.Conversely,thecarbonatomofthecarbonylgroupinketonesisalways
bondedtotwoothercarbonatoms,andthereforecanneverbeattheendofacarbonchain.Wecanwritethe
aldehydeeitherexplicitlyas:

orasRCHOinacondensedstructuralformula.Thedifferencesbetweenaldehydesandketonesareshowninfigure
2.21.
FIGURE2.21Structuralformulaeandballandstickmodelsofanaldehydeandaketone.

WORKEDEXAMPLE2.11

Writingpossiblestructuresforaldehydes
WritecondensedstructuralformulaeforthetwoaldehydeswiththechemicalformulaC4H8O.

Analysis

Weknowthatthefunctionalgroupinaldehydescanbeonlyattheendofacarbonchain.Inthiscase,we
havefourcarbonatoms,andtherearetwopossiblewaysofconnectingthesesothattheCHOgroup
liesattheendofachain.

Solution

BeginbywritingtheCHOgroupandthenattachingtheremainingthreecarbonatoms.Wecanconnect
thefourcarbonatomsinastraightchainorabranchedchain.Thetwopossibilitiesareshownbelow.
PRACTICEEXERCISE2.14
Writecondensedstructuralformulaeforthethree
ketoneswiththemolecularformulaC5H10O.

CarboxylicAcids

Thefunctionalgroupfoundinallcarboxylicacidsisthecarboxylgroup,COOH.Wecanwritethisexplicitlyas:

or,morecommonly,asRCOOH.Asthecarbonatomofacarboxylgroupcanbondtoonlyoneotheratom,carboxyl
groupsarealwaysfoundattheendofacarbonchain.

WORKEDEXAMPLE2.12

Writingpossiblestructuresforcarboxylicacids
WriteacondensedstructuralformulaforthecarboxylicacidwiththemolecularformulaC3H6O2.

Analysis
Thereisonlyonepossiblecompoundwecandrawhere.Itmustcontainathreecarbonchainwitha
COOHgroupontheend.

Solution

BeginbydrawingtheCOOHgroupandthenattachtheremainingcarbonatoms.Finishbyadding
hydrogenatomssothatallthecarbonatomshavefourbonds.Thisgivesusthecompoundshownonthe
nextpage.

PRACTICEEXERCISE2.15
Writecondensedstructuralformulaeforthetwo
carboxylicacidsthathavethemolecularformula
C4H8O2.

TheNomenclatureofAlkanes
Thenamesofsomeorganiccompoundshavealreadybeenusedinthischapter,butwehavenotyetlearnedhow
thesenamesarederived.Organiccompounds,asmentionedpreviously,arenamedaccordingtotheirfunctional
group.Thefirststepinnamingmostorganiccompoundsistoidentifythefunctionalgroupthattheycontain.
However,wewillbeginbylookingataseriesofcompoundsthatarenotconsideredtocontainanyfunctionalgroup
atall:thealkanes.

Alkanesaremoleculesthatcontainonlycarbonandhydrogenandinwhichcarbonatomsarejoinedbysinglebonds
only.Alkanescanbedividedintotwoclasses,dependingontheoverallgeometryofthecarbonatoms.Alkanesin
whichthecarbonatomsarejoinedinchainsarecalledacyclicalkanesandhavethegeneralformulaCnH2n+2.The
carbonatomsinalkanescanalsobejoinedtogethertoformoneormorerings,andsuchcompoundsarecalled
cycloalkanes.Allalkanesbelongtoagroupoforganiccompoundscalledhydrocarbons,whicharemolecules
composedsolelyofcarbonandhydrogen.Alkanesaresometimescalledsaturatedhydrocarbons,todenotethefact
thatallthecarboncarbonbondsaresingle.Astherearenofunctionalgroupsinalkanes,wenamethemaccording
tothelengthofthelongestcarbonchain.Therearetwopartstothenameofanalkane:aprefix,indicatingthe
numberofcarbonatomsinthechain,andtheendingane.Theprefixesforcarbonchainlengthsupto10carbon
atomsareshownintable2.8.
TABLE2.8 PrefixesUsedintheIUPACSystemforChainLengthsof1to10CarbonAtoms
Prefix Numberofcarbonatoms
meth 1
eth 2
prop 3
but 4
pent 5
hex 6
hept 7
oct 8
non 9
dec 10

Thesimplestalkaneismethane,whichcontainsonecarbonatomandhastheformulaCH4.Notethatthesuffixand
prefixarenothyphenated,butarewrittentogetherasoneword.Thealkanewithsixcarbonatomsinastraightchain
(CH3CH2CH2CH2CH2CH3)islikewisecalledhexane.Namesforthestraightchainalkanesarestraightforward,but
thingsbecomemorecomplexforalkanesinwhichthecarbonchainisbranched.Inordertonamesuchalkanes,
identifythelongeststraightcarbonchain(theparentchain),andthentreatanygroupswhichbranchoffthischain
assubstituents.TheIUPACnameofanalkanewithabranchedchainconsistsofarootnamethatindicatesthe
longestchainofcarbonatomsinthecompound,substituentnamesthatindicatethegroupsbondedtotheparent
chain,andnumbersthatindicatethecarbonatomtowhichthesubstituentsareattached.Thisisillustratedbelowfor
4methyloctane,C9H20,inwhichthelongestcarbonchaincontainseightcarbonatoms(henceoctane)andthe
CH3(methyl)groupbondedtoC(4)isasubstituent(hence4methyl).

Thesubstituentsinalkanesarenamedaccordingtothealkanefromwhichtheyarederived.Forexample,aCH3
substituentisderivedfrommethane,CH4,throughtheremovalofoneHatom.Similarly,aC2H5substituentis
derivedfromethane,C2H6,byremovalofoneHatom.Asubstituentderivedfromanalkanebytheremovalofone
HatomiscalledanalkylgroupandiscommonlyrepresentedbythesymbolR.Alkylgroupsarenamedby
droppingtheanefromthenameoftheparentalkaneandaddingthesuffixyl.Therefore,aCH3substituentis
calledmethyl,andaC2H5substituentethyl.Table2.9givesnamesandstructuralformulaeforeightofthemost
commonalkylgroups.Notethat,whenalkylsubstituentscontainthreeormorecarbonatoms,thereismorethanone
possiblearrangementofthecarbonatomsinthesubstituent.Wedifferentiatebetweenthesepossibilitiesusingthe
prefixesiso,secandtert.IsoimpliesthepresenceofaCH(CH3)2groupattheendofthesubstituentcarbon
chain(theonlypossibilityforathreeatomchain),whiletheprefixessecandtertimplythatthesubstituentis
bondedtothelongestcarbonchainviaasecondaryortertiarycarbonatom,respectively.Whensecandtertare
partofaname,theyarealwaysitalicisedandhyphenated.However,iso,asusedinbothisopropylandisobutyl,is
nottreatedasaprefixlikesecandtert,andisneitheritalicisednorhyphenated.
TABLE2.9 Names,formulaeandabbreviationsofthemostcommonalkylgroups
Name Condensedstructuralformula Abbreviation
methyl CH3 Me

ethyl CH2CH3 Et
propyl CH2CH2CH3 Pr

isopropyl iPr

butyl CH2CH2CH2CH3 Bu

isobutyl iBu

secbutyl sBu
tertbutyl tBu

ThecompleteIUPACrulesfornamingalkanesare:
1.Thenameforanalkanewithanunbranchedchainofcarbonatomsconsistsofaprefixshowingthenumberof
carbonatomsinthechain(table2.8)andtheendingane.
2.Forbranchedchainalkanes,thelongestchainofcarbonatomsistheparentchain,anditsnamebecomesthe
rootname.
3.Foranalkanewithonesubstituent,numbertheparentchainsothatthecarbonatombearingthesubstituentis
giventhelowestpossiblenumber.Forexample,wenumberthefivecarbonchaininthefollowingcompound
fromtherighthandend.

4.Givethesubstituentontheparentchainanameandanumber.Thenumbershowsthecarbonatomofthe
parentchaintowhichthesubstituentisbonded.Useahyphentoconnectthenumbertothename.Forexample,
themethylgroupin2methylpropaneisattachedtoC(2),asshownbelow.

5.Iftherearetwoormoreidenticalsubstituents,numbertheparentchainfromtheendthatgivesthelower
numbertothesubstituentclosesttotheendofthechain.Iftherearetwoormoreidenticalsubstituents,the
numberoftimestheyoccurisindicatedbytheprefixesdi,tri,tetra,penta,hexaandsoon.Acommais
usedtoseparatepositionnumbers.Ofthetwopossibilitiesbelow,wechoosetheonethatnumbersthecarbon
atomstowhichthemethylgroupsareattachedas2and4,ratherthan3and5.

6.Ifstep5leadstomorethanonepossibility,numbertheparentchainsuchthatthefirstpointofdifferencehas
thelowestpossiblenumber.Ofthetwopossibilitiesbelow,wechoosetheonethatnumbersthemethylgroup
showninred3ratherthan4.

7.Iftherearetwoormoredifferentsubstituents,listtheminalphabeticalorder,and(asusual)numberthechain
fromtheendthatgivesthelowernumbertothesubstituentencounteredfirstorthatprovidesthefirstpointof
difference.Iftherearedifferentsubstituentsinequivalentpositionsonoppositeendsoftheparentchain,the
substituentofloweralphabeticalorderisgiventhelowernumber.Theimportanceofalphabeticallyorderingthe
substituentsisshowninthefollowingexample.
8.Theprefixesdi,tri,tetraandsoon,andthehyphenatedprefixessecandtertaredisregardedforthe
purposesofplacingthesubstituentsinalphabeticalorder.Notethatbothisobutylandisopropylsubstituentsare
treatedasbeginningwiththeletteri.Putthenamesofthesubstituentsinalphabeticalorderfirst,andthen
inserttheprefix.Inthefollowingexample,thesubstituentsareorderedasethylandmethyl,notdimethyland
ethyl.

WORKEDEXAMPLE2.13

WritingIUPACnamesforalkanes
WriteIUPACnamesforthefollowingalkanes.
(a)

(b)

Analysis

Weneedtofollowtherulesfornamingalkanesoutlinedpreviously.Whennamingalkanes,startby
identifyingthelongestcarbonchain,andthenidentifyandnumberthesubstituents.

Solution

Wewillconsidereachalkaneinturn.Thelongestcarbonchainin(a)containsfourcarbonatomsand
thereforewillbenamedasasubstitutedbutane.Wethennumbertheparentchaintogivethemethyl
substituentthelowestpossiblenumber.Thisisdoneineitherofthetwoequivalentwaysshownbelow
(notethatthesubstituentisatC(2)inbothcases).

(a)

Wenownamethesubstituentandspecifyitspositionontheparentchaintoobtainthefullname.This
alkaneisthereforenamed2methylbutane.

Thelongestcarbonchainin(b)containssevencarbonatoms,andthereforeitwillbenamedasa
substitutedheptane.Therearetwosubstituentsinthismolecule:amethylgroupandanisopropylgroup,
andthereforewemustnumberthechaintogivethesubstituentclosesttotheendofthechainthelowest
number.Thisisshowninthefollowingdiagram,whereweagainhavetwoequivalentpossibilities.

(b)

Tonamethealkane,listthesubstituentsinalphabeticalorderandspecifytheirpositionsontheparent
chain.Asisopropylcomesbeforemethyl,thisalkaneisnamed4isopropyl2methylheptane.

Isouranswerreasonable?

Theeasiestwaytochecktheanswerstothistypeofquestionistoworkbackwardsfromthenamewe
havededuced,andderivethechemicalstructure.Ifwedothatinthiscase,wefindthatouranswersare
correct.

PRACTICEEXERCISE2.16
WritetheIUPACnamesforthefollowingalkanes.
(a)

(b)

ConstitutionalIsomerisminAlkanes

Theconceptofisomerismwasmentionedpreviouslywithrespecttotherelativepositioningofthetwomethyl
groupsin1,2dimethylcyclopentane.Thealkanesprovideanexcellentexampleofthedifferentwaysinwhicha
particularnumberofcarbonandhydrogenatomsmaybejoined.Thereisonlyoneorderofattachment,andhence
onewayofwritingCH4(methane),C2H6(ethane)andC3H8(propane).However,whenwecometoC4H10two
ordersofattachmentofatomsarepossible.
Inoneofthese,butane,thefourcarbonatomsarebondedinastraightchainintheother,2methylpropane,three
carbonatomsarebondedinastraightchain,withthefourthcarbonatomasabranch.Butaneand2methylpropane
areconstitutionalisomers.Constitutionalisomersarecompoundswiththesamechemicalformulabutadifferent
orderofattachmentoftheconstituentatoms.Constitutionalisomerscanusuallybedistinguishedbytheirdiffering
physicalpropertiesbutaneand2methylpropaneprovideagoodexampleofthisbutaneboilsat0.5C,while2
methylpropaneboilsat11.6C.IfweconsiderC5H12,wecanobtainthethreeconstitutionalisomersshownbelow.

Thenumberofpossibleconstitutionalisomersbecomesverylargeveryquickly.Forexample,thealkanewiththe
chemicalformulaC25H52hasastaggering36797588possibleconstitutionalisomers.Constitutionalisomersarenot
uniquetoalkanes,andcanbefoundthroughoutorganicchemistryindeed,workedexamples2.10and2.11
involveddrawingconstitutionalisomersofalcoholsandaldehydesrespectively.

WORKEDEXAMPLE2.14

Recognisingconstitutionalisomers
Dothestructuralformulaeineachofthefollowingpairsofmoleculesrepresentthesamecompoundor
constitutionalisomers?
(a)

(b)

Analysis

Todeterminewhetherthesestructuralformulaerepresentthesamecompoundorconstitutionalisomers,
wemustfirstfindthelongestchainofcarbonatoms.Notethatitmakesnodifferencewhetherthechainis
drawnstraightorbent.Wethennumberthelongestchainfromtheendnearestthefirstbranchand
comparethelengthsofeachchain,andthesizesandlocationsofanybranches.Structuralformulaethat
havethesameorderofattachmentofatomsrepresentthesamecompoundthosewhichhavedifferent
ordersofattachmentofatomsrepresentconstitutionalisomers.Notethatsimilaritiesordifferences
betweenstructuralformulaearesometimesmadecleareriftheyaredrawnaslinestructures.

Solution
(a)Eachstructuralformulahasanunbranchedchainofsixcarbonatoms.Thetwostructuresare
identicalandrepresentthesamecompound.

(b)Eachstructuralformulahasachainoffivecarbonatomswithtwobranches.Althoughthe
branchesareidentical,theyareatdifferentlocationsonthechains.Therefore,thesestructural
formulaerepresentconstitutionalisomers.

PRACTICEEXERCISE2.17
Dothestructuralformulaeineachofthefollowingpairsof
moleculesrepresentthesamecompoundorconstitutional
isomers?
(a)

(b)
WORKEDEXAMPLE2.15

Drawingconstitutionalisomers
DrawstructuralformulaeforthefiveconstitutionalisomerswiththemolecularformulaC6H14.

Analysis

Therearesixcarbonatomsinthemolecule,sowecanexpectconstitutionalisomerswithlongestcarbon
chainlengthsofsix,five,fourandpossiblythree.Wemustdrawallpossibleisomerswiththesechain
lengths.

Solution

TheconstitutionalisomersofC6H14areasfollows.

NotethatwefindthatthereisnowayofwritingC6H14withonlythreecarbonatomsinthelongestchain.

Isouranswerreasonable?

Therearenootherpossiblearrangementsofsixcarbonatomsandfourteenhydrogenatoms,eachsingly
bondedtoeachother.Therefore,wecanbeconfidentouranswersarecorrect.

PRACTICEEXERCISE2.18
Drawthenineconstitutionalisomerswiththe
formulaC7H16.

GeneralOrganicNomenclature
TheprinciplesofIUPACnomenclatureasappliedtoalkanescanbeextendedtothenamingofanyorganic
compound.Thenamewegivetoanycompoundwithachainofcarbonatomsconsistsofthreeparts:aprefix,an
infixandasuffix.Eachpartprovidesspecificinformationaboutthestructuralformulaofthecompound.
1.Theprefixshowsthenumberofcarbonatomsintheparentchain.Prefixesthatshowthepresenceof1to10
carbonatomsinachainweregivenintable2.8.
2.Theinfixshowsthenatureofthecarboncarbonbondsintheparentchain.Thethreepossibilitiesaregivenin
table2.10.
TABLE2.10 TheThreePossibleInfixesandTheirMeanings
Infix Natureofcarboncarbonbondsintheparentchain

an allsinglebonds
en oneormoredoublebonds
yn oneormoretriplebonds

3.Thesuffixshowstheclassofcompoundtowhichthesubstancebelongs,andthereforethefunctionalgroup(s)
presentinthecompound.Thesuffixesfortheclassesofcompoundwehavealreadymetareasshownintable
2.11.
TABLE2.11 SomeSuffixesandtheClassofCompoundthattheyDesignate
Suffix Classofcompound
e hydrocarbon
ol alcohol
al aldehyde
one ketone
oicacid carboxylicacid

Wecanillustratetheuseofprefixes,infixesandsuffixeswithrespecttothefollowingfourorganiccompounds.We
willdivideeachnameintoaprefix,aninfixandasuffix,andspecifytheinformationaboutthestructuralformula
thatiscontainedineachpartofthename.
(a)

Theprefixpropmeansthreecarbonatomsintheparentchain.Theinfixenreferstothepresenceofoneor
moreC Cdoublebondsinthemolecule,whilethesuffixemeansthatthecompoundisahydrocarbon,
composedofonlycarbonandhydrogenatoms.
(b)

Theprefixethmeanstwocarbonatomsintheparentchain.Theinfixanmeanstherearenocarbon
carbonmultiplebondsinthemolecule,andthesuffixolmeansthatthereisanalcoholfunctionalgroupin
themolecule.
(c)

Theprefixpentmeansfivecarbonatomsintheparentchain.Theinfixanmeanstherearenocarbon
carbonmultiplebondsinthemolecule,andthesuffixoicacidreferstothepresenceofacarboxylicacidin
themolecule.
(d)
(d)

Theprefixethmeanstwocarbonatomsintheparentchain.Theinfixynmeansthatthereareoneormore
C Ctriplebondsinthemolecule.Thesuffixemeansthatthecompoundisahydrocarbon,composedof
onlycarbonandhydrogenatoms.

Wecansummarisethisinformationinthefollowingdiagram.
(a)
(b)

(c)

(d)

Noticethat,ineachoftheseexamples,thereisnoambiguityaboutthepositionofthefunctionalgroup.Wewilldeal
laterwithexampleswherethepositionisnotasclear.

PRACTICEEXERCISE2.19
Combinetheproperprefix,infixandsuffix,and
writetheIUPACnameforeachofthefollowing
compounds.
(a)

(b)

Theexamplesgiveninthissectionserveonlyasanintroductiontoorganicnomenclatureyouwillfindmore
detailedexamplesintheappropriatechapterslaterinthebook.

Wehaveseeninthischapterthatsuchapparentlydisparatetopicsasunits,nomenclatureandrepresentationsof
moleculesareallpartofthelanguageofchemistry.Thereisstillmuchofthislanguageforyoutolearn,butthis
chapterhasintroducedmanyofthefundamentalsthatyouwillneedinordertounderstandandappreciatethe
followingchapters.Indeed,itislikelythatyouwilloftenneedtoreferbacktothischapterwhenyoucomeacross
examplesofmeasurement,representationsofmoleculesornomenclaturelaterinthisbook.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
SUMMARY
Measurement
Allmeasurementshaveanassociatedunitanduncertainty.Theunitsusedformeasurementsarebased
onthesetofsevenSIbaseunits,whichcanbecombinedtogivevariousderivedunits.TheSIbase
unitsarethemetre,kilogram,second,kelvin,mole,ampereandcandela.Prefixescanbeusedtodenote
multiplicationoftheseunitsbypowersof10.Dimensionalanalysis,whichusesthefactthatunits
undergothesamekindsofmathematicaloperationsasthenumberstowhichtheyareattached,canbe
usedasanaidtodeterminingthecorrectformofanequation.SomenonSIunitsareincommonusage
butcanbeconvertedtoSIunitsusingaconversionfactor.

Uncertaintiesariseinanymeasurementfromthelimitationsoftheapparatususedtomakethe
measurement.Someideaoftheuncertaintyandthereforeprecisioninameasurementcanbeobtained
fromthenumberofsignificantfigurestowhichthemeasurementisquoted.

Expressinganumberinscientificnotationcanmakeiteasiertodeterminethenumberofsignificant
figures.Therewillalwaysbeuncertaintyinthefinalfigureofanymeasurement.Theaccuracyofa
measurementshowshowclosetothetruevaluethemeasurementis,whiletheprecisionofa
measurementrepresentshowreproducibleitis.

Whenmeasurementsaremanipulatedinequations,thefollowingrulesapply:
Whenmeasurementsaremultipliedordivided,thenumberofsignificantfiguresintheanswer
shouldnotbegreaterthanthenumberofsignificantfiguresintheleastprecisemeasurement.
Whenmeasurementsareaddedorsubtracted,theanswershouldhavethesamenumberofdecimal
placesasthequantitywiththefewestnumberofdecimalplaces.

RepresentationsofMolecules
Thechemicalformulaofasubstanceshowstherelativenumberofeachtypeofatompresent,butgives
nostructuralinformation.Therulesforwritingchemicalformulaeofbinarycompoundsareasfollows:
1.Withtheexceptionofhydrogen,theelementfurthertotheleftintheperiodictableappearsfirst.
2.Ifhydrogenispresent,itappearslastexceptwhentheotherelementisfromgroup16or17ofthe
periodictable.
3.Ifbothelementsarefromthesamegroupoftheperiodictable,theloweroneappearsfirst.

Thechemicalformulaeofioniccompoundsarewrittenwiththecationfollowedbytheanion,while
organiccompoundshaveCandHfirst,followedbytherestoftheelementsinalphabeticalorder.

Structuralformulaeattempttoshowparticularaspectsofmolecularstructureinbothtwoandthree
dimensions.Suchdepictionsareespeciallyimportantinorganicchemistrywherecatenationleadstoan
enormousnumberofpossiblecarbonbasedmolecules.Structuralformulaearedrawnusingonelineto
representsinglebonds,twolinesfordoublebondsandthreelinesfortriplebonds.Carbonatomsatthe
endofacarbonchainarecalledterminalcarbonatoms.Structuralformulaecanhelpdistinguish
betweenisomers.Twotypesofshorthandstructuralformulaearewidelyusedcondensedstructural
formulaedonotincludeexplicitdepictionsofbondsbetweenatoms,whilelinestructuresremoveatom
labelsforcarbonatomsandallhydrogenatomsthatarebondedtocarbonatoms.Threedimensional
aspectscanbeintroducedintostructuralformulaethroughtheuseofhashedandsolidwedges,which
showbondsgoingawayfromandcomingtowardstheobserverrespectively.

Ballandstickmodelsandspacefillingmodelsaretwoothermethodswherethreedimensionalitymay
beshown.
Mechanisticarrowscanbeusedtoshowthemovementofelectronsinchemicalprocesses.Thetailof
thearrowissituatedattheelectronsourceandthearrowheadshowsthedestination.

Nomenclature
ChemicalspeciescanbenamedaccordingtosetsofrulesprescribedbyIUPAC.Therulesfornaming
nonmetallicbinarycompoundsareasfollows:
1.Theelementclosertotheleftoftheperiodictableappearsfirst.Ifbothelementsarefromthe
samegroupoftheperiodictable,theloweroneappearsfirst.
2.Theelementthatappearsfirstretainsitselementalname.
3.Thesecondelementbeginswitharootderivedfromitselementalnameandendswiththesuffix
ide.
4.Whenthereismorethanoneatomofagivenelementintheformula,thenameoftheelement
usuallycontainsaprefixthatspecifiesthenumberofatomspresent.

Binarycompoundscontaininghydrogencanbenamedwithhydrogeneitherfirstorsecond,depending
onthepositionoftheotherelementintheperiodictable,accordingtotheaboverules.

Ioniccompoundsarenamedwiththecationfirst,followedbytheanion,whileoxoanionsarenamed
accordingtoanextensivesetofrules.

Organiccompoundsarenamedprimarilyaccordingtotheirfunctionalgroupthoseofimportanceinthis
chapteraretheOHgroupfoundinalcohols,theCHOgroupfoundinaldehydes,theC Ogroup
foundinketonesandtheCOOHgroupfoundincarboxylicacids.Alkanesbelongtothegroupof
compoundscalledhydrocarbonsandaresometimescalledsaturatedhydrocarbons.Thoseconsisting
solelyofchainsofcarbonatomsarecalledacyclicalkanes,whilethosecontainingoneormoreringsof
carbonatomsarecalledcycloalkanes.Theirnomenclatureisbasedonthelongestcarbonchainwithin
themolecule,withaprefixdenotingthelengthofthatchain.Substituentsonthechainarenumbered
suchthatthesumofthenumbersforthesubstituentspresentisthelowestpossiblenumber.Namesof
organiccompoundsgenerallycompriseaprefix,infixandsuffix.Theprefixshowsthenumberof
carbonatomsintheparentchain,theinfixshowsthenatureofthecarboncarbonbondsintheparent
chain,andthesuffixshowstheclassofcompoundtowhichthesubstancebelongs,andthereforethe
functionalgroup(s)presentinthecompound.

Constitutionalisomersofalkaneshavethesamechemicalformulaebutdifferentstructuralformulaeand
hencedifferentnames.Theseisomersgenerallyhavedifferentphysicalproperties.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYCONCEPTSANDEQUATIONS
SIunits(section2.1)
ThebaseSIunits:metre,kilogram,second,kelvin,mole,ampereandcandelaareusedeitherdirectlyor
toderiveunitsforanymeasurementinchemistry.

SIprefixes(section2.1)
SIprefixesareusedtocreatelargerandsmallerunits.Theprefixeshelpustoconvertbetween
differentlysizedunits.

Dimensionalanalysis(section2.1)
Dimensionalanalysisassistsindeterminingthecorrectformofanequationthroughknowledgeofthe
unitsofallcomponentsoftheequation.

Rulesforsignificantfiguresincalculations(section2.1)
Thefollowingrulesareusedtoroundanswerstothecorrectnumberofsignificantfigures.
Whenmeasurementsaremultipliedordivided,thenumberofsignificantfiguresintheanswer
shouldnotbegreaterthanthenumberofsignificantfiguresintheleastprecisemeasurement.
Whenmeasurementsareaddedorsubtracted,theanswershouldhavethesamenumberofdecimal
placesasthequantitywiththefewestnumberofdecimalplaces.

Rulesforwritingchemicalformulaeofbinarycompounds(section2.2)
Thefollowingrulesareusedtowritethecorrectchemicalformulaeforcompoundscontainingonlytwo
elements.
1.Withtheexceptionofhydrogen,theelementfurthertotheleftintheperiodictableappearsfirst.
2.Ifhydrogenispresent,itappearslastexceptwhentheotherelementisfromgroup16or17ofthe
periodictable.
3.Ifbothelementsarefromthesamegroupoftheperiodictable,theloweroneappearsfirst.
4.Ifthecompoundisionic,wewritethecationfirst,followedbytheanion.

Rulesfordrawinglinestructures(section2.2)
Theserulesareusedforconvertingstructuralformulaetolinestructures,andcanalsobeusedtocarry
outthereverseoperation.
1.AllbondsexceptCHbondsareshownaslines.
2.CHbondsandHatomsattachedtocarbonarenotshowninthelinestructure.
3.Singlebondsareshownasonelinedoublebondsareshownastwolinestriplebondsareshown
asthreelines.
4.Carbonatomsarenotlabelled.Allotheratomsarelabelledwiththeirelementalsymbols.

Hashedandsolidwedges(section2.2)
Theseareusedtointroducethreedimensionalaspectsintostructuralformulae.

Asolidwedge( )representsabondcomingoutofthepage,whileahashedwedge( )representsa


bondgoingbackintothepage.Anormallineisusedforbondsintheplaneofthepage.

Mechanisticarrows(section2.2)
Theseareusedtoshowthemovementofelectronsinchemicalprocesses.Singleheadedarrowsshow
themovementofasingleelectron,whiletwoheadedarrowsshowthemovementofelectronpairs.The
directionofelectronmovementisfromthetailofthearrowtothehead.

Namingnonmetallicbinarycompounds(section2.3)
Theserulesareusedtonamecompoundscontainingonlytwononmetallicelements.
1.Theelementclosertotheleftoftheperiodictableappearsfirst.Ifbothelementsarefromthe
samegroupoftheperiodictable,theloweroneappearsfirst.
2.Theelementthatappearsfirstretainsitselementalname.
3.Thesecondelementbeginswitharootderivedfromitselementalnameandendswiththesuffix
ide.
4.Whenthereismorethanoneatomofagivenelementintheformula,thenameoftheelement
usuallycontainsaprefixthatspecifiesthenumberofatomspresent.

Namingoxoanions(section2.3)
Theserulesareusedtonameanionscontainingoxygenandatleastoneotherelement.
1.Thenamehasaroottakenfromthenameofthecentralatom.
2.Whenanelementformstwodifferentoxoanions,theonewithfeweroxygenatomsendsinite
andtheotherendsinate.
3.Chlorine,bromineandiodineeachformfourdifferentoxoanionsthataredistinguishedby
prefixesandsuffixes.
4.Apolyatomicanionwithachargemorenegativethan1mayaddH+togiveanotheranion.
Theseanionsarenamedfromtheparentanionbyaddingthewordhydrogen.

Functionalgroups(section2.3)
Functionalgroupsarethebasisfornamingorganiccompounds.
Alcoholscontainahydroxylgroup.
Aldehydescontainaterminalcarbonylgroup.
Ketonescontainanonterminalcarbonylgroup.
Carboxylicacidscontainacarboxylgroup.

Namingalkanes(section2.3)
Therearetwopartstothenameofanalkane:aprefix,indicatingthenumberofcarbonatomsinthe
chain,andthesuffixane.

Prefixesforcarbonchainlength(section2.3)
Knowledgeoftheseprefixesisnecessaryfornaminganyorganiccompound:1,meth2,eth3,prop
4,but5,pent6,hex7,hept8,oct9,non10,dec.

Generalorganicnomenclature(section2.3)
Theprefix,infixandsuffixofthenameofanorganiccompoundreflectthestructureofthatcompound.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWQUESTIONS
Measurement
2.1Whymustmeasurementsalwaysbewrittenwithaunit?
2.2WhatdoestheabbreviationSIstandfor?
2.3WhichSIbaseunitisdefinedintermsofaphysicalobject?
2.4WhatistheonlySIbaseunitthatincludesadecimalprefix?
2.5Newton'ssecondlawstatesthatforceisequaltomasstimesacceleration.WhatistheSIderived
unitforforce?(Theunitiscalledthenewton,abbreviatedN.)
2.6Whatisthemeaningofeachofthefollowingprefixes?
(a)centi
(b)milli
(c)kilo
(d)micro
(e)nano
(f) pico
(g)mega
2.7Whatabbreviationisusedforeachoftheprefixesnamedinquestion2.6?
2.8Whatunitsaremostusefulinthelaboratoryformeasuringthefollowing?
(a)length
(b)volume
(c)mass
2.9Definethetermsignificantfigures.
2.10Whatisthedifferencebetweenaccuracyandprecision?
2.11Aconcentrationof1.5gmL1ofatoxinisfoundinasampleofapatient'sblood.Howhigh
mighttheconcentrationactuallyhavebeen?Supposethatthemeasurementhadbeenwrittenas
1.50gmL1ofblood.Howhighmighttheconcentrationhavebeeninthiscase?
2.12Thereare3600sin1hour.Bywhatconversionfactorwouldyoumultiply250stoconvertitto
hours?Bywhatconversionfactorwouldyoumultiply3.84htoconvertittoseconds?
RepresentationsofMolecules
2.13Listtherulesfortheconversionofstructuralformulaetolinestructures.
2.14Whatmustbetrueabouttwosubstancesiftheyaretobecalledisomersofeachother?
2.15Writethechemicalformulaforeachofthefollowingsubstances.
(a)stearicacid,whichcontains36hydrogenatoms,18carbonatomsand2oxygenatoms
(b)silicontetrachloride,whichcontains1siliconatomand4chlorineatoms
(c)Freon113,whichcontains3atomseachoffluorineandchlorineand2atomsofcarbon
2.16Thelinestructuresthatfollowrepresentstartingmaterialsformakingplastics.Foreachofthem,
drawthestructuralformulaandgivethechemicalformula.
(a)
(b)

(c)

2.17Writelinestructuresforcompounds(a)to(f).
(a)

(b)

(c)(CH3)2CHCH(CH3)2
(d)

(e)(CH3)3CH
(f) CH3(CH2)3CH(CH3)2
2.18Writethechemicalformulaandthecondensedstructuralformulaforeachofthefollowing
alkanes.
(a)

(b)
(c)

2.19Provideanevenmoreabbreviatedformulaforeachofthefollowingcondensedstructural
formulae,usingparenthesesandsubscripts.
(a)

(b)

(c)

Nomenclature
2.20Writechemicalformulaeforthefollowingcompounds.
(a)chlorinemonofluoride
(b)seleniumtrioxide
(c)hydrogenbromide
(d)silicontetrachloride
(e)sulfurdioxide
(f) hydrogenperoxide
2.21Namethefollowingcompounds.
(a)ClF3
(b)H2Se
(c)ClO2
(d)SbCl3
(e)PCl5
(f) N2O5
(g)N2Cl4
(h)NH3
2.22Drawthestructuralformulaeofthefollowingmolecules.
(a)butane
(b)3methylpentane
(c)2,3dimethylhexane
2.23Whydowenothavetolabelaldehydesasprimaryorsecondary,orcarboxylicacidsasbeing
primary,secondaryortertiary?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWPROBLEMS
2.24Whatnumbershouldreplacethequestionmarkineachofthefollowing?
(a)1cm=?m
(b)1km=?m
(c)1m=?pm
(d)1dm=?m
(e)1g=?kg
(f) 1cg=?g
(g)1nm=?m
(h)1g=?g
(i) 1kg=?g
(j) 1Mg=?g
(k)1mg=?g
(l) 1dg=?g
2.25Converteachofthefollowingmeasurementstothegivenunits.
(a)60CtoK
(b)30CtoK
(c)273KtoC
(d)299KtoC
(e)40CtoK
2.26Naturalgasismostlymethane,asubstancethatboilsatatemperatureof111K.Whatisitsboiling
pointinC?
2.27Heliumhasthelowestboilingpointofanyliquid.Itboilsat4K.WhatisitsboilingpointinC?
2.28Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)37.53cm
(b)37.240cm
(c)202.0g
(d)0.00024kg
(e)0.07080m
(f) 2400mL
2.29Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)0.0230g
(b)105.303m
(c)0.007kg
(d)614.00mg
(e)10L
(f) 3.8105mm
2.30Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)1.0230kg
(b)3.0200m
(c)0.0030L
(d)27.300g
(e)0.04320mm
2.31Howmanysignificantfiguresdothefollowingmeasuredquantitieshave?
(a)2.303ng
(b)0.04030kg
(c)20030mL
(d)9200g
(e)0.0101dL
2.32Performthefollowingarithmeticandroundtheanswerstothecorrectnumberofsignificant
figures.
(a)0.0023m315m
(b)84.25kg0.01075kg
(c)(84.45g94.45g)/(31.4mL9.9mL)
(d)(23.4g+102.4g+0.003g)/(6.478mL)
(e)(313.44cm209.1cm)8.2234cm
2.33Performthefollowingarithmeticandroundtheanswerstothecorrectnumberofsignificant
figures.
(a)3.58g/1.739mL
(b)4.02mL+0.001mL
(c)(22.4g8.3g)/(1.142mL0.002mL)
(d)(1.345g+0.022g)/(13.36mL8.4115mL)
(e)(74.335m74.332m)/(4.75s1.114s)
2.34Expressthefollowingnumbersinscientificnotationtothreesignificantfigures.
(a)4340
(b)32000000
(c)0.003287
(d)42000
(e)0.00000800
(f) 324300
2.35Expressthefollowingnumbersinscientificnotation.Assume,inthisproblem,thatonlythenon
zerodigitsaresignificantfigures.
(a)489
(b)0.00375
(c)82300
(d)0.01225
(e)2.43
(f) 27320
2.36Writethefollowingnumbersinstandard(nonscientific)form.
(a) 3.110 5
(b)4.3510 6
(c) 3.910 3
(d)4.410 12
(e) 35.610 7
(f) 8.810 8
2.37Writethefollowingnumbersinstandard(nonscientific)form.
(a) 5.2710 8
(b)7.1210 5
(c) 43.510 9
(d)2.3510 2
(e) 4.000010 7
(f) 37.210 2
2.38Performthefollowingarithmeticandexpresstheanswersinscientificnotation.
(a) (4.010 7)(2.110 5)
(b)(3.010 2)+(3.2110 5)
(c) (2.110 7)(2.110 5)
(d)(3.010 4)(8.210 5)
(e) (9.1010 12)/(2.010 3)2
2.39Performthefollowingarithmeticandexpresstheanswersinscientificnotation.
(a) (3.010 4)(2.110 5)
(b)(8.010 12)/(2.010 3)2
(c) (6.710 5)(8.210 5)
(d)(1.410 5)(3.010 4)
(e) (3.310 4)+(2.5210 2)
2.40Converteachofthefollowingmeasurementstothegivenunits.
(a)32.0dmtokm
(b)8.2mgtog
(c)75.3mgtokg
(d)137.5mLtoL
(e)0.025LtomL
(f) 342pmtodm
2.41Converteachofthefollowingmeasurementstothegivenunits.
(a)92dLtomL
(b)22ngtog
(c)83pLtonL
(d)230kmtom
(e)87.3cmtokm
(f) 238mmtonm
2.42Converteachofthefollowingmeasurementstothegivenunitsandexpressyouranswersin
scientificnotation.
(a)230kmtocm
(b)423kgtomg
(c)423kgtoMg
(d)430LtomL
(e)27ngtokg
(f) 730nLtokL
2.43Converteachofthefollowingmeasurementstothegivenunitsandexpressyouranswersin
scientificnotation.
(a)183nmtocm
(b)3.55gtodg
(c)6.22kmtonm
(d)33dmtomm
(e)0.55dmtokm
(f) 53.8ngtopg
2.44Whichfunctionalgroupdoeseachofthefollowingcompoundscontain?
(a)CH3CH CH2
(b)CH3CH2OH
(c)CH3CH2CH2COOH
(d)HOCH2CH2CH3
2.45Whichfunctionalgroupdoeseachofthefollowingcompoundscontain?
(a)CH3C CH
(b)

(c)

2.46Decidewhetherthemembersofeachpairareidentical,isomersorunrelated.
(a)

(b)

(c)CH3CH2OHandCH3CH2CH2OH
(d)

(e)

(f)
(g)CH3CH2CH2NH2andCH3CH2NHCH3
2.47Examineeachpairanddecideiftheyareidentical,isomersorunrelated.
(a)

(b)

(c)

(d)

(e)

2.48WritetheIUPACnamesofthefollowinghydrocarbons.
(a)CH3CH2CH2CH2CH3
(b)

(c)

(d)

2.49Writestructuralformulaeforallofthesaturatedalcoholswiththreeorfewercarbonatomsper
molecule.
2.50WritestructuralformulaeforallofthepossiblealcoholswiththegeneralformulaC4H10O.
2.51Writechemicalformulaeforthemoleculeswhoseballandstickmodelsfollow.
(a)

(b)

(c)

(d)

(e)

(f)

(g)
2.52Writechemicalformulaeforthemoleculeswhoseballandstickmodelsfollow.
(a)

(b)

(c)

(d)

(e)

(f)

(g)
2.53Writestructuralformulaeforthemoleculesinquestions2.51and2.52.
2.54Convertthefollowingstructuralformulaeintolinestructures.
(a)

(b)

(c)

(d)

(e)

(f)
2.55Convertthefollowingstructuralformulaeintolinestructures.
(a)

(b)

(c)

(d)

(e)

(f)

2.56Convertthefollowinglinestructuresintostructuralformulae.
(a)

(b)

(c)
(d)
(e)

(f)

(g)

(h)

(i)

2.57Convertthefollowinglinestructuresintostructuralformulae.
(a)

(b)

(c)

(d)

(e)

(f)

(g)

2.58Whichofthefollowingstatementsaretrueaboutconstitutionalisomers?
(a)Theyhavethesamechemicalformula.
(b)Theyhavethesameatomicmass.
(c)Theyhavethesameorderofattachmentofatoms.
(d)Theyhavethesamephysicalproperties.
2.59Eachmemberofthefollowingsetofcompoundsisanalcohol.
i.
ii.

iii.

iv.

v.

vi.

vii.

viii.

Whichstructuralformulaerepresent:
(a)thesamecompound?
(b)differentcompoundsthatareconstitutionalisomers?
(c)differentcompoundsthatarenotconstitutionalisomers?
2.60Eachmemberofthefollowingsetofcompoundsiseitheranaldehydeoraketone.
i.

ii.

iii.

iv.

v.
vi.

vii.

viii.

Whichstructuralformulaerepresent:
(a)thesamecompound?
(b)differentcompoundsthatareconstitutionalisomers?
(c)differentcompoundsthatarenotconstitutionalisomers?
2.61Foreachofthefollowingpairsofcompounds,determinewhetherthestructuralformulaeshown
represent:
i. thesamecompound
ii. differentcompoundsthatareconstitutionalisomers
iii.differentcompoundsthatarenotconstitutionalisomers.
(a)

(b)

(c)

(d)

(e)

(f)
2.62Whichsetsofcompoundsareconstitutionalisomers?
(a)CH3CH2OHandCH3OCH3
(b)

(c)

(d)

(e)

(f)

2.63Drawlinestructuresfor:
(a)fouralcoholswithchemicalformulaC4H10O
(b)twoaldehydeswithchemicalformulaC4H8O
(c)oneketonewithchemicalformulaC4H8O
(d)threeketoneswithchemicalformulaC5H10O
(e)fourcarboxylicacidswithchemicalformulaC5H10O2.
2.64Writechemicalformulaeforthesecompounds.
(a)methane
(b)hydrogeniodide
(c)calciumhydride
(d)phosphorustrichloride
(e)dinitrogenpentaoxide
(f) sulfurhexafluoride
(g)borontrifluoride
2.65Writechemicalformulaeforthesecompounds.
(a)ammonia
(b)hydrogensulfide
(c)2chloropropane
(d)silicondioxide
(e)molecularnitrogen
(f) sulfurtetrafluoride
(g)brominepentafluoride
2.66Namethefollowingcompounds.
(a)S2Cl2
(b)IF7
(c)HBr
(d)N2O3
(e)SiC
(f) (f)CH3OH
2.67Namethefollowingcompounds.
(a)GeCl4
(b)N2F4
(c)LiH
(d)SeO2
(e)CH3CH2OH
2.68Writethechemicalformulaofeachcompound.
(a)hydrogenfluoride
(b)calciumfluoride
(c)aluminiumsulfate
(d)ammoniumsulfide
2.69Writethechemicalformulaofeachcompound.
(a)sodiumhypochlorite
(b)lithiumperiodate
(c)magnesiumbromide
2.70Nameeachofthefollowingcompounds.
(a)CaO
(b)K2CO3
(c)HBr
(d)Na2HPO4
2.71Nameeachofthefollowingcompounds.
(a)(NH4)2SO4
(b)KBr
(c)H2S
(d)Na2S
2.72Writechemicalformulaeforthesecompounds.
(a)sodiumsulfate
(b)potassiumsulfide
(c)potassiumdihydrogenphosphate
(d)sodiumhydrogencarbonate
(e)lithiumperbromate
2.73Writechemicalformulaeforthesecompounds.
(a)potassiumchlorate
(b)ammoniumhydrogencarbonate
(c)aluminiumchloride
(d)potassiumoxide
2.74Namethefollowingcompounds.
(a)K2CO3
(b)NaClO
(c)CuSO4
(d)KH2PO4
(e)NaNO3
(f) CaSO3
(g)KMnO4
2.75Nameeachofthefollowingcompounds.
(a)NaNO2
(b)Mg 3(PO4)2
(c)KHSO4
(d)CsBr
(e)Al(ClO4)3
2.76WriteIUPACnamesforthesealkanes.
(a)

(b)

(c)

(d)

2.77Drawlinestructuresforthesealkanes.
(a)2,2,4trimethylhexane
(b)2,2dimethylpropane
(c)3ethyl2,4,5trimethyloctane
(d)5butyl2,2dimethylnonane
(e)4isopropyloctane
(f) 3,3dimethylpentane
2.78ExplainwhyeachofthefollowingnamesisanincorrectIUPACname,andwritethecorrect
IUPACnamefortheintendedcompound.
(a)1,3dimethylbutane
(b)4methylpentane
(c)2,2diethylbutane
(d)2ethyl3methylpentane
(e)2propylpentane
(f) 2,2diethylheptane
(g)2,2dimethylcyclopropane
(h)1ethyl5methylcyclohexane
2.79Drawastructuralformulaforeachofthefollowingcompounds.
(a)ethanol
(b)ethanal
(c)ethanoicacid
(d)butanone
(e)butanal
(f) butanoicacid
(g)propanal
2.80WritetheIUPACnameforeachcompound.
(a)

(b)

(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
ADDITIONALEXERCISES
2.81Whenanobjectisheatedtoahightemperature,itglowsandgivesofflight.Thecolourbalanceof
thislightdependsonthetemperatureoftheglowingobject.Photographiclightingisdescribed,in
termsofitscolourbalance,asatemperatureinkelvin.Forexample,acertainelectronicflashgives
acolourbalance(calledcolourtemperature)ratedat5800K.Whatisthistemperatureexpressed
inC?
2.82TheIUPACsystemdividesthenameofacompoundintoaprefix(showingthenumberofcarbon
atoms),aninfix(showingthepresenceofcarboncarbonsingle,doubleortriplebonds),anda
suffix(showingthepresenceofanalcohol,analdehyde,aketoneoracarboxylicacid).Assume
forthepurposesofthisproblemthat,tobeanalcohol(ol),thehydroxyloraminogroupmustbe
bondedtoacarbonatomwhichhasonlysinglebondstootherattachedatoms.

Giventhisinformation,writethestructuralformulaofacompoundwithanunbranchedchainof
fourcarbonatomsthatisan:
(a) alkane
(b) alkene
(c) alkyne
(d) alkanol
(e) alkenol
(f) alkynol
(g) alkanal
(h) alkenal
(i) alkynal
(j) alkanone
(k) alkenone
(l) alkynone
(m)alkanoicacid
(n) alkenoicacid
(o) alkynoicacid.
(Note:Thereisonlyonestructuralformulapossibleforsomepartsofthisproblem.Forotherparts,
twoormorestructuralformulaearepossible.Wheretwoormorearepossible,wewilldealwith
howtheIUPACsystemdistinguishesbetweenthemwhenwecometothechaptersonthose
particularfunctionalgroups.)
2.83Ineverydaylife,weencounterchemicalswithunsystematicnames.Whatisthenameachemist
woulduseforeachofthefollowingsubstances?
(a)dryice,CO2
(b)saltpetre,KNO3
(c)salt,NaCl
(d)bakingsoda,NaHCO3
(e)sodaash,Na2CO3
(f) lye,NaOH
(g)lime,CaO
(h)milkofmagnesia,Mg(OH)2
2.84AmineralisachemicalcompoundfoundintheEarth'scrust.Whatarethechemicalnamesofthe
followingminerals?
(a)TiO2(rutile)
(b)PbS(galena)
(c)Al2O3(bauxite)
(d)CaCO3(limestone)
(e)BaSO4(barite)
(f) HgS(cinnabar)
(g)Sb 2S3(stibnite)
2.85Thelinestructuresofthreedifferentplantgrowthhormonesaregivenbelow.Writethechemical
formulaforeachcompound.
(a)

(b)

(c)

2.86Thefollowingmoleculesareknownfortheircharacteristicfragrances.Converteachlinestructure
intoacompletestructuralformula.
(a)
(b)

(c)

(d)

(e)

2.87Thecompoundsinthefollowingpairsofsubstancesarequitedifferentfromeachotherdespite
havingsimilarnames.Writecorrectformulaeforeachpair.
(a)sodiumnitriteandsodiumnitrate
(b)potassiumcarbonateandpotassiumhydrogencarbonate
(c)iodineandiodideion
(d)sodiumchlorideandsodiumhypochlorite
(e)nitrogenoxideandnitrogendioxide
(f) potassiumchlorateandpotassiumperchlorate
(g)ammoniaandammoniumion
2.88ProvideIUPACapprovednamesforeachofthefollowingcompounds.
(a)NH4Cl
(b)BrF5
(c)SO2
2.89ProvideIUPACapprovednamesforeachofthefollowingcompounds.
(a)KClO3
(b)KClO2
(c)KClO
(d)KCl
(e)Na2HPO4
2.90Expresstheresultsofthefollowinglogarithmiccalculationstothecorrectnumberofsignificant
figures.
(a) log(2.7510 5)
(b)antilog(2.53)
(c)ln(2.0)
(d)log(1.56+0.254)
(e) e7.21
(f)

2.91Surfacetension(),thephenomenonthatallowssmallinsectstowalkonwater,canbedefined
bythefollowingequation.

GiventhatE(energy)ismeasuredinJ,andA(area)ismeasuredinm2,determinetheunitsof
surfacetension.
2.92RememberingthatJisaderivedunit(seetable2.2),expressyouranswertoquestion2.91using
onlySIunits.
2.93Theratelawforthegasphasereaction

is

Determinetheunitsoftherateconstantk,giventhattherateofreactionhasunitsofmolL1s1
andtheconcentrationsofNOandH2aremeasuredinmolL1.
2.94Fromknowledgeoftheirgivenunits,determineanequationrelatingeachofthefollowinggroups
ofvariablesandconstants.
(a) volume(V,L),concentration(c,molL1)andamount(n,mol).Makeamountthesubject.
(b)speedoflight(c,ms1),energy(E,J),Planck'sconstant(h,Js)andwavelength(,m).
Makeenergythesubject.
(c) specificheat(c,Jg 1K1),temperaturechange(T,K),mass(m,g)andheat(q,J).Make
massthesubject.
(d)gasdensity(p,kgm3),pressure(p,Pa),molarmass(M,kgmol1),thegasconstant(R,J
mol1K1)andtemperature(T,K).Makepressurethesubject.(Hint:RecallthatPaisa
derivedunit.)
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYTERMS
absoluteuncertainty hashedwedge precision
accuracy heterolytic primarycarbonatom
acyclicalkanes homolytic saturatedhydrocarbon
alkane hydrate scientificnotation
alkylgroup hydrocarbon second
ampere(A) isomers secondarycarbonatom
anhydrous kelvin SI(SystmeInternational)
ballandstickmodel kilogram units
binarycompound linestructure significantfigures
candela mechanisticarrows solidwedge
catenation metre spacefillingmodel
chemicalformula mole structuralformula
condensedstructuralformula molecularformula substituent
constitutionalisomers nomenclature terminalcarbon
cycloalkane oxoanion tertiarycarbonatom
dimensionalanalysis parentchain unit
functionalgroup percentageuncertainty

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

3 ChemicalReactionsand
Stoichiometry
Chemicalplantsproducelargequantitiesofbasicchemicalsusedineverydayconsumergoods,industrial
processesandresearchlaboratories.However,ifyoumanageaplantliketheQueenslandAluminaRefinery
(pictured)andwanttorunitefficiently,youmustknowhowmuchstartingmaterialisneededtosynthesisea
productwiththebestpossibleyield.Someoftheinformationcomesfromchemicalequations.Chemical
equationsconvenientlyandsuccinctlysummariseinformationaboutchemicalreactions.Theyshowthe
substancesyoustartwithandthesubstancesyouendupwith.Theyalsoshowtherelativeamountsofeach
substance.Inthischapter,youwilllearnhowtousebalancedchemicalequationsandtherulesof
stoichiometrytoworkoutthemassofthesubstancesrequiredtoformadesiredmassofaproduct.Agood
understandingofstoicinvolvedhiometryisessentialforindustrialscaleproduction,pharmaceutical
manufactureandcontrollingreactionsinresearchlaboratories.Itisalsoessentialforstudentswantingto
understandbasicchemistry.

KEYTOPICS

3.1Chemicalequations
3.2Balancingchemicalequations
3.3Themole
3.4Empiricalformulae
3.4Empiricalformulae
3.5Stoichiometry,limitingreagentsandpercentageyield
3.6Solutionstoichiometry

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.1ChemicalEquations
Theproductionofnewsubstancesfromoneormorechemicalspeciesiscalledachemicalreaction.A
chemicalequation,aconceptwebrieflyintroducedinchapter1,maybeusedtodescribewhathappens
whenachemicalreactionoccurs.Ituseschemicalformulaetoprovideabeforeandafterpictureofthe
chemicalsubstancesinvolved.Consider,forexample,thereactionbetweenhydrogenandoxygen(a
combustionreaction)togivewater.Thechemicalequationthatdescribesthisreactionis:

Thetwoformulaethatappeartotheleftofthearrowarethoseofthereactants,hydrogenandoxygen,
i.e.thesubstancesthatreacttoformtheproduct.Theformulaoftheproduct,water,iswrittentothe
rightofthearrow.Productsarethesubstancesthatareformedinthereaction.Thearrowmeansreact
toproduce.Thus,thisequationtellsusthathydrogenandoxygenreacttoproducewater.Thereverse
process,thereactionofwatertoformhydrogenandoxygen,canalsooccur,butonlytoaverysmall
extent.Reactionsinwhichboththeforwardandreversereactionsoccurarecalledreversiblereactions.
Themajorityofchemicalreactionsarereversibletosomeextent,but,fornow,wewillbeconcerned
onlywiththeforwardreaction.Wewilllearnmoreaboutreversiblereactionsinchapter9.

Inthisexample,onlyonesubstanceisformedinthereaction,sothereisonlyoneproduct.Aswewill
see,however,inmostchemicalreactionsthereismorethanoneproduct.Ifweareconcernedonlywith
determiningtheidentityoftheproducts,weareengagedinqualitativeanalysiswesimplydetermine
whichsubstancesarepresentinasamplewithoutmeasuringtheiramounts.Bycontrast,inquantitative
analysis,ourgoalistomeasuretheamountsofthevarioussubstancesinasample.

Stoichiometry(fromtheGreekstoicheionmeaningelementandmetreinmeaningmeasuring)is
concernedwiththerelativeamountsofreactantsandproductsinachemicalreaction.Intheequationfor
thereactionofhydrogenandoxygen,thenumber2precedestheformulaeofhydrogenandwater.The
numbersinfrontoftheformulaearecalledstoichiometriccoefficients,andtheyindicatethenumberof
moleculesofeachkindamongthereactantsandproducts.Thus,2H2means2moleculesofH2,and
2H2Omeans2moleculesofH2O.Whennonumberiswritten,thestoichiometriccoefficientis1(sothe
coefficientofO2equals1).Stoichiometriccoefficientscanalsorefertoionsoratoms.

Stoichiometriccoefficientsarerequiredtoensuretheequationconformstothelawofconservationof
mass(section1.2).Becauseatomscannotbecreatedordestroyedinachemicalreaction,wemusthave
thesamenumberofatomsofeachkindpresentbeforeandafterthereaction(i.e.onbothsidesofthe
arrow),asshowninfigure3.1.Thisisanexampleofabalancedchemicalequation.Anotherexample
isshowninfigure3.2:theequationforthereactionofbutane,C4H10,withoxygen,O2.Butanecanbe
usedasthefuelincampingstoves.

FIGURE3.1Thereactionbetween2moleculesofhydrogenand1moleculeofoxygengives2moleculesof
waterasdepictedbythespacefillingmodelsandchemicalequationshownhere.
FIGURE3.2Thechemicalequationforthecombustionofbutane,C4 H10 .Theproductsarecarbondioxide
andwatervapour.

The2beforeC4H10tellsusthat2moleculesofbutaneareinvolvedinthereaction.Thisinvolvesatotal
of8carbonatomsand20hydrogenatoms(seefigure3.3).Noticethatwehavemultipliedthenumbers
ofatomsofCandHin1moleculeofC4H10bythecoefficient2.The13infrontofO2meansthat13
moleculesofO2arerequiredforcompletereactionof2moleculesofC4H10.Ontheright,wefind8
moleculesofCO2,whichcontainatotalof8carbonatoms.Similarly,10watermoleculescontain20
hydrogenatoms.Finally,wecancount26oxygenatomsonbothsidesoftheequation.

FIGURE3.3Understandingcoefficientsinanequation.Theexpression2C4 H10 describes2moleculesof


butane(depictedhereasballandstickmodels),eachofwhichcontains4carbonand10
hydrogenatoms.Thisgivesatotalof8carbonand20hydrogenatoms.

SpecifyingStatesofMatter
Inachemicalequation,itisusefultospecifythephysicalstatesofthereactantsandproducts,i.e.
whethertheyaresolids,liquidsorgases.Thisisdonebywriting(s)forsolid,(l)forliquidor(g)forgas
afterthechemicalformula.Forexample,theequationforthecombustionofcarboninacharcoal
briquettecanbewrittenas:

Attimes,wewillalsofinditusefultoindicatethataparticularsubstanceisdissolvedinwater.Wedo
thisbywriting(aq),meaningaqueoussolution,aftertheformula.Forinstance,thereactionbetween
stomachacid(anaqueoussolutionofHCl)andCaCO3,theactiveingredientinsomeantacids,is:

Thistypeofchemicalequationiscalledamolecularequation.Itshowsallreactantsandproducts,with
molecularsubstanceswrittenasdiscretemoleculesandioniccompoundswrittenintermsoftheir
empiricalformulae(seesection3.4).Ifioniccompoundsareinvolvedwecanalsowritenetionic
equationsthatonlyshowtheionsinvolvedintheactualreaction(seep.97).

PRACTICEEXERCISE3.1
Howmanyatomsofeachelementappearon
eachsideofthearrowinthefollowing
equation?

PRACTICEEXERCISE3.2
Rewritetheequationinpracticeexercise3.1
toshowthatMg(OH)2isasolid,HCland
MgCl2aredissolvedinwater,andH2Oisa
liquid.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.2BalancingChemicalEquations
Wehavelearnedthatachemicalequationisashorthand,quantitativedescriptionofachemicalreaction.
Anequationisbalancedwhentheatomspresentamongthereactantsarealsopresentinthesame
numberamongtheproducts.Aswelearned,stoichiometriccoefficients(thenumbersinfrontof
formulae)aremultipliernumbersfortheirrespectiveformulae,andthevaluesofthecoefficients
determinewhetheranequationisbalanced.

Alwaysapproachthebalancingofanequationasatwostepprocess.
Step1:Writetheunbalancedequation.Organisetheformulaeinthepatternofanequationwith
plussignsandanarrow.
Step2:Adjustthecoefficientssothatthereareequalnumbersofeachkindofatomoneachsideof
thearrow.Applythefollowingguidelinesinsequence:
a.BalanceelementsotherthanHandO.
b.Balanceasagroupthosepolyatomicions(ionsconsistingoftwoormorecovalentlybonded
atomsseechapter2)thatappearunchangedonbothsidesofthearrow.
c.Balanceionssothattheoverallchargeisthesameonbothsidesofthearrow.
d.Balancethosespeciesthatappearontheirown(aselementsorions).
e.BalancethenumberofHandOatomsonbothsides(e.g.byusingH OorOH).
2
Theguidelinesarederivedfromexperience,butarenothardandfastrules.Thesequenceofrulesis
chosensothatthespeciesthataremostdifficulttobalancearehandledfirstandtheeasiestoneslast(H
andOareeasilybalancedinaqueoussolutions).

Whenyoucarryoutstep2,makenochangesintheformulae,eitherintheatomicsymbolsortheir
subscripts.Ifyoudo,theequationwillinvolvedifferentsubstancesfromthoseintended.Itmaystill
balance,buttheequationwillnotbeforthereactionyouwant.

Wewillbeginwithsimpleequationsthatcanbebalancedbyinspection.Anexampleisthereactionof
aluminiummetalwithhydrochloricacid(seefigure3.4).First,weneedthecorrectformulaeandthe
correctphysicalstates.Inthisexample,weusethemolecularequation(seeabove)eventhoughboth
HClandAlCl3existasionsinaqueoussolution.Thereactantsarealuminium,Al(s),andhydrochloric
acid,HCl(aq).Wealsoneedformulaefortheproducts.Thereactionresultsintheformationofaqueous
aluminiumchloride,whichwewriteasAlCl3(aq),andhydrogengas,H2(g).Recallfromthechemical
equationonp.4thathydrogennormallyexistsasdiatomicmoleculesandnotasindividualatoms.
FIGURE3.4Aluminiumandhydrochloricacidreacttoformaluminiumchlorideandhydrogengas.

Step1:Writeanunbalancedequation.

Step2:Adjustthecoefficientstogetequalnumbersofeachkindofatomonbothsidesofthearrow
byapplyingtheguidelinesintheordergivenabove.Usingtheguidelines,wewilllookatClfirstin
ourexample.Becausethereare3Clatomstotherightofthearrowbutonly1totheleft,weputa3
infrontoftheHClontheleftside.Theresultis:

Sincetherearenopolyatomicionsinthisexample,welooknextatspeciesthatappearontheirown
(AlandH2,inthisexample).YoucanseethatAllooksbalanced,butthereare3Hatomsontheleft
andonly2ontheright.Wecanbalancethesebyputtingacoefficientof3infrontofH2andthen
doublingthecoefficientforHCl.

However,Clisnownotbalancedthereare6Clatomsontheleftandonly3ontheright.Therefore,
weneedacoefficientof2infrontofAlCl3.

EverythingisnowbalancedexceptforAlthereis1Alatomontheleftbut2ontheright.Weputa
coefficientof2infrontofAltogive:

Nowthereare2Al,6Hand6Clatomsoneachsideoftheequationandeverythingisbalanced.
Notethattheequation4Al(s)+12HCl(aq)4AlCl3(aq)+6H2(g)isalsobalanced,butitisusualto
writebalancedequationsusingthesmallestwholenumbercoefficients.

WORKEDEXAMPLE3.1

WritingaBalancedEquation
Aqueoussolutionsofcalciumhydroxide,Ca(OH)2,andphosphoricacid,H3PO4,reactto
givecalciumphosphate,Ca3(PO4)2,andwater.Thecalciumphosphateprecipitatesfrom
solution.Writethebalancedequationforthisreaction.

Analysis

First,writeanunbalancedequationthatincludesthereactantformulaeonthelefthandside
andtheproductformulaeontheright.Includethedesignation(aq)forallsubstances
dissolvedinwaterand(l)forH2Oitselfwhenitisinitsliquidstate.Thenadjust
stoichiometriccoefficients(neversubscripts!)untilthereisthesamenumberofeachtypeof
atomontheleftandrightsidesoftheequation.

Solution

Thereareseveralthingsnotinbalance,butourguidelinessuggestthatweworkwithCafirst,
ratherthanwithOandHatoms,orthePO43polyatomicions,whichremainunchangedon
bothsidesoftheequation.Thereare3Caatomsontherightside,soweputa3infrontof
Ca(OH)2ontheleft,asatrial.

NowtheCaatomsareinbalance.ThePO43anionsarenotbalancedthereare2ontheright
sideandonly1ontheleftside.Weputa2infrontofH3PO4asthenextstep.

NotcountingthePO43anions,wehaveontheleft6Oand6Hatomsin3Ca(OH)2plus6H
atomsinH3PO4,foranettotalof6Oand12Hatomsontheleft.Ontheright,inH2O,we
have1Oand2Hatoms.Theratioof6Oto12Hatomsontheleftisequivalenttotheratio
of1Oto2Hatomsontheright,sowewritethemultiplier(coefficient)6infrontofH2O.

Wenowhaveabalancedequation.

Isouranswerreasonable?

Acountofthetotalnumberofatomsoneachsideoftheequationshowsthattheyarethe
same.Oneachsidewehave3Ca,12H,2Pand14Oatoms.Thecoefficientsusedcannot
bereducedtosmallerwholenumbersandsowehaveanequationbalancedwiththesmallest
wholenumbercoefficients.

PRACTICEEXERCISE3.3
Whenaqueoussolutionsofbariumchloride,
BaCl2,andaluminiumsulfate,Al2(SO4)3,are
mixed,areactionoccursinwhichsolid
bariumsulfate,BaSO4,precipitatesfromthe
solution.TheotherproductisAlCl3(aq).
Writethebalancedequationforthisreaction.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.3TheMole
Intheprecedingsections,youhaveseenthatchemicalformulaetellusabouttherelativenumerical
proportionsofatomsinmoleculesorioniccompounds,andthatchemicalequationsareaconvenient
waytosummarisewhathappensinchemicalreactions.Inthisandthefollowingsections,youwill
investigatethequantitativerelationshipsfurtherandfindthatthesearegovernedbytherulesof
stoichiometry.

Inachemicalreaction,therelativeratiosofreactantsresultinginagivenratioofproductsaregivenby
thechemicalequationsthatwelookedatinearliersectionsofthischapter.That,however,isonan
atomicormolecularlevel.Forexample:

tellsyouthat1moleculeofAreactswith2moleculesofBtoform1moleculeofAB2.Supposethatwe
wantedtocarryoutthisreactioninthelaboratory.Giventhatwecannotseeorcountindividualatoms,
ionsormolecules,weneedtoweighoutandworkwithlargerquantities,buthowdoweknowwhat
massesofAandBtouse?Itturnsoutthatsomeoftheinformationweneedtoanswerthisquestionis
giveninthebalancedchemicalequation.

Thinkaboutitthisway.Ifyouneed50000sheetsofwhitephotocopypaperandyouorderthemfroma
papermill,themillwillweighthemoutratherthancountingtheindividualsheets.Thisprocedureis
muchsimplerandquickerandreliesonthefactthatweknowthemassofonesheetofpaper,andthat
everysheetofpaperweighsthesame(atleasttoaverygoodapproximation).Itis,therefore,easyto
calculatetheweightthatcorrespondsto50000sheetsofpaper.Thesameprincipleappliestocounting
largenumbersofcoinsifyouwanttodepositthematabank.

Wecantakeasimilarapproachtocountingions,atomsandmolecules.Everyatomhasacertainmass.
Aswesawinchapter1,themassesofindividualatomscanbemeasuredinatomicmassunits(u),where
1u=1.6605410 24g,exactly ofthemassofa12Catom.Ifwereversethisdefinition,weseethat
6.0221410 23u=1g,so12gof12Ccontainsexactly6.0221410 23atoms.Itisclearthatevena
smallmassofasubstancecontainsaverylargenumberofatoms.Therefore,weuseaquantitycalled
themole.Themole(unitsymbol:mol)istheSIunitofamountofsubstance.Onemoleistheamountof
substancethatcontainsthesamenumberofspecifiedentitiesasthereareatomsinexactly12gof12C.
ThisnumberiscalledtheAvogadroconstant(NA),anditunderpinsallofchemistry.

WewillgenerallyquotetheAvogadroconstanttofoursignificantfigures.Whenwetalkaboutan
amount,wemeananamountofsubstanceinmoles.ThenumericalvalueoftheAvogadroconstantis
almostbeyondcomprehension.Forexample,6.02210 23grainsofsandwouldcoverAustraliaand
NewZealandtoadepthofabout1.3metres.However,becauseatomsaresoincrediblysmall,amoleof
atoms,moleculesorionstakesupcomparativelylittlespace(seefigures3.5and3.6).Onemoleof
anythingcontains6.02210 23entities.Inchemistryterms,theseentitiesareusuallyatoms,ionsor
molecules,butthedefinitionofamoledoesnotrestrictthenatureoftheseentities.Forexample,one
moleofeggswouldcontain6.02210 23eggs.Wecaninfactthinkofthemoleasbeingthechemist's
dozenjustas12eggsconstituteadozen,6.02210 23eggsconstituteamole.Mostimportantly,the
moleconvenientlylinksatomicmassandmacroscopicamountswhateveranythingweighsinatomic
massunits,amoleofitwillweighingrams.
FIGURE3.5Onemoleofdifferentelements(clockwisefromtopleft:sulfur,aluminium,mercuryandcopper).
Eachsampleoftheseelementscontains6.0221023 atoms.

FIGURE3.6Onemoleofdifferentcompounds(clockwisefromtopleft):coppersulfatepentahydrate,water,
sodiumchromateandsodiumchloride.

Itisimportantthatwespecifyexactlywhichparticularspecieswearediscussingwhenweusethemole.
Forexample,thephrase1moleofoxygenisambiguous,becausewehavenotspecifiedwhetherwe
aretalkingabout1moleofoxygenatoms,O,oroxygenmolecules,O2,soitisusualtoincludea
chemicalformulawheneverthemoleisused.

Ofparticularinteresttousinchemistryisthemassof1mole.Wesawinthedefinitionofthemole
abovethat1molof12Cweighs12g,butitstandstoreasonthat1molofeggsisgoingtoweighrather
morethanthis.Therefore,whilethenumberofspecifiedentitiesinamoleisconstant,themassof1
moleofthoseentitiesdependsonthemassoftheindividualentities.Wecallthemassof1molofany
specifiedentitythemolarmass(M).Thisservesasthelinkbetweenmass(m)andamountofsubstance
(n)throughtheequation:

TheSIunitofmolarmassisactuallykgmol1,butthisisrarelyusedinpractice.Molarmassvaluesare
almostalwaysquotedinunitsofgmol1thatis,thenumberofgramspermoleofsubstance.
Inchapter1,weintroducedtheconceptofatomicmass,themassofasingleatomofanelement,which
wemeasuredinatomicmassunits.Themolarmass,whichasthemassof1moleofatomsofan
element,isnumericallyequaltotheatomicmass,buttheunitsdiffer.Valuesofmolarmassforthe
elementsaretabulatedinsidethefrontcoverofthisbook,anditisinformativetolookatsomeofthese.
Notethatthesevaluesrefertoamoleofatomsoftheelements,regardlessofwhethertheelements
themselvesexistinatomicform.Forexample,thetabulatedmolarmassofHis1.00794gmol1even
thoughelementalhydrogenexistsasH2molecules,notHatoms.ThemolarmassofCis12.0107g
mol1,avaluethatmightsurpriseyou,giventhatwestatedpreviouslythat1moleof12Cweighsexactly
12g.Weneedtoappreciatethatthemolarmassofanelementisdeterminedbytheisotopicmakeupof
thatelement.Carbon,forexample,hastwomajornaturallyoccurringisotopes,namely12Cand13C,and
anysampleofcarbonwillcontaintheseisotopesin98.89%and1.11%abundance,respectively.This
meansthatthemolarmassofnaturallyoccurringcarbonisnotexactly12gmol1,butjustalittle
greater,reflectingthesmallamountoftheheavier13Cisotopepresent.Themolarmassesofallelements
withmorethanonenaturallyoccurringisotopereflecttherelativemassandabundanceofeachisotope.

Becausenoelementhasamolarmassexactlyequaltoaninteger(eventhosewithasingleisotope,as
wesawonp.10),forsimplicityofcalculationsinthisbookwewillusuallyusemolarmassestofour
significantfigures.Thereisnoneedtolearnthevaluesofmolarmass(theywillalwaysbeavailable),
butitisimportanttolearnhowtousethem.Theequation:

whichdefinesmolarmass,isoneofthemostimportantinallofchemistry,andwewilluseitoften.With
it,andjustoneotherequation(whichwewillencounterlaterinthischapter),wehaveeverythingwe
needtosolveanystoichiometryproblem.Theapproachtodoingstoichiometryproblemsisdeciding
howtoapplythesetwoequations.

WORKEDEXAMPLE3.2

CalculatinganAmountfromaMass
TheGoldenJubileediamondisthelargestfaceteddiamondintheworld.Ithasamassof
109.13g.Ifthestoneconsistsofpurecarbon,whatamountofCdoesthestonecontain,
giventhatthemolarmassofCis12.01gmol1?

Analysis

Agoodmethodtofollowwhenbeginninganystoichiometryproblemistoasktwoquestions:
Whatvaluedoesthequestionwantmetodetermine?,andWhatdatahaveIbeengiven?.
Writedowntheanswerstothesequestionsandthenlookforanequationthatcontainsas
manyaspossibleofthese.Inthiscase,weareaskedtodetermineanamount(n),andwe
havebeengivenamolarmass(M)andamass(m).Theequationthatcontainsalloftheseis
.

Solution

Werearrange tosolveforn: Hence:


Therefore,thisdiamondcontains9.087molesofcarbon.

Isouranswerreasonable?

Wehave109.13gofcarboninthediamond.Giventhat1moleofChasamassof12.01g,
10moleswouldhaveamassof120.1g.Weshouldthereforeexpectananswerofslightly
fewerthan10moles,whichwehave.Ouranswerthereforeseemsreasonable.

PRACTICEEXERCISE3.4
Whatamountofsulfurmolecules,S8,is
presentin35.6gofsulfur?Themolarmass
ofatomicsulfur,S,is32.06gmol1.

Whensolvingthistypeofproblem,alwayschecktheunitsoftheanswer.Thisisespeciallyimportantif
itisnecessarytorearrangetheequationtosolvetheproblem.Theunitswillalwaysbecorrectifyou
haverearrangedtheequationcorrectly.Inworkedexample3.2,wearedividingmassbymolarmass.
Gramsinthenumerator(thetopline)willcancelgramsinthedenominator(thebottomline),leaving

asourfinalunit.Thisisthesameas ,whichismol,meaningthatourunitsarecorrect.As

wesawonp.28,unitsarealsoverypowerfulinhelpingyoutorememberequations.Theequation
iseasytorememberifyouknowthattheunitsofmolarmassaregmol1:inotherwords,grams
(theunitofmass)dividedbymoles(theunitofamount).Thisthengivesthecorrectformofthe
equation.

WORKEDEXAMPLE3.3

CalculatingaMassfromanAmount
Calciumphosphate,Ca3(PO4)2,isoftenusedtocoatsomeofthesurfacesofboneordental
implantstopermitbonetobondwiththeimplantsurface.Aschematicisshowninfigure3.7.
FIGURE3.7Somesurfacesonboneimplantsarecoatedwithcalciumphosphatetopermitbone
tobondtothesurface.

Ifacoatingprocedurecandeposit0.115molofpureCa3(PO4)2onanimplant,whatisthe
massofthecoating?ThemolarmassofCais40.08gmol1,ofPis30.97gmol1andofOis
16.00gmol1.

Analysis

Weareaskedtocalculateamass(m)andwearegivenanamount(n)andthemolarmasses
(M)ofCa,PandO.Wewillthereforeuse again,butwewillhavetocalculatethe
molarmassofCa3(PO4)2fromtheindividualmolarmassesoftheelementsbeforewecan
substitutethedataintotheequation.

Solution

Wenowrearrange tomakemthesubject:

Substitutionofthedatagives:

Therefore,thecoatingofCa3(PO4)2weighs35.7g.

Isouranswerreasonable?

Thecoatingcontainsalittleover0.1ofamoleofCa3(PO4)2.Since0.1of310gis31g,and
ouranswerof35.7gisslightlymorethan31g,itmakessense.

PRACTICEEXERCISE3.5
Whatmassofsodiumcarbonate,Na2CO3,
correspondsto0.125molofNa2CO3?

PRACTICEEXERCISE3.6
DeterminetheamountofH2SO4ina45.8g
sampleofH2SO4.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.4EmpiricalFormulae
Wheneveranewcompoundisprepared,itisusuallyanalysedtodeterminethemasspercentagesoftheelementsit
contains.Fromthesemasspercentages,itispossibletoobtainanempiricalformulaofthecompound.Theempirical
formulaisthesimplestwholenumberratioofatomswithinthatcompound.Forexample,theempiricalformulaof
butane(chemicalformulaC4H10)isC2H5.Ifweknowtheratiobymassofeachelementwithinacompound,wecan
determineitsempiricalformulausingtherelationship .

ChemicalConnections

CampbellMicroanalyticalLaboratory

Arguablythemostimportantaspectofchemistryisthesynthesisofnewcompounds.Chemistsaroundthe
worldprepareatleastonemillionneverbeforemadecompoundseveryyear,andeveryoneofthesemustbe
characterisedinsomeway.Oneofthefundamentaltechniquesusediselementalanalysis,inwhichthemass
percentagesofelementsinthenewcompoundaredetermined.Aswewillseeinthischapter,masspercentage
dataallowustoobtainanempiricalformulaforthecompoundwecanusethis,incombinationwithavariety
ofothermethods,whichwewillmeetinlaterchapters,todetermineitsstructure.

TheCampbellMicroanalyticalLaboratoryintheDepartmentofChemistryattheUniversityofOtagoisoneof
theveryfewmicroanalyticalservicesavailableinAustralasia.Ithasover50yearsofexpertiseinelemental
analysisandcarriesoutanalysesformanyuniversitiesinNewZealandandAustralia.

RoutineelementalanalysesinvolvedeterminationofthemasspercentagesofC,H,NandSinacompound,
andareoftencarriedoutusinganautomatedelementalanalysersuchastheoneshownintheschematic
diagraminfigure3.8.Thesamplesarecombustedwithoxygenathightemperature(oxidation)inthe
presenceofacatalyst.Theresultinggasesarethenpassedoveracatalystlayerandthroughcoppertoremove
excessO2andtoreducenitrogenoxidestonitrogen(reduction).Thegases,CO2,H2O,SO2andN2,arethen
separatedbyinjectionontoachromatographycolumn,andtheamountofeachismeasuredusingavery
sensitivethermalconductivitydetector.ThesedataarethenconvertedtomasspercentagesofC,H,NandS,
respectively.
FIGURE3.8Diagramofanautomatedelementalanalysissystemforcarbon,hydrogen,nitrogenandsulfur.The
diagramillustratesthecombustionchamber,thechromatographycolumn,athermalconductivity
detector,andasampleofachromatogramwithpeaksforN2 ,CO2 ,H2 OandSO2 .

ElementsotherthanC,H,NorSinasamplemustbeanalysedmanually,andstandardmethodsareavailable
forthese.NotethatOisnotusuallyanalyseddirectly,anditsmasspercentageinanorganiccompoundis
generallyobtainedbysubtractingthetotalmasspercentagesofalltheotherelementsfrom100.

MoleRatiosfromChemicalFormulae
Considerthechemicalformulaforwater,H2O:
1moleculeofwatercontains2Hatomsand1Oatom.
2moleculesofwatercontain4Hatomsand2Oatoms.
1dozenmoleculesofwatercontain2dozenHatomsand1dozenOatoms.
1moleofmoleculesofwatercontains2molesofHatomsand1moleofOatoms.

Whetherwearedealingwithatoms,dozensofatomsormolesofatoms,thechemicalformulatellsusthattheratioof
HatomstoOatomsinH2Oisalways2to1.Forchemicalcompounds,moleratiosarethesameastheratiosofthe
individualatoms.

Thisfactletsuspreparemoletomoleconversionfactorsinvolvingelementsincompoundsasweneedthem.For
example,intheformulaP4O10,thesubscriptsmeanthatthereare4molesofPforevery10molesofOinthis
compound.Wealsoknowthat1moleofP4O10contains4molesofPand10molesofO.

Inthelaboratory,stoichiometryiscommonlyusedtorelatethemassesoftwostartingmaterialsthatareneededto
synthesiseacompoundandtodeterminereactionyields,aswewillseelaterinthischapter.

WORKEDEXAMPLE3.4

CalculatingAmountsofElementsWithinaCompound
Leaveshaveacharacteristicgreencolour(figure3.9)duetothepresenceofthegreenpigmentchlorophyll,
whichhastheformulaC55H72MgN4O5.Aparticularsampleofchlorophyllwasfoundtocontain0.0011g
ofMg.Whatmassofcarbonwaspresentinthesample?(M C=12.01gmol1M Mg=24.31gmol1)

FIGURE3.9Thecharacteristicgreencolourofleavesisimpartedbythepresenceofthepigmentchlorophyll.

Analysis

Weareaskedtocalculateamassofcarbon(mC)andaregivenamassofmagnesium(mMg)andmolar
massesofbothcarbonandmagnesium.Thedatagivenallowustocalculatetheamountofmagnesium(n)
inthesampleusing wethenusethemoleratiobetweenMgandC,whichisimplicitintheformula
ofchlorophyll,todeterminetheamountofCpresent.

Oncewehavethisamount,wethenuse againtoconvertittomass.

SolutionFirst,wecalculatetheamountofMgcorrespondingto0.0011gofMg:

Wenowlookattheformulaofchlorophyll,C55H72MgN4O5,toobtainthemoleratiobetweenMgandC.In
1moleculeofchlorophyll,wehave1atomofMgand55atomsofC.Therefore,in1moleofchlorophyll,
wehave1moleofMgand55molesofC.ThemoleratiobetweenMgandCistherefore1:55,meaning
thatthereis55timestheamountofCasthereisMginchlorophyll.Inthisproblem,wehave4.510 5mol
Mg,soweobtaintheamountofCfrom:

Nowweknowtheamountofcarbon,wecanconvertthistomass:

Therefore,0.030gCwaspresentinthesample.

Isouranswerreasonable?
ThemolarmassofmagnesiumisabouttwicethatofC.Sinceweneed55molCforevery1molMg,the
massofCwerequireshouldbeabout30timesthatofMg.Ouranswerwas0.030gCfor0.0011gMg,so
themassofCwegotisabout30timesthemassofthemagnesiumwestartedwith.Thisseemsreasonable.

PRACTICEEXERCISE3.7
Whatmassofironisina15.0gsampleofFe2O3?

PRACTICEEXERCISE3.8
Whatmassofironisrequiredtoreactwith25.6gof
OtoformFe2O3?Assumethatthereaction
proceedstocompletion.

TheDeterminationofChemicalFormulae
Inresearchlaboratories,chemistsoftensynthesiseentirelynewcompoundsorisolatepreviouslyunknowncompounds
fromplantandanimaltissues.Theymustthendeterminetheformulaandstructureofthecompound.Thisusually
involvesmassspectrometry(seechapter20),whichgivesanexperimentalvalueforthemolarmass.Thecompound
canalsobedecomposedchemicallytofindthemassesofelementswithinagivenamountofcompound,aprocess
calledelementalanalysis(seeChemicalConnectionsonp.78).Letusseehowexperimentalmassmeasurementscan
beusedtodeterminethecompound'sformula.

Theusualformfordescribingtherelativemassesoftheelementsinacompoundisalistofpercentagesbymasscalled
thecompound'smasspercentagecomposition.Ingeneral,apercentagebymassisfoundbyusingthefollowing
equation:

WORKEDEXAMPLE3.5

CalculatingaPercentageCompositionfromChemicalAnalysis
Asampleofaliquidwithamassof8.657gwasfoundtocontain5.217gofcarbon,0.9620gofhydrogen
and2.478gofoxygen.Whatisthepercentagecompositionofthiscompound?

Analysis

Wemustapplythepercentagecompositionequationforeachelement.Themassofwholesamplehereis
8.657g,sowetakeeachelementinturnanddothecalculations.

Solution
Oneoftheusefulthingsaboutapercentagecompositionisthatitallowsustoworkoutthemassofeachof
theelementsin100gofthesubstancewithoutfurthercalculation.Forexample,theresultsinthisproblem
tellusthatin100.00goftheliquidthereis60.26gofcarbon,11.11gofhydrogenand28.62gofoxygen.

Isouranswerreasonable?

Thecheckisthatthepercentagesmustaddupto100%iftheindividualmassesadduptothetotalmass,
allowingforsmalldifferencescausedbyroundingandexperimentalerror.

PRACTICEEXERCISE3.9
From0.5462gofacompound,0.1417gof
nitrogenand0.4045gofoxygenwasisolated.
Whatisthepercentagecompositionofthis
compound?Areanyotherelementspresent?

Elementscancombineinmanydifferentways.Nitrogenandoxygen,forexample,formallofthefollowing
compounds:N2O,NO,NO2,N2O3,N2O4andN2O5.Toidentifyanunknownsampleofacompoundofnitrogenand
oxygen,wecomparethepercentagecompositionfoundbyexperimentwiththecalculatedpercentagesforeach
possibleformula.

WORKEDEXAMPLE3.6

CalculatingaTheoreticalPercentageCompositionfromaChemical
Formula
Arethemasspercentagesof25.92%Nand74.09%OconsistentwiththeformulaN2O5?(M N=14.01g
mol1M O=16.00gmol1)

Analysis

Essentially,weareaskedtocalculatethemasspercentagesofNandOinthecompoundN2O5.Thedatawe
aregivenarethemolarmasses(M)ofNandO.Theonlyequationweknowthatcontainsmolarmassis
sowewillhavetousethisatsomestage.TocalculatethetheoreticalpercentagesbymassofN
andOinN2O5,weneedthemassesofNandOinaspecificsampleofN2O5.Ifwechoose1moleofthe
givencompoundasthesample,calculatingtherestofthedatawillbeeasier.

Solution

Weknowthat1moleofN2O5contains2molesofNand5molesofO.ThecorrespondingmassesofNand
Oarefoundusing asfollows:
Themassof1moleofN2O5will,therefore,bethesumofthemassofNandthemassofOin1moleofthe
moleculethatis,28.02g+80.00g=108.02g.

Wecannowcalculatethepercentagesbymassaswedidinworkedexample3.5:

ThereforetheexperimentaldataareconsistentwiththeformulaN2O5.

Isouranswerreasonable?

Wegetagoodmatchbetweenthecalculatedandexperimentalvalues,whichisalwaysencouraging!In
problemslikethis,youshoulddoublecheckyourcalculationsandmakesurethatthepercentagesofallthe
elementspresentaddupto100%iftheindividualmassesadduptothetotalmass,withinroundingand
experimentalerror.

PRACTICEEXERCISE3.10
CalculatethepercentagecompositionofN2O4.

DeterminationofEmpiricalFormulae
ThecompoundthatformswhenphosphorusburnsinoxygenconsistsofmoleculeswiththeformulaP4O10.Whena
formulagivesthecompositionofonemolecule,itiscalledthemolecularformula.Notice,however,thatboththe
subscripts4and10aredivisibleby2,sothesmallestnumbersthattellustheratioofPtoOis2to5.Asimpler(but
lessinformative)formulathatexpressesthisratioisP2O5.Thisissometimescalledthesimplestformulaforthe
compound.Itisalsocalledtheempiricalformulabecauseitcanbeobtainedfromanexperimentalanalysisofthe
compound.

Toobtainanempiricalformulaexperimentally,weneedtodeterminethemassofeachelementinasampleofthe
compound.Frommass,wethencalculateamount,fromwhichweobtainthemoleratiosoftheelements.Becausethe
ratiobymolesisthesameastheratiobyatoms,wecanconstructtheempiricalformula.

Onlyrarelyisitpossibletoobtainthemassesofeveryelementinacompoundbytheuseofjustoneweighedsample
twoormoreanalysesondifferentsamplesmayberequired.Forexample,supposeananalystisgivenacompound
knowntoconsistexclusivelyofcalcium,chlorineandoxygen.Themassofcalciuminoneweighedsampleandthe
massofchlorineinanothersamplewouldbedeterminedinseparateexperiments.Thenthemassdataforcalciumand
chlorinewouldbeconvertedtopercentagesbymass(equivalenttothemassofeachoftheseelementsinasampleof
100g).Thisallowsthedatafromdifferentsamplestobecompareddirectly.Themasspercentageofoxygenwould
thenbecalculatedbydifferencebecause%Ca+%Cl+%O=100%.Eachmasspercentagecanberelatedtothe
correspondingamountoftheelement.Themoleproportionsareconvertedtowholenumbersaswehavejuststudied,
givingusthesubscriptsfortheempiricalformula.

Therefore,thethreestepsnecessarytodetermineanempiricalformulaare:
1.Assumewearestudying100gofthecompound.Therefore,theindividualmasspercentagescorrespondtothe
actualmassesoftheelementsin100gofthecompound.
2.Converttheratioofelementsbymasstoaratiobyamount,bydividingthemassofeachelementbyitsmolar
mass.
3.Dividetheresultingnumbersbythesmallestone,whichwillgivethesmallestratiooftheelementsinthe
compound.Ifthisgivesanynumbersthatarenotintegers,multiplyallnumbersintheratiobythesmallestfactor
thatwillresultinallnumbersbeingintegers.

WORKEDEXAMPLE3.7

CalculatingAnEmpiricalFormulafromPercentageComposition
Awhitepowderusedinpaints,enamelsandceramicshasthefollowingmasspercentagecomposition:Ba,
69.6%C,6.09%andO,24.3%.Whatisitsempiricalformula?(M Ba =137.3gmol1M C=12.01gmol
1M 1)
O=16.00gmol

Analysis

Weareaskedtocalculateanempiricalformula,andwearegivenmasspercentagecompositionsandmolar
mass(M)values.Wecanconvertmasspercentagetomass(m)simplybychoosing100gofcompoundto
study.WecanthencalculateamountsofBa,CandObyusing ,andusethesetoobtainthe
necessarymoleratiosfortheempiricalformula.

Solution

A100gsampleofthecompoundwillcontain69.6gBa,6.09gCand24.3gO.Wefirstrelatethese
massestoamounts:

OurratioofBa:C:Oistherefore0.507:0.507:1.52.However,chemicalformulaecontainwhole
numbers,sowedivideeachamountbythesmallestamount.Theratiothenbecomes:

Therefore,ourmoleratiois1Ba:1C:3O,andtheempiricalformulaisBaCO3.

Isouranswerreasonable?

Iftheformulaiscorrect,thereare3molesofoxygenforevery1moleofcarboninthecompound.So,for
every1mole(12g)ofcarboninthecompound,thereshouldbe3moles(48g)ofoxygen.Thecarbonto
oxygenmassratiois12:48,or1:4.Thisisconsistentwiththeratioofcarbonandoxygenpercentages
(6.09:24.31:4).

PRACTICEEXERCISE3.11
Awhitesolidusedtowhitenpaperhasthe
followingmasspercentagecomposition:Na,32.4%
S,22.6%.Therestofthemassisoxygen.Whatis
theempiricalformulaofthecompound?
Inpractice,acompoundisseldombrokendowncompletelytoitselementsinaquantitativeanalysis.Instead,the
compoundischangedintoothercompounds.Thereactionsseparatetheelementsbycapturingeachoneentirely
(quantitatively)inaseparatecompoundwithaknownformula.

Inthefollowingexample,weillustrateanindirectanalysisofacompoundmadeentirelyofcarbon,hydrogenand
oxygen.Suchcompoundsburncompletelyinpureoxygenthereactioniscalledcombustionandthesole
productsarecarbondioxideandwatervapour.Thecompletecombustionofethanol,CH3CH2OH,forexample,occurs
accordingtothefollowingequation.

Thecarbondioxideandwatercanbeseparatedandthentheirmassesdetermined.Noticethatallofthecarbonatoms
intheoriginalcompoundendupamongtheCO2moleculesandallofthehydrogenatomsareinH2Omolecules.In
thiswayatleasttwooftheoriginalelements,CandH,areentirelyseparated.

ModernmicroanalyticaltechniquesallowthesimultaneousdeterminationofC,H,NandS,asdescribedinChemical
Connectionsonp.78.Initialcombustionofthesampleandsubsequentpassageoftheresultinggasmixtureovera
catalystresultsintheconversionofallCinthesampletoCO2,alltheHtoH2O,alltheNtoN2andalltheStoS2.The
massofeachgas,andhencethemassofeachelement(C,H,NandS),isthendetermined.Weconvertthemassesof
theelementsintopercentagesoftheelementbymassinthecompound.Wethenaddupthepercentagesandsubtract
from100togetthepercentageofO.Wethencalculatetheempiricalformulafromthepercentagecompositionas
describedearlier.

Theempiricalformulaisallthatweneedforioniccompounds.Formolecularcompounds,however,chemistsprefer
molecularformulaebecausetheygivethenumberofatomsofeachtypeinamolecule,ratherthanjusttheratioofthe
elementsinacompound,astheempiricalformuladoes.

Sometimesanempiricalformulaandamolecularformulaarethesame.TwoexamplesareH2OandNH3.Moreoften,
however,thesubscriptsofamolecularformulaarewholenumbermultiplesofthoseintheempiricalformula.The
subscriptsofthemolecularformulaP4O10,forexample,areeachtwotimesthoseintheempiricalformula,P2O5,aswe
sawearlier.ThemolarmassofP4O10islikewisetwotimesthemolarmassofP2O5.Thisobservationhelpsusfindthe
molecularformulaforacompound,providedwehaveawayofexperimentallydeterminingthemolarmassofthe
compound.Iftheexperimentalmolarmassequalsthecalculatedmassofanempiricalformula,theempiricalformula
itselfisalsoamolecularformula.Otherwise,theexperimentalmolarmasswillbesomewholenumbermultipleofthe
valuecalculatedfromtheempiricalformula.Whateverthewholenumberis,itisacommonmultiplierforthe
subscriptsoftheempiricalformula.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.5Stoichiometry,LimitingReagentsandPercentageYield
Sofarwehavefocusedonrelationshipsbetweenelementswithinasinglecompound.Wehaveseenthatthecriticallinkbetween
amountsofelementswithinacompoundisthemoletomoleratioobtainedfromtheformulaofthecompound.Inthissection,wewill
seethatthesametechniquescanbeusedtorelateamountsofsubstancesinvolvedinachemicalreaction.Thecriticallinkbetween
amountsofsubstancesinvolvedinareactionisamoletomoleratioobtainedfromthechemicalequationthatdescribesthereaction.

Toseehowachemicalequationcanbeusedtoobtainmoletomolerelationships,considertheequationthatdescribestheburningof
octane,C8H18,inoxygen,O2,togivecarbondioxideandwatervapour:

Thisequationcanbeinterpretedonamolecularscaleasfollows:forevery2moleculesofliquidoctanethatreactwith25moleculesof
oxygengas,16moleculesofcarbondioxidegasand18moleculesofwatervapourareproduced.

Wecanalsointerprettheequationonamolarscaleasfollows2molesofliquidoctanereactwith25molesofoxygengastoproduce
16molesofcarbondioxidegasand18molesofwatervapour.

Tousetheserelationshipsinastoichiometryproblem,theequationmustbebalanced.Wemustalwayschecktoseewhetherthisisso
foragivenequationbeforewecanusethecoefficientsintheequationtocalculatestoichiometricratios.

First,letusseehowmoletomolerelationshipsobtainedfromachemicalequationcanbeusedtorelatetheamountofonesubstance
totheamountofanotherwhenbothsubstancesareinvolvedinachemicalreaction.

WORKEDEXAMPLE3.8

StoichiometryofChemicalReactions
Whatamountofsodiumphosphate,Na3PO4,canbemadefrom0.240molofNaOHbythefollowingreaction?

Analysis

Weuseasimilarapproachtothatusedinworkedexample3.4but,inthiscase,werequirethemoleratiobetweendifferent
compounds.Weobtainthismoleratiodirectlyfromthestoichiometryofthebalancedchemicalequation.

Solution

Wecanseefromthestoichiometriccoefficientsthat3molesofNaOHwillreacttogive1moleofNa3PO4.Therefore,ifwe
startwith0.240molNaOH,wewillobtain:

Isouranswerreasonable?

Therearereallyonlytwopossibleanswerswecouldgettothisproblemthecorrectone(0.0800mol)andtheincorrect
one(0.720mol),whichwouldbeobtainedbymultiplyingratherthandividingby3.Lookingatthebalancedchemical
equation,wecanseethattheamountofNa3PO4producedislessthantheoriginalamountofNaOH.Inthiscase,our
answershouldbelessthan0.240mol,anditis.

PRACTICEEXERCISE3.12
Whatamountofsulfuricacid,H2SO4,isneededtoreact
completelywith0.366molofNaOHaccordingtothe
followingreaction?

PRACTICEEXERCISE3.13
If0.575molofCO2isproducedbythecombustionof
propane,C3H8,whatamountofoxygenisconsumed?The
balancedchemicalequationisasfollows:

MoleRatiosinChemicalReactions
Weoftenneedtorelatemassofonesubstancetomassofanotherinachemicalreaction.Consider,forexample,thereactionof
glucose,C6H12O6,oneofthebody'sprimaryenergysourceswithoxygen.Thebodycombinesglucoseandoxygentogivecarbon
dioxideandwater.Thebalancedequationfortheoverallreactionis:

Whatmassofoxygenmustthebodytakeintocompletelyprocess1.00gofglucose(thatis,1.00gC6H12O6)?

Thefirstthingweshouldnoticeaboutthisproblemisthatwearerelatingamountsoftwodifferentsubstancesinareaction.Thelink
betweentheamountsofsubstancesisthemoletomolerelationshipbetweenglucoseandO2givenbythechemicalequation.Inthis
case,theequationtellsusthat1moleofC6H12O6willreactcompletelywith6molesofO2.

Ifweinsertthemoletomoleconversionbetweenourstartingpoint(1.00gC6H12O6)andthedesiredquantity(gO2),wecutthe
problemintothreesimplesteps:

WeobtaintheamountofC6H12O6fromthemassofC6H12O6usingthemolarmassofC6H12O6.Wethenobtaintheamountof
C6H12O6fromtheamountofO2,usingthestoichiometryofthebalancedequation.Finally,weobtainthemassofO2fromtheamount
ofO2usingthemolarmassofO2.Ifwehavecarriedoutthesemanipulationscorrectly,theanswershouldbe1.07gO2.

Oneofthemostcommonmistakesmadeinstoichiometryproblemslikethisistheincorrectdeterminationanduseofthemoleratios
forsubstancesinthereaction.

Considerthegeneralchemicalreaction:

whereA,B,CandDarereactantsandproductsinthereaction,anda,b,canddarethestoichiometriccoefficientsofeach.Forthis
reaction,thefollowingalwaysholds:

Applyingthistotheexampleabove,wefindthat:

and,ifwelimitourselvestothemoleratiobetweenglucoseandoxygen,wefind:

Havingcalculatedtheamountofglucose,weknowfromthepreviousequationthatthisisequalton O2/6.Wethenrearrangethis
equationtomaken O2thesubject:

andwefindthatwemustmultiply by6toobtainouranswer.

WORKEDEXAMPLE3.9

StoichiometricMassCalculations
Metallicironcanbemadebythethermitereaction,thespectacularreactionofaluminiumwithironoxide,Fe2O3.Somuch
heatisgeneratedthattheironformsintheliquidstate.Theequationis:

Assumethatyouneedtoproduce86.0gofFeinaweldingoperation.

WhatmassofbothFe2O3andaluminiummustbeusedforthisoperation,assumingalltheFe2O3isconvertedtoFe?(M Fe =
55.85gmol1M O=16.00gmol1M Al=26.98gmol1)
Analysis

WeareaskedtofindthemassesofAlandFe2O3requiredtoprepare86.0gofFe.WearegivenamassofFe(m)andthe
molarmassofFe(M)sowecancalculatetheamountofFe(n)using .Wethenusethemoleratiosinthebalanced
chemicalequationtocalculatetheamountsofAlandFe2O3.Thefinalstepistouse toobtainthemassesfrom
theseamounts.

Insummary:

Solution

Firstly,wecalculatetheamountofFein86.0g:

Usingthestoichiometriccoefficientsfromthebalancedchemicalequation,wecanseethat:

Therefore,theformationof2molesofFerequires2molesofAland1moleofFe2O3.Inotherwords,wewillrequirethe
sameamountofAl,buthalftheamountofFe2O3.Therefore:

Thus,n Al=n Fe .Wethenuse toobtainthemassesfromtheseamounts:

Isouranswerreasonable?

AstheformationofFefromFe2O3involveslossofoxygenfromFe2O3,wewouldexpectthemassofFe2O3requiredtobe
greaterthanthemassofFeproduced.Giventhat2molesofAlgive2molesofFe,wewouldexpectthemassofAl
requiredtobelessthanthemassofFeproduced(86.0g),asthemolarmassofAlislessthanthatofFe.Hence,our
answersappearreasonable.

PRACTICEEXERCISE3.14
Whatmassofaluminiumoxideisalsoproducedwhen86.0
gofFeisformedbythereactiondescribedinworked
example3.9?

LimitingReagents
Wehaveseenthatbalancedchemicalequationscantellushowtomixreactantstogetherinjusttherightproportionstogetacertain
amountofproduct.Forexample,ethanol,CH3CH2OH,ispreparedindustriallyasfollows:

Theequationtellsusthat1moleofethenewillreactwith1moleofwatertogive1moleofethanol.Wecanalsointerprettheequation
onamolecularleveleverymoleculeofethenethatreactsrequires1moleculeofwatertoproduce1moleculeofethanol:
Ifwehave3moleculesofethenereactingwith3moleculesofwater,3ethanolmoleculesareproduced:

Whathappensifwemix3moleculesofethenewith5moleculesofwater?Theethenewillbecompletelyusedupbeforeallthewater,
andtheproductmixturewillcontain2unreactedwatermolecules,asshownbelow.

Thissituationcanbeaprobleminthemanufactureofchemicalsbecausewewasteoneofourreactants(water,inthiscase)andalso
obtainaproductthatiscontaminatedwithunusedreactant.Conversely,thiscanbeusedtoadvantageinsituationswhereoneofthe
reactantsischeapandeasilyrecoverable.Aswewillseeinchapter9,wecansometimesforcereactionstofavourtheformationof
productsbyaddinganexcessofoneofthereactants.AnexampleofthisisthepreparationofmargarinefromthereactionofH2with
animalorvegetableoilsuseofexcessH2makestheoilthelimitingreagentandensurescompleteconversionoftheoilto
margarine,andtheexcessH2canbeeasilyrecoveredandreused.

Inthereactionmixtureatthebottomofthepreviouspage,etheneiscalledthelimitingreagentbecauseitlimitstheamountofproduct
(ethanol)thatcanform.Wateriscalledanexcessreagentbecausewehavemoreofitthanisneededtocompletelyconsumeallthe
ethene.

Topredicttheamountofproductwemaytheoreticallyobtaininareaction,weneedtoknowwhichofthereactantsisthelimiting
reagent.Inthepreviousexample,wesawthatweneededonlythreeH2OmoleculestoreactwiththreeC2H4moleculeswehadfive
H2Omolecules,soH2OispresentinexcessandC2H4isthelimitingreagent.
Oncewehaveidentifiedthelimitingreagent,itispossibletocalculatetheamountofproductthatmightformandtheamountofexcess
reagentthatwouldbeleftover.

WORKEDEXAMPLE3.10

LimitingReagent
Gold(III)hydroxide,Au(OH)3,isusedforelectroplatinggoldontoothermetals.Itcanbemadebythefollowingreaction:

ToprepareafreshsupplyofAu(OH)3,achemistatanelectroplatingplantmixed20.00gofKAuCl4with25.00gof
Na2CO3(bothdissolvedinalargeexcessofwater).

WhatisthemaximummassofAu(OH)3thatcanform?(
)

Analysis

WeareaskedtodeterminethemaximummassofAu(OH)3thatcanbeformed.Wearegivenmasses(m)ofbothKAuCl4
andNa2CO3andtheirmolarmasses(M).ThisallowsustocalculatetheamountsofbothKAuCl4andNa2CO3using
.Wethenhavetousetheratiosofamountstostoichiometriccoefficientsinthebalancedchemicalequationto
determineifeitherKAuCl4orNa2CO3ispresentinexcess.Theothersubstancewouldthenbethelimitingreagent.

Solution

BeginbycalculatingtheamountsofKAuCl4andNa2CO3using :

Weknow,fromthestoichiometryofthereaction,that2molesofKAuCl4require3molesofNa2CO3forcompletereaction.
Inotherwords:

Ifwefindthatthisisthecase,thenthereactantsarepresentinexactlythecorrectstoichiometricamounts.Iftheratiosare
unequal,thesmallernumberindicatesthelimitingreagent.Intheexperiment,weuse:

ThismeansthatwehavetoomuchNa2CO3,soKAuCl4isthelimitingreagent.TheamountofKAuCl4nowdeterminesthe
amountofAu(OH)3thatcanbeformed.TocalculatehowmuchAu(OH)3willbeformed,weagainusethestoichiometric
coefficientsfromthebalancedchemicalequation.Weseethat2molesofKAuCl4willform2molesofAu(OH)3so:

ConvertingthisamountofAu(OH)3tomassgives:

Therefore,usingthereactionconditionsgiven,weobtainamaximumof13.13gofAu(OH)3.

Isouranswerreasonable?

Themainthingincalculationsofthistypeistogetthemoleratioscorrectand,indeed,tointerpretthemcorrectly.Wecan
seethatthemolarmassofKAuCl4ismorethanthreetimesthatofNa2CO3.SinceweareusingalargermassofNa2CO3in
thereaction,wewillhaveasignificantlylargeramountofNa2CO3thanKAuCl4,andourcalculationsbearthisout.The
molarmassofAu(OH)3isabouttwothirdsthatofKAuCl4and,giventhattheirmoleratiointhebalancedchemical
equationis1:1,wewouldexpectthemassofAu(OH)3tobeabouttwothirdstheinitialmassofKAuCl4,whichitis.The
answerisreasonable.

PRACTICEEXERCISE3.15
Inanindustrialprocessforproducingnitricacid,thefirst
stepisthereactionofammoniawithoxygenathigh
temperatureinthepresenceofaplatinumgauzetoform
nitrogenmonoxideasfollows:

Whatisthemaximummassofnitrogenmonoxidethatcan
formfromaninitialmixtureof30.00gofNH3and40.00g
ofO2?

PercentageYield
Inmostchemicalsyntheses,theamountofaproductactuallyisolatedfallsshortofthecalculatedmaximumamount.Lossesoccurfor
severalreasons.Somearemechanical,suchasmaterialsstickingtoglassware.Insomereactions,lossesoccurbytheevaporationofa
volatileproduct.Inothers,asolidproductseparatesfromthesolutionasitformsbecauseitislargelyinsoluble.Thesolidisremoved
byfiltration.Whatstaysinsolution,althoughrelativelysmall,contributestosomelossofproduct.

Oneofthecommoncausesofobtaininglessthanthestoichiometricamountofaproductistheoccurrenceofareactionorreactions
thatcompetewiththemainreaction.Acompetingreactionproducesabyproduct,i.e.asubstanceotherthantheproductthatwe
wanttoobtain.(Note:Asecondproductofthemainreactionisalsocalledabyproducthowever,itdoesnotreducetheyield.)The
synthesisofphosphorustrichloridefromPandCl2,forexample,givessomephosphoruspentachlorideaswell,becausePCl3canreact
furtherwithCl2.

ThecompetitionisbetweennewlyformedPCl3andunreactedphosphorusforchlorine.Anothercauseoflowerthantheoreticalyields
isareversiblereaction,wheretheforwardandbackwardreactionsoccurconcurrently.

Thetheoreticalyieldofaproductiswhatwouldbeobtainedifthemaximumamountofproductwasformedandnolossesoccurred.
Itiscalculatedbasedonthebalancedchemicalequationandtheamountsofthereactantsavailable.Theactualyieldoftheproductis
simplyhowmuchhasbeenisolatedinpractice.Chemistscalculatethepercentageyieldofproducttodescribehowsuccessfulthe
preparationwas.Thepercentageyieldistheactualyieldcalculatedasapercentageofthetheoreticalyield:

Boththeactualandtheoreticalyieldsmust,ofcourse,beinthesameunits.

Itisimportanttorealisethattheactualyieldisanexperimentallydetermined(ratherthancalculated)quantity.Thetheoreticalyieldis
alwaysacalculatedquantitybasedonachemicalequationandtheamountsofthereactantsavailable.

WORKEDEXAMPLE3.11

CalculatingaPercentageYield
Achemistsetupasynthesisofphosphorustrichloride,PCl3,bymixing12.0gofPwith35.0gofCl2andobtained42.4g
ofPCl3.Theequationforthereactionis:

Calculatethepercentageyieldofthiscompound.( )
Analysis

Weareaskedtocalculateapercentageyield.Wearegivenmassesofallthreecomponentsinthereactionandtheirmolar
masses(M).Thismeanswecancalculatetheamountsofallthreeusing .Tocalculatethepercentageyield,wemust
firstdecideonwhichreactanttobaseourcalculations.Wemustcalculatetheamountsofeachbeforewecanmakethat
decision.Ifwefindthatoneofthereactantsisalimitingreagent,thepercentageyieldisbasedonthatreactant.Tocalculate
thepercentageyield,wemustfirstcalculatethetheoreticalyield:inotherwords,howmuchproductwouldhavebeen
formedifthereactionwenttocompletion.Wedoallofthisusing andthestoichiometryofthebalancedchemical
equation.

Solution

WebeginbycalculatingtheamountsofbothPandCl2used.

Fromthebalancedchemicalequation,weknowthatPreactswithCl2inthemoleratio2:3.Therefore,forcomplete
reaction,theoretically:

Theexperimentalratiosare0.494mol/3=0.165forCl2and0.387mol/2=0.194forP.Thismeansthatwedonothave
sufficientCl2toreactwithallthePpresent,soCl2isthelimitingreagent.Wenowbaseoursubsequentcalculationsonthis.
Fromthebalancedchemicalequation,weknowthat:

Therefore,0.165mol ,so .Convertingthistomass,weobtain:

Theactualmassobtainedwas42.4g,sothepercentageyieldisgivenby:

Isouranswerreasonable?

Theobviouscheckisthattheactualyieldcanneverbemorethanthetheoreticalyield.So,onthisscore,ouransweris
reasonable.Again,themostcommonplacewhereerrorsaremadeisintheuseofthemoleratios.Inthisexample,wemust
endupwithfewermolesofrPCl3thanCl2,sowemustmultiplyn Cl2by ,not .Weappeartohavedonethecalculations
correctly,sotheanswerisreasonable.

PRACTICEEXERCISE3.16
Ethanol,CH3CH2OH,canbeconvertedtoaceticacid(theacidinvinegar),CH3COOH,bytheactionofsodiumdichromate,
Na2Cr2O7,inaqueoussulfuricacidaccordingtothefollowingequation:

Inoneexperiment,24.0gofCH3CH2OH,90.0gofNa2Cr2O7andaknownexcessofsulfuricacidwasmixed,and26.6gof
aceticacidwasisolated.CalculatethepercentageyieldofCH3COOH.

Anotherwaytolookattheyieldofareactionistotakeintoaccountthesocalledatomefficiency.Bythiswemeanthatthereisa
differencebetweenareactionwheremostoftheatomsofthestartingmaterial(s)endupformingthedesiredproductandareaction
wherealargefractionoftheatomsinthestartingmaterialendupasunwantedbyproducts.Thereclearlyisatradeoffbetweenthe
percentageyieldofareactionandtheatomefficiency.Concernsaboutpollutionandcostcertainlyfavourreactions(atleastonthe
industrialscale)thatproducetheleastamountofwastematerial.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
3.6SolutionStoichiometry
Chemicalreactionsaremostoftencarriedoutinsolutionbecausethisallowsintimatemixingofthereactants,whichleadstomorerapidreaction.Asolution
isahomogeneousmixtureinwhichtheatoms,moleculesorionsofthecomponentsfreelyintermingle(seefigure3.10).Whenasolutionforms,atleasttwo
substancesareinvolved.Oneiscalledthesolventandalloftheothersarecalledsolutes.Thesolventisusuallytakentobethecomponentpresentinlargest
amountandisthemediumintowhichthesolutesaremixedordissolved.Liquidwaterisatypicalandverycommonsolvent,butthesolventcanactuallybe
inanyphysicalstatesolid,liquid,orgas.Unlessstatedotherwise,wewillassumethatanysolutionswementionareaqueoussolutions,sothatliquid
waterisunderstoodtobethesolvent.

FIGURE3.10Inthephotoontheleft,acrystalofiodine,I2 ,thatwasaddedtoabeakercontainingethanolstarteddissolvingonitswaytothebottomofthebeaker,the
purplishiodinecrystalformingareddishbrownsolution.Thephotoontherightshowshowafterstirringthemixturewithaspatulathesolutiontakesona
homogeneousreddishbrowncolour,duetotheiodinemoleculesdissolvedinthesolventasindicatedintheschematicbelowthepicture.Calledtinctureof
iodine,suchsolutionswereoncewidelyusedasantiseptics.

Asoluteisanysubstancedissolvedinthesolvent.Itmightbeagas,likethecarbondioxidedissolvedincarbonateddrinks.Somesolutesareliquids,like
theethyleneglycoldissolvedinwatertostopitfromfreezinginacar'sradiator.Solids,ofcourse,canbesolutes,likethesugardissolvedinlemonadeorthe
saltdissolvedinseawater.

TheConcentrationofSolutions
Weusetheconcentrationofasolutiontodescribeitscomposition.Theconcentrationisdefinedastheamountofsolutedissolvedinaparticularvolumeof
solution.TheconcentrationofasubstanceXisoftenrepresentedas[X].Whentheamountisgiveninmolesandthevolumeinlitres,itiscalledthemolarity
ormolarconcentrationandhastheunitsmolL1(oftenabbreviatedm,nottobeconfusedwiththeabbreviationformolarmass,M).Theequationthat
definesconcentration(c)is:

Westatedearlierthattherewereonlytwoequationsneededtosolveanystoichiometricproblem. wasthefirst,andthisisthesecond.Again,we
mustcommitthistomemory,butitiseasytorememberwhenweconsidertheunitsofconcentrationmolL1impliesamountdividedbyvolume(inL).

Thus,a1.00Lsolutionthatcontains0.100molofNaClhasamolarityof0.100M,andwewouldrefertothissolutionas0.100molarNaCloras0.100M
NaCl.A0.100Lsolutioncontaining0.0100molofNaClwouldhavethesameconcentrationbecausetheratioofamountofsolutetovolumeofsolutionis
thesame.

Concentrationisparticularlyusefulbecauseitletsusobtainagivenamountofasubstancesimplybymeasuringavolumeofapreviouslypreparedsolution,
andthismeasurementisquickandeasytodointhelaboratory.Ifwehadastocksupplyof0.100MNaClsolution,forexample,andweneeded0.100mol
ofNaClforareaction,wewouldsimplymeasureout1.00Lofthesolutionbecausethereis0.100molofNaClinthisvolume.

Weneednot(andseldomdo)workwithwholelitresofsolutions.Itistheratiooftheamountofsolutetothevolumeofsolution,notthetotalvolume,that
matters.Suppose,forexample,thatwedissolved0.0200molofsodiumchromate,Na2CrO4,insufficientsolventtogiveafinalvolumeof0.250L.The
concentrationofthesolutionwouldbefoundby:

Suchasolutioncanbeaccuratelypreparedinavolumetricflask,whichisanarrowneckedcontainerwithanetchedmarkhighonitsneck.Whenfilledup
tothemark,theflaskcontainsthevolumegivenbytheflask'slabel.Figure3.11showshowtousea250mLvolumetricflasktoprepareasolutionof
knownconcentration.

FIGURE3.11 Thepreparationofasolutionofknownmolarity:
(a)A250mLvolumetricflask,oneofanumberofsizesavailableforpreparingsolutions.Whenfilledtothelineetchedarounditsneck,thisflask
containsexactly250mLofsolution.Theflaskherealreadycontainsaweighedamountofsolute.
(b)Waterisbeingadded.
(c)Thesoluteisbroughtcompletelyintosolutionbeforethelevelisbroughtuptothenarrowneckoftheflask.
(d)Morewaterisaddedtobringthelevelofthesolutiontotheetchedlineoruptothemark.
(e)Theflaskisstopperedandtheninvertedmanytimestomixitscontentsthoroughly.

Wheneverwehavetodealwithaproblemthatinvolvesanamountofachemicalandavolumeofasolutionofthatsubstance,wewillusetheequation
.

WORKEDEXAMPLE3.12

CalculatingtheConcentrationofaSolution
AstudentpreparedasolutionofNaClbydissolving1.461gofNaClinwaterandmakinguptothefinalvolumeof250.0mLinavolumetric
flasktostudytheeffectofdissolvedsaltontherustingofanironsample.Whatistheconcentrationofthissolution?

Solution

Firstly,weconvertthemassofNaCltoamountusing:

Wethensubstitutethedatainto andsolveforc:

Therefore,theconcentrationoftheNaClsolutionis1.00010 1molL1.

Isouranswerreasonable?

A1molL1solutionofNaClwouldcontain58.44gofNaClin1litre,soa0.1molL1solutionwouldcontainabout6gin1L.Wehave0.25L,
sowewouldexpectabout(0.256g)=1.5gin0.25L,whichisroughlywhatwehave.Theansweriscertainlyreasonable.Aneasymistaketo
makeinproblemsofthistypeistoforgettoconvertmLtoL.RememberthattheunitsofconcentrationmustalwayscomeoutasmolL1so,if
thesolutionvolumeisgiveninmL,wemustdivideby1000toconverttoL.

PRACTICEEXERCISE3.17
AspartofastudytodetermineifjustthechlorideioninNaCl
acceleratestherustingofiron,astudentdecidedtoseeifironrustedas
rapidlywhenexposedtoasolutionofNa2SO4.Thissolutionwasmade
bydissolving3.550gofNa2SO4inwaterandmakingupthefinal
volumeto100.0mLinavolumetricflask.Whatistheconcentrationof
thissolution?

Noticethatworkedexample3.12usesboth and .Aswehavestressed,withthesetwoequations,thereisnostoichiometricproblemwe


cannotsolve!

Inthelaboratory,weoftenmustprepareasolutionwithaspecificconcentration.Usually,weselectthevolumeofsolutionthatwewillmakeandthen
calculatehowmuchsolutemustbeused.Dependingontheaccuracythatyourequirefortheconcentration,youwillneedtouseabalancethatallowsyou
toweighyoursampletotherequirednumberofsignificantfigures.Figure3.12showsarangeofbalancesandglasswareusedinthepreparationofsolutions
ofknownconcentration.Workedexample3.13illustratesthekindofcalculationrequiredandalsodemonstratesthefollowingusefulrelationship:whenever
weknowboththevolumeandtheconcentrationofasolution,wecancalculatetheamountofsolutefrom .

FIGURE3.12 (a)Glasswarethatcanbeusedformeasuringvolumestodifferentaccuraciesand
(b)ananalyticalbalancethatcanbereadto1107 g.

WORKEDEXAMPLE3.13

PreparingaSolutionofKnownConcentration
Strontiumnitrate,Sr(NO3)2,isusedinfireworkstoproducebrilliantredcolourslikethoseshowninfigure3.13.Whatmassofstrontiumnitrate
wouldachemistneedtoprepare250.0mLofa0.100MSr(NO3)2solution?

FIGURE3.13Theredcolourinsomefireworksisaresultofthepresenceofstrontiumnitrate,Sr(NO3 )2 .

Analysis

Weareaskedtocalculateamass(m)ofstrontiumnitrateandwearegiventhevolume(V)andconcentration(c)ofastrontiumnitratesolution,as
wellasthemolarmass(M)ofstrontiumnitrate.Theconcentrationandvolumewillallowustocalculatetheamount(n)ofstrontiumnitrateusing
,andwecanthenusethisamountintheequation tocalculatethemassofstrontiumnitrate.

Solution

Werearrange tosolveforn:
Wecannowuse toobtainthemass:

Therefore,thechemistwouldrequire5.29gofSr(NO3)2topreparethesolution.

Isouranswerreasonable?

In1litreof0.100MSr(NO3)2,therewouldbe0.1molofSr(NO3)2,about20g.Therefore,in0.25Lofthissolution,wewouldhaveroughly
(0.2520g)=5g.Theanswer,5.29g,isclosetothis,soitmakessense.

PRACTICEEXERCISE3.18
WhatmassofAgNO3isneededtoprepare250mLof0.0125M
AgNO3solution?

DilutingaSolution
Itisnotalwaysnecessarytobeginwithasoluteinpureformtoprepareasolutionwithaknownconcentration.Thesolutecanalreadybedissolvedina
solutionofrelativelyhighconcentration,oftencalledthestocksolution,andthiscanbedilutedwiththesamepuresolventtomakeasolutionofthedesired
lowerconcentration.Dilutionisaccomplishedbyaddingmoresolventtothesolution,whichcausestheconcentration(theamountperunitvolume)to
decrease(figure3.14).Thechoiceofapparatususeddependsontheprecisionrequired.Ifhighprecisionisnecessary,pipettesandvolumetricflasksare
used(figure3.12a).Ifwecandowithlessprecision,wemightusegraduatedcylindersinstead.Workedexample3.14showshowwecanuse to
calculatethefinalconcentrationofadilutedsolution.

FIGURE3.14Dilutingasolution.Whensolventisaddedtoasolution,thesoluteparticlesbecomemorespreadoutandthesolutionbecomesmoredilute.The
concentrationofthesoluteinthesolutionbecomeslower,whilethetotalamountofsoluteremainsconstant.

WORKEDEXAMPLE3.14

PreparingaSolutionofKnownConcentrationbyDilution
Howcouldweprepare100.0mLof0.0400MK2Cr2O7fromasolutionof0.200MK2Cr2O7?

Analysis

Weareaskedhowtodiluteaconcentratedsolutiontogiveasolutionofaparticularconcentration.Weknowboththevolume(V)andthe
concentration(c)ofthefinalsolution,souseof willallowustocalculatenfromthesedata.Asweknowtheconcentrationoftheinitial
solution,andwehavecalculatedtherequiredn, willallowustocalculateV,thevolumeoftheinitialsolutionrequired.

Solution

Wearegoingtouse twice,tocalculatetwodifferentthings.Firstly,wecalculate inourfinalsolution:

ThisistheamountofK2Cr2O7that,whendissolvedin100.0mL,willgiveaconcentrationof0.0400M.Wenowturnourattentiontotheinitial
solutionandusethiscalculatedamount,inconjunctionwiththeconcentration,tocalculateV,thevolumeoftheinitialsolutionrequired.
Therefore,wetake20.0mLoftheoriginalsolution,pouritintoa100.0mLvolumetricflaskandmakeituptothemarkwithwatertogeta0.0400
MsolutionofK2Cr2O7(figure3.15).

FIGURE3.15 Preparingasolutionbydilution:
(a)Thecalculatedvolumeofthemoreconcentratedsolutioniswithdrawnfromthestocksolutionbymeansofavolumetricpipette.
(b)Thesolutionisallowedtodrainentirelyfromthepipetteintothevolumetricflask.
(c)Waterisaddedtotheflask,thecontentsaremixedandthefinalvolumeisbroughtuptothemarkonthenarrowneckoftheflask.

Isouranswerreasonable?

Thinkaboutthemagnitudeofthedilution,from0.2Mto0.04M.Noticethattheconcentratedsolutionisfivetimesasconcentratedasthedilute
solution(50.04=0.2).Toreducetheconcentrationbyafactoroffiverequiresthatweincreasethevolumebyafactoroffive,andweseethat
100mLis520mL.Theanswerappearstobecorrect.

Inadilution,theamountofsubstanceintheconcentratedsolutionisthesameasinthedilutedsolution.Thisallowsustouseashortcutforthecalculation
thatwecarriedoutinworkedexample3.14.

Ifwedefinec1andV1astheconcentrationandvolumeoftheinitialsolutionandc2andV2asthoseofthefinalsolution,becausenisthesameinboth
solutionswecanwriten=c1V1andn=c2V2.Astheamount,n,isthesameforbothsolutions,wecanthencanceloutn,togivetheequationc1V1=c2V2.If
weknowtheinitialconcentrationandthefinalvolumeandconcentrationwecansolvefortheinitialvolume:

Thatis,ifwemultiplythefinalvolumebytheratiooffinaltoinitialconcentration,weobtaintherequiredvolumeoftheinitialsolution.Forworked
example3.14,wecouldwrite:
PRACTICEEXERCISE3.19
Howcould0.1mLof0.125MH2SO4solutionbemadefroma0.500
MH2SO4solution?

ApplicationsofSolutionStoichiometry
Whenwedealquantitativelywithreactionsinsolution,weoftenworkwithvolumesofsolutionsandconcentrations.

WORKEDEXAMPLE3.15

StoichiometryInvolvingReactionsinSolution
Beforetheadventofdigitalcameras,silverbromide,AgBr,wasusedextensivelyinphotographicfilm.Thiscompoundisessentiallyinsolublein
water,andonewaytoprepareitistomixsolutionsofthewatersolublecompounds,silvernitrateandcalciumbromide(seefigure3.16).

FIGURE3.16AdditionofCaBr2 (aq)toAgNO3 (aq)resultsinprecipitationofcreamywhiteAgBr(s).

SupposewewishedtoprepareAgBrbythefollowingprecipitationreaction:

Whatvolumeof0.125MCaBr2solutionwouldberequiredtoreactcompletelywith50.0mLof0.115MAgNO3?

Analysis

WeareaskedtocalculateavolumeofCaBr2solution,andwearegiventhevolume(V)andconcentration(c)ofaAgNO3solution.Wecan
calculatetheamount(n)ofAgNO3using .Wearealsogivenabalancedchemicalequation,andwewillneedtousethistoobtainthemole
ratiobetweenAgNO3andCaBr2.Wethenusethestoichiometriccoefficientsfromthebalancedchemicalequationtocalculate .Finally,
wewilluse alongwiththeconcentrationoftheCaBr2solutiontocalculatethevolumeoftheinitialsolutionrequired.
Solution

Westartbycalculatingn AgNO3:

Fromthebalancedchemicalequation,weknowthat2molesofAgNO3willreactwith1moleofCaBr2.Therefore:

Wenowknow andtheconcentrationoftheCaBr2solution,sowecansubstitutethesevaluesinto tocalculateV,thevolumeofthe


CaBr2solutionrequired.

Therefore,23.0mLoftheCaBr2solutionwillreactcompletelywith50.0mLofthe0.115MAgNO3solution.

Isouranswerreasonable?

Themolaritiesofthetwosolutionsareaboutthesame,butonly1moleofCaBr2isneededforevery2molesofAgNO3.Therefore,thevolume
ofCaBr2solutionneeded(23.0mL)shouldbeabouthalfthevolumeofAgNO3solutiontaken(50.0mL),whichitis.

PRACTICEEXERCISE3.20
Whatvolumeof0.124MNaOHisrequiredtoreactcompletelywith
15.4mLof0.108MH2SO4accordingtothefollowingequation?

StoichiometryofSolutionsContainingIons
Inworkedexample3.15,weusedanequationinvolvingioniccompoundstosolveastoichiometryproblem.Ioniccompoundsdissociateintotheir
constituentionsiftheydissolveinwaterandthiscanhaveimportantconsequencesinstoichiometriccalculationsinvolvingsuchsolutions.Forexample,in
workedexample3.15,weusedcalciumbromide,CaBr2,asareactant.Supposeweareworkingwithanaqueoussolutionlabelled0.10MCaBr2.This
meansthereis0.10moleofCaBr2dissolvedineachlitreofthissolutiondissociatedintoCa2+andBrions.

Fromthestoichiometryofthedissociation,weseethat1moleofCa2+(aq)and2molesofBr(aq)areformedfromeachmoleofCaBr2(s).Therefore,0.10
moleofCaBr2(s)willyield0.10moleofCa2+(aq)and0.20molesofBr(aq).In0.10MCaBr2,then,theconcentrationofCa2+(aq)is0.10Mandthe
concentrationofBr(aq)is0.20M.Noticethattheconcentrationofaparticularionequalstheconcentrationofthesaltmultipliedbythenumberofionsof
thatkindintheformulaofthesalt.

Weusethetermdissolutiontodescribetheprocessofasolutedissolvinginasolvent,anditisimportantthatyouunderstandthedifferencebetweenthe
termsdissolutionanddissociation.Whenanioniccompoundundergoesdissolution(dissolves)inasolvent,itundergoesdissociationintoitsconstituent
ions.WeshowedtheequationforthisprocesswithreferencetoCaBr2(s)above,andassumedthatthesaltdissociatesfully.However,dissociationreactions
donotnecessarilydothat,andtheextentofsuchreactionsdependsonthenatureoftheioniccompound.Wewillassume100%dissociationofallionic
compoundsintheremainingexamplesinthischapter.Wewillinvestigatepartialdissociationinchapter10.

Initiallyyoumayfinditdifficulttoknowexactlywhichionicspeciesdissolveinwaterandwhichonesdonot,butwithexperienceyouwillbeabletomake
reasonableassessments.Inthefirstinstanceatableofsolubilityrulescanbeagreathelp.Table3.1summarisestherulesforthesolubilitiesofmany
commonioniccompoundsandyoumayfindithelpfultobefamiliarwiththese.
TABLE3.1 Solubilityofcommonbinaryioniccompoundsinwater
Iftheanionis thecompoundisusually exceptfor

F soluble Mg 2+,Ca2+,Sr2+,Ba2+andPb 2+(Al3+)

Cl soluble Ag +andHg 22+(Pb 2+)

Br soluble Ag +andHg 22+(Hg 2+andPb 2+)

I soluble Ag +,Hg 2+,Hg 22+andPb 2+

NO3 soluble none

SO42 soluble Sr2+,Ba2+,Hg 22+andPb 2+(Ag +andCa2+)

CH3COO soluble none(Ag +andHg 22+)


OH insoluble Li+,Na+,K+andBa2+(Ca2+andSr2+)

SO32 insoluble Li+,Na+,K+,NH4+andMg 2+

PO43 insoluble Na+,K+andNH4+

CO32 insoluble Li+,Na+,K+andNH4+

C2O42 insoluble Li+,Na+,K+andNH4+

Note:Forthepurposesofthistable,insolublecompoundsarearbitrarilydeemedtohavemolarsolubilitiesoflessthan110 2Minwater,slightly
solublecompoundshavemolarsolubilitiesinwaterbetween110 1Mand110 2M,whilesolublecompoundshavemolarsolubilitiesgreaterthan
110 1Minwater.Cationsinparenthesesformslightlysolublecompoundswiththespecifiedanion.Mostoxidesandsulfidesareinsolubleinwater
apparentexceptionstothisrule(e.g.Li2OandMgS)aregenerallycomplicatedbyhydrolysisreactionsandarethereforenotlisted.

Notethat,inworkedexample3.15,wewrotethebalancedchemicalequationasthemolecularequation:

Wecanalsowritethisintermsoftheionspresentastheionicequation:

Thenetreactionthatoccurredwas:

andtheNO3andCa2+tooknopartinthereaction,remainingsimplyasaqueousionsthroughout.Wecallsuchionsspectatorions.Balancedionic
equationswrittenwithouttheinclusionofspectatorionsarecallednetionicequations.Thatis,netionicequationsshowonlythoseionsthatparticipatein
thereaction.

WORKEDEXAMPLE3.16

CalculatingtheConcentrationsofIonsinaSolution
Whataretheconcentrationsoftheionsina0.20MsolutionofAl2(SO4)3(aq)?

Analysis

Theconcentrationsoftheionsaredeterminedbytheconcentrationofthesaltanditsstoichiometry.Weneedtowriteabalancedchemical
equationforthedissolutionofthesaltinwaterfromthis,wecandeterminetheconcentrationofeachioninthesolutionusingthegiven
concentrationofthesalt.

Solution

WhenAl2(SO4)3dissolves,itdissociatesasfollows:

EachmoleofAl2(SO4)3yields2molesofAl3+ionsand3molesofSO42ionsondissolution,assumingcompletedissociation.Therefore,ifwe
consider1litreofsolution,the0.20molofAl2(SO4)3willyield0.40molAl3+and0.60molSO42.Hence,theconcentrationsoftheionsinthe
solutionwillbe0.40MAl3+and0.60MSO42.

PRACTICEEXERCISE3.21
Whatarethemolarconcentrationsoftheionsin0.40MFeCl3(aq)?

PRACTICEEXERCISE3.22

InanaqueoussolutionofNa3PO4,thePO43concentrationwas
determinedtobe0.250M.Whatwasthesodiumionconcentrationin
thesolution?

Wehaveseenthatanetionicequationisconvenientforfocusingonthenetchemicalchangeinreactionsinvolvingions.Letusstudysomeexamplesthat
illustratehowsuchequationscanbeusedinstoichiometriccalculations.

WORKEDEXAMPLE3.17

StoichiometryCalculationsUsingNetIonicEquations
WhenaqueoussolutionsofAgNO3andCaCl2aremixed,awhiteprecipitateofAgCl(s)isformed(seefigure3.17).Thenetionicequationforthe
formationofthisprecipitateis:

Whatvolumeof0.100MAgNO3solutionisneededtoreactcompletelywith25.0mLof0.400MCaCl2solutiontoformAgCl(s)?

FIGURE3.17AsolutionofAgNO3 (aq)isaddedtoasolutionofCaCl2 (aq),producingaprecipitateofAgCl(s).

Analysis

WeareaskedtocalculateavolumeofAgNO3solution.Thevolume(V)andconcentration(c)oftheCaCl2solutiongiveninthequestionallow
ustocalculaten CaCl2andhence using .Fromthestoichiometryofthereaction,wecanthendeterminetherequired .Wecan
thencalculatetherequiredvolumeusingthegivenconcentrationoftheAgNO3solution.

Solution

WearegivenavolumeandaconcentrationoftheCaCl2solution,sowesubstitutethesevaluesinto .

Weknowthat1moleofCaCl2willgive2molesofClondissolutioninwater(assumingcompletedissociation),so:

ThestoichiometryofthebalancedchemicalequationforthereactionofAg +andClshowsthat1moleofClwillreactwith1moleofAg +.
Therefore,wecansaythat:

Beforewecalculatetherequiredvolume,weneedtolookatthestoichiometryofAgNO3.Because1moleofAgNO3willgiveus1moleofAg +
whendissolvedinsolution:

Nowweobtain:

Thus,werequire200mLof0.100MAgNO3solution.

Isouranswerreasonable?

Silverionsreactwithchlorideionsina1:1ratio.CaCl2solutionisfourtimestheconcentrationoftheAgNO3solutionand,as1moleofCaCl2
dissolvestogive2molesofCl,theClconcentrationinthissolutioniseighttimestheconcentrationoftheAgNO3solution.Therefore,wewould
expectavolumeofAgNO3solutioneighttimesthevolumeoftheCaCl2solution.As825=200,ouranswerappearscorrect.

PRACTICEEXERCISE3.23
Whatvolumeof0.500MKOHisneededtoreactcompletelywith60.0
mLofa0.250MFeCl2solutiontoprecipitateFe(OH)2?

Earlierinthischapter(pp.868),welearnedhowtorecogniseandsolvelimitingreagentproblems.Similarproblemscanbeencounteredwhenworking
withnetionicequations.

WORKEDEXAMPLE3.18
CalculationInvolvingtheStoichiometryofAnIonicReaction

AsuspensionofMg(OH)2inwaterissometimesusedasanantacid.ItcanbemadebyaddingNaOHtoasolutioncontainingMg 2+.Supposethat
40.0mLofa0.200MNaOHsolutionisaddedto25.0mLofa0.300MMgCl2solution.Thenetionicequationforthereactionis:

WhatmassofMg(OH)2willbeformed,andwhatwilltheconcentrationsoftheionsinthesolutionbeafterthereactioniscomplete?(M Mg(OH)2=
58.33gmol1)

Analysis

WeareaskedtocalculatethemassofMg(OH)2andtheconcentrationsofionsinsolutionattheendofthereaction.Wearegivenconcentrations
(c)andvolumes(V)ofboththeNaOHandMgCl2solutions,whichallowustocalculateamounts(n)oftheseusing .Wearealsogiventhe
molarmass(M)ofMg(OH)2,whichallowsustouse tocalculatethemass(m)ofMg(OH)2.Thisproblemissimilartoworkedexample
3.17,butslightlymorecomplex.WemustcalculatetheamountsofMg 2+andOHpresentinitially,andworkoutwhichofthesewillbelimiting.
Wethenproceedinthesamewayaswehavedoneinotherlimitingreagentproblems,using tocalculatethemassofMg(OH)2formed.
Weobtaintheconcentrationsoftheionsleftinsolutionbydifference.

Solution

WebeginbycalculatingtheamountsofbothNaOH(aq)andMgCl2(aq),andthencalculatingn Mg2+and fromthese.

As1moleofNaOHgives1moleofOHondissolutioninwater:

Similarly:

Since1moleofMgCl2gives1moleofMg 2+ondissolutioninwater:

Lookingatthebalancedchemicalequation,weseethat1moleofMg 2+willreactwith2molesofOHso forcomplete


reaction.Therefore,wewouldrequire1.5010 2molofOH,butwehaveonly8.0010 3mol,meaningthatOHisthelimitingreagent.
Therefore,fromthebalancedchemicalequation,8.0010 3molOHwillreactwith4.0010 3molMg 2+togive4.0010 3molMg(OH)2.We
canobtainthemassofthisamountusing andthegivenmolarmassofMg(OH)2.

Therefore,thereactionforms0.233gMg(OH)2(s).

Westillhavetocalculatetheconcentrationsoftheionsinsolutionattheendofthereaction.TheionspresentwillbeMg 2+,ClandNa+.We
havealreadycalculatedtheamountofNaOHas8.0010 3mol,so .Thefinalvolumeofthesolutionis65.0mL(40.0
mLofNaOHsolutionplus25.0mLofMgCl2solution),so:

WehavealsocalculatedtheamountofMgCl2as7.5010 3mol,and,as1moleofMgCl2gives2molesofClondissolutioninwater,
.Wecanthenobtaintheconcentrationfrom:

WewillassumethatalloftheOHinsolutionhasprecipitatedasMg(OH)2sothefinalconcentrationofOHwillbe0.00molL1(infact,in
chapter10,wewillseethataverysmallamountofOHwillremaininsolution,butnotenoughtomakeasignificantdifferencetoourcalculation
here).ThefinalconcentrationweneedtocalculateisthatofMg 2+.Thisisslightlymoreinvolvedthantheothers,asweneedtorememberthat
someoftheMg 2+hasbeenprecipitatedasMg(OH)2.Earlier,wecalculatedtheinitialamountofMg 2+as7.5010 3mol.Wealsocalculatedthat
4.0010 3molofMg 2+hasprecipitatedasMg(OH)2,sowecanobtaintheamountofMg 2+insolutionbydifference.

Therefore,theconcentrationofMg 2+insolutionis:

Isouranswerreasonable?

Thiswasafairlycomplexproblemandtherearenosimplecalculationswecanmaketoverifyouranswers.However,thereareacoupleofkey
stepswemightdoublecheck.First,wecancheckthatwehaveidentifiedthelimitingreagentcorrectly.Inthepreviouscalculation,weselected
Mg 2+anddeterminediftherewasenoughOHtoreactwithit.Asacheck,letuslookatOHtoseeifthereisenoughMg 2+.Webeganwith8
10 3molofOH,whichrequireshalfthatamountofMg 2+(410 3molMg 2+)toreactcompletely.TheamountofMg 2+available(7.510 3
mol)ismorethanenough,soMg 2+willbeleftoverandOHislimiting.Ouranalysisconfirmsthatwehaveselectedthecorrectlimitingreagent.

Anotherplacetobecarefulisinthecalculationofthefinalconcentrationsoftheionsinthereactionmixture.Wheneverweaddoneaqueous
solutiontoanother,themixturewillhaveafinalvolumethatisthesumofthevolumesofthetwosolutionscombined.Whencalculatingthe
concentrationsofanythinginthefinalmixture,wehavetousethefinalcombinedvolumeofthemixture.Weseethatwehavetakenthisinto
account,sowecanfeelconfidentwe'vedonethispartofthecalculationcorrectly.

PRACTICEEXERCISE3.24
WhatamountofBaSO4willformif20.0mLof0.600MBaCl2is
mixedwith30.0mLof0.500MMgSO4?Determinetheconcentration
ofeachioninthefinalreactionmixture.

Theworkedexamplesinthischaptersofarhavespecifiedthereactantsandproductsinvolved.Therewillbeoccasionswhenwedonotknowthe
compositionofoneofthese,butstoichiometrycanstillhelptodeterminetheamountofaparticularelementinanunknowncompound.Thecalculations
requiredforthesekindsofproblemsarenotnewtheyaresimplyapplicationsofthestoichiometriccalculationswehavealreadylearned.

WORKEDEXAMPLE3.19

CalculationInvolvinganUnknownCompound
Acompoundusedasaninsecticidecontainscarbon,hydrogenandchlorine.Reactionswerecarriedoutona1.340gsampleofthecompound
thatconvertedallofitschlorinetochlorideionsdissolvedinwater.ThisaqueoussolutionwastreatedwithanexcessofAgNO3solution,andthe
AgClprecipitatewascollectedandthenweighed.Itsmasswas2.709g.WhatwasthepercentagebymassofClintheoriginalinsecticide
sample?(M Cl=35.45gmol1M AgCl=143.32gmol1)

Analysis

Weareaskedtocalculateapercentagebymass.Wearegiventhemass(m)andmolarmass(M)ofAgClsowecancalculatetheamountofAgCl
using .Wecanobtaintherestofthenecessarydatausingmoleratios.Theimportantpointtounderstandinthisproblemisthatallthe
chlorineintheAgClthatwascollectedoriginatedfromtheinsecticidesample.Thestrategy,therefore,istodeterminethemassofClin2.709gof
AgCl.Wethenassumethatthisisthemassofchlorineintheoriginal1.340gsampleofinsecticideandcalculatethepercentageClasfollows:

Solution

WebeginbycalculatingtheamountofAgClusing .

As1moleofAgClcontains1moleofCl,theamountofClintheoriginalinsecticidesamplemustbe1.89010 2mol.Wecalculatethemassof
thisamountusing .

Wecannowcalculatethe%Clbymass.

Isouranswerreasonable?

LetusconsiderthemolarmassesofAgClandCl(143.32gmol1and35.45gmol1,respectively).Ifweroundtheseto140and35,wecansay
thatAgClisapproximately25%ofClbymass(35/140=0.25).Approximately3gofAgClwasobtained25%of3gequals0.75gofCl,which
isclosetothevalueweobtained.Theoriginalsampleweighed1.34g,whichisnearlytwice0.75g(themassofCl),soananswerof50%Clby
massseemsreasonable.

PRACTICEEXERCISE3.25
AsampleofamixturecontainingCaCl2andMgCl2weighed2.000g.
Thesamplewasdissolvedinwater,andH2SO4wasaddeduntilthe
precipitationofCaSO4wascomplete.TheCaSO4wasfiltered,dried
completelyandweighed.Atotalof0.736gofCaSO4wasobtained.
WhatamountofCa2+wasintheoriginal2.000gsample?
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
SUMMARY
ChemicalEquations
Achemicalreactionistheformationofnewsubstances(products)fromoneormorestartingmaterials
(reactants).Achemicalequationisabeforeandafterdescriptionofachemicalreaction.Aqualitative
analysisisconcernedonlywithwhichsubstancesarepresent.Aquantitativeanalysisisconcernedwith
theamountsofallthevarioussubstances.Stoichiometryisconcernedwiththerelativeamountsof
productsandreactantsinareaction.Stoichiometriccoefficientsarewritteninfrontofformulaein
chemicalequationstoindicatethenumberofspecifiedentitiesofeachkindamongthereactantsand
products.Abalancedchemicalequationhasthesamenumberofatomsofeachkindintheproductsand
reactants,thusconformingtothelawofconservationofmass.Thephysicalstatesofreactantsand
productscanbeshowninchemicalequationsusing(s)forsolid,(l)forliquidand(g)forgas.Weuse
(aq)toindicateanaqueoussolution(thatis,whenasubstanceisdissolvedinwater).

BalancingChemicalEquations
Achemicalequationisbalancedwhenallatomspresentamongthereactantsarealsosomewhereamong
theproducts.Tobalanceanequation,wefirstwritetheunbalancedequationandthenadjustthe
stoichiometriccoefficientstogetequalnumbersofeachkindofatomoneachsideofthearrow.

TheMole
Themole(mol)isthebaseSIunitforamount.Itistheamountofanysubstancewiththesamenumber
ofatomsormoleculesasthereareatomsinexactly12gof12C.TheAvogadroconstant,NA,is6.022
10 23mol1andgivesthenumberofspecifiedentitiesin1molofasubstance.Themolarmass,M,isthe
massof1molofasubstance.

EmpiricalFormulae
Theactualcompositionofamoleculeisgivenbyitsmolecularformula.Anempiricalformulagivesthe
ratioofatoms,butinthesmallestwholenumbers,anditisgenerallytheonlyformulawewriteforionic
compounds.Themolarmassofamolecularcompoundisequaltothatcalculatedfromthecompound's
empiricalformulaortoasimplemultipleofit.Whenthetwocalculatedmassesarethesame,the
molecularformulaisthesameastheempiricalformula.

Anempiricalformulacanbefoundfromthemassesoftheelementsobtainedbythequantitative
analysisofaknownsampleofthecompound,oritcanbecalculatedfromthepercentagecomposition
(thepercentageofanelementinacompoundisthesameasthenumberofgramsoftheelementin100
gofthecompound).IfthereisJ%ofXinXx Zz,then100gofXx ZzcontainsJgofX.TheamountsofX
andZcanbecalculatedfromthemassesofXandZ.Thesubscriptsintheempiricalformulaare
obtainedbyadjustingtheseamountstotheircorrespondingwholenumberratios.

Stoichiometry,LimitingReagentsandPercentageYield
Achemicalformulaisatoolforstoichiometriccalculations,becauseitssubscriptstellusthemoleratios
inwhichthevariouselementsarecombined.In1moleofXx Zz,xmolesofXarecombinedwithzmoles
ofZ.

Abalancedequationisatoolforreactionstoichiometrybecauseitscoefficientsdisclosethe
stoichiometricrelationships.Allproblemsofreactionstoichiometrymustbesolvedatthemolelevelof
thesubstancesinvolved.Ifmassesaregiven,theymustfirstbechangedtoamounts.

FromthegenericbalancedequationaA+bBcC+dD,itfollowsthatthemoleratiosforexact
stoichiometricreactionare:

Incaseswherethisequationdoesnothold,thereactantpresentinthesmallestmoleratioiscalledthe
limitingreagent.Theotherreactantiscalledtheexcessreagent.Thetheoreticalyieldofaproductcanbe
nomorethanthatpermittedbythelimitingreagent.Sometimes,competingreactions(sidereactions)
thatproducebyproductsreducetheactualyield.Theratiooftheactualyieldtothetheoreticalyield,
expressedasapercentage,isthepercentageyield.

SolutionStoichiometry
Asolutionisahomogeneousmixtureinwhichoneormoresolutesaredissolvedinasolvent.
Concentrationistheratiooftheamountofsolutetothevolumeofsolution.Solutionsofknown
concentrationcanbepreparedbyweighingaccuratemassesofcompoundsusingananalyticalbalance
andthenmakingthemuptoaparticularvolumewithsolventinavolumetricflask.Concentrated
solutionsofknownconcentrationcanbedilutedquantitativelyusingvolumetricglasswaresuchas
pipettesandvolumetricflasks.Molarityisausefulconcentrationunitforanycalculationinvolvingthe
stoichiometryofreactionsinsolution.Inionicreactions,theconcentrationsoftheionsinasolutionofa
saltcanbederivedfromthemolarconcentrationofthesalt,takingintoaccountthenumberofions
formedondissolutionofthesalt.Forreactionsinvolvingionstherearethreepossiblewaystowrite
reactionequations.Amolecularequationusestheempiricalformulaforeachcompoundtoaid
stoichiometriccalculations.Theionicequationshowsalltheionsthatareformedinsolution,whilethe
netionicequationshowsonlythoseionsthatareactuallyinvolvedinthenetreaction(i.e.excluding
spectatorions).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYCONCEPTSANDEQUATIONS
Chemicalformula(section3.1)
Weusesubscriptsinaformulatoestablishatomratiosandmoleratiosbetweentheelementsinthe
substance.

Balancedchemicalequation(section3.2)
Weusecoefficientstoestablishstoichiometricequivalenciesthatrelatetheamountofonesubstanceto
theamountofanotherinachemicalreaction.Thecoefficientsalsoestablishtheratiosofreactantsand
productsinvolvedinthereaction.

Themole(section3.3)
Themoleprovidesthebasisfordeterminationoftheamountofsubstance.

Avogadroconstant(NA)(section3.3)
TheAvogadroconstantrelatesmacroscopicquantitiesusedinalaboratorytonumbersofindividual
atomicsizedparticles,suchasatoms,moleculesandions.

Molarmass(M)(section3.3)
Molarmasscanbeusedtocalculatethemassof1moleofanysubstanceortoconvertbetweenamount
andmassusing .

(section3.3)
Thisequationrepresentstherelationshipbetweenmass(m),amount(n)andmolarmass(M).

Percentagecomposition(section3.4)
Weusepercentagecompositiontorepresentthecompositionofacompoundandasthebasisfor
calculatingtheempiricalformula.Comparingexperimentalandtheoreticalpercentagecompositionscan
helptoestablishtheidentityofacompound.

Theoretical,actualandpercentageyields(section3.5)
Weusethesevaluestoestimatetheefficiencyofareaction.Rememberthattheoreticalyieldis
calculatedfromthelimitingreagentusingthebalancedchemicalequation.Thepercentageyieldisgiven
bytheequation:percentageyield=(actualyield/theoreticalyield)100%.

Balancedequationsandmoleratios(section3.5)
Forthegenericbalancedequation:

themoleratiosforexactstoichiometricreactionare:

(section3.6)
Thisequationrepresentstherelationshipbetweenconcentration(c),amount(n)andvolume(V).
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWQUESTIONS
ChemicalEquations
3.1Whatdowemeanwhenwesayachemicalequationisbalanced?Whydowebalancechemical
equations?
3.2Inachemicalreaction,whatdowemeanbythetermreactants?Whatdowemeanbytheterm
products?
3.3Whatdowecallthenumbersthatarewritteninfrontoftheformulaeinabalancedchemical
equation?
3.4Thecombustionofathinwireofmagnesiummetal,Mg,inanatmosphereofpureoxygenproduces
thebrilliantlightofaflashbulb,oncecommonlyusedinphotography.Afterthereaction,athinfilm
ofmagnesiumoxideisseenontheinsideofthebulb.Theequationforthereactionis:

(a)Stateinwordshowthisequationisread.
(b)Givetheformulaeofthereactants.
(c)Givetheformulaoftheproduct.
(d)RewritetheequationtoshowthatMgandMgOaresolidsandO2isagas.
BalancingChemicalEquations
3.5Whengiventheunbalancedequation:

andaskedtobalanceit,studentAwrote:

andstudentBwrote:

(a)Bothequationsarebalanced,butwhichstudentiscorrect?
(b)Explainwhytheotherstudent'sanswerisincorrect.
TheMole
3.6Definethetermmole.
3.7Whyaremolesusedwhenallstoichiometryproblemscouldbedoneusingonlyatomicmassunits?
3.8Whatinformationisrequiredtocalculatetheamountofasubstancefromagivenmassofthatsame
substance?
3.9Givetheequationthatrelatesmolarmass,amountandmass.
3.10Howwouldyouestimatethenumberofatomsinagramofiron,usingatomicmassunits?
3.11Whichcontainsmoremolecules:2.5molesofH2Oor2.5molesofH2?
3.12Whatamountofironatomsisin1molofFe2O3?Howmanyironatomsarein1molofFe2O3?
3.13Whyistheexpression1.0molofoxygenambiguous?
EmpiricalFormulae
3.14Ingeneral,whatfundamentalinformation,obtainedfromexperimentalmeasurements,isrequired
tocalculatetheempiricalformulaofacompound?
3.15Whyisthechangingofsubscriptsnotallowedwhenbalancingachemicalequation?
3.16GiveastepbystepprocedureforestimatingthemassofArequiredtocompletelyreactwith10
molesofB,giventhefollowinginformation:
i. AandBreacttoformA5B2.
ii. Ahasamolarmassof100.0gmol1.
iii.Bhasamolarmassof200.0gmol1.
iv.Thereare6.02210 23moleculesofAin1moleofA.Whichofthesepiecesofinformation
wasnotneeded?
Stoichiometry,LimitingReagentsandPercentageYield
3.17Whatinformationisrequiredtodeterminethemassofsulfurthatwouldreactwith1gramof
arsenic?
3.18Amixtureof0.020molofMgand0.020molofCl2reactedcompletelytoformMgCl2according
totheequation:

(a)Whatinformationdescribesthestoichiometryofthisreaction?
(b)Whatinformationgivesthescaleofthereaction?
3.19Inareporttoasupervisor,achemistdescribedanexperimentinthefollowingway:0.0800mol
ofH2O2decomposedinto0.0800molofH2Oand0.0400molofO2.Expressthechemistryand
stoichiometryofthisreactionbyaconventionalchemicalequation.
SolutionStoichiometry
3.20Givetheequationthatrelatesconcentration,volumeandamount.
3.21Whatisthedefinitionofmolarity?Showthattheratioofmillimoles(mmol)tomillilitres(mL)is
equivalenttotheratioofmolestolitres.
3.22Whatarespectatorions?
3.23Whenasolutionlabelled0.50MHNO3isdilutedwithwatertogive0.25MHNO3,whathappens
totheamountofHNO3inthesolution?
3.24SolutionsAandBarelabelled0.10MCaCl2and0.20MCaCl2,respectively.Bothsolutions
containthesameamountofCaCl2.IfsolutionAhasavolumeof50mL,whatisthevolumeof
solutionB?
3.25Whatisthedifferencebetweenaqualitativeanalysisandaquantitativeanalysis?
3.26Thefollowingequationshowstheformationofcobalt(II)hydroxide,acompoundusedtoimprove
thedryingpropertiesoflithographicinks:

Whicharethespectatorions?Writethenetionicequation.
3.27Whyisthefollowingequationnotbalanced?Findtheerrorsandfixthem.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWPROBLEMS
3.28Considerthebalancedequation:

(a)HowmanyatomsofNaareoneachsideoftheequation?
(b)HowmanyatomsofCareoneachsideoftheequation?
(c)HowmanyatomsofOareoneachsideoftheequation?
3.29Whensulfurimpuritiesinfuelsburn,theyproducepollutantssuchassulfurdioxide,amajorcontributortoacidrain.Thefollowingisaballand
stickmodelofatypicalreaction.

Ontheleftarereactantmoleculesandontherightareproductmoleculesinachemicalreaction.Writethebalancedchemicalequationforthis
reaction,usingthestoichiometriccoefficientsthatgivethesmallestwholenumberofproductmolecules
3.30Writetheequationthatexpressesinacceptablechemicalshorthandthefollowingstatement:Ironcanbemadetoreactwithmolecularoxygen,
O2,togiveironoxidewiththeformulaFe2O3.
3.31Racecardriverscangetextrapowerbyburningmethylalcoholwithnitrousoxide.Belowontheleftarethereactantmoleculesandontheright
areproductmoleculesofthechemicalreaction.Writethebalancedchemicalequationforthisreaction,usingthestoichiometriccoefficientsthat
givethesmallestwholenumberofproductmolecules.

3.32Isthefollowingchemicalequationbalanced?Thisreactionisusedfortheproductionofnitricacid,HNO3,andisoneofthereactionsresponsible
foracidrain.

Iftheequationisnotbalanced,findcoefficientsthatwouldmakeitbalanced.
3.33Writethebalancedchemicalequationforthechemicalreactiondepictedbythespacefillingmodelsbelow.
3.34Writethebalancedchemicalequationforthechemicalreactiondepictedbythespacefillingmodelsbelow.

3.35Balancethefollowingequations:
(a)Ca(OH)2+HClCaCl2+H2O
(b)NaHCO3+H2SO4Na2SO4+H2O+CO2
(c)AgNO3+CaCl2Ca(NO3)2+AgCl
(d)C4H10+O2CO2+H2O
(e)Fe2O3+CFe+CO2
3.36Giventhebalancedchemicalequation

determinethenumberofmoleculesofSO2thatwouldbeformedstartingfromtheactualnumberofmoleculesofC2H5SHandO2shownbelow.

3.37Usingthebalancedchemicalequationfromquestion3.35,whichofC2H5SHorO2wasthelimitingreagentiftheproductdistributionforthe
reactionwasthatshownbelow?

3.38InwhatsmallestwholenumberratiomustNandOatomscombinetomakedinitrogentetroxide,N2O4?Whatisthemoleratiooftheelementsin
thiscompound?
3.39Whatamountofsodiumatomscorrespondsto1.5610 21atomsofsodium?
3.40WhatamountofAlatomsareneededtocombinewith1.58molofOatomstomakealuminiumoxide,Al2O3?
3.41WhatamountofH2andN2canbeformedbythedecompositionof0.145molofammonia,NH3?
3.42WhatamountofUF6wouldhavetobedecomposedtoprovideenoughfluorinetoprepare1.25molofCF4?(Assumesufficientcarbonis
available.)
3.43Quantitativeanalysisofa0.896gsampleofsodiumpertechnetatefound0.111gofsodiumand0.477goftechnetium.Theremainderwas
oxygen.Calculatetheempiricalformulaofsodiumpertechnetate.(Radioactivesodiumpertechnetateisusedasabrainscanningagentin
medicine.)
3.44Thecompositionofadrycleaningfluid,composedofonlycarbonandchlorine,wasfoundtobe14.5%Cand85.5%Cl(bymass).Whatisthe
3.44Thecompositionofadrycleaningfluid,composedofonlycarbonandchlorine,wasfoundtobe14.5%Cand85.5%Cl(bymass).Whatisthe
empiricalformulaofthiscompound?
3.45When0.684gofanorganiccompoundcontainingonlycarbon,hydrogenandoxygenwasburnedinoxygen,1.312gCO2and0.805gH2Owas
obtained.Whatistheempiricalformulaofthecompound?
3.46Asampleofacompoundofmercuryandbrominewithamassof0.389gwasfoundtocontain0.111gbromine.Itsmolarmasswasfoundtobe
561gmol1.Whatareitsempiricalandmolecularformulae?

3.47Determinethemassingramsofeachofthefollowing:
(a)1.35molFe,
(b)24.5molO,
(c)0.876molCa.
3.48Whatisthemass,ingrams,of2.0010 12atomsofpotassium?
3.49Whatamountofnickelisin17.7gofNi?
3.50Calculatethemolarmassofeachofthefollowing:
(a)NaHCO3,
(b)K2Cr2O7,
(c)(NH4)2CO3,
(d)Al2(SO4)3,
(e)CuSO4.5H2O.
3.51Calculatethemassingramsofeachofthefollowing:
(a)1.25molCa3(PO4)2,
(b)0.625molFe(NO3)3,
(c)0.600molC4H10,
(d)1.45mol(NH4)2CO3.
3.52Calculatetheamountofthecompoundineachofthefollowingsamples:
(a)21.5gCaCO3,
(b)1.56gNH3,
(c)16.8gSr(NO3)2,
(d)6.98gNa2CrO4.
3.53Whatmassofafertilisermadeofpure(NH4)2CO3wouldberequiredtosupply1kgofnitrogentothesoil?
3.54Calculatethepercentagecompositionbymassofallelementsineachofthefollowing:
(a)NaH2PO4,
(b)NH4H2PO4,
(c)(CH3)2CO,
(d)CaSO4,
(e)CaSO42H2O.
3.55WhatmassofOiscombinedwith7.1410 21atomsofNinthecompoundN O ?
2 5
3.56Chlorineisusedbytextilemanufacturerstobleachcloth.Excesschlorineisdestroyedbyitsreactionwithsodiumthiosulfate,Na2S2O3,as
follows:

(a)WhatamountofNa2S2O3isneededtoreactwith0.12molofCl2?
(b)WhatamountofHClcanformfrom0.12molofCl2?
(c)WhatamountofH2Oisrequiredforthereactionof0.12molofCl2?
(d)WhatamountofH2Oreactsif0.24molHClisformed?

3.57Thefollowingreactionisusedtoextractgoldfrompretreatedgoldore:

(a) WhatmassofZnisneededtoreactwith0.11molofAu(CN) ?
2
(b)WhatmassofAucanformfrom0.11molofAu(CN) ?
2
(c) WhatmassofAu(CN) isrequiredforthereactionof0.11molofZn?
2
3.58TheincandescentwhiteofafireworksdisplayiscausedbythereactionofphosphoruswithO2togiveP4O10.
(a)Writethebalancedchemicalequationforthereaction.
(b)WhatmassofO2isneededtocombinewith6.85gofP?
(c)WhatmassofP4O10canbemadefrom8.00gofO2?
(d)WhatmassofPisneededtomake7.46gofP4O10?
3.59Oxygengascanbeproducedinthelaboratorybydecompositionofhydrogenperoxide,H2O2:

WhatmassofO2canbeproducedfrom1.0kgofH2O2?
3.60Thereactionofpowderedaluminiumandiron(III)oxide:

producessomuchheatthattheironthatformsismolten.Becauseofthis,thereactionisusedwhenlayingrailwaytrackstoprovidemoltensteel
toweldsteelrailstogether.Supposethat,inonebatchofreactants,4.20molofAlwasmixedwith1.75molofFe2O3.
(a)Whichreactant,ifeither,wasthelimitingreagent?
(b)Calculatethemassofironthatcanbeformedfromthismixtureofreactants.
3.61Silvernitrate,AgNO3,reactswithiron(III)chloride,FeCl3,togivesilverchloride,AgCl,andiron(III)nitrate,Fe(NO3)3.Asolutioncontaining
18.0gofAgNO3wasmixedwithasolutioncontaining32.4gofFeCl3.Whatmassofwhichreactantremainsafterthereactioniscomplete?
3.62Bariumsulfate,BaSO4,ismadebythefollowingreaction:

Anexperimentwasbegunwith75.00gofBa(NO3)2andanexcessofNa2SO4.Aftercollectinganddryingtheproduct,64.45gofBaSO4was
obtained.CalculatethetheoreticalyieldandpercentageyieldofBaSO4.
3.63Thepotassiumsaltofbenzoicacid(potassiumbenzoate,C6H5COOK),canbemadebytheactionofpotassiumpermanganate,KMnO4,on
toluene,C6H5CH3,asfollows:

Iftheyieldofpotassiumbenzoatecannotrealisticallybeexpectedtobemorethan71%,whatistheminimummassoftolueneneededtoachieve
thisyieldwhileproducing11.5gofpotassiumbenzoate?
3.64Calculatetheconcentrationofasolutionpreparedbydissolving:
(a)4.00gofNaOHin100.0mLofsolution
(b)16.0gofCaCl2in250.0mLofsolution
(c)14.0gofKOHin75.0mLofsolution
(d)6.75gofHO2CCO2Hin500mLofsolution.
3.65Calculatethemassofeachsoluteneededtomakeeachofthefollowingsolutions.
(a)125mLof0.200MNaCl(aq)
(b)250mLof0.360MC6H12O6(aq)(glucose)

(c)250mLof0.250MH2SO4(aq)
3.66If25.0mLof0.56MH2SO4isdilutedtoavolumeof125mL,whatistheconcentrationoftheresultingsolution?
3.67Towhatvolumemust25.0mLof18.0MH2SO4bedilutedtoproduce1.50MH2SO4(aq)?
3.68Calculatetheamountsofeachoftheionsinthefollowingsolutions.
(a)35.0mLof1.25MKOH(aq)
(b)32.3mLof0.45MCaCl2(aq)
(c)50.0mLof0.40MAlCl3(aq)
3.69Calculatetheconcentrationsofeachoftheionsin:
(a)0.25MCr(NO3)2(aq),
(b)0.10MCuSO4(aq),
(c)0.16MNa3PO4(aq),
(d)0.075MAl2(SO4)3(aq).
3.70InasolutionofAl (SO ) (aq),theAl3+concentrationis0.12M.WhatmassofAl (SO ) isin50.0mLofthissolution?
2 43 2 43
3.71Whatvolumeof0.25MNiCl2(aq)solutionisneededtoreactcompletelywith20.0mLof0.15MNa2CO3(aq)solution?WhatmassofNiCO3will
beformed?Thereactionis:

3.72Whatvolumeof0.150MFeCl3(aq)solutionisneededtoreactcompletelywith20.0mLof0.0450MAgNO3(aq)solution?WhatmassofAgCl
willbeformed?Thenetionicequationforthereactionis:

3.73Considerthereactionofaluminiumchloridewithsilveracetate.Whatvolumeof0.250MAlCl3(aq)wouldbeneededtoreactcompletelywith
20.0mLof0.500MAgOOCCH3(aq)solution?Thenetionicequationforthereactionis:

3.74Supposethat25.0mLof0.440MNaCl(aq)isaddedto25.0mLof0.320MAgNO3(aq).
(a)WhatamountofAgClwouldprecipitate?
(b)Determinetheconcentrationofeachoftheionsinthereactionmixtureafterthereaction.
3.75Amixtureispreparedbyadding25.0mLof0.185MNa3PO4(aq)to34.0mLof0.140MCa(NO3)2(aq).
(a)WhatmassofCa3(PO4)2willbeformed?
(a)WhatmassofCa3(PO4)2willbeformed?
(b)Determinetheconcentrationofeachoftheionsinthemixtureafterreaction.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
ADDITIONALEXERCISES
3.76Writethenetionicequationsforthefollowingreactions.Includethedesignationsforthestates
solid,liquid,gasandaqueoussolution.(Foranysubstancesolubleinwater,assumethatitisused
asanaqueoussolution.)
(a)CaCO3+2HNO3Ca(NO3)2+CO2+H2O
(b)CaCO3+H2SO4CaSO4+CO2+H2O
(c)FeS+2HBrH2S+FeBr2
(d)2KOH+SnCl22KCl+Sn(OH)2
3.77A0.113gsampleofamixtureofsodiumchlorideandsodiumnitratewasdissolvedinwater,and
enoughsilvernitratesolutionwasaddedtoprecipitateallofthechlorideions.Themassofsilver
chlorideobtainedwas0.277g.Whatmasspercentageofthesamplewassodiumchloride?
3.78Inanexperiment,40.0mLof0.270MBa(OH)2(aq)wasmixedwith25.0mLof0.330M
Al2(SO4)3(aq).
(a)Writethenetionicequationforthereactionthattakesplace.
(b)Whatisthetotalmassofprecipitatethatforms?
(c)Whatarethemolarconcentrationsoftheionsthatremaininthesolutionafterthereaction
iscomplete?
3.79Whatvolumeof0.10MHCl(aq)mustbeaddedto50.0mLof0.40MHCl(aq)togiveafinal
solutionthathasamolarityof0.25M?
3.80AnswerthefollowingquestionsaboutaninsecticidewiththechemicalformulaC12H11NO2.
(a)Whatamountofcarbonatomsistherein8.3gofthecompound?
(b)Whatmassofoxygenistherein4.5gofthecompound?
(c)Thelabelona75mLbottleofgardeninsecticidestatesthatthesolutioncontains0.010%
insecticideand99.99%inertingredients.Whatamountandhowmanymoleculesofthe
insecticideareinthebottle?(Assumethatthedensityofthesolutionis1.00gmL1.)
(d)Theinstructionsonthebottleofinsecticidein(c)aretodilutetheinsecticidebyadding1.0
mLofthesolutionto4.0litresofwater.Ifyouspray60litresofthedilutedinsecticide
mixtureonyourrosegarden,Whatamountoftheactiveingredientisdispersed?
3.81SolutionAispreparedbydissolving90.0gofNa3PO4inenoughwatertomake1.5Lofsolution.
SolutionBis2.5Lof0.705MNa2SO4(aq).
(a)WhatisthemolarconcentrationofNa3PO4insolutionA?
(b)WhatvolumeofsolutionAcontains2.50gofNa3PO4?
(c)A50.0mLsampleofsolutionBismixedwitha75.00mLsampleofsolutionA.Calculate
theconcentrationofNa+ionsinthefinalsolution.
3.82Policeofficersconfiscateapacketofwhitepowderthattheybelievecontainsheroin.Purification
byaforensicchemistyieldsa38.70mgsampleforcombustionanalysis.Thissampleproduces
97.46mgCO2and20.81mgH2Ooncompletecombustion.Asecondsampleisanalysedforits
nitrogencontent,whichis3.8%.Showbycalculationswhetherthesedataareconsistentwiththe
formulaforheroin,C21H22NO5.
3.83WhenanunknowncompoundisburnedcompletelyinO2,1.23gofCO2and97.02gofH2Ois
recovered.Whatadditionalinformationisneededbeforethemolecularformulaoftheunknown
compoundcanbedetermined?
3.84Asulfurcontainingoreofcopperreleasessulfurdioxidewhenheatedinair.A5.26gsampleof
theorereleases2.12gofSO2onheating.Assumingthattheorecontainsonlycopperandsulfur,
whatistheempiricalformula?
3.85ThemineralturquoisehastheformulaCuAl6(PO4)4(OH)84H2O.
(a)Whatmassofaluminiumisina7.25gsampleofturquoise?
(b)Howmanyphosphateionsareinasampleofturquoisethatcontains5.5010 3gof
oxygen?
(c)Whatisthechargeofthecopperioninturquoise?
3.86Achemistneedsasolutionthatcontainsaluminiumions,sodiumionsandsulfateions.Inthe
laboratoryshefindsalargevolumeof0.355Msodiumsulfatesolutionandabottleofsolid
Al2(SO4)318H2O.Thechemistputs250mLofthesodiumsulfatesolutionand5.13gof
aluminiumsulfatehydrateina500mLvolumetricflask.Theflaskismadeuptothemarkwith
water.Determinethemolarityofaluminiumions,sodiumionsandsulfateionsinthesolution.
3.87Adenosinetriphosphate(ATP)isusedtogeneratechemicalenergyinplantandanimalcells.The
molecularformulaofATPisC10H16N5O13P3.AnswerthefollowingquestionsaboutATP.
(a)WhatisthepercentagecompositionbymassofeachelementinATP?
(b)HowmanyPatomsarein1.75gofATP?
(c)Ifacellconsumes3.0pmolofATP,whatmasshasitconsumed?
(d)WhatmassofATPcontainsthesamenumberofatomsofHasthenumberofNatomsin
37.5mgofATP?
3.88Thewatersoftheoceanscontainmanyelementsintraceamounts.Rubidium,forexample,is
presentatthelevelof2.2nM(nanomolar).Howmanyionsofrubidiumarepresentin1.00Lof
seawater?Howmanylitreswouldhavetobeprocessedtorecover1.00kgofrubidium,assuming
therecoveryprocesswas100%efficient?
3.89VitaminB12isalargemoleculecalledcobalamin.Thereis1atomofcobaltineachmoleculeof
vitaminB12,andthemasspercentageofcobaltis4.34%.Calculatethemolarmassofcobalamin.
3.90ElementEformsacompoundwiththeformulaECl5.Elementalanalysisshowsthatthecompound
is85.13%chlorinebymass.IdentifyelementE.
3.91Pureaceticacid,CH3COOH,hasaconcentrationof17.4M.Alaboratoryworkermeasuredout
100.0mLofpureaceticacidandaddedenoughwatertomake500.0mLofsolution.A75.0mL
portionoftheaceticacidsolutionwasthenmixedwithenoughwatertomake1.50Lofdilute
solution.Whatwasthefinalmolarityofaceticacidinthedilutesolution?
3.92Aworkerinabiologicallaboratoryneededasolutionthatwas0.30Minsodiumacetate,
NaOOCCH3,and0.15Minaceticacid,CH3COOH.Onhandwerestocksolutionsof5.0M
sodiumacetateand5.0Maceticacid.Describehowtheworkerprepared1.5Lofthedesired
solution.
3.93Thethyroidglandproduceshormonesthathelpregulatebodytemperature,metabolicrate,
reproduction,synthesisofredbloodcellsandmore.Iodinemustbepresentinthediettoproduce
thesethyroidhormones.Iodinedeficiencyleadstosluggishnessandweightgain,andcancause
severeproblemsinthedevelopmentofafoetus.Onethyroidhormoneisthyroxine,withthe
chemicalformulaC15H11I4NO4.Whatmassofthyroxinecanbeproducedfrom210mgofiodine
atoms,theamountatypicaladultconsumesperday?Howmanymoleculesisthis?
3.94Asampleofacomponentofpetroleumwassubjectedtocombustionanalysis.Anemptyvialof
mass2.7534gwasfilledwiththesample,afterwhichthevialplussamplehadamassof2.8954g.
ThesamplewasburnedandtheresultingCO2andH2Owerecollectedinseparatetraps.Before
combustion,theCO2traphadamassof54.4375gandtheH2Otraphadamassof47.8845g.At
theendoftheanalysis,theCO2traphadanewmassof54.9140gandtheH2Otraphadanew
massof47.9961g.Determinetheempiricalformulaofthiscomponentofpetroleum.
3.95Aluminiumsulfateisusedinthemanufactureofpaperandinthewaterpurificationindustry.In
thesolidstate,aluminiumsulfateisahydratewiththeformulaAl2(SO4)318H2O.
(a)Whatmassofsulfuristherein0.570molesofsolidaluminiumsulfate?
(b)Howmanywatermoleculesarethereina5.1gsampleofsolidaluminiumsulfate?
(c)Whatamountofsulfateionsisthereinasampleofsolidaluminiumsulfatethatcontains
12.5molesofoxygenatoms?
(d)Anaqueoussolutionofaluminiumsulfatecontains1.25%aluminiumbymassandhasa
densityof1.05gmL1.Whatisthemolarityofaluminiumionsinthesolution?
3.96IntheHabersynthesisofammonia,N2andH2reactathightemperature,buttheyneverreact
completely.Inatypicalreaction,24.0kgofH2and84.0kgofN2reacttoproduce68kgofNH3.
Findthetheoreticalyield,thepercentageyieldandthemassesofH2andN2thatremainunreacted,
assumingthatnootherproductsform.
3.97Silicontetrachlorideisusedintheelectronicsindustrytomakeelementalsiliconforcomputer
chips.Silicontetrachlorideispreparedfromsilicondioxide,graphiteandchlorinegasaccordingto
theequation:

Ifthereactionachieves95.7%yield,howmuchsilicontetrachloridecanbepreparedfrom75.0g
ofeachstartingmaterial,andhowmuchofeachreactantremainsunreacted?
3.98Silverjewelleryisusuallymadefromsilverandcopperalloys.Theamountofcopperinanalloy
canvaryconsiderably.Thefinestqualityalloyissterlingsilver,whichis92.5%silverbymass.To
determinethecompositionofasilvercopperalloy,ajewellerdissolved0.135gofmetalshavings
in50mLofconcentratednitricacidandthenadded1.00MKClsolutionuntilnomoreprecipitate
formed.Filtrationanddryingyielded0.156gofAgClprecipitate.Whatwasthemasscomposition
ofthesilveralloy?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYTERMS
actualyield empiricalformula product
amountofsubstance excessreagent qualitativeanalysis
Avogadroconstant(NA) limitingreagent quantitativeanalysis
balancedchemicalequation mainreaction reactant
byproduct masspercentagecomposition reversiblereaction
chemicalequation molarmass(M) solute
chemicalreaction molarity(c) solution
combustion mole solvent
competingreaction molecularformula spectatorion
concentration netionicequation stoichiometriccoefficients
dissociation percentagebymass stoichiometry
elementalanalysis percentageyield theoreticalyield

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
CHAPTER

4 AtomicEnergyLevels
Intherightcombination,atomsandlightcombinetocreateoneofthemostremarkabletools
ofmoderntechnology,thelaser.Laserlightismorehighlyorganisedthannormallight.
Laserlightismonochromatic(hasasinglewavelength)andishighlydirectional,whereas
conventionallightsourcestypicallyproducedisperselightofmanywavelengths.The
picturesonthispagedemonstratethesedifferences.Inthetoptwofiguresweseeredand
greenlaserlightwithwavelengthsof650and532nm,respectivelypassthroughaprism.
Whilethelightisdiffracted,thereisnosplittingintodifferentcolours,asweseeforwhite
lightinthebottomfigure.Thisconfirmsthatlaserlightconsistsofonlyonewavelength
whilenormalwhitelightcomprisesmanywavelengths.Manyoftheapplicationsoflasers
takeadvantageofthehighdegreeoforganisation.

Lasersarealsousedin,forexample,DVDscanners,eyesurgeryandfibreoptics
communications.Lasershavealsobecomeversatiletoolsforscientificresearch.For
example,finelytunedlasershavebeenusedtodepositvapourphaseatomsonsolidsurfaces
inregularpatterns.Theabilitytomanipulateindividualatomsislikelytohaveimportant
applicationsinnanotechnology.

Everylaserisbasedontheinteractionsbetweenlightandatomsormolecules.Inthischapter,
wedescribethepropertiesofatomsandlightandtheenergychangesthataccompanythe
interactionsbetweenthem.Thenwedescribethepropertiesofelectronsboundtoatomsand
howthesecontributetoatomicstructure.Weexplorethedetailsoforbitalenergiesandrelate
themtotheorderingofatomsthatleadstothefamiliarformandstructureoftheperiodic
table.Orbitalenergylevelshaveconsequencesthatarefarreaching.Orbitalenergies
determinethestabilityofatomsandhowatomsreact.Theperiodictableisbasedonorbital
energylevelsandprovidesthefoundationforinterpretingpatternsofchemicalbehaviour
relatedtoanelement'spositioninthetable.

KEYTOPICS

4.1Characteristicsofatoms
4.2Characteristicsoflight
4.3Propertiesofelectrons
4.4Quantisationandquantumnumbers
4.5Atomicorbitalelectrondistributionsandenergies
4.6Structureoftheperiodictable
4.7Electronconfigurations
4.8Periodicityofatomicproperties
4.9Ionsandchemicalperiodicity
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.1CharacteristicsofAtoms
Weintroducedtheconceptoftheatominchapter1,andstatedthatitwasthefundamentalbuilding
blockofallmatter.Inthischapter,wewillinvestigatethepropertiesofatomsinmoredetail.Wewill
startbyoutliningthebasiccharacteristicsofatomswereadaboutmanyofthesecharacteristicsin
chapter1.

Atomspossessmass,mostofwhich,asRutherfordshowed,isconcentratedinthenucleus.Thenucleus
ofanatomissmallandpositivelycharged,andallnuclei,exceptthatofthehydrogenatom1H,consist
ofbothpositivelychargedprotonsandneutralneutrons.Thepositivechargeofthenucleusisexactly
balancedbynegativelychargedelectrons,whichoccupytheregionofspacearoundthenucleus.A
neutralatomcontainsequalnumbersofprotonsandelectrons.Atomsoccupyvolume,themajorityof
whichistakenupbytheelectroncloud.Thechemicalpropertiesofelementsaredeterminedtoalarge
extentbyboththeiratomicsizeandtheirnumberofaccessible(valence)electrons.Finally,atomscan
attractoneanother,and,asaresult,cancombinetoformmolecules.

Thischapterexaminesindetailhowboththenumberofelectronsandtheirspecificarrangement
influencechemicalproperties.Sincetherearesimilaritiesbetweenthepropertiesoflightandelectrons,
andlightisanessentialtoolforprobingthepropertiesofelectrons,wewillbeginourdiscussionby
describinglightanditsinteractionwithatoms.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.2CharacteristicsofLight
Themostusefultoolforstudyingthestructureofatomsiselectromagneticradiation.Whatwecalllightisoneformofthis
radiation,withotherformsincludingradiowaves,microwavesandXrays.Weneedtoknowaboutthefundamental
propertiesoflighttounderstandwhatelectromagneticradiationrevealsaboutatomicstructure.

WavelikePropertiesofLight
Lighthaswavelikeproperties.Awaveisaregularoscillationinsomeparticularproperty,suchastheupanddown
variationinpositionofwaterwaves.Waterwavesvarywithtime.Asurferwaitingforabigonebobsupanddownas
smallonespassby.Lightwavesvarywithtimetoo,inamoreregularmannerthanwaterwaves.Thisvariationis
characterisedbythewave'sfrequency(),whichisthenumberofwavecrestspassingapointinspacein1second(sothe
unitiss1,alsodesignatedhertzorHz).Waterwavesalsovaryinheightasyoumoveawayfromthebeachthatis,the
heightofthewavevarieswithposition.Lightwavesvaryinspaceinamannerillustratedinfigure4.1.Thisvariationin
spaceischaracterisedbythewavelength(),whichisthedistancebetweensuccessivewavecrests.Wavelengthsare
measuredinunitsoflength,suchasmetresornanometres.Aswewillseebelow,frequencyandwavelengtharenot
independentvariables,butareinverselyproportionaltoeachother.

FIGURE4.1Alightwavecanbedescribedbyitswavelengthorfrequency.Aswavelengthincreases,frequencydecreases,andvice
versa.

Amplitudeisthemaximumdisplacementofawavefromitscentre.Theamplitudeofalightwavedeterminestheintensity
ofthelight.Asfigure4.2shows,abrightlightismoreintensethanadimoneasitswaveshavehigheramplitudes.Itis
importanttonotethattheintensityoflightisproportionaltothesquareofitsamplitude.Theamplitudeitselfhasno
physicalmeaningbecauseatanymomentintimetheamplitudeofthewavecanbenegativeorpositive,whilethesquareis
alwayspositiveandequivalenttophotondensity.
FIGURE4.2Theamplitudeofalightwavedeterminestheintensityofthelight.Abrightlightismoreintenseandhasahigher
amplitudethanadimlight.

Wavescanalsobedescribedintermsoftheirphase.Phasereferstothestartingpositionofawavewithrespecttoone
wavelength.Wecanseethatwavesinfigures4.3aand4.3bhavethesameamplitudeandwavelengths,butdifferent
startingpoints.Wesaythatthetwowaveshavedifferentphases.Wecanseethismoreclearlyinfigure4.3cwhichshows
thetwowavessuperimposed.Iftheyhadthesamephase(andthesameamplitudeandwavelength),theywouldlineup
perfectly.Aswewillseeonp.189,whenwavesinteract,theoutcomeisinfluenced,amongotherthings,bytheirrelative
phases.

FIGURE4.3Phasereferstothestartingpositionofawavewithrespecttoonewavelength.Thewavesin(a)and(b)havedifferent
phases(c)showsanoverlapof(a)and(b).

Lightwaves,andallothertypesofelectromagneticradiation,alwaysmovethroughavacuumatthesamespeed.Thespeed
oflightisafundamentalconstant,denotedbythesymbolc:c=2.9979245810 8ms1(wewillrounditto2.99810 8
ms1).Foranywave,itsfrequency()(inunitsofs1)multipliedbyitswavelength()(inunitsofm)equalsitsspeedc(m
s1),i.e.

WORKEDEXAMPLE4.1

WavelengthfrequencyConversion
AnFMradiostationtransmitsitssignalat88.1MHz.Whatisthewavelengthofthesignal?

Analysis

Thelinkbetweenwavelength()andfrequency()isgivenbyc=.

Solution

First,wesummarisethedata.

Next,werearrangetheequationtosolveforwavelength.

Toobtainequivalentunits,convertthefrequencyunitsfromMHztoHz.TheprefixMstandsformega,which
isafactorof10 6.RememberthatHzisequivalenttos1.
Isouranswerreasonable?

Thewavelengthof3.40mmayseemratherlong,butradiowavesareknownaslongwavelengthradiation.See
figure4.4forasenseofthewavelengthsofelectromagneticradiation.

FIGURE4.4Theelectromagneticspectrum,showingitsvariousregionsandtheassociatedwavelengthsand
frequencies.

PRACTICEEXERCISE4.1
Whatisthefrequencyofelectromagneticradiation
thathasawavelengthof1.40cm?

Thewavelengthsorfrequenciesofelectromagneticradiationcoveranimmenserange.Figure4.4showsthatthevisible
spectrumcoversthewavelengthrangefromabout380nm(violet)to780nm(red).Thecentreofthisrangeisyellowlight,
withawavelengthofabout580nmandafrequencyaround5.210 14s1.Althoughvisiblelightisextremelyimportantto
livingcreaturesforvision,thegammaray,Xray,ultraviolet,infrared,microwaveandradiofrequencyportionsofthe
electromagneticspectrumalsohavediverseeffectson,andusesin,ourlives.

Radiationwithshortwavelengths,intheXrayandgammarayregions,cangenerateionsbyremovingelectronsfrom
atomsandmolecules.Theseionsarehighlyreactiveandcancauseseriousdamagetothematerialthatabsorbsthe
radiation.However,undercloselycontrolledconditions,Xraysareusedinmedicalimaging,andgammaraysareusedto
treatcancer.Thewavelengthofultraviolet(UV)radiationliesbetweenthatofXraysandvisiblelight.Ultravioletradiation
canalsodamagematerials,especiallyinhighdoses.HighratesofskincancerinAustraliaandNewZealandareadirect
resultofexposuretodamagingUVradiationinsunlight.

Radiationwithlongwavelengthsfallsintheinfrared,microwaveorradiofrequencyregions.Heatlampsmakeuseof
infraredradiation,microwaveovenscookwithmicrowaveradiation,andradioandtelevisionsignalsaretransmittedby
radiowaves.

Whatweperceiveaswhitelightactuallycontainsarangeofwavelengths.Thisbecomesapparentwhensunlightpasses
throughaprism(seep.109)orthroughraindrops(whichcreatesarainbowasshowninfigure4.5).Theseobjectsdiffract
differentwavelengthsoflightthroughdifferentangles,sothelightthatpassesthroughspreadsoutinspace,witheach
wavelengthappearingatitsowncharacteristicangle.
FIGURE4.5Lightraysbendastheypassthroughraindrops,causingwhitelighttoseparateintoitsrainbowofcolours.

ParticlePropertiesofLight
Lightcarriesenergy.Whenourbodiesabsorbsunlight,forexample,wefeelwarmbecauseenergyfromthesunlighthas
beentransferredtoourskin.Aphenomenonknownasthephotoelectriceffectshowshowtheenergyoflightdependson
itsfrequencyandintensity.Thephotoelectriceffectisthebasisformanylightsensingdevices,suchasautomaticdoor
openersandcameraexposuremeters.Figure4.6illustratesaphotoelectricexperimentinwhichabeamoflightstrikesthe
surfaceofametal.Undertherightconditions,thelightcauseselectronstobeejectedfromthemetalsurface.Adetailed
studyofthephotoelectriceffectrevealshowthebehaviouroftheseelectronsisrelatedtothecharacteristicsofthelight:
1.Belowacharacteristicthresholdfrequency,0,noelectronsareobserved,regardlessofthelight'sintensity.

FIGURE4.6Adiagrammaticviewofthephotoelectriceffect.Whenlightofahighenoughfrequencystrikesametal,electrons
areejectedfromthesurface.

2.Abovethethresholdfrequency,themaximumkineticenergyofejectedelectronsincreaseslinearlywiththe
frequencyofthelight,asshowninfigure4.7.(Kineticenergyisafunctionoftheelectron'sspeed.Wewilllearn
moreaboutkineticenergywithreferencetogasesinchapter6.)
FIGURE4.7Variationinthemaximumkineticenergyofelectronsejectedfromtwodifferentmetalsurfaces(aandb)asa
functionofthefrequencyofincominglight.

3.Abovethethresholdfrequency,thenumberofemittedelectronsincreaseswiththelight'sintensity,butthekinetic
energyperelectrondoesnotdependonthelight'sintensity.
4.Allmetalsexhibitthesamebehaviour,but,asfigure4.7shows,eachmetalhasadifferentthresholdfrequency.

In1905,AlbertEinsteinpostulatedthatlightcomesinpacketsorbundles,calledphotons.Eachphotonhasanenergy
thatisdirectlyproportionaltoitsfrequency.

Inthisequation,Eistheenergyofaphotonoflightandisitsfrequency.Theproportionalityconstantbetweenenergyand
frequencyisknownasPlanck'sconstant(h)andhasavalueof6.6260693(11)10 34Js(wewilluse6.62610 34Js).
The11inparenthesesreferstotheuncertaintyinthefinaldigitstherefore,h=(6.62606930.0000011)10 34Js.

WORKEDEXAMPLE4.2

Theenergyoflight
Whatistheenergyofaphotonofredlightwithawavelengthof655nm?

Analysis

Thisconversionproblemrequirestwosteps.WedonothaveanequationthatwillcalculateEbasedonthedata
wehave,but,bycombiningthetwoequationswedoknow,wecanrelatetheenergyofaphotontoitsfrequency
andwavelength.

Solution

First,wesummarisethedata.

Thenwecombinetheequationsintoanequationthatrelatesenergytowavelength.

Substitutingourdata,wefind:

Isouranswerreasonable?

Anenergyof10 19Jseemsverysmall,butwemustrememberthatthisistheenergyofasinglephoton.Ifwe
wanttocalculatetheenergyofamoleofthesephotons,weneedtomultiplyourresultbytheAvogadro
constant,i.e.Eonemoleofphotons=EphotonNA=(3.0310 19J)(6.02210 23mol1)=18210 3Jmol1=
182kJmol1.Thisenergyiscomparabletotheenergiesofchemicalbonds.

PRACTICEEXERCISE4.2
Whatistheenergyofaphotonwithawavelengthof
254nm(UVradiation)?
Einsteinconcludedthattheenergyofaphotonthathasthethresholdfrequency(0)correspondstothebindingenergyof
theelectron.Energybeyondthethresholdfrequencyincreasestheelectron'skineticenergyasshowninfigure4.8.Thiscan
bedescribedby:

FIGURE4.8Diagramoftheenergybalanceforthephotoelectriceffect.

Einstein'sexplanationaccountsfortheobservedpropertiesofthephotoelectriceffect.Whentheenergyofthephotonisless
thanh0(lowfrequencylight),noelectronscanescapefromthemetalsurface,nomatterhowintensethelight.Whenthe
energyofthephotonisgreaterthanh0,anelectronisejectedandanyexcessenergyistransferredtothatelectronas
kineticenergy.Theintensityofalightbeamisameasureofthenumberofphotonsperunittimelightofahigher
amplitudecarriesmorephotonsthanlightofloweramplitude.Theintensityofthelightdoesnotdeterminetheamountof
energyperphoton.Morephotonsstrikingthemetalresultinmoreelectronsbeingejected,buttheenergyofeachphoton
andeachelectronisunchanged.Finally,thefactthateachmetalhasitsowncharacteristicthresholdfrequencysuggeststhat
electronsareboundmoretightlytosomemetalsthantoothers.

ChemistryResearch

TheAustralianSynchrotron

Electromagneticradiationinitsmanyformsisfrequentlyusedtoprobethenatureofchemicalcompounds,
whethertheyareemployedasmaterialsforelectronicdevices,newlydevelopeddrugsoranythinginbetween.
Theintensity,coherenceandwavelengthoftheavailableradiationstronglyinfluencethedetailedinformation
thatcanbeextractedandwhichisneededtoadvancechemistryinallitsforms.Importantpropertiesof
electromagneticradiationcanbemaximisedusingasynchrotronsourceand,inthiscontext,theopeningofthe
AustralianSynchrotroninMelbournein2007hasbeenahighlightfortheadvancementofAustralasianscience
(figure4.9).Theopeningofthefacilityhasbroughtthesynchrotronhome,inasense,sinceitwasAustralian
physicistSirMarcusOliphantwhoiscreditedwiththeoriginalideaforaprotonsynchrotron(thefacilityin
Melbourneisactuallyanelectronsynchrotron).Whilescientistsfromourregionhavepreviouslyused
synchrotronsaroundtheglobe(therearenowabout50ofthesefacilitiesintheworld),thesynchrotronin
MelbourneallowscurrentandfutureAustralianandNewZealandscientistsunprecedentedaccesstosucha
facility.Figure4.10showsabeamlinescientistandtwostudentsfromtheUniversityofSydneyaligningasample
onthepowderdiffractionbeamlineattheAustralianSynchrotron.Sofarabout2000scientists,mainlyfrom
AustraliaandNewZealand,haveusedbeamlinesattheAustralianSynchrotronfortheirresearch.Manyofthese
usersarestudentsworkingontheirHonoursorPhDtheses,andonedayyoumightusethefacilityyourself.
FIGURE4.9AerialviewoftheAustralianSynchrotronbuildinglocatedinClayton,Victoria.
AustralianSynchrotron

FIGURE4.10Beamlinescientist(middle)helpingpostgraduatestudentsusingtheAustralianSynchrotronfacilitiesto
assisttheirstudies.

Australianscientistshaveusedsynchrotronsforapplicationsasdiverseasestablishingthepresenceofarsenicin
theracehorsePharLapunderstandinghowsomenativeplantsimmobiliseheavymetalsandhencecanbeused
toremediatecontaminatedsoilsstudyingtheuptakeofleadinteethwithaviewtoenhancingneonatalcare
aroundBrokenHilldesigningdrugs,includingtheantiviraldrugRelenzabytheAustralianbiotechnology
companyBiotaanddevelopingcopperbasedantiinflammatorydrugsfortreatingarthritisinhorsesanddogs.
Synchrotronradiationcanalsobeusedinlessobviousareassuchasstudyingtheearlystagesoflung
developmentinnewborntammarwallabies,inarchaeologybothtoidentifytheoriginsofartefactsandto
understandhowtheyweremade,aswellasinfoodsciencetodeveloplowfatpotatochips.Recenthighlightsof
theworkbymanyvisitingscientistsattheAustralianSynchrotronincludeinvestigationsofchemicalcompounds
forthedevelopmentofanticancerdrugs,scanninganentireArthurStreetonpaintingtoidentifyindividual
brushstrokesofdifferentcoloursbasedonthedistributionofdifferentelementsonthecanvas,andinvestigation
ofadvancedmaterialsforincorporationintorechargeableLiionbatteries.

Inordertoimproveourunderstandingofsynchrotronscienceweneedtodiscusstheoriginoftheradiation.
Whenelectronsareforcedtotravelinacircularorbitatspeedsapproachingthespeedoflight,theyemitradiation
intheformofphotonsofvariouswavelengths,rangingfrominfraredtohardXrays(wavelengthsof10 6to10
11m,respectively,seefigure4.4).Thisradiationiscalledsynchrotronradiationandischaracterisedbyitshigh
intensity(figure4.11),makingitveryusefulforstudyingtheabsorption,reflectionanddiffractionpropertiesof
matter.Thegenerationofsynchrotronradiationisnotatrivialmatter,and,aswehaveseenabove,thereisa
limitednumberoffacilitiesaroundtheworldinwhichsynchrotronexperimentscanbecarriedout.
FIGURE4.11Comparisonofbrightness(intensity)ofradiationfromarangeofsources.

Figure4.12showsaschematicoftheAustralianSynchrotron.Electronsaregeneratednearthecentre(electron
gun)andacceleratedtoalmostthespeedoflightbythelinearaccelerator(linac)andtheboosterring.Theyare
thentransferredtotheouterstoragering.Theelectronsareconfinedtothecircularorbitbyaseriesofbending
magnetsseparatedbystraightsections.Astheelectronsaredeflectedthroughthemagneticfieldcreatedbythe
bendingmagnets,theygiveoffelectromagneticradiation,sothatabeamofsynchrotronradiationisproducedat
eachbendingmagnet.Theseintensebeamsofwhiteradiation(i.e.withaspectrumofwavelengthsfrominfrared
tohardXrays)canbecapturedanddirectedtoabeamlineendstationwhereaspecificwavelengthappropriate
foraparticulartechniqueorspecificexperimentcanbeselected.

FIGURE4.12SchematicoftheAustralianSynchrotron.
Source:IllustratorMichaelPayne.ImagesuppliedcourtesyofAustralianSynchrotron.

AtthisstagetheAustralianSynchrotronhasatotalofninebeamlines,ofwhicheightareoperational.Eachof
thesebeamlinesisdedicatedtothespecificpurposesoutlinedinthetablebelow.

Beamlinename Capabilities
Beamline1 Dedicatedfacilityforcrystallographyoflargeproteincrystals,setupwithrobotic
loadingandcentring,andforremoteoperation
Highthroughput
protein
crystallography
Beamline2 FacilitywithfinelyfocusedXraybeamfordeterminingthecrystalstructureand
electrondensitymapsofsmall,hardtocrystalliseproteins,nucleicacids,andfor
Proteinmicrocrystal smallmolecules
andsmallmolecule
diffraction
Beamline3 Versatile,highresolutionpowderdiffractionfacilityequippedwithsample
chambersforawiderangeofinsituexperiments
Powderdiffraction
Beamline4 Measurementoflongrangeorderincomplexmoleculesandmaterials

Smallandwide
angleXray
scattering
Beamline5 Measurementofshortandmediumrangeorder,bondlengths,coordination
numbersandlocalcoordinationgeometry,andtheoxidationstateofatomsfrom
Xrayabsorption atomicnumberZ=20upwards
spectroscopy
Beamline6 Asforbeamline5,forthelightelements,Z<20alsofortheanalysisofsurfaces
andthinfilms
SoftXray
spectroscopy
Beamline7 Analysisofbondsincomplexmolecules,biologicalmaterials,mineralsandband
structuresincertainsemiconductors
Infrared
spectroscopy
Beamline8 Forproductionofhighresolutionmapsofelementaldistributioninasamplealso
fordeterminationoftheoxidationstateandcoordinationgeometryofatomsin
Microspectroscopy particlesdowntosubmicronsize
Beamline9 Veryflexiblebeamlineforresearchintohighcontrastimagingofobjectsfrom
smallanimalsthroughtoengineeringcomponentsalsoforresearchintothe
Imagingand physicsandbiophysicsofcancertherapytechniques
medicaltherapy

Theintensityoftheradiationcanbefurtherincreasedbytheuseofinsertiondevicesinthestraightsectionsof
thering.Therearetwoclassesofinsertiondevices,multipolewigglersandundulators.Current(third
generation)designsofsynchrotronsaimtooptimisetheintensitythatcanbeobtainedfrominsertiondevices.In
particular,attentionisgiventothesizeandpositioningofthestraightsectionsthataccommodatetheinsertion
devices.TheAustralianSynchrotronisanadvancedthirdgenerationdesign.Itaccommodatesthethreedifferent
typesoflightsources(bendingmagnets,multipolewigglersandundulators)toenableawiderangeofadvanced
experimentsandmeasurementstobecarriedout.

Einstein'sexplanationofthephotoelectriceffectshowedthatlighthassomepropertiesofparticles.Acompletedescription
oflightincludesbothwavelikeandparticlelikeproperties.Whenlightinteractswitharelativelylargebodysuchasa
raindroporaprism,itswavepropertiesdominatetheinteraction.Ontheotherhand,whenlightinteractswithasmallbody
suchasanatomoranelectron,particlepropertiesdominatetheinteraction.Eachviewprovidesdifferentinformationabout
thepropertiesoflight,and,whenwethinkaboutlight,wemustthinkofparticlewavesthatcombinebothtypesoffeatures.

AbsorptionandEmissionSpectra
Inthephotoelectriceffect,whenphotonsstrikeametalsurface,theenergyabsorbedprovidesinformationaboutthe
bindingenergiesofelectronstometalsurfaces.Whenlightinteractswithfreeatoms,theinteractionrevealsinformation
aboutelectronswithinindividualatoms.
LightandAtoms
Attractiveelectrostaticforcesholdanelectronwithinanatom.Energymustbesuppliedtoremovetheelectronfromthe
atom.Thelowertheatom'senergystate,themoreenergyisrequiredtoremoveitselectron.Theenergyrequiredis
measuredrelativetotheenergyofafreeelectron.Wedefinetheenergyofahypotheticalfreestationaryelectrontobezero.
Asfigure4.13indicates,thekineticenergyofafreelymovingelectronispositiverelativetothisconventionalzeropoint.In
contrast,boundelectronsarelowerinenergythanthehypotheticalfreestationaryelectron,soweassignthemnegative
energyvalues.

FIGURE4.13Byconvention,afreestationaryelectronhaszeroenergy,andboundelectronshavenegativeenergies.

Theabsorptionofphotonsbyfreeatomshastwopossibleresults,dependingontheenergyofthephoton.Whenanatom
absorbsaphotonofsufficientlyhighenergy,anelectronisejected(i.e.theatomionises).Thisprocessisdescribedlaterin
thischapter.Here,wefocusonthesecondtypeofresult,inwhichtheatomgainsenergy,butdoesnotionise.Instead,the
atommovesfromthelowestenergyorgroundstatetoahigherenergystatecalledanexcitedstate.Aswesawinchapter
1,thisprocessiscalledanelectronictransition.Excitedstatesarenotstableandatomsinexcitedstatessubsequentlygive
uptheirexcessenergytoreturntolowerenergystates,andeventuallythegroundstate.Theylosetheirexcessenergyin
collisionswithotheratomsorbyemittingphotons.

Thekeyfeatureintheexchangeofenergybetweenatomsandlight(photons)isthatenergyisconserved.Thisrequiresthat
thechangeinenergyoftheatomexactlyequalstheenergyofthephoton.

Whenanatomabsorbsaphoton,theatomgainsthephoton'senergy,soEatomispositive.Whenanatomemitsaphoton,
theatomlosesthephoton'senergy,soEatomisnegative.Asanatomreturnsfromanexcitedstatetothegroundstate,it
mustloseexactlytheamountofenergythatitoriginallygained.However,excitedatomsusuallyloseexcessenergyin
severalstepsinvolvingsmallenergychanges,sothefrequenciesofemittedphotonsareoftenlowerthanthoseofabsorbed
photons.

WORKEDEXAMPLE4.3

EmissionEnergies
Asodiumvapourstreetlampemitsyellowlight(figure4.14)atawavelengthof589nm.Whatistheenergy
changeforasodiumatominvolvedinthisemission?Howmuchenergyisreleasedpermoleofsodiumatoms?
FIGURE4.14Sodiumvapourlampsemityellowlight.

Analysis

Thisproblemrelatesenergiesofphotonstoenergychangesofatoms.Thesolutionrequiresaconversion
involvingwavelengthandenergy.

Solution

Sodiumatomsloseenergybyemittingphotonsoflight(=589nm).Wecanrelatethewavelengthofoneof
thesephotonstoitsenergy.

Energyisconserved,sotheenergyoftheemittedphotonmustexactlyequaltheenergylostbytheatom.

Theequalityincludesanegativesignbecausetheatomlosesenergy.

Tocalculatetheenergyofaphoton,weneedthefollowingdata.

Thiscalculationgivestheenergychangeforonesodiumatomemittingonephoton.Wemultiplythisvalueby
theAvogadroconstanttoconvertfromenergyperatomtoenergypermole.

Rememberingthatthenegativesignsimplymeansthattheatomislosingenergy,theactualenergyreleasedis
theabsolutevalueofthis,i.e.203kJmol1.

PRACTICEEXERCISE4.3
Mercurylampsemitphotonswithawavelengthof436
nm.Calculatetheenergychangeofthemercuryatoms
inJatom1andkJmol1.

AtomicSpectra
Whenalightbeampassesthroughatubecontainingagasconsistingofatomsofasingleelement,theatomsabsorb
specificfrequenciesoflightcharacteristicofthatelement.Asaresult,thebeamemergingfromthesampletubehasfewer
photonsatthesespecificfrequencies.Thefrequencieswithdiminishedintensityinthevisibleportionofthespectrumcan
bedetectedbypassingtheemerginglightthroughaprism.Theprismdiffractsthelight,withdifferentfrequencies
diffractingthroughdifferentangles.Afterleavingtheprism,thebeamstrikesascreen,wherethefrequencieswith
diminishedintensityappearasgapsordarkbandscalledlines,whichareimagesoftheslit.Thesearethefrequenciesof
lightabsorbedbytheatomsinthesampletube.Theresultingpattern,shownschematicallyinfigure4.15,iscalledan
absorptionspectrum.

FIGURE4.15Schematicrepresentationofanapparatusthatmeasurestheabsorptionspectrumofamonatomicgas.Thegasinthe
tubeabsorbslightatspecificwavelengths,calledlines,sotheintensityoftransmittedlightislowand,therefore,dark
linesappearattheseparticularwavelengths.

Anabsorptionspectrumisusedtodeterminethefrequenciesofthephotonsthatanatomabsorbs.Asimilarexperimentcan
measuretheenergiesofthephotonsemittedbyatomsinexcitedstates.Figure4.19outlinesthefeaturesofanapparatusthat
measurestheseemittedphotons.Anelectricaldischargeexcitesacollectionofatomsfromtheirgroundstateintohigher
energystates.Theseexcitedatomsthenloseall,orpartof,theirexcessenergybyemittingphotons.Thisemittedlightcan
beanalysedbypassingitthroughaprismtogiveanemissionspectrum.Thisisaplotoftheintensityoflightemittedasa
functionoffrequency.Theemissionspectrumforatomichydrogen,showninfigure4.22,showsseveralsharpemission
linesofhighintensity.Thefrequenciesoftheselinescorrespondtophotonsemittedbythehydrogenatomsastheyreturn
totheirgroundstate.

Eachelementhasuniqueabsorptionandemissionspectra.Thatis,eachelementhasasetofcharacteristicfrequenciesof
lightthatitcanabsorboremit.Itisimportanttonotethatfigures4.15,4.19,4.20and4.22showonlythevisibleportionsof
theabsorptionandemissionspectra.Electronictransitionsalsotakeplaceinregionsoftheelectromagneticspectrumthat
thehumaneyecannotdetect.Instrumentsallowscientiststoobserveelectromagneticradiationintheseregions.

ChemicalConnections

PhotoelectronSpectroscopy

DrDanielSoutham,DepartmentofChemistry,CurtinUniversity

Therelativeenergiesofelectronswithinatomscanbemeasuredusingasuiteoftechniquescalledphotoelectron
spectroscopy(PES).PESexploitsthephotoelectriceffect(seepp.11213)tomeasurethekineticenergyof
ejectedelectronsfromatomsandmolecules.InPES,anatomisexcitedbyamonochromaticbeamofphotons
withaknownenergy(Ephoton).Theenergyoftheincidentphotonbeamiswellinexcessoftheionisation
energiesofelectronswithinallvalenceandsomecoreshellsofmanyatoms.Whenanincidentphotonexcitesthe
atomormolecule,anelectronabsorbsenergyandisejectedfromitsorbital(seefigure4.16).Theejected
electronsarecalledphotoelectrons.
FIGURE4.16 (a)TheprocessofionisationofanelementMcausedbytheincidentphotonejectingaphotoelectron.
(b)Anillustrationoftheatomicscaleprocessshowinganincidentphotonexcitinganelectronwhich
isejectedfromtheatomwithameasurablekineticenergy.

Thekineticenergyofthephotoelectroncanbecomparedwiththeenergyoftheincidentphotontogiveits
bindingenergy.Thebindingenergyofeachelectronischaracteristicnotonlyoftheatomandtheorbitalin
whichtheelectronresides,butalsooftheoxidationstateoftheatomorionandthesurroundingchemical
bondingenvironment.PESgivesstrongexperimentalevidenceforthequantisednatureoftheatomandthe
existenceofatomicandmolecularorbitals(seesection5.7).Forexample,infigure4.17,thephotoelectron
spectraofelementsfromthesecondperiodoftheperiodictableconfirmsthat,astheatomicnumberincreases,
thecore1selectronsalsoincreaseinenergy.Theirbindingenergiesthereforeincrease,andtheybecomemore
difficulttoremove.

FIGURE4.17Photoelectronspectraofelementsfromthesecondperiodoftheperiodictable.Theregionofthespectra
correspondingtoionisationof1selectronsisshownforeachelement.

TheincidentphotonsusedinPESareoftenderivedfromXrayemissionsofmagnesium(121.0MJmol1)and
aluminium(143.4MJmol1),makingXrayphotoelectronspectroscopy(XPSalsocalledelectronspectroscopy
forchemicalanalysis,ESCA)themostfrequentlyencounteredtechniqueofthesuite.XPSismostoftenusedfor
theanalysisofsurfaces,suchassemiconductors,polymers,ceramicsandmetalalloys.XPSallowsthe
quantitativedeterminationofelementalabundance,andsomeinstrumentscanachievespatialelementalmapping,
whichisusefulinawiderangeofdisciplinessuchasmaterialsscienceandgeology.Arecentexampledisplays
theutilityofXPSinmodernscientificresearch.Theinvestigatorsdepositedatomicallyprecisenanoribbonsof
graphenesheetsinachevronpatternontoagoldsurface,asshowninfigures4.18a,bandusedXPStoensure
thatthegraphenedidnotsufferanyoxidationduringthisprocess.Asshowninfigure4.18c,thecarbon1speak
hasachemicalbondingenvironmentcharacteristicoftheabsenceofoxygen.
FIGURE4.18 (a)Thechemicalstructureofagraphenenanoribbon,
(b)ascanningtunnellingmicrograph(seechapter1)illustratingdepositionofnanoribbonsonagold
surfaceand
(c)aphotoelectronspectrumofthesurfaceindicatingthelackofoxidationofgraphene.

FIGURE4.19Schematicrepresentationofanapparatusthatmeasurestheemissionspectrumofagaseouselement.Emissionlines
appearbrightagainstadarkbackground.Thespectrumshownistheemissionspectrumforhydrogenatoms.

FIGURE4.20Emissionpatternsforhydrogen,neon,sodiumandmercury.Eachelementhasauniqueemissionpatternthat
providesvaluablecluesaboutitsatomicstructure.

Eachfrequencyabsorbedoremittedbyanatomcorrespondstoaparticularenergychangefortheatom.These
characteristicpatternsofenergygainsandlossesprovideinformationaboutatomicstructure.Figure4.20showsthe
emissionspectraforselectedatoms.

QuantisationofEnergy
Whenanatomabsorbsaphotonoflightoffrequency,thelightbeamlosesenergyequaltoh,andtheatomgainsthat
amountofenergy.Whathappenstotheenergythattheatomgains?Aclueisthat,whenthefrequencyoftheincoming(or
absorbed)lightishighenough,itproducescationsandfreeelectrons.Inotherwords,aphotonwithhighenoughenergy
cancauseanatomtoloseoneofitselectrons,i.e.ionise.Thisimpliesthatabsorptionofaphotonresultsinanenergygain
foranelectronintheatom.Statedasanequation:

Theatomicspectraofmostelementsarecomplexandshowlittleapparentregularity.However,in1885,theSwiss
mathematicianandphysicistJohannBalmerwasabletoproposeasingleequationthatcoulddescribetheemission
spectrumofthehydrogenatom.Theequationwas:

inwhichn 1andn 2areintegers(1,2,3etc.).In1913,theDanishphysicistNielsBohrusedEinstein'spostulate(E=h)to


interpretBalmer'sobservations.Combiningthetwoequations,Bohrwasabletodescribetheenergylevelsoftheelectronin
thehydrogenatomwiththefollowingequation,wherenisapositiveinteger.

Thenegativesignintheequationreflectsthefactthatboundelectronsarelowerinenergythanastationaryfreeelectron
(withitsenergydefinedaszero).

Bohrrealisedthattheemissionfrequencieshavespecificvaluesbecausetheelectroninahydrogenatomisrestrictedto
specificenergies.Bohr'sideaofrestrictedenergylevelswasrevolutionarybecausescientistsatthattimethoughtthatthe
electroninahydrogenatomcouldhaveanyenergy.Incontrast,Bohrinterpretedthehydrogenemissionspectrumtomean
thatelectronsboundtoatomscanhaveonlycertainspecificenergyvalues.HewontheNobelPrizeinphysicsin1922for
thisinterpretation.Apropertythatcannotchangecontinuously,andisrestrictedtospecificvalues,issaidtobequantised.
Theatomicenergylevelsofhydrogen(andotherelements)arequantised.Eachintegervalueofndescribesoneofthe
allowedenergylevelsofthehydrogenatom.Forexample,theenergyofanelectroninhydrogen'sfourthlevelis:

Whenanelectronchangesenergylevels,thechangeisanelectronictransitionbetweenquantisedlevels.Whenahydrogen
atomabsorbsoremitsaphoton,itselectronmovesfromoneenergyleveltoanother.Thus,thechangeinenergy(E)of
theatomistheenergydifferencebetweenthetwolevels.

Photonsalwayshavepositiveenergies,butenergychanges(E)canbepositiveornegative.Whenaphotonisabsorbed,
anelectronispromotedtoahigherenergylevel,theatomgainsenergyandEfortheatomispositive.

Whenaphotonisemitted,anelectronfallsfromahigherenergyleveltoalowerone,theatomlosesenergyandEforthe
atomisnegative.

Wecancombinethesetwoequationsbyusingabsolutevalues.

WORKEDEXAMPLE4.4

EnergylevelsoftheHydrogenAtom
Whatistheenergychangewhentheelectroninahydrogenatomundergoesatransitionfromthefourthenergy
leveltothesecondenergylevel?Whatisthewavelengthofthephotonemitted?

Analysis

Thequestionasksaboutenergyandthewavelengthofaphotonemittedbyahydrogenatom.Wavelengthis
relatedtoenergy,andphotonenergyisdeterminedbythedifferenceinenergybetweenthetwolevelsinvolved
inthetransition.Inthiscase,theelectronmovesfromthefourthtothesecondenergylevel.Theenergy
differencebetweenthesetwostatesisgivenby:

Solution

Asshownabove,E4=1.3610 19J.Asimilarcalculationgivestheenergyofthesecondlevel.

Thisenergychangeisnegativebecausetheatomlosesenergy.Theenergydifferencebetweenthetwolevelsis:

Thenegativesignfortheenergychangeisconsistentwiththeatomlosingenergy.Thislostenergyappearsasa
photonwithenergyof:

Todeterminethewavelengthofthephoton,weuse:

Solvingforgives:

Isouranswerreasonable?

Thesignsoftheenergiesareconsistenttheatomlosesenergyandthephotonemittedhaspositiveenergy.
Fromfigure4.4(p.112)wecanseethatlightwithawavelengthof486nmhasabluegreencolour.Cross
checkingagainsttheemissionspectrumofhydrogen(figure4.20),wecanseethatithassuchabluegreenline.
Therefore,wecanbeconfidentthatouransweriscorrect.

PRACTICEEXERCISE4.4
Whatenergyandwavelengthmustaphotonhaveto
exciteahydrogenatomfromitsgroundstate,i.e.n=
1,tothen=4level?

EnergyLevelDiagrams
Electronictransitionsinatomscanberepresentedusinganenergyleveldiagramsuchastheoneshowninfigure4.21b.
Energyleveldiagramsareaconcisewaytosummariseinformationaboutatomicenergies.Theyshowenergyalongthe
verticalaxisandeachenergystateoftheatomisrepresentedbyahorizontalline.
FIGURE4.21 (a)Aballonastaircaseshowssomeofthepropertiesofquantisedenergylevels.
(b)Quantisedenergylevelscanbedepictedusinganenergyleveldiagram.
(c)Electronictransitionsoccurbetweenquantisedenergylevelsthrougheitherabsorptionoremissionof
photons.

Wecanbegintounderstandthequantumlevelsofanelectronboundtoanatombypicturingaballonastaircase.As
illustratedinfigure4.21,aballmaysitonanyofthesteps.Tomoveaballfromthebottomofthestaircasetostep5
requirestheadditionofaspecificamountofenergy,E=E5E1.Iftoolittleenergyissupplied,theballcannotreachthis
step.Conversely,ifaballmovesdownthestaircase,itreleasesspecificamountsofenergy.Ifaballmovesfromstep5to
step3,itlosesenergy,E=E3E5.Althoughaballmayrestsquarelyonanystep,itcannotbesuspendedbetweenthe
steps.Electronsinatoms,likeballsonsteps,cannotexistbetweensteps,butmustoccupyoneofthespecific,quantised
energylevels.Rememberthatthisisananalogyatomicenergylevelsarenotatallsimilartostaircasesexceptinbeing
quantised.

Ahydrogenatomhasaregularprogressionofquantisedenergylevels.Figure4.22showstheenergyleveldiagramfor
hydrogenatomsarrowsrepresentsomeofthepossibleabsorptionandemissiontransitions.Noticethattheenergiesof
absorptionfromthelowestenergylevelareidenticaltotheenergiesofemissiontothelowestenergylevel.Thismeansthat
thewavelengthsoflightabsorbedintheseupwardtransitionsareidenticaltothewavelengthsoflightemittedinthe
correspondingdownwardtransitions.
FIGURE4.22Energylevelsforthehydrogenatomandsomeofthetransitionsthatoccurbetweenlevels,aswellastheresulting
emissionspectrum.Upwardarrowsrepresentabsorptiontransitions,anddownwardarrowsrepresentemissions.

Elementsotherthanhydrogenalsohavequantisedenergylevels,butaswewillseelaterinthischaptertheycannotbeso
simplydescribedbecausetheyhavemorethanoneelectron.Inthesecases,scientistsuseexperimentalvaluesforobserved
absorptionandemissionlinestocalculatetheallowedenergylevelsforeachdifferentelement.

WORKEDEXAMPLE4.5

EnergyLevelDiagrams

RubylasersusecrystalsofAl2O3.ThecrystalscontainsmallamountsofCr3+ions,whichabsorblightbetween
400and560nm.Theexcitedstateionslosesomeenergyasheat.Afterlosingheat,theCr3+ionsreturntothe
groundstatebyemittingredlightwithawavelengthof694nm.
(a) CalculatetheenergyinkJmol1ofthe500nmradiationusedtoexcitetheCr3+ions.
(b)CalculatetheenergyinkJmol1oftheemittedlight.
(c)Calculatethefractionoftheexcitationenergyemittedasredphotonsandthefractionlostasheat.
(d)Drawanenergyleveldiagramthatsummarisestheseprocesses.

Analysis

Thisproblemasksaboutenergies,lightandions.Withmultipartproblems,thebeststrategyistoworkthrough
thepartsoneatatime.Parts(a)and(b)concernthelinkbetweenlightandenergyasdiscussedearlierinthis
section.Oncethetransitionenergieshavebeendetermined,wecancalculatethefractionoftheexcitedstate
energylostasheatforpart(c),andwecanalsodrawanenergyleveldiagramthatshowshowthelevelsare
relatedforpart(d).

Solution

Wesolve(a)usingthefollowingequationsandtheAvogadroconstant.
Thisistheenergychangeperion.Tocalculatethechangepermole,wemultiplybytheAvogadroconstant.We
alsoneedtoconvertfromJtokJ.

Applythesamereasoningto(b).Theresultgivestheenergyoftheredphoton.

Tosolve(c),rememberthatenergyisconserved.Thesumoftheemittedheatandtheemittedphotonmustequal
theenergyabsorbedbytheion.

Because239kJmol1isabsorbedand172kJmol1isemitted,thefractionoftheexcitationenergyreemittedis
.Thefractionconvertedtoheatisthedifferencebetweenthisvalueand1.000,whichis0.280.In
otherwords,72.0%oftheenergyabsorbedbythechromiumionisemittedasredlight,andtheother28.0%is
lostasheat.

Part(d)asksforanenergyleveldiagramforthisprocess.Theelectronstartsinthegroundstate.Onabsorption
ofaphoton,theelectronmovestoanenergylevelthatishigherby239kJmol1.Thechromiumionloses
28.0%ofitsexcitedstateenergyasheatastheelectronmovestoalevelthatis172kJmol1abovetheground
state.Finally,emissionoftheredphotonreturnstheCr3+iontothegroundstate.Thenumericalvaluesallowus
toconstructanaccuratediagram.

Isouranswerreasonable?

WhenCr3+ionsabsorblight,theyarepromotedtoanenergylevelhigherthantheenergythattheylateremit.If
calculationshadshownthattheemittedlighthadalargerenergythantheabsorbedlight,theresultwouldhave
beenunreasonablebecausethesystemwouldviolatethelawofconservationofenergy.

PRACTICEEXERCISE4.5
Afterexcitationinanelectricdischarge,anatomof
Hgreturnstothegroundstatebyemittingtwophotons
withwavelengthsof436nmand254nm.Calculate
theexcitationenergyoftheexcitedstateinkJmol1.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.3PropertiesofElectrons
Theenergiesofelectronsinatomsplayacentralroleindeterminingchemicalbehaviour.Severalother
propertiesofelectronsalsoinfluencethephysicalandchemicalcharacteristicsofatomsandmolecules.
Somepropertiesarecharacteristicofallelectrons,butothersariseonlywhenelectronsareboundto
atomsormolecules.Inthissection,wedescribethepropertiescharacteristicofallelectrons.

Everyelectronhasamassof9.10910 31kgandachargeof1.60210 19C.Electronshavemagnetic


propertiesthatarisefromapropertycalledspin,whichwemetbrieflyinchapter1andwilldescribein
moredetailinsection4.4.

TheFrenchphysicistLouisdeBroglie(18921987,NobelPrizeinphysics,1929)wasthefirsttosuggest
that,likephotons,electronsalsodisplaywaveparticleduality,whichmeansthattheyhavebothparticle
andwaveproperties.

Experimentshadshownthatabeamoflightshiningonanobjectexertsapressure,whichimpliesthata
photonhasmomentum.Quantitativemeasurementsofthepressureexertedbylightshowedthatasimple
equationrelatesthemomentumoflight(p)toitsenergy.

Aswehavealreadydescribed,lightenergyisalsorelatedtoitswavelength.

Combiningthesetwoenergyexpressionsgivesanexpressionrelatingpto.

Thespeedoflightcancels,leavinganequationthatdeBrogliesuggestedshouldapplytoelectronsand
otherparticlesaswellastophotons.

Themomentumofaparticleistheproductofitsmassandvelocity(u),p=mu.Substitutingthisand
solvingforgivesaformofthedeBroglieequationthatlinksthewavelengthofaparticlewithitsmass
andvelocity.

DeBroglie'stheorypredictedthatelectronsarewavelike.Howmightthisbeconfirmed?Figure4.23
showsexamplesofthecharacteristicintensitypatternsdisplayedbywaves.Infigure4.23a,waterwaves
radiateawayfromtwobobbingfloatsandformastandingpattern.Infigure4.23b,diffractedXrays
formasimilarwavepattern.Highenergyphotonshavepassedthroughtheregulararrayofatomsina
crystal,whoseelectroncloudsscatterthephotonwaves.Ifelectronshavewaveproperties,theyshould
displayregularwavepatternslikethese.
FIGURE4.23 Examplesofwavepatterns:
(a)Floatsproducestandingwaterwaves,
(b)Xraysgeneratewaveinterferencepatternsand
(c)protrudingatomsonametalsurfacegeneratestandingelectronwaves.

In1927,AmericanphysicistsClintonDavissonandLesterGermer,andBritishphysicistGeorge
Thomson,separatelycarriedoutexperimentsinwhichtheyexposedmetalfilmstoelectronbeamswith
welldefinedkineticenergies.Bothexperimentsgeneratedpatternslikethoseshowninfigure4.23b,
confirmingthevalidityofthedeBroglieequationforelectronwavelengths.Thisestablishedthewave
natureofelectrons.DavissonandThomsonwereawardedtheNobelPrizeinphysicsin1937forthis
discovery.

Inrecentyears,scanningtunnellingelectronmicroscopeshaveproducedimagesofelectronwaves,an
exampleofwhichappearsinfigure4.23c.Here,twoatomsonanotherwisesmoothmetalsurfaceact
likethefloatsinfigure4.23a,andcausetheelectronsinthemetaltosetupastandingwavepattern.

Bothphotonsandelectronshavewaveandparticleproperties,butdifferentequationsdescribetheir
properties.Table4.1summarisesthepropertiesofphotonsandfreeelectrons.
TABLE4.1 Equationsforphotonsandfreeelectrons
Property Photonequation Electronequation
energy

wavelength

speed

h:Planck'sconstant:frequencym:massu:velocity

WORKEDEXAMPLE4.6

Wavelengths
Thestructureofacrystalcanbestudiedbyobservingthewaveinterferencepatternsthat
resultfrompassingparticlewavesthroughthecrystal.Togeneratewelldefinedpatterns,the
wavelengthoftheparticlewavemustbesimilartothedistancebetweenatomsinthecrystal.
Determinetheenergyofaphotonparticlewavebeamwithawavelengthof0.25nmandthe
energyofanelectronparticlewavebeamwiththiswavelength.

Analysis

Thisproblemhastwoparts,onedealingwithphotonsandtheotherwithelectrons.Weare
askedtorelatethewavelengthsoftheparticlewavestotheircorrespondingenergies.Table
4.1emphasisesthatphotonsandelectronshavedifferentrelationshipsbetweenenergyand
wavelength.Thus,weusedifferentequationsforthetwocalculations.

Solution

PhotonenergyisgivenbyE=h=hc/.Wesubstituteandevaluate,beingcarefulwithunits.

Foranelectron,weneedtoworkwithtwoequations.ThedeBroglieequationlinksthe
velocityofanelectronwithitswavelength.

Thekineticenergyequationlinksthevelocityofanelectronwithitskineticenergy.

Beginbydeterminingthevelocityoftheelectron,recallingfromchapter2that1J=1kgm2
s2.

Next,usethevelocitytofindthekineticenergyoftheelectron.

Isouranswerreasonable?

Theenergyofthephotonishigherthanthekineticenergyoftheelectron,whichisreasonable
sincetheelectronhasamass.

PRACTICEEXERCISE4.6
Inaphotoelectriceffectexperiment,a
photonwithanenergyof1.2510 18Jis
absorbed,causingtheejectionofanelectron
withakineticenergyof2.510 19J.
Calculatethewavelength(innm)associated
witheach.
ThedeBroglieequationpredictsthateveryparticlehaswavecharacteristics.Thewavepropertiesof
subatomicparticlessuchaselectronsandneutronsplayimportantrolesintheirbehaviour,butforlarger
objects,suchastabletennisballsorcars,theydonot.Thereasonisthescaleofthewaves.Forallexcept
subatomicparticles,thewavelengthsinvolvedaresoshortthatweareunabletodetectthewave
properties.

WORKEDEXAMPLE4.7

MatterWaves

Calculatethewavelengthsofanelectrontravellingat1.0010 5ms1andatabletennisball
withamassof11gtravellingat2.5ms1.

Analysis

Thisproblemdealswithparticlewavesthathavemass.ThedeBroglieequationrelatesthe
massandspeedofanobjecttoitswavelength.

Solution

Fortheelectron:melectron=9.10910 31kg,u=1.0010 5ms1

Forthetabletennisball:mball=11g,u=2.5ms1

Isouranswerreasonable?

Thewavelengthoftheelectronisintheorderoftheatomicsize,whichisconsistentwiththe
factthatelectronshaveparticlewaveduality.Thewavelengthofthetabletennisballis
extremelysmall,whichisexpectedaswedonotobservewavecharacteristicsforthetable
tennisball.

PRACTICEEXERCISE4.7
Calculatethewavelengthassociatedwitha
protonthatismovingataspeedof2.85
10 5ms1.
TheHeisenbergUncertaintyPrinciple
Aparticleoccupiesaparticularlocation,butawavehasnoexactposition.Awaveextendsoversome
regionofspace.Becauseoftheirwaveproperties,electronsarealwaysspreadoutratherthanlocatedin
oneparticularplace.Asaresult,thepositionofamovingelectroncannotbepreciselydefined.We
describeelectronsasdelocalisedbecausetheirwavesarespreadoutratherthanpinpointed.

Mathematically,thepositionandmomentumofaparticlewavearelinked.WernerHeisenberg(1901
1976,NobelPrizeinphysics,1932),aGermanphysicist,showedinthe1920sthatthemomentumand
positionofaparticlewavecannotbesimultaneouslydetermined.Ifaparticularparticlewavecanbe
pinpointedinaspecificlocation,itsmomentumcannotbeknownaccurately.Conversely,ifthe
momentumofaparticlewaveisknownprecisely,itslocationcannotbeidentified.Heisenberg
summarisedthisuncertaintyinwhathasbecomeknownastheuncertaintyprinciple:themore
accuratelyweknowposition,themoreuncertainweareaboutmomentum,andviceversa.Uncertaintyis
afeatureofallobjects,butitbecomesimportantonlyforverytinyobjectslikeelectrons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.4QuantisationandQuantumNumbers
Thepropertiesofelectronsmentionedsofar(mass,charge,spinandwavenature)applytoallelectrons.
Electronstravellingfreelyinspace,electronsmovinginacopperwireandelectronsboundtoatomsall
havethesecharacteristics.Boundelectrons,thoseheldinaspecificregionofanatombyelectrostatic
forces,haveadditionalimportantpropertiesrelatingtotheirenergiesandtheshapesoftheirwaves.These
additionalpropertiescanhaveonlycertainspecificvalues,i.e.theyarequantised.

Asdescribedinsection4.2,atomsofeachelementhaveunique,quantisedelectronicenergylevels(see
figures4.21and4.22).Thisquantisationofenergyisapropertyofboundelectrons.Theabsorptionand
emissionspectraofatomsconsistofspecificdiscreteenergiesbecauseelectronsundergotransitionsfrom
oneboundstatetoanother.Incontrast,ifanatomabsorbsenoughenergytoremoveanelectron
completely,theelectronisnolongerboundandcantakeonanyamountofkineticenergy.Bound
electronshavequantisedenergiesfreeelectronscanhaveanyamountofenergy.

Experimentalvaluesforthequantisedenergiesofatomicelectronscanbecalculatedfromabsorptionand
emissionspectra.Thetheoryofquantummechanicsprovidesamathematicalexplanationthatlinks
quantisedenergiestothewavecharacteristicsofelectrons.Thesewavepropertiesofatomicelectronsare
describedbytheSchrdingerequation:

where istheHamiltonianoperator(containingtermsforthekineticandpotentialenergy)forthesystem,
Eistheenergyofthesystemandisthewavefunctionforthesystem.Inparticular,istheamplitudeof
theelectron'smatterwave.Aswithlight,theamplitudeitselfdoesnothaveanyphysicalmeaning,butits
squarerepresentstheelectrondensitydistributionorprobabilityoffindinganelectron.Awavefunctionis
amathematicalfunctionthatgivesusinformationaboutanelectron'spositioninanatom.Thesolutionof
theSchrdingerequationgivesusboththeenergiesandtheassociatedwavefunctionsofachemical
system.Despiteitsconciseform,theSchrdingerequationcanbesolvedexactlyonlyforsystems
containingoneelectron.

TheSchrdingerequationhassolutionsonlyforspecificenergyvaluesbecausetheenergyofanatomis
quantised.Foreachquantisedenergyvalue,theSchrdingerequationgeneratesawavefunctionthat
describeshowtheelectronsaredistributedinspace.Aoneelectronwavefunctioniscalledanorbital.We
willdescribethepropertiesoforbitalsinsection4.5.

Eachdescribedpropertycanbeidentified,orindexed,usingaquantumnumber.Thesearenumbersthat
specifythevaluesoftheelectron'squantisedproperties.Eachelectroninanatomhasthreequantum
numbersthatspecifyitsthreevariableproperties:energy(ororbitalsize),angularmomentum(ororbital
shape)andorbitalorientation.Afourthquantumnumberdescribesthespinofanelectron.Todescribean
atomicelectroncompletely,chemistsspecifyavalueforeachofitsfourquantumnumbers:theprincipal
quantumnumber,azimuthalquantumnumber,magneticquantumnumberandspinquantumnumber.

PrincipalQuantumNumber(n)
Themostimportantquantisedpropertyofanatomicelectronisitsenergy.Thequantumnumberthat
indexesenergyforanatomorioncontainingonlyasingleelectronistheprincipalquantumnumber(n).
Forthesimplestatom,hydrogen,wecanuse tocalculatetheenergyofthe
electronifweknown(asseeninsection4.2).However,thatequationappliesonlytothehydrogenatom
orotheroneelectron,hydrogenic(hydrogenlike)ions(suchasHe+andLi2+).
Noknownequationprovidestheexactenergiesofanatomthathasmorethanoneelectron.Nevertheless,
eachelectroninamultielectronatomcanbeassignedavalueofnthatisapositiveintegerandwhich
broadlycorrelateswiththeenergyoftheelectron.Thelowestenergyforanatomicelectroncorresponds
ton=1,andeachsuccessivelyhighervalueofndescribesahigherenergystate.Theprincipalquantum
numbermustbeapositiveinteger:n=1,2,3etc.

Theprincipalquantumnumberalsotellsussomethingaboutthesizeofanatomicorbital,becausethe
energyofanelectroniscorrelatedwithitsdistributioninspace.Thehighertheprincipalquantumnumber,
themoreenergytheelectronhasandthegreaterisitsaveragedistancefromthenucleus.

Summarising,theprincipalquantumnumber(n)canhaveanypositiveintegervalue.Itindexestheenergy
oftheelectronandiscorrelatedwithorbitalsize.Asnincreases,theenergyoftheelectronincreases,its
orbitalgetsbiggerandtheelectronislesstightlyboundtotheatom.

AzimuthalQuantumNumber(l)
Asecondquantumnumberindexestheangularmomentumofanatomicorbital.Thisquantumnumberis
theazimuthalquantumnumber(l).ThesolutionsfortheSchrdingerequationandexperimental
evidenceshowthattheelectrondistributionassociatedwithorbitalscanbedescribedbyavarietyof
shapes.Notethatitistechnicallyincorrecttotalkabouttheshapeofanorbitalitself.Aswehaveseen,
anorbitalismerelyamathematicalfunction.Anorbitalistheamplitudeofanelectron'sthreedimensional
matterwave.Becausetheamplitudecanfluctuatebetweenpositiveandnegativevalues(justlikeany
otherwave),ithasnophysicalmeaningbyitself.Wecan,however,talkabouttheshapeoftheelectron
distributionassociatedwithaparticularorbital,andthistellsuswherewearemostlikelytofindan
electronwithinthisorbital.

Wecancategorisetheshapesofobjects,suchasthesoccerball,rugbyballandfourleafclovershownin
figure4.24,accordingtotheirpreferredaxes.Apreferredaxisisalinethroughthecentreofmassofan
objectorshape,aboutwhichtheshapecanbealignedordistributed.Asoccerballhasnopreferredaxis
becauseitsmassisdistributedequallyinalldirectionsaboutitscentre.Arugbyballhasonepreferred
axis,withmoremassalongthisaxisthaninanyotherdirection.Afourleafcloverhastwopreferredaxes,
atrightanglestoeachother.Inananalogousfashion,electrondensityinanorbitalcanbeconcentrated
alongpreferredaxes.

FIGURE4.24Someeverydayobjectshavetheirmassesconcentratedalongpreferredaxes.Asoccerballhasno
suchaxis,butarugbyballhasoneandafourleafcloverhastwo.

Thevalueoflcorrelateswiththenumberofpreferredaxesinaparticularorbitalandtherebyidentifiesthe
shapeoftheelectrondistributionwithintheorbital.Accordingtoquantumtheory,theseshapesarehighly
restricted.Theserestrictionsarelinkedtoenergy,sothevalueoftheprincipalquantumnumber(n)limits
thepossiblevaluesofl.Thesmallerthevalueofnis,themorecompacttheorbitalandthemorerestricted
itspossibleelectrondistributions.Theazimuthalquantumnumber(l)canbezerooranypositiveinteger
smallerthann:l=0,1,2,,(n1)i.e.therearenvaluesofl.

Historically,orbitalshavebeenidentifiedwithlettersratherthannumbers.Theseletterdesignations
correspondtothevaluesoflasshownbelow.

Anorbitalisnamedbylistingthenumericalvalueforn,followedbytheletterthatcorrespondstothe
numericalvalueforl.Thus,a3sorbitalhasquantumnumbersn=3,l=0.A5forbitalhasn=5,l=3.
Noticethattherestrictionsonlmeanthat,whenn=1,lcanbeonlyzero.Inotherwords,1sorbitalsexist,
butthereareno1p,1d,1for1gorbitals.Similarly,thereare2sand2porbitalsbutno2d,2for2gorbitals.

MagneticQuantumNumber(ml)

Aspherehasnopreferredaxis,soithasnodirectionalityinspace.Whenthereisapreferredaxis,asfora
rugbyball,figure4.25showsthattheaxiscanpointinmanydifferentdirectionsrelativetoanxyz
coordinatesystem.Thus,objectswithpreferredaxeshavedirectionalityaswellasshape.

FIGURE4.25Arugbyballhasdirectionalityandshape.Thefigureshowsthreeofthemanywaysinwhicha
rugbyballcanbeorientedrelativetoasetofx,yandzaxes.

Theelectrondistributionwithinansorbitalissphericalandhasnodirectionality.Electrondistributionsin
otherorbitalsarenonsphericalandthereforehaveadirectionaldependence.Likeenergyandorbital
electrondistribution,thisdirectionaldependenceisquantised.Unlikerugbyballs,theelectron
distributionswithinp,dandforbitalshaverestrictednumbersofpossibleorientations.Themagnetic
quantumnumber(ml)indexestheserestrictions.

Justasorbitalsize(n)limitsthenumberofpreferredaxes(l),thenumberofpreferredaxes(l)limitsthe
possibleorientationsofthepreferredaxes(ml).Whenl=0,thereisnopreferredaxisandthereforeno
preferredorientation,soml=0forsorbitals.Onepreferredaxis(l=1)canorientinanyofthree
directions,givingthreepossiblevaluesforml:+1,0and1.Twopreferredaxes(l=2)canorientinanyof
fivedirections,givingfivepossiblevaluesforml:+2,+1,0,1and2.Eachtimelincreasesinvalueby
oneunit,twoadditionalvaluesofmlbecomepossible,andthenumberofpossibleorientationsincreases
bytwo.Themagneticquantumnumber(ml)canbeanypositiveornegativeintegerbetween0andl:ml=
0,1,2,,li.e.thereare(2l+1)valuesofml.

SpinQuantumNumber(ms)

Aswesawinsection1.5,allelectronshaveapropertycalledspin.Thismeansthatelectronscanbehave
inoneoftwowayswhenplacedinamagneticfield.Whenabeamofsilveratomsispassedthrougha
magneticfield(similartotheexperimentcarriedoutbyOttoSternandWalterGerlachin1921,seefigure
4.26),theatombeamissplit,someatomsaredeflectedinonedirectionandtherestaredeflectedinthe
oppositedirection.Sinceclassicalphysicsassociatesaspinningelectricchargewithamagneticfield,the
experimentalobservationwasexplainedbytheDutchphysicistsGeorgeUhlenbeckandSamuel
Gouldsmitwithapropertytheycalledelectronspin.(Note:(Thereisnophysicalevidencethatanelectron
actuallyspins.)Thefactthatonlytworesponsesareobserveddemonstratesthatspinisquantised.The
spinquantumnumber(ms)indexesthisbehaviour.Thetwopossiblevaluesofmsare and .

FIGURE4.26TheSternGerlachmagneticfieldexperiment.

ThePauliExclusionPrinciple
Acompletedescriptionofanatomicelectronrequiresasetoffourquantumnumbers:n,l,mlandms,
whichmustmeetalltherestrictionsmentionedearlier,assummarisedintable4.2.Eachelectroninan
atomhasauniquesetofquantumnumbersnotwoelectronsinanatomhaveexactlythesamesetof
quantumnumbers.ThiswasfirstpostulatedbytheAustrianphysicistWolfgangPauli(19001958,Nobel
Prizeinphysics,1945)andisknownasthePauliexclusionprinciple.Theprincipleisderivedfrom
quantummechanicsandsupportedbyallexperimentalevidence.
TABLE4.2 Restrictionsonquantumnumbersforelectronsinatoms
Quantumnumber Restrictions Range
n positiveintegers 1,2,,
l positiveintegerslessthann 0,1,,(n1)
ml integersbetweenlandl l,,1,0,+1,,+l

ms

Thenumberofpossiblesetsofquantumnumbersincreasesrapidlyasnincreases.Anatomicorbitalis
designatedbyitsnandlvalues,suchas1s,3d,4pandsoon.Whenl>0,thereismorethanoneorbitalof
eachdesignationthatis,whenl=1,therearethreeporbitalsandforl=2therearefivedorbitals.An
electroninanyorbitalcanhaveaspinquantumnumber(ms)ofeither or .Thus,therearemany
setsofvalidquantumnumbers.Anelectronina3porbital,forexample,canhaveanyoneofsixvalidsets
ofquantumnumbers.
AdirectconsequenceofthePauliexclusionprincipleisthatanyorbitalcancontainamaximumoftwo
electrons(wesaythatanorbitalcontainingtwoelectronsisfull)andthatthetwoelectronsinafullorbital
mustbeofoppositespin.

WORKEDEXAMPLE4.8

ValidQuantumNumbers
Howmanyvalidsetsofquantumnumbersexistfor4dorbitals?Givetwoexamples.

Analysis

Thequestionasksforthesetsofquantumnumbersthathaven=4andl=2.Eachsetmust
meetalltherestrictionslistedintable4.2.Theeasiestwaytoseehowmanyvalidsetsthereare
istolistallthevalidquantumnumbers.

Solution

Becausethisisa4dorbital,nandlarespecifiedandcannotvary.Theothertwoquantum
numbers,however,haveseveralacceptablevalues.Foreachvalueofml,eithervalueofmsis
acceptable,sothetotalnumberofpossibilitiesistheproductofthenumberofpossiblevalues
foreachquantumnumber.Thisisshownonthenextpage.

Quantumnumber n l ml ms

Possiblevalues 4 2 2,1,0,1,2

Numberofpossiblevalues 1 1 5 2
Possiblesetsofvaluesfora4delectron:(1)(1)(5)(2)=10

Thereare10setsofquantumnumbersthatcandescribea4dorbital.Twoofthemareshown
below.

Youshouldbeabletolisttheothereightsets.

Isouranswerreasonable?

Ifyouwritedownallthepossiblesets,youwillfindthatthereare10.Noticethatthereare
always2l+1possiblevaluesofmland2possiblevaluesofms,soeveryndsetoforbitalshas
10possiblesetsofquantumnumbers.
PRACTICEEXERCISE4.8
Writeallthevalidsetsofquantumnumbers
ofthe5p

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.5AtomicOrbitalElectronDistributionsand
Energies
Thechemicalpropertiesofatomsaredeterminedbythebehaviouroftheirelectrons.Becauseatomic
electronsaredescribedbyorbitals,theinteractionsofelectronscanbedescribedintermsoforbital
interactions.Thetwocharacteristicsoforbitalsthatdeterminehowelectronsinteractaretheirelectron
distributionsinthreedimensionalspaceandtheirenergies.

OrbitalElectronDistributions
Wavelikepropertiescauseelectronstobesmearedoutratherthanlocalisedatanexactposition.This
smearedoutdistributioncanbedescribedusingelectrondensity.Whereelectronsaremostlikelytobe
found,thereishighelectrondensity.Lowelectrondensityoccursinregionswhereelectronsarelesslikely
tobefound.Eachelectron,ratherthanbeingapointcharge,isathreedimensionalparticlewavethatis
distributedoverspaceasanorbital.Orbitalsdescribethedelocalisationofelectrons.Moreover,whenthe
energyofanelectronchanges,thesizeandshapeofitsdistributioninspacechangeaswell.Eachatomic
energylevelisassociatedwithaspecificthreedimensionalatomicorbital.

Anatomthatcontainsmanyelectronscanbedescribedbysuperimposing(addingtogether)theorbitalsfor
allofitselectronstoobtaintheoverallsizeandshapeoftheatom.

Thequantumnumbersnandldeterminethesizeandelectrondistributionofanorbital.Asnincreases,the
sizeoftheorbitalincreases,and,aslincreases,theelectrondistributionoftheorbitalbecomesmore
elaborate.Thesecanbenodalplanesorradialnodes,andthenumberofthesedependsonnandli.e.for
everyorbital,therearen1nodes,ofwhichlarenodalplanesandtheremainderarespherical(radial)
nodes.

OrbitalDepictions
Weneedwaystovisualiseelectronsasparticlewavesdelocalisedinthreedimensionalspace.Orbital
picturesprovidemapsofhowanelectronwaveisdistributedinspace.Thereareseveralwaystorepresent
thesethreedimensionalmaps.Eachoneshowssomeimportantorbitalfeatures,butnoneshowsallofthem.
Weusethreedifferentrepresentations:electrondensityplots,electrondensitypicturesandboundary
surfacediagrams.

Anelectrondensityplotrepresentstheelectrondistributioninanorbitalasatwodimensionalgraph.These
graphsshowelectrondensityalongtheyaxisanddistancefromthenucleus,r,alongthexaxis.Figure
4.27ashowsanelectrondensityplotforthe2sorbital.
FIGURE4.27 Differentdepictionsofthe2sorbital:
(a)Anelectrondensityplotversusdistancefromthenucleus,
(b)anelectrondensitypictureand
(c)aboundarysurfacediagram.

Electrondensityplotsareusefulbecauseplotsforseveralorbitalscanbesuperimposedtoindicatethe
relativesizesofvariousorbitals.Electrondensityplotsdonot,however,showthethreedimensionalityof
anorbital.

Electrondensitypicturescanindicatethethreedimensionalnatureoforbitals.Onetypeoforbitalpicture
isatwodimensionalcolourpatterninwhichthedensityofcolourrepresentselectrondensity.Figure4.27b
showssuchanelectrondensitypictureofthe2sorbital.Thistwodimensionalpatternofcolourdensity
showsacrosssectionalslicethroughthemiddleoftheorbital.Figures4.27a,4.27bshowthatthe2sorbital
hasonesphericalnode,aswediscussedonthepreviouspage.

Aboundarysurfacediagramprovidesasimplifiedorbitalpicture.Inthisrepresentation,wedrawasolid
surfacethatenclosesmost(usually90%)oftheelectrondensity.Thus,theelectrondensityishighinside
theboundarysurfacebutverylowoutside.Figure4.27cshowsaboundarysurfacediagramofthe2s
orbital.Onedrawbackofboundarysurfacediagramsisthattheydonotshowdetailsofelectrondensity
belowthesurface,includingsphericalnodes.Theydo,however,showallplanarnodes,andfromthoseitis
possibletodeducethenumberofhiddensphericalnodes.

Ausefulanalogyforunderstandingthevalueofboundarysurfacesisaswarmofbeesaroundahive.At
anyonetime,somebeeswillbeoffforagingfornectar,soaboundarysurfacedrawnaroundallthebees
mightcoverseveralhectares.Thiswouldnotbeaveryusefulmapofbeedensity.Aboundarysurface
containing90%ofthebees,ontheotherhand,wouldbeonlyslightlybiggerthanthehiveitself.This
wouldbeaveryusefulmapofbeedensity,becauseanyoneinsidethatboundarysurfacewouldsurely
interactwithbees.

Anotherdrawbackofboundarysurfacediagramsisthatalldetailsofelectrondensityinsidethesurfaceare
lost.Thus,ifwewanttoconveythemaximuminformationaboutorbitals,wemustusecombinationsofthe
variousdepictions.

Theadvantagesanddisadvantagesofthethreetypesofplotscanbeseenbyhowtheyshowone
characteristicfeatureoforbitals.Figure4.27ashowsclearlythatthereisavalueforrwheretheelectron
densityfallstozero.Aplacewhereelectrondensityiszeroiscalledanode.Figure4.27bshowsthenode
forthe2sorbitalasawhitering.Inthreedimensions,thisnodeisasphericalsurface.Figure4.27cdoesnot
showthenode,becausethesphericalnodalsurfaceishiddeninsidethe90%boundarysurface.Thetwo
dimensionalgraphshowsthelocationofthenodemostclearly,theelectrondensitypicturegivesthebest
senseoftheshapeofthenode,whiletheboundarysurfacediagramfailstoshowitatall.

OrbitalSize
Experimentsthatdetermineatomicradiiprovideinformationaboutthesizesoforbitals.Inaddition,
theoreticalmodelsoftheatomcanpredicthowtheelectrondensityofaparticularorbitalchangeswith
distancefromthenucleus.

Inanyparticularatom,orbitalsgetlargerasthevalueofnincreases.Then=2orbitalsarelargerthanthen
=1orbital,then=3orbitalsarelargerthanthen=2orbitals,andsoon.Theelectrondensityplotsin
figure4.28showthistrendforthefirstthreesorbitalsofthehydrogenatom.Thisplotalsoshowsthatthe
numberofnodesincreasesasnincreases.

FIGURE4.28Electrondensityplotsforthe1s,2sand3satomicorbitalsofthehydrogenatom.Theverticallines
indicatethevaluesofrwherethe90%boundarysurfacewouldbelocated.

Inanyparticularatom,allorbitalswiththesameprincipalquantumnumberaresimilarinsize.Asan
example,figure4.29showsthatthen=3orbitalsofthecopperatomhavetheirmaximumelectron
densitiesatsimilardistancesfromthenucleus.Thesameregularityholdsforallotheratoms.Thequantum
numbersotherthannaffectorbitalsizeonlyslightly.Wedescribethesesmalleffectsinthecontextof
orbitalenergieslaterinthissection.
FIGURE4.29Electrondensityplotsforthe3s(redline),3p(blueline),and3d(greenline)orbitalsforthecopper
atom.Allthreeorbitalsarenearlythesamesize.

Aspecificorbitalbecomessmallerastheatomicnuclearchargeincreases.Asthepositivechargeofthe
nucleusincreases,theelectrostaticforceexertedbythenucleusonthenegativelychargedelectrons
increasesandelectronsbecomemoretightlybound.Thisreducestheradiusoftheorbital.Asaresult,each
orbitalshrinksinsizeasatomicnumberincreases.Forexample,figure4.30showsthatthe2sorbital
steadilydecreasesinsizeacrossthesecondrowoftheperiodictablefromLi(Z=3)toNe(Z=10).The
atomicnumber,Z,isequaltothenumberofprotonsinthenucleus,soincreasingZmeansincreasing
nuclearcharge.

FIGURE4.30Theradiusofthe2sorbitaldecreasesasZincreases.Thenumberatthebottomofeachcolumnis
theradiusofthe2sorbitalinpm(picometres).

DetailsofOrbitalElectronDistributions
Theelectrondistributionsoforbitalsstronglyinfluencechemicalinteractions.Hence,weneedtohave
detailedpicturesoftheseelectrondistributionstounderstandthechemistryoftheelements.

Thequantumnumberl=0correspondstoansorbital.Accordingtotherestrictionsonquantumnumbers,
thereisonlyonesorbitalforeachvalueoftheprincipalquantumnumber.Theelectrondistributionofs
orbitalsisspherical,withradiiandnumberofnodesthatincreaseasnincreases.Figure4.31showsa
boundarysurfacediagramofthe1sorbital.

FIGURE4.31Boundarysurfacediagramofthe1sorbital.

Weintroducedtheconceptofthephaseofawaveinsection4.2,andthisconceptalsoappliestoorbitals.
Ansorbitalhasasinglephase,whichwerefertoaseitherpositive(+)ornegative().Wegenerallydepict
differentphasesusing+andsignssuperimposedontheorbitalelectrondistribution,orbyusingdifferent
colourscorrespondingto+andphases.
Thequantumnumberl=1correspondstoaporbital.Anelectroninaporbitalcanhaveanyofthree
valuesforml,soforeachvalueofntherearethreedifferentporbitals.Thenonsphericalelectron
distributionofporbitalscanbeshowninvariousways.Themostconvenientrepresentationshowsthethree
orbitalswithidenticalelectrondistributionsbutpointinginthreedifferentdirections.Figure4.32shows
boundarysurfacediagramsofthe2porbitals.Eachporbitalhashighelectrondensityinoneparticular
direction,perpendiculartotheothertwoorbitals,withthenucleusatthecentreofthesystem.Thethree
differentorbitalscanberepresentedsothateachhasitselectrondensityconcentratedonbothsidesofthe
nucleusalongapreferredaxis.Wecanwritesubscriptsontheorbitalstodistinguishthethreedistinct
orientations:p x ,p y andp z.Eachporbitalalsohasanodalplanethatpassesthroughthenucleus.Thenodal
planeforthep x orbitalistheyzplane,forthep y orbitalthenodalplaneisthexzplaneandforthep zorbital
itisthexyplane.Thetwolobesofasingleporbitalhaveoppositephasesthisisshowninfigure4.32by
usingadifferentcolourforeachlobe.

FIGURE4.32Boundarysurfacediagramsofthethree2porbitals.Thethreeorbitalshavethesameoverallelectron
distribution,buteachisorientedperpendiculartotheothertwo.Thenodalplaneineachcaseis
illustratedbythegreyhatchedsurface.

Asnincreases,thenumberofnodeswithineachporbitalincreases,justasforsorbitals.Nevertheless,the
directionalityoftheelectrondistributiondoesnotchange.Eachporbitalisperpendiculartotheothertwoin
itssetandhasitslobesalongitspreferredaxis,whereelectrondensityishigh.Toanapproachingatom,
therefore,anelectronina3porbitalpresentsthesamecharacteristicsasoneina2porbital,exceptthatthe
3porbitalisbigger.Consequently,theelectrondistributionsandrelativeorientationsofthe2porbitalsin
figure4.32representtheprominentspatialfeaturesofallporbitals.

Thequantumnumberl=2correspondstoadorbital.Anelectroninadorbitalcanhaveanyoffivevalues
forml(2,1,0,+1and+2),sotherearefivedifferentorbitalsineachset.Eachdorbitalhastwonodal
planes.Consequently,theelectrondistributionsofthedorbitalsaremorecomplicatedthantheirsandp
counterparts.Theboundarysurfacediagramsinfigure4.33showtheseorbitalsinthemostconvenient
way.Inthesedrawings,threeorbitalshaveelectrondistributionsthatlooklikethreedimensional
cloverleaveslyinginaplanewiththelobespointedbetweentheaxes.Asubscriptidentifiestheplanein
whicheachlies:d xy ,d xzandd yz.Afourthorbitalhasanelectrondistributionthatisacloverleafinthexy
plane,butitslobespointalongthexandyaxes.Thisorbitalisdesignated .Ineachofthese
cloverleaforbitals,thelobessituatedoppositeeachotherhavethesamephases,asshowninfigure4.33.
Theelectrondistributioninthefifthorbitalisquitedifferent.Itsmajorlobespointalongthezaxis,butthere
isalsoadoughnutofelectrondensityinthexyplane.Thisorbitalisdesignated .Thetwolobeshave
thesamephase,whilethedoughnutisofoppositephase.
FIGURE4.33Boundarysurfacediagramsofthedorbitals.Fourofthefivehavethesamecloverleafshapewithtwo
nodalplanesatrightanglestoeachother.The orbitalhasthezaxisasitspreferredaxis.Ithas
twonodesthatareshapedlikecones,oneaboveandonebelowthexyplane.

Thequantumnumberl=3correspondstoanforbital.Thepossiblevaluesofml(3,2,1,0,+1,+2and
+3)meanthattherearesevenforbitals,butastheybecomeimportantonlyforthelanthanoidelementsand
beyond,wewillnotdetailtheirpropertieshere.

OrbitalEnergies
Ahydrogenatomcanabsorbaphotonandchangefromitsmoststable,lowestenergystate(groundstate)
toalessstable,higherenergystate(excitedstate),asdescribedinsection4.2.Wecanexplainthisprocess
usingatomicorbitals.Whenahydrogenatomabsorbsaphoton,itselectroncanundergoatransitiontoan
orbitalthathasalargerprincipalquantumnumber,i.e.ahigherenergy.Figure4.34illustratesthisprocess
forthe1s2ptransitioninthehydrogenatom.
FIGURE4.34Whenahydrogenatominitsgroundstateabsorbslightofwavelength121.6nm,itisconvertedto
anexcitedstate,inwhichtheelectronoccupiesa2porbital.

Electronictransitionscannotnecessarilyoccurbetweenanysetoforbitalsinthehydrogenatom,andother
oneelectronsystems,theyaregovernedbythefollowingselectionrules:
1.n=anything.Thereisnorestrictiononthevaluesoftheinitialandfinalprincipalquantum
numbers.
2.l=1.Theazimuthalquantumnumbermustincreaseordecreaseby1.Thismeansthatwecannot
haveatransitionfromansorbitaltoanothersorbital,orfromaporbitaltoanotherporbital.
3.ml=0,1.Themagneticquantumnumbermaystaythesame,oritcanincreaseordecreaseby1.

Theatomicorbitalmodelexplainsthespectraandenergylevelsofthehydrogenatomperfectly.Foraone
electronsystemlikethehydrogenatom,theenergylevelsforallorbitalsdependonlyontheprincipal
quantumnumber,n.Allorbitalshavingthesamevalueofnhavethesameenergyandaresaidtobe
degenerate.Formultielectronsystems,experimentsshowthattheunderlyingprinciplesarethesame,
althoughthedetailsforeachkindofatomaredifferent.Variationsinnuclearchargeandthenumberof
electronschangethemagnitudesoftheelectricalforcesthatholdelectronsintheirorbitals.Differencesin
forcescausechangesinorbitalenergiesthatcanbeunderstoodqualitativelyusingforcesofelectrical
attractionandrepulsion,aswedescribelaterinthischapter.Asaconsequence,thedegeneracyoforbitals
foreachlevelofnispartiallyremoved.
TheEffectofNuclearCharge
Ahelium+1cation,likeahydrogenatom,hasoneelectron.Absorptionandemissionspectrashowthat
He+hasenergylevelsthatdependonnonly,justlikethehydrogenatom.Nevertheless,figure4.35shows
thattheemissionspectraofHe+andHdiffer,whichmeansthatthesetwospeciesmusthavedifferent
energylevels.Weconcludethatsomethingbesidesninfluencesorbitalenergy.

FIGURE4.35TheemissionspectraofHe+andHrevealtransitionsatcharacteristicenergies.Mostoftheemitted
photonshavedifferentenergiesbecauseHe+hasquantisedenergylevelsthataredifferentfrom
thoseofH.

ThedifferencebetweenHe+andHisintheirnuclei.Ahydrogennucleusisasingleprotonwitha+1
charge,whereasaheliumnucleuscontainstwoprotons(andtwoneutrons)andhasachargeof+2.The
largernuclearchargeofHe+attractsitssingleelectronmorestronglythanthesmallerchargeofH.Asa
result,He+bindstheelectronwithastrongerforce.Thus,anygivenenergylevelintheheliumionislower
inenergythanthecorrespondinglevelinthehydrogenatom.

Theenergyofanorbitalcanbedeterminedbymeasuringtheamountofenergyrequiredtoremovean
electroncompletelyfromthatorbital.Thisistheionisationenergy(Ei).

TheionisationenergyofHe+isfourtimesthatofH.Thus,thegroundstateorbitalforHe+mustbefour
timeslowerinenergythanthegroundstateorbitalforH.Spectralanalysisshowsthateachorbitalofa
heliumcationisfourtimeslowerinenergythanitscounterpartorbitalinahydrogenatom,showingthat
orbitalenergydependsonZ2inaoneelectronsystem.WhiletheenergylevelsinHandHe+aredifferent
forcorrespondingorbitalsduetotheZ2relationship,therearesomeorbitalenergiesthatcoincideandhence
wecangetemissionenergiesthatareidenticalforbothspecies(seefigure4.35).Figure4.36showsthe
relationshipbetweentheenergylevelsofHe+andH.Thediagramisinexactagreementwithcalculations
basedontheSchrdingerequation.
FIGURE4.36AnenergyleveldiagramforHe+andH.Eachspecieshasoneelectron,butthedifferentnuclear
chargesmakeeachHe+orbitalfourtimeslowerinenergythanthecorrespondingHorbital.

TheEffectofOtherElectrons
Ahydrogenatomoraheliumcationarerareexamplesofoneelectronsystemsmostotheratomsandions
containcollectionsofelectrons.Inamultielectronatom,electronsaffecteachother'sproperties.These
electronelectroninteractionsmaketheorbitalenergiesofeveryelementunique.

Agivenorbitalisofhigherenergyinamultielectronatomthanitisinthesingleelectronionwiththe
samenuclearcharge.Forinstance,figure4.37showsthatittakesmorethantwiceasmuchenergyto
removetheelectronfromHe+(oneelectron)asitdoestoremoveoneoftheelectronsfromaneutralHe
atom(twoelectrons).Thisdemonstratesthatthe1sorbitalinHe+ismorethantwotimeslowerinenergy
thanthe1sorbitalinneutralHe.Thenuclearchargeofbothspeciesis+2,sothesmallerionisationenergy
forHemustresultfromthepresenceofthesecondelectron.Anegativelychargedelectroninamulti
electronatomisattractedtothepositivelychargednucleus,butitisrepelledbytheothernegatively
chargedelectrons.Thiselectronelectronrepulsioncontributestothelowerionisationenergyofthehelium
atom.
FIGURE4.37Ionisationenergies.

Shielding

Figure4.38showsafreeelectronapproachingaHe+cation.The+2chargeofthenucleusattractsthe
incomingelectron,butthenegativechargeoftheHe+1selectronrepelsit.Aselectronshavealikecharge,
electronelectronrepulsioncancelsaportionoftheattractionbetweenthenucleusandtheincoming
electron.Chemistscallthispartialcancellationshielding.

FIGURE4.38AsafreeelectronapproachesaHe+cation,itisattractedtothe+2chargeonthenucleusbut
repelledbythe1chargeonthe1selectron.Whenitisfarfromthecation,thefreeelectron
experiencesanetchargeof+1.

Withits1charge,aboundelectroncouldreducethetotalchargebyamaximumof1chargeunit.Indeed,
whenanapproachingelectronisfarenoughawayfromaHe+ion,itfeelsanattractionduetothenet
chargeontheion,+1.However,the1sorbitalisspreadoutallaroundthenucleus.Thismeansthat,asan
approachingelectrongetscloseenough,the1selectronshieldsonlypartofthetotalnuclearcharge.
Consequently,anapproachingelectronissubjecttoanetattractionresultingfromsomeeffectivenuclear
charge(Zeff)lessthan+2butgreaterthan+1.

Incompleteshieldingcanbeseenintheionisationenergiesofhydrogenatoms,heliumatomsandhelium
ions(figure4.37).Withoutshielding,theionisationenergyofaheliumatomwouldbethesameasthatofa
heliumionbothwouldbe8.7210 18J.Withcompleteshielding,oneheliumelectronwouldcompensate
foroneoftheprotonsinthenucleus,makingZeff=+1.Theenergyrequiredtoremoveanelectronfroma
heliumatomwouldthenbethesameastheenergyrequiredtoremoveanelectronfromahydrogenatom,
2.1810 18J.Theactualionisationenergyofaheliumatomis3.9410 18J,abouttwicethefully
shieldedvalueandabouthalfthetotallyunshieldedvalue(figure4.39).Shieldingisincompletebecause
bothelectronsinheliumoccupyanextendedregionofspace,soneitheriscompletelyeffectiveatshielding
theotherfromthe+2chargeofthenucleus.
FIGURE4.39Ionisationenergiesofaheliumatomwithdifferentamountsofshielding.

Electronsincompactorbitalspackaroundthenucleusmoretightlythanelectronsinlarge,diffuseorbitals.
Asaresult,theeffectivenessinshieldingnuclearchargedecreasesasorbitalsizeincreases.Becausethe
sizeofanorbitalincreaseswithn,anelectron'sabilitytoshielddecreasesasnincreases.Inamultielectron
atom,lowernelectronsareconcentratedbetweenthenucleusandhighernelectrons.Thenegativecharges
oftheseinnerelectronscounteractmostofthepositivechargeofthenucleus.

Theefficientshieldingbyelectronswithsmallvaluesofncanbeappreciatedbycomparingtheionisation
energiesofelectronsinthe2porbitalsinfigure4.37.Consideranexcitedstateheliumatomthathasoneof
itselectronsinthe1sorbitalanditsotherelectronina2porbital.Ittakes0.58510 18Jtoremovethe2p
electronfromthisexcitedstateheliumatom.Thisvalueisclosetothatofanexcitedhydrogenatomwithits
loneelectronina2porbital,0.54510 18J.Itismuchlessthanthe2porbitalionisationenergyofan
excitedHe+ion,2.1810 18J.ThesedatashowthatZeffisquitecloseto+1forthe2porbitalofanexcited
atom.IntheexcitedHeatom,theelectroninthe1sorbitalisveryeffectiveatshieldingtheelectroninthe
2porbitalfromthefull+2chargeofthenucleus.

Inmultielectronatoms,electronswithagivenvalueofngenerallyprovideeffectiveshieldingfororbitals
withalargervalueofn.Thatis,n=1electronsshieldthen=2,n=3andlargerorbitals,whereasn=2
electronsprovideeffectiveshieldingforthen=3,n=4andlargerorbitalsbutprovidelittleshieldingfor
then=1orbital.Theamountofshieldingalsodependsontheelectrondistributionoftheshieldedorbital
anddecreaseswithincreasingazimuthalquantumnumber,l.Theshadedareaoftheelectrondensityplotin
figure4.40emphasisesthatthe2sorbitalhasaregionofsignificantelectrondensitynearthenucleus.A2p
orbitallacksthisinnerlayer,sovirtuallyallofitselectrondensityliesoutsidetheregionoccupiedbythe1s
orbital.Consequently,a1sorbitalshieldsthe2porbitalmoreeffectivelythanthe2sorbital,eventhough
bothn=2orbitalsareaboutthesamesize.Thus,a2selectronissubjecttoalargereffectivenuclearcharge
thana2pelectron.Thisresultsinstrongerelectrostaticattractiontothenucleus,whichmakesthe2sorbital
lowerinenergythanthe2porbitals.The2porbitalsofanymultielectronatomarealwaysslightlyhigherin
energythanthe2sorbital.
FIGURE4.40Electrondensityplotsforthe1s,2sand2porbitals.Unlikethe2porbital,the2sorbitalhas
significantelectrondensityverynearthenucleus(shadedregion).

Theshieldingdifferencesexperiencedbythe2sand2porbitalsalsoextendtolargervaluesofn.The3s
orbitalisoflowerenergythanthe3p,the4sorbitalisoflowerenergythanthe4p,andsoon.Orbitalswith
higherlvaluesshowsimilareffects.The3dorbitalsarealwayshigherinenergythanthe3porbitals,and
the4dorbitalsarehigherinenergythanthe4porbitals.Theseeffectscanbesummarisedinasingle
generalstatement:Thehigherthevalueofthelquantumnumber,themorethatorbitalisshieldedby
electronsinsmaller,lowerenergyorbitals.

Inaoneelectronsystem(H,He+,Li2+andsoon)theenergyoftheorbitalsdependsonlyonZandn.In
multielectronsystems,orbitalenergydependsprimarilyonZandn,butitalsodependssignificantlyonl.
Inasense,lfinetunesorbitalenergiesandasaconsequencetherearefewerdegenerateorbitals.

Therelativeorbitalenergiesforamultielectronatomareshowninfigure4.41.Itcanbeseenthat,whereas
inaoneelectronsystemthens,npandndorbitalsaredegenerate,thisisnotthecaseinamultielectron
atom.

FIGURE4.41Anenergyleveldiagram(nottoscale)foramultielectronatom.Theorbitalenergiesnowdepend
onlinadditiontobothZandn,andso,incontrasttooneelectronsystems(figure4.36),orbitals
havingthesameprincipalquantumnumbernarenolongerdegenerate.

Electronswiththesamelvaluebutdifferentvaluesofmldonotshieldoneanothereffectively.For
example,whenelectronsoccupydifferentporbitals,theamountofmutualshieldingisslight.Thisis
becauseshieldingiseffectiveonlywhenmuchoftheelectrondensityofoneorbitalliesbetweenthe
nucleusandtheelectrondensityofanother.Recallfromfigure4.32(p.133)thattheporbitalsare
perpendiculartooneanother,withhighelectrondensitiesindifferentregionsofspace.Theelectrondensity
ofthe2p x orbitaldoesnotliebetweenthe2p y orbitalandthenucleus,sothereislittleshielding.Thed
orbitalsalsooccupydifferentregionsofspacefromoneanother,somutualshieldingamongelectronsin
theseorbitalsissmallaswell.

WORKEDEXAMPLE4.9

Shielding
Drawaqualitativeelectrondensityplotshowingthe1s,2pand3dorbitalstoscale.Labelthe
plotinawaythatsummarisestheshieldingpropertiesoftheseorbitals.

Analysis

Thisisaqualitativeproblemthatasksustocombineinformationaboutthreedifferentorbitalson
asingleplot.Weneedtofindelectrondensityinformationanddrawasinglegraphtoscale.
Solution

Figures4.28,4.29and4.40showelectrondensityplotsofthen=1,n=2andn=3orbitals.We
extracttheelectrondistributionsofthe1s,2pand3dorbitalsfromthesegraphs.Thenweadd
labelsthatsummarisetheshieldingpropertiesoftheseorbitals.Shieldingisprovidedbysmall
orbitalswhoseelectrondensityisconcentratedclosertothenucleusthanthatoflargerorbitals.
Inthiscase,1sshieldsboth2pand3d2pshields3d,butnot1sand3dshieldsneither1snor
2p.Theshieldingpatternscanbelabelledasshown.

Isouranswerreasonable?

Weknowthatthemostimportantfactorfororbitalsizeisthevalueofnandthatsmallorbitals
shieldbetterthanlargeones,sotheshieldingsequencemakessense.

PRACTICEEXERCISE4.9
Constructandlabelagraphillustratingthatthe
2sorbitalshieldsthe3sorbitalmore
effectivelythanthe3sshieldsthe2s.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.6StructureofthePeriodicTable
Aswehaveseeninchapter1,theperiodictableliststheelementsinorderofincreasingatomicnumber.
Becausethenumberofelectronsinaneutralatomisthesameasitsatomicnumber,thislistisalsoinorder
ofincreasingnumberofatomicelectrons.Theperiodictableorganisesatomsinrows(periods)andgroups
suchthatatomswiththesamevalenceelectronconfiguration,leadingtosimilarchemicalproperties,are
locatedinthesamegroup.Wehavesincelearnedthattheelectronsaremainlyresponsibleforanatom's
chemicalproperties,andequippedwiththeknowledgeoforbitalelectrondistributionsandenergieswecan
nowstarttounderstandthereasonsfortheplacementofatomsintheperiodictable.

TheAufbauPrincipleandOrderofOrbitalFilling
Thegroundstateofanatomis,bydefinition,themoststablearrangementofitselectrons.Moststablemeans
thattheelectronsoccupythelowestenergyorbitalsavailable.Weconstructthegroundstateconfiguration
ofanatombyplacingelectronsintheorbitalsstartingwiththelowestinenergyandmovingprogressively
upward.Wehaveseenearlierthatshieldingcausestheorbitalswiththesameprincipalquantumnumberto
increaseinenergyaslincreases.Consequently,the2sorbital,beingoflowerenergythanthe2porbital,fills
first.Similarly,3sfillsbefore3p.Theenergydifferencesbetweenorbitalsbecomelesspronouncedthe
furtherawaytheorbitalsarefromthenucleus.Theconsequenceofthisisthat,fororbitalswithprincipal
quantumnumberslargerthann=2,theorderoforbitalenergiesisnotnecessarilyasexpected.Forexample,
the4sorbitalfillsbeforethe3dorbitals.Therefore,theorderoforbitalfillingisasgiveninfigure4.42a.At
higherlevels,thereareanumberofexceptionstothisfillingsequence.Thesewillbediscussedonpp.145
6.InaccordancewiththePauliexclusionprinciple,eachsuccessiveelectronisplacedinthelowestenergy
orbitalwhosequantumnumbersarenotalreadyassignedtoanotherelectron.ThisiscalledtheAufbau
principle(AufbauisaGermanwordliterallymeaningbuildup).
FIGURE4.42 (a)Theorderoffillingorbitalswithelectrons
(b)Aneasywaytorememberthegeneralorderofelectronfilling.Orbitalsfillinorderof
increasing(n+l).Whereorbitalshavethesamevalueof(n+l),theonewiththelowestnwill
fillfirst,followedbytheothersinincreasingorderofn.Note,however,forhighervaluesofn,
thereareanumberofexceptionstothisgeneralorder(seetheelectronconfigurationsgiven
infigure4.44).

InapplyingtheAufbauprinciple,rememberthatafulldescriptionofanelectronrequiresfourquantum
numbers:n,l,mlandms.Eachcombinationofnandldescribesonequantisedenergylevel.Moreover,each
levelwithl>1includesmultipleorbitals,eachwithadifferentvalueofml.Foranycombinationofnandl,
allorbitalswiththesamevalueoflaredegenerate,i.e.inanatomtheyhavethesameenergy.Forexample,
the2penergylevel(n=2,l=1)consistsofthreedistinctporbitals(ml=1,0and+1),allwiththesame
energy.Inaddition,thespinquantumnumber,ms,describesthetwopossibledifferentspinorientationsof
anelectron.

Inotherwords,the2penergylevelconsistsof3orbitalswithdifferentmlvaluesthatcanholdasmanyas6
electronswithoutviolatingthePauliexclusionprinciple.Thesameistrueofeverysetofporbitals(3p,4p
etc.).Eachsetcanbedescribedby6differentsetsofquantumnumbersandcanthereforehold6electrons.
Asimilaranalysisforothervaluesoflshowsthateachsenergylevelcontainsasingleorbitalandcanhold
upto2electrons,eachdenergylevelconsistsof5differentorbitalsthatcanholdupto10electrons,and
eachfenergylevelconsistsof7differentorbitalsthatcanholdupto14electrons.

ThePauliexclusionandAufbauprinciplesdictatethelengthoftheperiodsintheperiodictable.After2
electronshavebeenplacedinthe1sorbital(He),thenextelectronmustgoinahigherenergy2sorbital(Li).
After8additionalelectronshavebeenplacedinthe2sand2porbitals(Ne),thenextelectronmustgoina
higherenergy3sorbital(Na).Theperiodictableorganisesatomsinrows(periods)andgroupssuchthat
atomswithsimilarchemicalproperties,asindicatedbytheirvalenceelectronconfiguration,arelocatedin
thesamegroup.Becausetheperiodictablestartswiththefillingofthe1sorbital,everyrowhastofinish
beforethenextsorbitalwithhigherprincipalquantumnumberhastobefilled.Thestartofthenextrowis
anatomwithoneelectroninthatsorbital.

Hereisasummaryoftheconditionsforatomicgroundstates:
1.Theelectronsintheatomoccupythelowestenergyorbitals(seefigure4.42a).
2.Notwoelectronscanhaveidenticalsetsofquantumnumbers.
3.Orbitalcapacitiesareasfollows:shas2electronspsethas6electronsdsethas10electronsfset
has14electrons.

Armedwiththeseconditions,wecancorrelatetherowsandcolumnsoftheperiodictablewithvaluesofthe
quantumnumbersnandl.Thisisshownintheperiodictableinfigure4.43.Rememberthattheelementsare
arrangedsothatZincreasesoneunitatatimefromlefttorightacrossarow.Attheendofeachrow,we
movetothenexthighervalueofZonerowdownontheleftsideoftheperiodictable.

FIGURE4.43Theperiodictableinblockform,showingthefillingsequenceoftheatomicorbitals.Fillingproceeds
fromlefttorightacrosseachrowandfromtherightendofeachrowtotheleftendofthesucceeding
row.

Thenumberofelementsperrowincreasesasweincreasen.Thefirstperiodcontainsonlyhydrogenand
helium.Thentherearetwo8elementperiods,followedbytwo18elementperiods,andfinallytwo32
elementperiods.

Infigure4.44,eachrowislabelledwiththehighestprincipalquantumnumberofanyofitsoccupied
orbitals.Forexample,elementsofthethirdrow(NatoAr)haveelectronsinorbitalswithn=3(inaddition
toelectronswithn=1and2).Eachcolumnislabelledwithitsgroupnumber,startingwithgroup1onthe
leftandproceedingtogroup18ontheright(thefblockdoesnothavegroupnumbers).Ingeneral,elements
inthesamegroupoftheperiodictablehavethesamearrangementofelectronsintheirhighestenergy
occupiedorbitals,givingrisetotheirsimilarchemicalproperties.
FIGURE4.44Theperiodictablewithitsrowsandblockslabelledtoshowtherelationshipbetweensectorsofthe
tableandgroundstateconfigurations.Rowsarelabelledwiththehighestprincipalquantumnumber
oftheoccupiedorbitals,andeachblockislabelledwiththeletter(s,p,d,f)indicatingtheorbitalset
thatisfilling.Electronconfigurationsforelements103118aretentative,andarebasedonthe
electronconfigurationsofotherelementsinthesamegroup.

Everyperiodendsattheendofthepblock.Thisindicatesthat,whenthenporbitalsarefull,thenextorbital
toacceptelectronsisthe(n+1)sorbital.Forexample,afterfillingthe3porbitalsfromAl(Z=13)toAr(Z=
18),thenextelement,potassium,hasitsfinalelectroninthe4sorbitalratherthaninoneofthe3dorbitals.
Thisconfirms(seefigure4.42a)thatthe4sorbitalofthepotassiumatomisoflowerenergythanthe3d
orbital.AccordingtotheAufbauprinciple,the3dorbitalsfillafterthe4sorbitalisfull,startingwith
scandium(Z=21).

Asimilarsituationexistsattheendofthenextrow.Whenthe4porbitalisfull(Kr,Z=36),thenextelement
(Rb,Z=37)hasanelectroninthe5sorbitalratherthaneithera4dor4forbital.Infact,electronsarenot
addedtothe4forbitalsuntilelement58,afterthe5s,5pand6sorbitalshavefilled.

Thesevenforbitalscanhold14electrons,andthereforethereshouldbe14fblockelements.However,the
periodictableshowninfigure4.44shows15elementsinboththelanthanoidandactinoidseries.This
reflectsthedebateoverwhetherthefirstelementineachrow(LaandAc,respectively)ispartofthedblock
orfblock.OlderversionsoftheperiodictableplaceLaandAcdirectlybeneathScandY,giving14
lanthanoidandactinoidelements.However,itisclearthatthechemistryofbothLaandAcresemblesthatof
thelanthanoidsandactinoidsrespectively,morethanmaingrouportransitionelements,despitetheirf0
electronconfigurations(indeed,thetermslanthanoidsandactinoidsderivefromlanthanumandactinum,
respectively).

WORKEDEXAMPLE4.10
OrbitalFillingSequence
Whichorbitalsarefilled,andwhichsetoforbitalsispartiallyfilled,inagermaniumatom?

Analysis

Forthisqualitativeproblem,usetheperiodictabletodeterminetheorderoforbitalfilling.Locate
theelementinablockandidentifyitsrowandcolumn,thenusefigure4.43toestablishthe
sequenceoffilledorbitals.

Solution

Germaniumiselement32.Consultfigure4.43todeterminethatGeisingroup14,row4ofthep
block.

Startingfromthetopleftoftheperiodictableandworkinglefttorightacrosstherowsuntilwe
reachGe,weidentifythefilledorbitals:1s,2s,2p,3s,3p,4sand3d.Germaniumisinrow4of
thepblock,sothe4psetoforbitalsispartiallyfilled.

Isouranswerreasonable?

GehasZ=32,meaningitsneutralatomscontain32electrons.Wecancounthowmanyelectrons
eachorbitalcanhold:2foreachsorbital,6foreachporbitalsetand10foreachdorbitalset.
2(1s)+2(2s)+6(2p)+2(3s)+6(3p)+2(4s)+10(3d)=30electrons,leaving2inthepartially
filled4porbitalset.

PRACTICEEXERCISE4.10
Determinewhichorbitalsarefilledandwhich
setispartiallyfilledfortheelementZr.

ValenceElectrons
Thechemicalbehaviourofanatomisdeterminedbyitssizeandtheelectronsthatareaccessibletoan
approachingchemicalreagent.Accessibilityhasaspatialcomponentandanenergeticcomponent.An
electronisaccessiblespatiallywhenitoccupiesoneofthelargestorbitalsoftheatom.Electronsonthe
perimeteroftheatom,farthestfromthenucleus,arethefirstonesencounteredbyanincomingchemical
reagent.Anelectronisaccessibleenergeticallywhenitoccupiesoneofthehighestenergyoccupiedorbitals
oftheatom.Electronsinhighenergyorbitalsaremorechemicallyactivethanelectronsinlowerenergy
orbitals.

Similarelectronaccessibilitygeneratessimilarchemicalbehaviour.Forexample,iodinehasmanymore
electronsthanchlorine,butthesetwoelementsdisplaysimilarchemicalbehaviour,asreflectedbytheir
placementinthesamegroupoftheperiodictable.Thisisbecausethechemistryofchlorineandiodineis
determinedbythenumberofelectronsintheirlargestandhighestenergyoccupiedorbitals:3sand3pfor
chlorine,and5sand5pforiodine.Eachoftheseelementshassevenaccessibleelectrons,andthisaccounts
fortheirchemicalsimilarities.

Accessibleelectronsarecalledvalenceelectrons,andinaccessibleelectronsarecalledcoreelectrons.
Valenceelectronsmayparticipateinchemicalreactions,whilecoreelectronsdonot.Ingeneral,valence
electronsarethosethathavebeenaddedintheperiodoftheperiodictable(seefigure4.44)thattheatomis
locatedin.Forexample,carbonwithZ=6islocatedinperiod2,soitsvalenceelectronsarethoseinthe2s
and2porbitals(totalling4).Thesituationissimilarforphosphorusinperiod3,whichhas3sand3pvalence
electrons(totalling5).Manganeseinperiod4hasvalenceelectronsinthe4sand3dorbitals(totalling7).

Thenearlyequalenergiesofnsand(n1)dorbitalscreatesomeambiguityaboutvalenceandcoreelectrons
forelementsinthedandfblocks.Forexample,titaniumformsachlorideandanoxidewithchemical
formulaeconsistentwithfourvalenceelectrons:TiCl4andTiO2.Thisshowsthatthetwo3delectronsof
titaniumparticipateinchemicalreactions.Ontheotherhand,zincformscompounds,suchasZnCl2and
ZnO,withonlytwoelectronsinvolvedinitschemistry.Thischemicalbehaviourindicatesthatzinc'sten3d
electrons,whichcompletelyfillthe3dorbitals,areinaccessibleforchemicalreactions.Whenthedorbitals
arepartiallyfilled,thedelectronsparticipateinchemicalreactions,but,whenthedorbitalsarecompletely
filled,thedelectronsdonotgenerallyparticipateinreactions(seebelowforafewexceptions).The
predominantoxidationstateof3+throughoutthefblockelementsalsosuggeststhatgenerallyonlyonedor
felectron(seegroundstateconfigurationsinfigure4.44)isaccessibleforchemicalreactions.The
definitionsofcoreandvalenceelectronsdonotdependonwhethertheelectronsareusedinchemical
reactions,butratherwhethertheyareinanaccessibleenergylevelornot.

Wefindthatthenumberofvalenceelectronscanbedeterminedeasilyfromgroupnumbersintheperiodic
table.Forgroups110,thenumberofvalenceelectronsequalsthegroupnumber.Asexamples,potassium
andrubidium,membersofgroup1,havejustonevalenceelectroneach.Tungsten,ingroup6,hassix
valenceelectrons:two6selectronsandfour5delectrons.Forgroups1218,thenumberofvalence
electronsequalsthegroupnumberminus10(thenumberofelectronsittakestofillthedorbitals).Thus,
antimonyandnitrogen,ingroup15,have1510=5valenceelectronseach(twosandthreep).Forgroup
11,thenumberofvalenceelectronsisexpectedtobe1(theoneselectron).However,oftencompoundsof
theseelementsinvolvetheirdelectrons.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.7ElectronConfigurations
Acompletespecificationofhowanatom'selectronsaredistributedinitsorbitalsiscalledanelectron
configuration.Therearethreecommonwaystorepresentelectronconfigurations.Oneisacomplete
specificationofquantumnumbers.Thesecondisashorthandnotationfromwhichthequantum
numberscanbeinferred.Thethirdisadiagrammaticrepresentationoforbitalenergylevelsandtheir
occupancies.

Alistofthevaluesofallquantumnumbersiseasyforthesingleelectroninahydrogenatom:

Eitherdesignationisequallyvalid,becauseundernormalconditionsthesetwostatesareequalin
energy.Inalargecollectionofhydrogenatoms,halftheatomshaveonedesignationandtheotherhalf
havetheotherdesignation.

Asthenumberofelectronsinanatomincreases,alistingofallquantumnumbersquicklybecomes
tedious.Forexample,iron,with26electrons,wouldrequirethespecificationofatleast26setsoffour
quantumnumbers.Tosavetimeandspace,chemistshavedevisedashorthandnotationtowriteelectron
configurations.Theorbitalsymbols(1s,2p,4detc.)arefollowedbysuperscriptsdesignatinghowmany
electronsareineachsetoforbitals.Thecompactconfigurationforahydrogenatomis1s1,indicating1
electroninthe1sorbital.Foranironatomthecompactconfigurationis1s22s22p 63s23p 64s23d 6.

Thethirdwaytorepresentanelectronconfigurationusesanenergyleveldiagramtodesignateorbitals.
Eachorbitalisindicatedbyahorizontallinearrangedverticallyinorderofincreasingenergy.Each
electronisrepresentedbyanarrowandisplacedontheappropriatehorizontalline(orbital).The
directionofthearrowindicatesthevalueofms.Byconvention,wefillorbitalsstartingfromtheleft
handside,andthearrowpointsupwardfor anddownwardfor .Theconfiguration
ofhydrogencanberepresentedbyasinglearrowina1sorbital.

Aneutralheliumatomhastwoelectrons.TowritethegroundstateelectronconfigurationofHe,we
applytheAufbauprinciple.Oneuniquesetofquantumnumbersisassignedtoeachelectron,moving
fromthelowestenergyorbitalupwarduntilallelectronshavebeenassigned.Thelowestenergyorbital
isalways1s(n=1,l=0,ml=0).Bothheliumelectronscanoccupythe1sorbital,providedoneofthem
has andtheotherhas .Belowarethethreerepresentationsofhelium'sground
stateelectronconfiguration.

Thetwoelectronsinthisconfigurationaresaidtobepairedelectrons,meaningthattheyareinthesame
orbital,withopposingspins.Opposingspinscancel,sopairedelectronshavezeronetspin.

Alithiumatomhasthreeelectrons.Thefirsttwoelectronsfilllithium'slowestpossibleenergylevel,the
1sorbital,andthethirdelectronoccupiesthe2sorbital.Thethreerepresentationsforthegroundstate
electronconfigurationofalithiumatomareshownbelow.

Thesetn=2,l=0,ml=0, isequallyvalidforthethirdelectron.

Thenextatomsoftheperiodictableareberylliumandboron.Youshouldbeabletowritethethree
differentrepresentations(thesetofquantumnumbers,theshorthandnotationandtheenergylevel
diagram)forthegroundstateconfigurationsoftheseelements.Thefillingprinciplesarethesameaswe
movetohigheratomicnumbers.

WORKEDEXAMPLE4.11

AnElectronConfiguration
Constructanenergyleveldiagramandtheshorthandnotationofthegroundstate
configurationofaluminium.Provideonesetofvalidquantumnumbersforthehighest
energyelectron.

Analysis

Firstconsulttheperiodictabletolocatealuminiumanddeterminehowmanyelectronsare
presentinaneutralatom.Thenconstructtheelectronconfigurationusingthepatternsofthe
periodictable.

Solution

AluminiumhasZ=13,soaneutralatomofAlhas13electrons.Placethe13electrons
sequentially,usingarrows,intothelowestenergyorbitalsavailable.Then=1orbitalisfilled
bytwoelectrons,eightelectronsfillthen=2orbitals,twoelectronsfillthe3sorbital,and
oneelectrongoesina3porbital.

Thelastelectroncouldbeplacedinanyofthe3porbitals,becausethesethreeorbitalsare
equalinenergy.Thefinalelectroncouldalsobegiveneitherspinorientation.Byconvention,
weplaceelectronsinunfilledorbitalsstartingwiththelefthandside,withspinspointedup.

Theshorthandnotationis1s22s22p 63s23p 1.
Thehighestenergyelectronisina3porbital,meaningn=3andl=1.Thevalueofmlcan
beanyofthreevalues:+1,1or0.Thespinquantumnumber,ms,canbe or .One
validsetofquantumnumbersis:

Youshouldbeabletowritetheotherfivepossiblesets.

Isouranswerreasonable?

Aluminium,ingroup13,hasthreevalenceelectrons.Theconfigurationsshowthree
electronswithn=3,sotheconfigurationisconsistentwiththevalenceelectroncount.

PRACTICEEXERCISE4.11
Determinetheenergyleveldiagramand
shorthandnotationfortheelectron
configurationofthefluorineatom.

Electronconfigurationsbecomelongerasthenumberofelectronsincreases.Tomakethewritingofa
configurationevenmorecompact,chemistsmakeuseoftheregularpatternfortheelectronswithlower
principalquantumnumbers.Comparetheconfigurationsofneonandaluminiumshownbelow.

Thedescriptionofthefirst10electronsintheconfigurationofaluminiumisidenticaltothatofneon.
Wecantakeadvantageofthispatternandrepresentthatportionas[Ne].Withthisnotation,the
configurationofAlbecomes[Ne]3s23p 1.Theelementattheendofeachrowoftheperiodictablehasa
noblegasconfiguration.Theseconfigurationscanbewritteninthefollowingshorthandnotation.

Notation Configuration Element


[He] 1s2 He(2electrons)

[Ne] [He]2s22p 6 Ne(10electrons)

[Ar] [Ne]3s23p 6 Ar(18electrons)

[Kr] [Ar]4s23d 104p 6 Kr(36electrons)

[Xe] [Kr]5s24d 105p 6 Xe(54electrons)

[Rn] [Xe]6s25d 104f14f6p 6 Rn(86electrons)

Towritetheconfigurationofanyotherelement,wefirstconsulttheperiodictabletofinditslocation
relativetothenoblegases.Thenwespecifytheconfigurationoftheprecedingnoblegasandbuildthe
remainingportionoftheconfigurationaccordingtotheAufbauprinciple.
WORKEDEXAMPLE4.12

AShorthandElectronConfiguration
Determinetheelectronconfigurationofindium,firstinshorthandformandtheninfullform.

Analysis

Locatetheelementintheperiodictable,andfindthenearestnoblegaswithasmalleratomic
number.Startwiththeelectronconfigurationofthatnoblegas,andaddenoughadditional
electronstothenextfillingorbitalstogivetheneutralatom.

SolutionIndium,In,(Z=49)isinrow5,group13.ThenearestnoblegasofsmallerZisKr
(Z=36).Thus,theconfigurationofInhas36electronsintheKrconfigurationand13
additionalelectrons.ThelastorbitaltofillinKris4p,andtheperiodictableshowsthatthe
nextorbitalstofillarethe5s,4dand5porbitals.
Configurationofindium:[Kr]5s24d 105p 1
Towritethefullconfiguration,expandthekryptonconfiguration.
[Kr]=[Ar]4s23d 104p 6=1s22s22p 63s23p 64s23d 104p 6
FullconfigurationofIn(49electrons):1s22s22p 63s23p 64s23d 104p 65s24d 105p 1

Notethatitisusualtoindicateemptyorbitalsinanenergyleveldiagramwhentheyarepart
ofasetofdegenerateorbitals.Forexample,intheenergyleveldiagramabove,weshowthe
twoemptyporbitalsofthe5psetbecauseoneofthesetcontainsasingleelectron.

Isouranswerreasonable?
Indium,ingroup13,hasthreevalenceelectrons.Theconfigurationsshowthreeelectrons
withn=5,sotheconfigurationisconsistentwiththevalenceelectroncount.

PRACTICEEXERCISE4.12
Determinethecompactnotationforthe
electronconfigurationofthecadmiumatom.

ElectronelectronRepulsion
TheAufbauprincipleallowsustoassignquantumnumberstoaluminium's13electronswithout
ambiguity.Thefirst12electronsfillthe1s,2s,2pand3senergylevels,andthelastelectroncanoccupy
any3porbitalwitheitherspinorientation.Butwhathappenswhenmorethanoneelectronmustbe
placedinapenergylevel?Carbonatoms,forexample,havesixelectrons,twoofwhichoccupy2p
orbitals.Howshouldthesetwoelectronsbearrangedinthe2porbitals?Asfigure4.45shows,three
differentarrangements(ofthe15possible)oftheseelectronsobeythePauliexclusionprinciple:
1.Theelectronscouldbepairedinthesame2porbital(samemlvaluebutdifferentmsvalues).
2.Theelectronscouldoccupydifferent2porbitalswithoppositespinorientations(differentml
valuesanddifferentmsvalues).
3.Theelectronscouldoccupydifferent2porbitalswiththesamespinorientation(differentml
valuesbutthesamemsvalue).

FIGURE4.45Threedifferentarrangementsoftwo2pelectronsthatobeythePauliexclusionprinciple.

Thesethreearrangementshavedifferentenergiesbecauseelectronsthatareclosetogetherrepeleach
othermorethanelectronsthatarefarapart.Asaresult,fortwoormoredegenerateorbitals,thelowest
energysituationresultswhenelectronsoccupytheorbitalsthatkeepthemfurthestapart.Placingtwo
electronsindifferentporbitalskeepsthemrelativelyfarapart,soanatomisoflowerenergywiththe
twoelectronsindifferentporbitals.Thus,arrangements2and3areoflowerenergythanarrangement
1.

Arrangements2and3lookspatiallyequivalent,butexperimentsshowthataconfigurationthatgives
unpairedelectronsthesamespinorientationisalwaysoflowerenergythanonethatgivesthemopposite
orientations.Hund'srulesummarisesthewayinwhichelectronsoccupyorbitalsofequalenergies.The
lowestenergyconfigurationinvolvingorbitalsofequalenergiesistheonewiththemaximumnumberof
electronswiththesamespinorientation.

AccordingtoHund'srule,arrangement3offigure4.45isconsistentwiththegroundstateconfiguration
forcarbonatoms.
WORKEDEXAMPLE4.13

ApplyingHund'sRule
Writetheshorthandelectronconfigurationanddrawthegroundstateorbitalenergylevel
diagramforthevalenceelectronsinasulfuratom.

Analysis

Fromtheperiodictable,weseethatsulfurhas16electronsandisinthepblock,group16.
Tobuildthegroundstateconfiguration,applytheAufbauandthePauliexclusionprinciples
andthenapplyHund'sruleifneeded.

Solution

Thefirst12electronsfillthefourlowestenergyorbitals.

Sulfur'sremainingfourelectronsoccupythethree3porbitals.Thecompleteconfigurationis
1s22s22p 63s23p 4or[Ne]3s23p 4.

Tominimiseelectronelectronrepulsion,putthreeofthe3pelectronsindifferentorbitals,all
withthesamespin,andthenplacethefourthelectron,withoppositespin,inthefirstorbital.
InaccordwithHund'srule,thisgivesthesamevalueofmstoallelectronsthatarenotpaired.
Belowistheenergyleveldiagramforsulfur'svalenceelectrons.

Isouranswerreasonable?

Sulfur,inrow3andgroup16,hassixvalenceelectrons.Theconfigurationsshowsix
electronswithn=3,sotheconfigurationisconsistentwiththevalenceelectroncount.The
electronsarespreadamongthethree3porbitals,whichminimiseselectronelectron
repulsion.

PRACTICEEXERCISE4.13
Determinethecompactelectron
configurationforthenitrogenatomand
writeonevalidsetofquantumnumbersfor
itsvalenceelectrons.
OrbitalswithNearlyEqualEnergies
Thefillingorderembodiedintheperiodictablepredictsaregularprogressionofgroundstate
configurations.Experimentsshow,however,thatsomeelementshavegroundstateconfigurations
differentfromthepredictionsoftheregularprogression.Amongthefirst40elements,thereareonly
twoexceptions:copperandchromium.Chromium(Z=24)isingroup6,fourelementsintothedblock.
Wewouldpredictthatthegroundstatevalenceconfigurationofchromiumshouldbe4s23d 4.Instead,
experimentsshowthatthegroundstateconfigurationofthiselementis4s13d 5.Likewise,the
configurationofcopper(Z=29)is4s13d 10ratherthanthepredicted4s23d 9.

Lookagainatfigure4.42a,whichshowsthatthesetwosetsoforbitalsarenearlythesameinenergy.
Each(n1)dorbitalhasnearlythesameenergyasitsnscounterpart.Inaddition,each(n2)forbital
hasnearlythesameenergyasits(n1)dcounterpart.Table4.3liststheseorbitalsandtheatomic
numbersforwhichthefillingsequencediffersfromtheexpectedpattern.Theseconfigurationsarealso
indicatedinfigure4.44.
TABLE4.3 Atomicorbitalswithnearlyequalenergies
Orbitals Atomicnumbersaffected Example
4s,3d 24,29 Cr:[Ar]4s13d 5
5s,4d 41,42,44,45,46,47 Ru:[Kr]5s14d 7
6s,5d,4f 57,58,64,78,79 Au:[Xe]6s14f145d 10
6d,5f 89,9193,96 U:[Rn]7s25f3f6d 1

Often,ansorbitalcontainsonlyoneelectronratherthantwo.Fiveoftheexceptionalgroundstate
configurationshaveacommonpatternandareeasytoremember:CrandMoares1d 5,andCu,Agand
Auares1d 10.Theotherexceptionalcasesfollownorecognisablepatterns,becausetheyaregenerated
bysubtleinteractionsbetweenalltheelectrons.Amongelementswithvalenceelectronsfillingorbitals
withnearlyequalenergies,severalfactorshelptodeterminethegroundstateconfiguration.Thedetails
arebeyondthescopeofthisbook,exceptthatyoushouldrecognisethatevenasubtlechangecancause
variationsinthefillingpatternpredictedbytheperiodictable.

ConfigurationsofIons
Theelectronconfigurationsofatomicionsarewrittenusingthesameprocedureasforneutralatoms,
takingintoaccountthepropernumberofelectrons.Ananionhasoneadditionalelectronforeachunit
ofnegativecharge.Acationhasonefewerelectronforeachunitofpositivecharge.
Formostatomicions,theelectronconfigurationcanbededucedeasilyfromthatofthecorresponding
neutralatom.Forexample,Na+,NeandFallcontain10electrons,andeachhastheconfiguration
1s22s22p 6.Atomsandionsthathavethesamenumberofelectronsaresaidtobeisoelectronic.

Ingeneral,youwouldexpectthatthelastelectrontobeaddedwouldbethefirstelectrontobeloston
ionisation.Thenearlyequalenergiesofnsand(n1)dorbitalscausestheconfigurationsofsome
cationstodifferfromtheconfigurationspredictedbythefillingpatternoftheperiodictable.Remember
thattheenergyrankingoforbitalssuchas4sand3ddependsonabalanceofseveralfactors,andthat
evenasmallvariationinthatbalancecanchangetheorderoftheorbitals.Thisfeatureisparticularly
importantforthetransitionmetals,forwhichthedorbitalsareoccupied.Experimentsshowthatin
transitionmetalcationsthe(n1)dorbitalsarealwaysoflowerenergythanthensorbitalstherefore,
thefirstelectronsarelostfromthesorbitalbeforethoseindorbitals.Forexample,anFe3+cation
contains23electrons.Thefirst18electronsfillthe1s,2s,2p,3sand3porbitals,aspredictedbythe
periodictable.However,thefiveremainingelectronspopulatethe3dset,leavingthe4sorbitalempty.
ThustheconfigurationoftheFe3+cationis[Ar]3d 5.

Vanadium,V,atoms([Ar]4s23d 3)andFe3+cations([Ar]3d 5)havedifferentconfigurations,eventhough


eachhas23electronsasshowninfigure4.46.

FIGURE4.46Transitionmetalatomsandcationshavedifferentvalenceelectronconfigurations,evenwhen
thespeciescontainthesamenumberofelectrons.

WORKEDEXAMPLE4.14

ConfigurationofaCation

WhatisthegroundstateelectronconfigurationofaCr3+cation?

Analysis

UsetheAufbauprinciple,rememberingthatbecauseCrisatransitionmetal,its4sorbitalwill
beemptiedbeforethe3dorbital.

SolutionAneutralchromiumatomhas24electrons,sothecorrespondingCr3+cationhas
21electrons.Thefirst18electronsfollowtheusualfillingordertogivetheargoncore
configuration:1s22s22p 63s23p 6,or[Ar].Placetheremainingthreeelectronsinthe3dsetof
orbitals,followingHund'srule:[Ar]3d 3.
Isouranswerreasonable?

Foranytransitionmetalcation,theempty4sorbitalisslightlyhigherinenergythanthe
partiallyfilled3dorbital.Thus,theisoelectronicV2+andCr3+cationsbothhavethe[Ar]3d 3
configuration.Ontheotherhand,theisoelectronicneutralatomscandiumhasthe
configuration[Ar]4s23d 1.

PRACTICEEXERCISE4.14
Determinethegroundstateelectron
configuration(compactform)ofaRu 3+
cation.

Wecansummarisethediscussioninthissectionintoguidelinesforbuildingatomicorionicelectron
configurations:
1.Countthetotalnumberofelectrons.
a.Addelectronsforanions.
b.Subtractelectronsforcations.
2.Fillorbitalstomatchthenearestnoblegasofsmalleratomicnumber.
3.AddremainingelectronstothenextorbitalstobefilledaccordingtothePauliexclusionand
Aufbauprinciples,aswellasHund'srule.
a.Forneutralatomsandanions,placeelectronsinnsbefore(n1)dand(n2)f).
b.Forcations,determinetheelectronconfigurationfortheneutralatomandremovethe
requirednumberofelectronswiththehighestenergy.
4.Lookforexceptionsandcorrecttheconfigurationifnecessary.

MagneticPropertiesofAtoms

HowdoweknowthatanFe3+ioninitsgroundstatehastheconfiguration[Ar]3d 5ratherthanthe
[Ar]4s23d 3configurationpredictedbytheorbitalfillingsequence?Rememberthatelectronspingives
risetomagneticproperties.Consequently,anyatomorionwithunpairedelectronshasnonzeronet
spinandisattractedbyastrongmagnet.Wecandividetheelectronsofanatomorionintotwo
categorieswithdifferentspincharacteristics.Infilledorbitals,alltheelectronsarepaired.Eachelectron
withspinorientation hasapartnerwithspinorientation .Thespinsoftheseelectronscancel
eachother,givinganetspinofzero.Anatomorionwithallelectronspairedisnotattractedbystrong
magnetsandistermeddiamagnetic.Incontrast,spinsdonotcancelwhenunpairedelectronsare
present(inthegroundstateofanatomwithspinsalignedinthesamedirection).Anatomorionwith
unpairedelectronsisattractedtostrongmagnetsandiscalledparamagnetic.Moreover,thespinsofall
theunpairedelectronsareadditive,sotheamountofparamagnetismshownbyanatomorionis
proportionaltothenumberofunpairedspins.

InFe3+,Hund'sruledictatesthatthefivedelectronsallhavethesamespinorientation.Forthesefive
electrons,thespinsallacttogether,givinganetspinof .Thealternativeconfigurationfor
Fe3+,[Ar]4s23d 3,isparamagnetic,too,butitsnetspinis asithasonlythreeunpaired
electrons.ExperimentsshowthatFe3+hasanetspinof .Infact,magneticmeasurementsonawide
rangeoftransitionmetalcationsareallconsistentwiththe(n1)dorbitalsbeingoccupiedratherthan
thensorbital.

WORKEDEXAMPLE4.15

UnpairedElectrons

Whichofthesespeciesisparamagnetic:F,Zn 2+orTi?

Analysis

Paramagnetismresultsfromunpairedspins,whichexistonlyinpartiallyfilledsetsoforbitals.
Weneedtobuildtheconfigurationsandthenlookforanyorbitalsthatarepartiallyfilled.

Solution

F:Afluorineatomhas9electrons,soFhas10electrons.Theconfigurationis1s22s22p 6.
Therearenopartiallyfilledorbitals,sothefluorideionisdiamagnetic.

Zn 2+:Theparentzincatomhas30electrons,andthecationhas28,sotheconfigurationfor
Zn 2+is[Ar]3d 10.Again,therearenopartiallyfilledorbitals,sothisionisalsodiamagnetic.

Ti:Aneutraltitaniumatomhas22electrons.Thegroundstateconfigurationis[Ar]4s23d 2.
Thespinsofthe4selectronscancel,butthetwoelectronsin3dorbitalshavethesamespin
orientation,sotheireffectisadditive.Thisionisparamagnetic,withanetspinof .

Isouranswerreasonable?

Filledorbitalsalwayshaveallelectronspaired,andtwoofthesethreespecieshaveno
partiallyfilledorbitals.OnlyTihasapartiallyfilledorbitalset.

PRACTICEEXERCISE4.15
Mosttransitionmetalcationsare
paramagnetic.Whichcationsinthefirst
transitionmetalserieshavenetchargesless
than+4andareexceptionstothis
generalisation?

Thegroundstateconfigurationsofmostneutralatomsandmanyionscontainunpairedelectrons,sowe
mightexpectmostmaterialstobeparamagnetic.Onthecontrary,mostsubstancesarediamagnetic.This
isbecausestablesubstancesseldomcontainfreeatoms.Instead,inmolecularsubstances,atomsare
bondedtogetherthroughpairingofelectronstogivemolecules(seechapter5),andsuchbonding
resultsinthecancellationofoverallspin.Asaresult,paramagnetismisobservedprimarilyamong
compoundsofthetransitionandlanthanoidmetals,whosecationshavepartiallyfilleddandforbitals.
Wewillexaminethemagneticpropertiesoftransitionmetalcomplexesindetailinchapter13.

ExcitedStates
Thegroundstateconfigurationisthelowestenergyarrangementofelectrons,soanatomorionwill
usuallyhavethisconfiguration.Whenanatomabsorbsenergy,however,itcanreachanexcitedstate
withanewelectronconfiguration.Forexample,sodiumatomsnormallyhavethegroundstate
configuration[Ne]3s1,butwhensodiumatomsareinthegasphase,anelectricaldischargecaninduce
transferofthe3selectrontoahigherenergyorbital,suchas4p.Excitedatomsareunstableand
spontaneouslyreturntothegroundstateconfiguration,givinguptheirexcessenergyintheprocess.

Excitedstateconfigurationsareperfectlyvalidaslongastheymeettherestrictionsgivenintable4.2.In
theelectricaldischargeofasodiumvapourlamp,forinstance,wefindsomesodiumatomsinexcited
stateswithconfigurationssuchas1s22s22p 63p 1or1s22s22p 53s2.Theseconfigurationsusevalidorbitals
andareinaccordwiththePauliexclusionprinciple,buttheydescribeatomsthatareofhigherenergy
thanthoseinthegroundstate.ItshouldbenotedthatboththeAufbauprincipleandHund'srulecanbe
violatedwhenwritingexcitedstateelectronicconfigurations,butthePauliexclusionprinciplemust
alwaysbeobeyed.

Excitedstatesplayimportantrolesinchemistry.Propertiesofatomscanbestudiedbyobservingexcited
states.Infact,chemistsandphysicistsusethecharacteristicsofexcitedstatesextensivelytoprobethe
structureandreactivityofatoms,ionsandmolecules.Excitedstatesalsohavepracticalapplications.For
example,sodiumvapourlamps,whichareusedforstreetlighting,usetheemissionsfromexcited
sodiumatomsreturningtotheirgroundstates,andthedazzlingcoloursofafireworksdisplaycome
fromphotonsemittedbyvariousmetalionsinexcitedstates.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.8PeriodicityofAtomicProperties
Theperiodicityofphysicalandchemicalproperties,whichissummarisedintheperiodictableofthe
elements,isoneofthemostusefulorganisingprinciplesinchemistry.Theregularperiodictrendscanbe
explainedusingelectronconfigurationsandnuclearcharges.Themostimportantofthosetrendsisthe
atomicradius,whichwewilldiscussfirst,sinceitinfluencesallotherperiodictrends.

AtomicRadii
Thesizeofanatomisdeterminedbyitselectroncloudandthereforebythesizesofitsorbitals.Aswehave
seenearlier,thesesizesaredeterminedbyanumberoffactors,includingeffectivenuclearcharge(Zeff),
orbitalenergyandelectrondistribution.

Assumeyouaremovingfromlefttorightacrossperiod2oftheperiodictable(n=2).WhileZincreases,the
electronsthatareaddeddonotshieldtheincreasingnuclearchargeeffectively,soZeffincreases.Alarger
Zeffexertsastrongerelectrostaticattractionontheelectroncloud,andthisresultsinsmallerorbitals.Moving
fromlefttorightacrossthatperiod,orbitalsbecomesmallerandoflowerenergy.

Nowassumeyouproceeddowngroup1oftheperiodictable.Asnincreases,wewouldexpectorbitalsto
increaseinenergyandbecomelarger.However,asZincreases,wewouldexpectorbitalstobecomesmaller
anddecreaseinenergy.Whichtrenddominateshere?Recallthatthenumberofcoreelectronsincreasesas
wemovedownanygroup.Forexample,sodium(Z=11)has10coreelectronsand1valenceelectron.In
thenextperiod,potassium(Z=19)has18coreelectronsand1valenceelectron.Theshieldingprovidedby
potassium'sadditional8coreelectronslargelycancelstheeffectoftheadditional8protonsinitsnucleus.
Consequently,increasedshieldinglargelyoffsetstheincreaseinZvaluefromoneperiodtothenextand,
therefore,valenceorbitalsbecomelargerandincreaseinenergyfromtoptobottomofagroup.

Insummarywecansaythatatomicsizedecreasesfromlefttorightandincreasesfromtoptobottomofthe
periodictable(figure4.47).

FIGURE4.47Representationoftheperiodictableshowingthatatomicradiusdecreasesfromlefttorightwithina
rowandincreasesfromtoptobottomwithinagroup.

Aconvenientmeasureofatomicsizeistheradiusoftheatom.Figure4.48showsthetrendsinatomicradii.
Forexample,theatomicradiusdecreasessmoothlyacrossthethirdperiod,from186pmforsodiumto97
pmforargon(bluearrow).Theatomicradiusincreasessmoothlydowngroup1,from152pmforlithiumto
265pmforcaesium(redarrow).Notice,however,thattheatomicradiuschangesverylittleacrossthedand
fblocks.Thisisduetoshielding.Fortheseelements,thelargestorbitalisthefillednsorbital.Movingfrom
lefttorightacrossarow,Zincreases,butelectronsaddtothesmaller(n1)dor(n2)forbitals.Anincrease
inZby1unitismatchedbytheadditionof1shieldingelectron.Fromtheperspectiveoftheoutlyings
orbital,theincreasesinZarebalancedbyincreasedshieldingfromtheaddeddorfelectrons.Thus,the
electronintheoutermostoccupiedorbital,ns,issubjecttoaneffectivenuclearchargethatchangesvery
littleacrosstheseblocks.Asaconsequence,therelativechangesinatomicsizeacrossthedandfblocksare
muchsmallerthanthosefoundinthesandpblocks.
FIGURE4.48Theradiiofatomsvaryinperiodicfashion(dataareforatomsinthegasphase).Atomicradius
decreasesfromlefttorightwithinanyrow(bluelines)andincreasesfromtoptobottomwithinany
group(redlines).

Aknowledgeofperiodictrendsinphysicalandchemicalpropertiesandanunderstandingoftheprinciples
thatgiverisetothesetrendsareimportantsincetheyenableyou,forexample,topredictcertainchemical
behaviours,evenifyouarenotfamiliarwithaparticularelement.

WORKEDEXAMPLE4.16

TrendsinAtomicRadii
Foreachofthefollowingpairs,predictwhichatomislargerandexplainwhy:
(a)SiorCl,
(b)SorSeand
(c)MoorAg.

Analysis

Qualitativepredictionsaboutatomicsizecanbemadeonthebasisofanatom'spositioninthe
periodictable.

Solution
(a)Siliconandchlorineareinthethirdrowoftheperiodictable.

Chlorine'snuclearcharge(+17)islargerthansilicon's(+14),sochlorine'snucleusexertsa
strongerpullonitselectroncloud.Chlorinealsohasthreemoreelectronsthansilicon,
whichincreasesthepossibilitythatshieldingeffectscouldcountertheextranuclear
charge.Remember,however,thatelectronsinthesametypeoforbitaldoapoorjobof
shieldingoneanotherfromthenuclearcharge.ForSiandCl,shieldingcomesmainly
fromthecoreelectrons,notfromtheelectronsinthe3porbitals.Becauseshieldingeffects
aresimilarfortheseelements,theeffectivenuclearchargeincreasesfromSitoCl.
Therefore,weconcludethatchlorine,withitsgreaternuclearattractionfortheelectron
cloud,isthesmalleratom.
(b)Sulfurandseleniumareingroup16oftheperiodictable.Althoughtheybothhavethe
s2p 2valenceconfigurations,selenium'sleaststableelectronsareinorbitalswithalargern
value.Orbitalsizeincreaseswithn.Seleniumalsohasagreaternuclearchargethansulfur,
whichraisesthepossibilitythatnuclearattractioncouldoffsetincreasedn.

Remember,however,thatmuchofthisextranuclearchargeisoffsetbytheshielding
influenceofthecoreelectrons.Seleniumhas18coreelectronsandsulfurhas10.Thus,
weconcludethatselenium,withitslargernvalue,islargerthansulfur.
(c)Molybdenumandsilverareinthesamerowofthedblock.

Theyhavethefollowingconfigurations.

Ineachcase,5sisthelargestoccupiedorbital(seep.132foranexplanation.)The4d
orbitalsaresmaller,withtheirelectrondensitylocatedmostlyinsidethe5sorbital.
Consequently,4diseffectiveatshielding5s.Thenuclearchargeofsilverisfiveunits
largerthanthatofmolybdenum,butsilveralsohasfiveextrashieldingelectronsind
orbitals.Theseoffsettheextranuclearcharge,makingMoandAgnearlythesamesize.

Isouranswerreasonable?

Thetrendsinfigure4.48confirmtheresults.Chlorineliestotherightofsiliconinthesamerow
oftheperiodictable.Sizedecreasesfromlefttorightinanyrowthus,chlorineissmallerthan
silicon.Seleniumisimmediatelybelowsulfurinthesamecolumnoftheperiodictable.Size
increasesdownacolumnthus,seleniumislargerthansulfur.Molybdenumandsilveroccupythe
samerowofthedblockoftheperiodictable,acrosswhichsizechangesrelativelylittlethus,
molybdenumandsilverarenearlythesamesize.

PRACTICEEXERCISE4.16
Useperiodictrendstodeterminewhichofthe
followingaresmallerthanAsandwhichare
larger:P,Ge,SeandSb.

IonisationEnergy
Whenanatomabsorbsaphoton,thegaininenergypromotesanelectrontoahigherenergyorbitalinwhich
theelectronis,onaverage,furtherfromthenucleusandthereforeexperienceslesselectricalattractiontothe
nucleus.Iftheabsorbedphotonhasenoughenergy,anelectroncanbeejectedfromtheatom.

Theminimumamountofenergyneededtoremoveanelectronfromaneutralatomisthefirstionisation
energy(Ei1).Ionisationenergiesaremeasuredforgaseouselementstoensurethattheatomsareisolated
fromoneanother.

Variationsinionisationenergymirrorvariationsinorbitalenergy,becauseanelectroninahigherenergy
orbitaliseasiertoremovethanoneinalowerenergyorbital.

Figures4.49and4.50showhowthefirstionisationenergiesofgaseousatomsvarywithatomicnumber.
Noticethegeneraltrendsinionisationenergy.Ionisationenergyincreasesfromlefttorightacrosseach
period(thirdperiod:496kJmol1forNato1520kJmol1forAr)anddecreasesfromtoptobottomofeach
group(group18:2372kJmol1forHeto1037kJmol1forRn).Aswithatomicradius,ionisationenergy
changeslessforelementsinthedandfblocks,becauseincreasedshieldingfromthedandforbitalsoffsets
increasesinZ.Asaruleofthumb,thetrendintheionisationenergiesisinversetothatoftheatomicradii,
i.e.smalleratomshavehigherionisationenergies.Therefore,thetrendintheionisationenergiescanbe
rationalisedinsimilarfashion.

FIGURE4.49Representationoftheperiodictableshowingthatfirstionisationenergyincreasesfromlefttoright
withinarowanddecreasesfromtoptobottomwithinagroup.
FIGURE4.50Thefirstionisationenergygenerallyincreasesfromlefttorightacrossaperiod(bluearrow)and
decreasesfromtoptobottomdownagroup(redarrow)oftheperiodictable.

HigherIonisations
Amultielectronatomcanlosemorethanoneelectron,butionisationbecomesmoredifficultascationic
chargeincreases.Thefirstthreeionisationenergiesforamagnesiumatominthegasphaseprovidean
illustration.

Process Configurations Ei

Noticethatthesecondionisationenergyofmagnesiumisalmosttwiceaslargeasthefirst,eventhougheach
electronisremovedfroma3sorbital.ThisisbecauseZeffincreasesasthenumberofelectronsdecreases.
Thatis,thepositivechargeonthemagnesiumnucleusremainsthesamethroughouttheionisationprocess,
butthenetchargeoftheelectronclouddecreaseswitheachsuccessiveionisation.Asthenumberof
electronsdecreases,eachelectronfeelsagreaterelectrostaticattractiontothenucleus(duetominimised
electronelectronrepulsion),resultinginalargerionisationenergy.

Thethirdionisationenergyofmagnesiumismorethan10timesthefirstionisationenergy.Thislarge
increaseoccursbecausethethirdionisationremovesacoreelectron(2p)ratherthanavalenceelectron(3s).
Removingcoreelectronsfromanyatomrequiresmuchmoreenergythanremovingvalenceelectrons.The
secondionisationenergyofanygroup1metalissubstantiallylargerthanthefirstionisationenergythe
thirdionisationenergyofanygroup2metalissubstantiallylargerthanthefirstorsecondionisationenergy,
andsoon.AppendixGgivesthefirstthreeionisationenergiesforthefirst36elements.

IrregularitiesinIonisationEnergies
Ionisationenergiesdeviatesomewhatfromsmoothperiodicbehaviour.Thesedeviationscanbeattributedto
shieldingeffectsandelectronelectronrepulsion.Aluminium,forexample,hasasmallerfirstionisation
energythaneitherofitsneighboursinrow3(seefigure4.48).

Element Z Atomconfiguration Ei1 Cationconfiguration


Mg 12 [Ne]3s2 738kJmol1 [Ne]3s1
Al 13 [Ne]3s23p 1 577kJmol1 [Ne]3s2
Si 14 [Ne]3s23p 2 786kJmol1 [Ne]3s23p 1

Theconfigurationsoftheseelementsshowthata3selectronmustberemovedtoionisemagnesium,
whereasa3pelectronmustberemovedtoionisealuminiumorsilicon.Shieldingmakesthe3porbitalsof
significantlyhigherenergythana3sorbital,andthisdifferenceinenergymorethanoffsetstheincreasein
nuclearchargeingoingfrommagnesiumtoaluminium.Asecondelectroninadifferent3porbitaldoesnot
contributetotheshieldingoftheother3pelectronandthustheincreasedZeffmeansthatitisharderto
removeanelectronfromSithanfromAl.

Asanotherexample,oxygenhasasmallerionisationenergythaneitherofitsneighboursinrow2.

Element Z Atomconfiguration Ei1 Cationconfiguration


N 7 1s22s22p 3 1402kJmol1 1s22s22p 2
O 8 1s22s22p 4 1314kJmol1 1s22s22p 3
F 9 1s22s22p 5 1681kJmol1 1s22s22p 4

Rememberthatelectronelectronrepulsionhasadestabilisingeffect.Theionisationenergyofoxygenisless
thanthatofnitrogen,despitetheincreasednuclearcharge,becausethep 4configurationintheOatomhas
significantlygreaterelectronelectronrepulsionthanthep 3configurationintheNatom.

ElectronAffinity
Aneutralatomcanaddanelectrontoformananion.Theenergychangewhenanelectronisaddedtoan
atominthegasphaseiscalledtheelectronaffinity(Eea).Bothionisationenergy(Ei)andelectronaffinity
measurethestabilityofaboundelectron,butfordifferentspecies.Below,forexample,arethevaluesfor
fluorine.

Energyisreleasedwhenanelectronisaddedtoafluorineatomtoformafluorideanion.Thismeansthata
fluorideanionisoflowerenergythanafluorineatomplusafreeelectron.Anotherwayofsayingthisisthat
fluorineatomshaveanaffinityforelectrons.

Theenergyassociatedwithremovinganelectrontoconvertananiontoaneutralatom(thatis,thereverseof
electronattachment)hasthesamemagnitudeastheelectronaffinity,buttheoppositesign.Removingan
electronfromF,forexample,requiresenergy,givingapositiveenergychange.

TheAufbauprinciplemustbeobeyedwhenanelectronisaddedtoaneutralatom,sotheelectrongoesinto
thelowestenergyorbitalavailable.Hence,weexpecttrendsinelectronaffinitytoparalleltrendsinorbital
energy.However,electronelectronrepulsionandshieldingaremoreimportantfornegativeionsthanfor
neutralatoms,sothereisnocleartrendinelectronaffinitiesasnincreases.Thus,thereisonlyonegeneral
pattern:Electronaffinitytendstobecomemorenegativefromlefttorightacrossaperiodoftheperiodic
table.

Theplotinfigure4.51showshowelectronaffinitychangeswithatomicnumber.Thebluelinesrevealthe
trend:Electronaffinityincreasesinmagnitudeacrosseachperiodoftheperiodictable.Thistrendisdueto
increasingeffectivenuclearcharge,whichbindstheaddedelectronmoretightlytothenucleus.Noticethat,
incontrasttothepatternforionisationenergies(figure4.50),valuesforelectronaffinitiesremainnearly
constantamongelementsoccupyingthesamegroupoftheperiodictable.

FIGURE4.51Theelectronaffinityofatomsvarieswithatomicnumber.Inmovingacrossanyperiod(bluelines),
theelectronaffinitybecomesmorenegative,butthisistheonlycleartrend.

Theelectronaffinityvaluesformanyoftheelementsshowninfigure4.51appeartolieonthexaxis.
Actually,theseelementshavepositiveelectronaffinities,meaningtheresultinganionisofhigherenergy
thantheneutralatom.Moreover,thesecondelectronaffinityofeveryelementislargeandpositive.Positive
electronaffinitiescannotbemeasureddirectly.Instead,thesevaluesareestimatedusingothermethods.

Althoughelectronaffinityvaluesshowonlyonecleartrend,thereisanotherrecognisablepatterninthe
valuesthatarepositive.Whentheelectronthatisaddedmustoccupyaneworbital,theresultinganionis
unstable.Thus,alltheelementsofgroup2havepositiveelectronaffinitiesbecausetheirvalencensorbitals
arefilled.Similarly,allthenoblegaseshavepositiveelectronaffinitiesbecausetheirvalencenporbitalsare
filled.Elementswithhalffilledorbitalsalsohavelessnegativeelectronaffinitiesthantheirneighbours.As
examples,N(halffilled2porbitalset)hasapositiveelectronaffinity,andsodoesMn(halffilled3dorbital
set).

SizesofIons
Anatomiccationisalwayssmallerthanthecorrespondingneutralatom.Conversely,anatomicanionis
alwayslargerthantheneutralatom.Figure4.52illustratesthesetrends,andelectronelectronrepulsion
explainsthem.Acationhasfewerelectronsthanitsparentneutralatom.Thisreductioninthenumberof
electronsmeansthatthecation'sremainingelectronsexperiencelesselectronelectronrepulsion.Ananion
hasmoreelectronsthanitsparentneutralatom.Thisincreasemeansthatthereismoreelectronelectron
repulsionintheanionthanintheparentneutralatom.
FIGURE4.52Comparisonofthesizes(radius,r,inpm)ofneutralatoms(brown)andtheirions(cationsyellow
anionsblack)forsomeelements.Thebluehighlightindicatesisoelectronicions.

Figure4.52alsohighlightstherelationshipsbetweenisoelectronicspecies,i.e.thosethatpossessequal
numbersofelectrons.Asnotedearlier,theFanionandtheNa+cationareisoelectronic,eachhaving10
electronsandtheconfiguration[He]2s22p 6.Forisoelectronicspecies,propertieschangeregularlywithZ.For
example,table4.4showstwopropertiesofthe10electronisoelectronicsequence.Aprogressiveincreasein
nuclearchargeresultsinacorrespondingdecreaseinionicradius,aresultofstrongerelectricalforce
betweenthenucleusandtheelectroncloud.Forthesamereason,asZincreases,itbecomesprogressively
moredifficulttoremoveanelectron.
TABLE4.4 Trendsinanisoelectronicsequence
Species
Property O2 F Na+ Mg2+
Z 8 9 11 12
radius(pm) 140 133 102 72

ionisationenergy(kJmol1) 322(Eea ) 4560(Ei2) 7730(Ei3)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
4.9IonsandChemicalPeriodicity
Theelementsthatformioniccompoundsarefoundinspecificplacesintheperiodictable.Atomicanionsarerestrictedto
elementsontherightsideofthetable:thehalogens,oxygenandsulfur.Alltheelementsinthes,dandfblocksform
compoundscontainingatomiccations.

CationStability
Knowingthattheenergycostofremovingcoreelectronsisalwaysverylarge,wecanpredictthattheionisationprocesswill
stopwhenallvalenceelectronshavebeenremoved.Thus,aknowledgeofgroundstateconfigurationsisallthatweneedto
makequalitativepredictionsaboutcationstability.

Eachelementingroup1oftheperiodictablehasonevalenceelectron.TheseelementsformioniccompoundscontainingM +
cations.ExamplesareKClandNa2CO3.Eachelementingroup2oftheperiodictablehastwovalenceelectronsandforms
ioniccompoundscontainingM 2+cations.ExamplesareCaCO3andMgCl2.

Beyondthesetwogroups,theremovalofallvalenceelectronsisusuallynotenergeticallypossible.Forexample,ironhaseight
valenceelectronsbutformsonlytwostablecations,Fe2+andFe3+.Compoundsofironcontainingtheseionsareabundantin
theEarth'scrust.Pyrite,FeS2,andiron(II)carbonate,FeCO3,orsiderite,areexamplesofFe2+salts.Iron(III)oxide,Fe2O3,or
haematite,canbedescribedasanarrangementofFe3+cationsandO2anions.Oneofthemostabundantironores,magnetite,
hasthechemicalformulaFe3O4andcontainsa2:1ratioofFe3+andFe2+cations.Theformulaofmagnetitecanalsobe
writtenasFeOFe2O3toemphasisethepresenceoftwodifferentcations.

Othermetallicelementsformioniccompoundswithcationchargesrangingfrom+1to+3.Aluminiumnitratenonahydrate,
Al(NO3)39H2O,(thewordnonahydratemeansninewatermoleculesareassociatedwiththecompound)iscomposedofAl3+
cations,NO3anions,andwatermolecules.Silvernitrate,AgNO3,whichcontainsAg +cations,isawatersolublesilversaltthat
isusedinsilverplating.

AnionStability
Halogens,theelementsingroup17oftheperiodictable,havethelargestelectronaffinitiesofalltheelements.Sohalogen
atoms(ns2np 5)readilyacceptelectronstoproducehalideanions(ns2np 6).Thisallowshalogenstoreactwithmanymetalsto
formbinarycompounds,calledhalides,whichcontainmetalcationsandhalideanions.ExamplesincludeNaCl(chloride
anion),CaF2(fluorideanion),AgBr(bromideanion)andKI(iodideanion).

Isolatedatomicanionswithchargesmorenegativethan1arealwaysunstable,butoxide(O2,1s22s22p 6)andsulfide(S2,
[Ne]3s23p 6)arefoundinmanyionicsolids,suchasCaOandNa2S.Thelatticeenergies(seepp.1701)ofthesesolidsare
largeenoughtomaketheoverallreactionenergyreleasingdespitethelargepositivesecondelectronaffinityoftheanions.In
addition,threedimensionalarraysofsurroundingcationsstabilisethe2anionsinthesesolids.

Metals,NonmetalsandMetalloids
Ionformationisonlyonepatternofchemicalbehaviour.Manyotherchemicaltrendscanbetracedtovalenceelectron
configurations,butweneedthedescriptionofchemicalbondingfromchapter5toexplainsuchperiodicproperties.
Nevertheless,wecanrelateimportantpatternsinchemicalbehaviourtotheabilityofsomeelementstoformions.Oneexample
isthesubdivisionoftheperiodictableintometals,nonmetalsandmetalloids,firstintroducedinchapter1.

Theelementsthatcanformcationsrelativelyeasilyaremetals.Allmetalshavesimilarproperties,inpartbecausetheir
outermostselectronsarerelativelyeasytoremove.Allelementsinthesblockhavens1orns2valenceconfigurations.Thed
blockelementshaveoneortwonselectronsandvariousnumbersof(n1)delectrons.Examplesaretitanium(4s23d 2)and
silver(5s14d 10).Elementsinthefblockhavetwonselectronsandanumberof(n2)felectrons.Samarium,forexample,has
thevalenceconfiguration6s24f6.Themetallicbehaviouroftheseelementsoccurspartlybecausetheselectronsareshared
readilyamongallatoms.Metalsformionicsaltsbecauseselectrons(andsomep,danddfelectrons)canbereadilyremoved
fromthemetalatomstoformcations.

Whereastheotherblockscontainonlymetals,elementalpropertiesvarywidelywithinthepblock.Wehavealreadynotedthat
aluminium(3s23p 1)canloseitsthreevalenceelectronstoformAl3+cations.Thesixelementswithinthetriangleinfigure4.53
alsolosepelectronseasilyandthereforehavemetallicproperties.Examplesaretin(5s25p 2)andbismuth(6s26p 3).

FIGURE4.53Thesesixelementslosepelectronseasilyandsohavemetallicproperties.

Incontrast,thehalogensandnoblegasesontherightofthepblockaredistinctlynonmetallic.Thenoblegases,group18ofthe
periodictable,aremonatomicgasesthatresistchemicalattackbecausetheirelectronconfigurationsinvolvecompletelyfilleds
andporbitals.

Elementsinanyintermediatecolumnofthepblockdisplayarangeofchemicalpropertieseventhoughtheyhavethesame
valenceconfigurations.Carbon,silicon,germaniumandtinallhavens2np 2valenceconfigurationsyetcarbonisanonmetal,
siliconandgermaniumaremetalloids,andtinisametal.

Qualitatively,wecanunderstandthisvariationbyrecallingthat,astheprincipalquantumnumberincreases,thevalenceorbitals
increaseinenergy.Intin,thefourn=5valenceelectronsareboundrelativelylooselytotheatom,resultinginthemetallic
propertiesassociatedwithelectronsthatareeasilyremoved.Incarbon,thefourn=2valenceelectronsareboundrelatively
tightlytotheatom,resultinginnonmetallicbehaviour.Silicon(n=3)andgermanium(n=4)fallinbetweenthesetwo
extremes.

WORKEDEXAMPLE4.17

ClassifyingElements
Nitrogenisacolourlessdiatomicgas.Phosphorushasseveralelementalforms,onebeingaredsolidthatisusedin
matchtips.Arsenicandantimonyaregreysolids,andbismuthisasilverysolid.Classifytheseelementsofgroup15
asmetals,nonmetalsormetalloids.

Analysis

Allelementsexceptthoseinthepblockaremetals.Group15,however,ispartofthepblock,withinwhich
elementsdisplayallformsofelementalbehaviour.Todecidetheclassificationsoftheseelements,wemustexamine
thisgrouprelativetothediagonalarrangementofthemetalloids.
Solution

Weseethatgroup15passesthroughallthreeclassesofelements.TheelementswiththelowestZvalues,nitrogen
andphosphorus,arenonmetals.TheelementwithhighestZvalue,bismuth,isametal,andthetwoelementswith
intermediateZvalues,arsenicandantimony,aremetalloids.

Isouranswerreasonable?

Astheprincipalquantumnumberincreases,valenceelectronsbecomeprogressivelyeasiertoremove,andmetals
arethoseelementswithvalenceelectronsthatareeasilyremoved.

PRACTICEEXERCISE4.17
Classifythe4psetofelements,fromGatoKrasmetals,
nonmetalsormetalloids.

sblockElements
Theelectronconfigurationofanyelementingroups1and2oftheperiodictablecontainsacoreoftightlyboundelectronsand
oneortwoselectronsthatarelooselybound.Thegroup1metals(ns1configuration)andthegroup2metals(ns2
configuration)formstableionicsaltsbecausetheirvalenceelectronsareeasilyremoved.Nearlyallsaltsofgroup1metalsand
manysaltsofgroup2metalsdissolvereadilyinwater,sonaturallyoccurringsourcesofwaterfrequentlycontaintheseions.

ThefourmostabundantsblockelementsintheEarth'scrustaresodium,potassium,magnesiumandcalcium(table4.5).These
elementsarefoundinnatureinsaltssuchasNaCl,KNO3,MgCl2,MgCO3andCaCO3.Portionsofthesesolidsaltsdissolvein
rainwaterasitpercolatesthroughtheEarth'scrust.Theresultingsolutionofanionsandcationseventuallyfindsitswaytothe
oceans.Whenwaterevaporatesfromtheoceans,theionsareleftbehind.Overmanyaeonsthecontinualinfluxofriverwater
containingtheseionshasbuiltupthesubstantialsaltconcentrationsfoundintheoceans.
TABLE4.5 Abundanceofsblockelements
AbundanceinEarth'scrust(%by Abundanceinseawater(mol Abundanceinhumanbloodplasma
Element mass) L1) (mol1)
Na 2.27 0.462 0.142
K 1.84 0.097 0.005
Mg 2.76 0.053 0.003
Ca 4.66 0.100 0.005

Table4.5showsthateachofthefourcommonsblockionsisabundantnotonlyinseawaterbutalsoinbodyfluids,where
theyplayessentialbiochemicalroles.Sodiumisthemostabundantcationinfluidsthatareoutsideofcells,andproper
functioningofbodycellsrequiresthatsodiumconcentrationsbemaintainedwithinanarrowrange.Oneofthemainfunctions
ofthekidneysistocontroltheexcretionofsodium.Whereassodiumcationsareabundantinthefluidsoutsidecells,potassium
cationsarethemostabundantionsinthefluidsinsidecells.Thedifferenceinionconcentrationacrosscellmembranesis
responsibleforthegenerationofnerveimpulsesthatdrivemusclecontraction.Ifthedifferenceinpotassiumionconcentration
acrosscellmembranesdeteriorates,muscularactivity,includingtheregularmusclecontractionsoftheheart,canbeseriously
disrupted.

ThecationsMg 2+andCa2+aremajorcomponentsofbones.Calciumoccursinhydroxyapatite,Ca5(PO4)3(OH).Thestructural
functionofmagnesiuminbonesisnotfullyunderstood.Inadditiontobeingessentialingredientsofbone,thesetwocations
playkeyrolesinvariousbiochemicalreactions,includingphotosynthesis,transmissionofnerveimpulses,musclecontraction
andtheformationofbloodclots.

Berylliumbehavesdifferentlyfromtheothersblockelementsbecauseitsn=2orbitalsaremorecompactthanorbitalswith
higherprincipalquantumnumbers.Thefirstionisationenergyofberyllium,899kJmol1,iscomparablewiththoseof
nonmetals,soberylliumdoesnotformcompoundsthatareclearlyionic.

Somecompoundsofthesblockelementsareimportantindustrialandagriculturalchemicals(figure4.54).Forexample,K2CO3
(potassiumcarbonateorpotash)isobtainedfrommineraldepositsandisthemostcommonsourceofpotassiumforfertilisers.
Potassiumisessentialforhealthyplantgrowth.However,potassiumsaltsarehighlysolubleinwater,sopotassiumquickly
becomesdepletedfromthesoil.Consequently,agriculturallandrequiresfrequentadditionofpotassiumfertilisers.

FIGURE4.54Potassium,anothersblockelement,isessentialforhealthyplantgrowthandisaddedtoagriculturalsoilinfertilisers.

Threeothercompoundsofsblockelementscalciumoxide,CaOorlime,sodiumhydroxide,NaOH,andsodium
carbonate,Na2CO3aremajorindustrialchemicals.Forexample,limeisthekeyingredientinconstructionmaterialssuchas
concrete,cement,mortarandplaster.Twoothercompounds,calciumchloride,CaCl2,andsodiumsulfate,Na2SO4,arealsoof
industrialimportance.

Manyindustrialprocessesmakeuseofanionssuchashydroxide,OH,carbonate,CO32,andchlorate,ClO3.Theseanions
mustbesuppliedaschemicalcompoundsthatincludecations.Sodiumismostfrequentlyusedasthisspectatorcationbecause
itisabundant,inexpensiveandrelativelynontoxic.Thehydroxideionisindustriallyimportantbecauseitisastrongbase(see
chapter11).Sodiumhydroxideisusedtomanufactureotherchemicals,textiles,paper,soapsanddetergents.Sodiumcarbonate
andsandarethemajorstartingmaterialsinthemanufactureofglass.Glasscontainssodiumandothercationsembeddedina
matrixofsilicate,SiO32,anions.Abouthalfthesodiumcarbonateproducedintheworldisusedinglassmaking.

pblockElements
Thepropertiesofelementsinthepblockvaryacrosstheentirespectrumofchemicalpossibilities.Theelementsingroup13,
withasingleelectroninaporbitalaswellastwovalenceselectrons,displaychemicalreactivitycharacteristicofthreevalence
electrons.Exceptforboron,theelementsofthisgrouparemetalsthatformstable+3cations.ExamplesareAl(OH)3andGaF3.
Metalliccharacterdiminishesrapidlyasadditionalpelectronsareadded.Thischangeculminatesintheelementsingroup18.
Withfilledporbitals,theseelementsaresounreactivethatformanyyearstheywerethoughttobecompletelyinert.Xenonis
nowknowntoformcompoundswiththemostreactivenonmetals:oxygen,fluorineandchlorinekryptonalsoformsafew
highlyunstablecompoundswiththeseelements.

Althoughthenonmetalsdonotreadilyformcations,manyofthemcombinewithoxygentoformpolyatomicoxoanions.These
anionshavevariousstoichiometries,buttherearesomecommonpatterns.Twosecondrowelementsformoxoanionswiththree
oxygenatoms:carbon(fourvalenceelectrons)formscarbonate,CO32,andnitrogen(fivevalenceelectrons)formsnitrate,
NO3.Inthethirdrow,themoststableoxoanionscontainfouroxygenatoms:SiO44,PO43,SO42andClO4.

ManyofthemineralsthatformtheEarth'scrustcontainoxoanions.ExamplesofcarbonatesareCaCO3(limestone)and
MgCa(CO3)2(dolomite).Barite,BaSO4,isasulfatemineral.AnimportantphosphateisCa5(PO4)3F(apatite).Twosilicatesare
zircon,ZrSiO4,andolivine,amixtureofMgSiO4andFeSiO4.

SeveralleadingindustrialchemicalscontainoxoanionsorareacidsresultingfromadditionofH+totheanions.Sulfuricacid,
H2SO4,nitricacid,HNO3,andphosphoricacid,H3PO4,areallindustriallyimportant.HeatingCaCO3drivesoffCO2toform
CaO,theessentialingredientofbuildingmaterialsmentionedearlier.Otherindustriallyimportantsaltsincludeammonium
sulfate,(NH4)2SO4,aluminiumsulfate,Al2(SO4)3,sodiumcarbonate,Na2CO3,andammoniumnitrate,NH4NO3.Wewilllearn
moreaboutthepblockelementsinchapter14.

ChemistryResearch

Counterterrorismusingseparationscience

ProfessorPaulHaddad,Director,AustralianCentreforResearchonSeparationScience,UniversityofTasmania

Animportantaspectincounterterrorismmeasuresistheabilitytorapidlyidentifythetypeofexplosiveusedina
terroristattack.Improvisedexplosivedevices(IEDs,figure4.55)arecommonlychosenbyterroristsinpreferenceto
highexplosives,suchasnitratedorganiccompounds,becauseoftherelativeeasewithwhichthecomponentsusedin
theirmanufacturecanbeprocuredandthelowcostofthesematerials.Typically,IEDsarehomemadeexplosives
createdfromunrestrictedmaterialsandconsistofaninitiationsystemtosupplyanelectricalcharge,adetonatorandan
explosivecharge.
FIGURE4.55Theabilitytoidentifyatypeofexplosiveisimportantincounterterrorism.

InorganicIEDsemployvigorouschemicalreactionsusingstronginorganicoxidiserscombinedwithasuitablefuel.
Afterdetonation,theseexplosivesleaveresiduescomprisingunconsumedreactantsandarangeofreactionproducts,
mostofwhichareinorganicanionsandcations.ResearchbeingconductedintheAustralianCentreforResearchon
SeparationScienceattheUniversityofTasmaniaisinvestigatingwhethertheseresiduescanbeusedtoidentify
explosivesbymeansofafingerprintofthedifferentionspresentintheresidues.Theanalyticalmethodologyused
forthisprocessmustbeabletobecarriedtoablastsiteandbeoperatedinthefieldratherthaninalaboratory.

Oneoftheanalyticaltechniquesunderinvestigationiscapillaryelectrophoresis(CE).Inthistechnique,amixtureof
sampleionsisintroducedintooneendofaveryfinecapillary(75minternaldiameter)madefromfusedsilica.A
largeelectricalfield(e.g.30000V)isappliedalongthelengthofthecapillaryandthisinducesthesampleionsto
migratetotheappropriateelectrode.Anionsmigratetothepositivelychargedanodeandcationsmigratetothe
negativelychargedcathode.Iftheratesofmigrationdifferbetweenions,theywillreachtheendofthecapillaryat
differenttimesandhencebeseparated.

AfterlookingatthepossibleresiduesfromawiderangeofIEDs,atargetsetof15anionsand12cationswaschosen.
SeparationofallthesespeciesallowsauniquefingerprinttobeobtainedforeachIED.Typicaloutputs(called
electropherograms)areshowninfigure4.56forthetypeofIEDusedinthe2002Balibombing.Theanionand
cationfingerprintsaredisplayed.OtherIEDsgivedifferentfingerprintsandcanbeidentifiedeasily.Theanalyses
shownwereperformedonaportableCEinstrumentthatisaboutthesizeofabriefcaseandcanthereforebe
transportedeasily.

FIGURE4.56Typicalelectropherogramsfromanalysisofresiduesfromimprovisedexplosivedevices(IEDs).

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
SUMMARY
CharacteristicsofAtoms
Allatomsdisplaycertainbasiccharacteristics.Theypossessmass,occupyvolume,attractoneanother
andcancombinewithoneanother.Atomscontainpositivelychargednucleiandnegativelycharged
electrons,andthepropertiesofelementsaredeterminedbyvariationsinnuclearchargesandnumbers
ofelectrons.

CharacteristicsofLight
Electromagneticradiationintheformoflightmaybeusedtoprobethestructureofatoms.Lighthas
bothwaveandparticlelikeproperties.

Thewavepropertiesarecharacterisedby:
frequency():thenumberofwavecrestspassingagivenpointin1second
wavelength():thedistancebetweensuccessivewavecrests
amplitude:theheightofthewave
phase:thestartingpositionofthewavewithrespecttoonewavelength.

Theintensity(orbrightness)oflightisproportionaltothesquareoftheamplitude.

Lightwavesmoveatthespeedoflight,c(approx.2.99810 8ms1)inavacuum.Therelationship
betweenspeed,frequencyandwavelengthoflightisc=.Visiblelighthaswavelengthsbetween380
and780nm.Theenergyoflightisinverselyrelatedtoitswavelengththeshorterthewavelength,the
highertheenergy.

Theparticlepropertiesoflightaredemonstratedbythephotoelectriceffect,wherelightstrikingthe
surfaceofametalcauseselectronstobeejectedfromthemetal.Einsteinpostulatedthatthisbehaviour
couldbeexplainedbypacketsorbundlesoflightcalledphotons.Theenergyofaphotonisgivenby
theequationEphoton=hphoton,wherehisPlanck'sconstant(approximately6.62610 34Js).Anatom
canabsorbaphotonofaparticularenergyandformahigherenergyexcitedstate.Theexcitedstate
atomcanthenreleasetheexcessenergybyemittingaphotonandreturningtoitsgroundstate.These
photonabsorptionandemissionprocessescanbeobservedinatomicspectra.Anabsorptionspectrum
givesdarklinesinthevisiblespectrumwherelightofaparticularwavelengthhasbeenabsorbed,while
anemissionspectrumgivescolouredlinesonadarkbackgroundwhichcorrespondtoemissionof
photons.Atomscanabsorboremitphotonsofonlycertaindefiniteenergies,meaningthattheelectrons
inatomshaveonlycertainspecificenergyvaluesthatis,theirenergiesarequantised.Weshowthe
quantisedenergylevelswithinanatombymeansofanenergyleveldiagram.

PropertiesofElectrons
Likeatoms,allelectronsdisplaycertainbasiccharacteristics.Everyelectronhasamassof9.10910 31
kgandachargeof1.60210 19C.Electronshavemagneticpropertiesand,likelight,electronsalso
displayparticlewaveduality.Thewavelengthassociatedwithanelectronisgivenbytheequation
.TheHeisenberguncertaintyprinciplestatesthatwecannotsimultaneouslyknowboththe
positionandthemomentumofanyparticle,andthisisparticularlyimportantforelectrons.

QuantisationandQuantumNumbers
Electronsboundtoatomshavequantisedenergies,whilefreeelectronscanhaveanyenergy.The
quantisedenergiesofboundelectronsarelinkedtotheirwavepropertiesbytheSchrdingerequation
,whichgivesboththeenergiesandwavefunctionsofachemicalsystem.Thisequationcanbe
solvedexactlyonlyforsystemscontainingoneelectron,andaoneelectronwavefunctioniscalledan
orbital.

Quantisedpropertiesofanatomcanbeindexedusingquantumnumbers.Theprincipalquantum
number(n)canhaveonlypositiveintegervalues,andindexesboththeenergyoftheelectronand
orbitalsize.Thesizeofanorbitalincreasesasnincreases.Theazimuthalquantumnumber(l)indexes
theangularmomentumofanatomicorbitalandidentifiestheshapeoftheelectrondistributionofan
orbitalitcanbezerooranypositiveintegervaluesmallerthann.Atomicorbitalsarelabelledaccording
totheirlvaluesorbitalshavel=0,porbitalshavel=1,dorbitalshavel=2andforbitalshavel=3.
Themagneticquantumnumber(ml)indexesthedifferentpossibleorientationsoftheelectron
distributionofanorbitalitcanhaveanypositiveornegativeintegervaluefrom0tol.Thespin
quantumnumber(ms)haspossiblevaluesof and ,correspondingtothetwopossiblespinstates
ofanelectron.Allelectronswithinanatomcanbedescribedusingsetsofthesefourquantumnumbers,
andthePauliexclusionprinciplestatesthateachelectronhasauniqueset.

AtomicOrbitalElectronDistributionsandEnergies
Theelectrondistributionofanorbitalcanbedepictedinavarietyofways.Anelectrondensityplot
showsthedistributiongraphicallyintwodimensions,anelectrondensitypictureshowsacrosssection
ofthedistribution,whileaboundarysurfacediagramshowsthesurfacewhichencompasses(usually)
90%oftheelectrondensity.Areasofzeroelectrondensitywithinanorbitalarecallednodes,andthe
numberoftheseincreaseasnincreases.Theelectrondistributionofansorbitalisspherical,whilethose
ofporbitalsandfourofthefivedorbitalsaredumbbellandcloverleafshaped,respectively.The
electrondistributionofthe orbitalresemblesthatofaporbitalsurroundedbyadoughnut.Thetwo
lobesofporbitalshaveoppositephases,whilethephasesofthefourlobesofacloverleafshapedd
orbitalalternate.Thedoughnutofa orbitalisofoppositephasetotherestoftheorbital.

TheenergyofanorbitalinaoneelectronsystemisdeterminedbyboththeatomicnumberZandthe
principalquantumnumbern.Allorbitalsinaoneelectronsystemwiththesamevalueofnhavethe
sameenergytheyaredegenerate.Thisdegeneracyisdestroyedinmultielectronatoms.Theenergy
ofanorbitalcanbedeterminedbymeasuringtheionisationenergy,whichistheenergyrequiredto
removeanelectroncompletelyfromthat(usuallyvalence)orbital.Ionisationenergiesaredependenton
manyfactors,oneofwhichistheshieldingofthevalenceelectronsfromthenuclearchargebycore
electrons.Consequently,avalenceelectroninamultielectronatomexperiencesachargelessthanthe
fullnuclearchargethisiscalledtheeffectivenuclearcharge(Zeff).Electronswithalowernshield
electronsofhighernveryefficiently,while,withingroupsofelectronsofthesamen,thosehavingthe
lowestvalueoflshieldthoseofhigherl.

StructureofthePeriodicTable
Thegroundstateconfigurationofanatomisthelowestpossibleenergyarrangementoftheelectrons.
Theorderoffillingatomicorbitalswithelectronsisdictatedby:theAufbauprinciple,whichstatesthat
orbitalsarefilledinorderofincreasingenergythePauliexclusionprinciple,whichstatesthatnotwo
electronsinanatomcanhaveidenticalsetsofthefourquantumnumbersandHund'srule,whichstates
thatelectronsoccupysetsofdegenerateorbitalssoastogivethemaximumnumberofunpairedspins.
Ansorbitalcanaccommodate2electrons,asetofporbitals6andasetofdorbitals10.

Theshapeoftheperiodictableoftheelementsderivesfromtheseorbitaloccupanciesandtheorderin
whichtheorbitalsarefilled.Elementswiththesamevalenceelectronconfigurationslieinthesame
groupoftheperiodictableandhavesimilarchemicalproperties.Valenceelectronslargelydetermine
thechemistryofanelement,whilecoreelectronsusuallydonotparticipateinchemicalreactions.
ElectronConfigurations
Theelectronconfigurationofanatomcanbewrittenbyrecordingquantumnumbersforallelectronsin
theatom,usingacompactconfigurationwhichshowstheelectronoccupancyofeachorbitaltype,or
throughanenergyleveldiagramwhichshowstheenergyandoccupancyofeachorbital.Inthelatter,
electronsaredepictedasarrowspointingeitherup( )ordown( ).Wecanalsousea
shorthandnotationthatdoesnotexplicitlyincludethecoreelectrons,butabbreviatesthemusingthe
noblegasconfigurationofthenearestnoblegaswithlowerZ.Someexceptionstotheorderoforbital
fillingoccur,mostnotablyforCrandCu.Theorderoforbitalfillingforionsisthesameasthatfor
atoms,asshownbythesameelectronconfigurationsfortheisoelectronicseriesNa+,NeandF.Atoms
orionshavingunpairedelectronsareparamagneticandwillbeattractedtoamagneticfield,while
specieshavingallelectronspairedarediamagneticandarenotattractedtoamagneticfield.The
electronconfigurationsofexcitedstatescanviolateHund'sruleandtheAufbauprinciplebutnotthe
Pauliexclusionprinciple.

PeriodicityofAtomicProperties
Thesizeofanatomisdeterminedbyfactorssuchasnuclearcharge,orbitalenergyandelectron
distribution,andshielding.Atomicradiigiveusameasureofthesizesofatoms.Atomicradiibecome
smalleracrossaperiodandlargerdownagroupoftheperiodictable.Thefirstionisationenergiesofthe
elementsgenerallyincreaseacrossaperiodanddecreasedownagroupoftheperiodictable.Exceptions
tothesegeneraltrendsoccurwhenporbitalsareoccupiedby1or4electrons.Electronaffinities
becomemorenegativeacrossaperiod,butthereisnocleartrenddownagroupoftheperiodictable.
Atomiccationsarealwayssmallerthantheneutralatomandatomicanionsarealwayslargerthanthe
neutralatom.

IonsandChemicalPeriodicity
Thenatureofcationsandanionsisdeterminedbytheelectronconfigurationoftheneutralatom.Group
1andgroup2elementsform1+and2+cationsrespectively,whilegroup17elementsform1anions.
Isolatedatomicanionswithchargesmorenegativethan1arealwaysunstable,andO2andS2are
foundonlyincombinationwithcationsinionicsolids.Metalsgenerallyformcationsreadilythrough
lossofsordelectrons.Thepblockelementsmaybemetals,metalloidsornonmetals.Thesblock
elementsarefoundintheEarth'scrustandalsoinlivingsystems,andpblockelementsdisplayawide
varietyofchemicalproperties.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYCONCEPTSANDEQUATIONS
Wavelengthfrequencyrelationship(section4.2)
Theproductofwavelength()andfrequency()isthespeedoflight(c).

Energyofaphoton(section4.2)
Thisequationisusedtocalculatetheenergycarriedbyaphotonoffrequency.Also,canbe
calculatedifEisknown.

deBroglieequation(section4.3)
Thislinksthewavelengthofaparticlewithitsspeedandmass.

Quantumnumbersforatoms(section4.4)
Eachelectroninanatomisdescribedbyauniquesetoffourquantumnumbers.Theallowedvaluesof
thesequantumnumbersareasfollows:

Quantumnumber Range
principalquantumnumber(n) 1,2,,
azimuthalquantumnumber(l) 0,1,,(n1)
magneticquantumnumber(ml) l,,1,0,+1,,+l
spinquantumnumber(ms)

Periodictable(section4.6)
Theperiodictableisanaidinwritingelectronconfigurationsoftheelements.Anelement'slocationin
thetableisrelatedtopropertiessuchasatomicradius,ionisationenergyandelectronaffinity.

Electronconfigurations(section4.7)
Theseguidelineshelpustowriteelectronconfigurationsforatomsorions.
1.Countthetotalnumberofelectrons.
a.Addelectronsforanions.
b.Subtractelectronsforcations.
2.Fillorbitalstomatchthenearestnoblegasofsmalleratomicnumber.
3.AddremainingelectronstothenextorbitalstobefilledaccordingtoHund'srule.
a.Forneutralatomsandanions,placeelectronsinnsbefore(n1)d.
b.Forcations,placeelectronsin(n1)dbeforens.
4.Lookforexceptionsandcorrecttheconfigurationifnecessary.
Periodictrendsinatomicandionicsize(section4.8)
Periodictrendsareevidentin,forexample:
atomicandionicsize
ionisationenergy
electronaffinity.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWQUESTIONS
CharacteristicsofAtoms
4.1Thedensityofsilveris1.05010 4kgm3,andthedensityofleadis1.13410 4kgm3.Foreach
metal:
(a)calculatethevolumeoccupiedperatom,
(b)estimatetheatomicdiameterand
(c) usingthisestimate,calculatethethicknessofametalfoilcontaining6.510 6atomiclayers
ofthemetal.
4.2Describeevidencethatindicatesthatatomshavemass.
4.3Describeevidencethatindicatesthatatomshavevolume.
CharacteristicsofLight
4.4Calculatethefrequencies(Hz)correspondingtothefollowingwavelengths,usingpoweroften
notation:
(a)4.33nm,
(b)2.3510 10m,
(c)735mm,
(d)4.57m.
4.5Calculatethewavelengthscorrespondingtothefollowingfrequencies,expressingtheresultinthe
indicatedunits:
(a)4.77GHz(m),
(b)28.9kHz(cm),
(c)60Hz(mm),
(d)2.88MHz(m).
4.6Calculatetheenergyinjoulesperphotonandinkilojoulespermoleofthefollowing:
(a)bluegreenlightwithawavelengthof490.6nm,
(b)Xrayswithawavelengthof25.5nm,
(c) microwaveswithafrequencyof2.543710 10Hz.
4.7Whatarethewavelengthandfrequencyofphotonswiththefollowingenergies?
(a) 745kJmol1
(b)3.5510 19Jphoton 1
4.8Whenlightoffrequency1.3010 15s1shinesonthesurfaceofcaesiummetal,electronsare
ejectedwithamaximumkineticenergyof5.210 19J.Calculate:
(a)thewavelengthofthislight,
(b)thebindingenergyofelectronstocaesiummetaland
(c)thelongestwavelengthoflightthatwillejectelectrons.
4.9Aphototubedeliversanelectricalcurrentwhenabeamoflightstrikesametalsurfaceinsidethe
tube.Phototubesdonotrespondtoinfraredphotons.Drawanenergyleveldiagramforelectronsin
themetalofaphototubeanduseittoexplainwhyphototubesdonotrespondtoinfraredlight.
4.10Refertofigure4.4toanswerthefollowingquestions.
(a)Whatisthewavelengthrangeforradiowaves?
(b)Whatcolourislightwithawavelengthof5.810 7m?
(c) Inwhatregiondoesradiationwithfrequencyof4.510 8Hzlie?
4.11Determinethewavelengthsofradiationthathydrogenatomsabsorbtoreachthen=8andn=9
statesfromthegroundstate.Inwhatregionoftheelectromagneticspectrumdothesephotonslie?
PropertiesofElectrons
4.12Whatisthechargeincoulombsofonemoleofelectrons?
4.13Determinethewavelengthsofelectronswiththefollowingkineticenergies:
(a) 1.1510 190J,
(b)3.55kJmol1,
(c) 7.4510 3Jmol1.
4.14Determinethekineticenergiesinjoulesofelectronswiththefollowingwavelengths:
(a)3.75nm,
(b)4.66m,
(c)8.85mm.
QuantisationandQuantumNumbers
4.15Listallthevalidsetsofquantumnumbersfora6p6electron.
4.16Ifyouknowthatanelectronhasn=3,whatarethepossiblevaluesforitsotherquantum
numbers?
4.17Forthefollowingsetsofquantumnumbers,determinewhichdescribeactualorbitalsandwhich
arenonexistent.Foreachonethatisnonexistent,listtherestrictionthatforbidsit.

n l ml ms

(a) 3 1 1

(b) 3 1 1

(c) 3 1 2

(d) 3 2 2

AtomicOrbitalElectronDistributionsandEnergies
4.18Refertofigure4.27.Drawtheanalogoussetofthreedepictionsforanorbitalthathasn=2,l=1.
4.19Shownbelowareelectrondensitypicturesandelectrondensityplotsforthe1s,2s,2pand3p
orbitals.Assignthevariousdepictionstotheirrespectiveorbitals.
(a)

(b)
(c)

(d)

4.20Whatarethelimitationsofplotsofelectrondensityversusr?
4.21Theconventionalmethodofshowingthethreedimensionalelectrondistributionofanorbitalisan
electroncontoursurface.Whatarethelimitationsofthisrepresentation?
4.22Foreachofthefollowingpairsoforbitals,determinewhichismorestableandexplainwhy.
(a)He1sandHe2s
(b)Kr5pandKr5s
(c) He2sandHe+2s
4.23Inahydrogenatomthe3s,3p3and3dorbitalsallhavethesameenergy.Inaheliumatom,
however,the3sorbitalislowerinenergythanthe3porbital,whichinturnislowerinenergythan
the3dorbital.Explainwhytheenergyrankingsofhydrogenandheliumaredifferent.
4.24Theenergyofthen=2orbitaloftheHe+ionisthesameastheenergyofthen=1orbitalofthe
Hatom.Explainthisfact.
4.25Refertofigure4.37toanswerthefollowingquestions.Ineachcase,provideabriefexplanationof
yourchoice.
(a)Whichionisationenergiesshowthatanelectronina1sorbitalprovidesnearlycomplete
shieldingofanelectronina2porbital?
(b)Whichionisationenergiesshowthatthestabilityofn=2orbitalsincreaseswithZ2?
StructureofthePeriodicTable
4.26Drawtheperiodictableinblockform,andoutlineandlabeleachofthefollowingsets:
(a)elementsthatare1electronshortoffilledporbitals,
(b)elementsforwhichn=3orbitalsarefilling,
(c)elementswithhalffilleddorbitals,
(d)thefirstelementthatcontainsa5selectron.
4.27Howmanyvalenceelectronsdoeseachofthefollowingatomshave?
(a)O,
(b)V,
(c)Rb,
(d)Sn,
(e)Cd
ElectronConfigurations
4.28Writethecompleteelectronconfiguration,andlistacorrectsetofquantumnumbersforeachof
thevalenceelectronsinthegroundstateconfigurationsof:
(a)Be,
(b)O,
(c)Ne,
(d)P.
4.29Whichoftheatomsfromquestion4.28areparamagnetic?Draworbitalenergyleveldiagramsto
supportyouranswer.
4.30Thefollowingarehypotheticalconfigurationsforaberylliumatom.Whichusenonexistent
orbitals,whichareforbiddenbythePauliprinciple,whichareexcitedstates,andwhichoneisthe
groundstateconfiguration?
(a) 1s32s1
(b)1s12s3
(c) 1s12p 3
(d)1s22s12p 1
(e) 1s22s2
(f) 1s21p 2
(g)1s22s12d 1
4.31Writethecorrectgroundstateelectronconfigurations,inshorthandnotation,forC,Cr,SbandBr.
PeriodicityofAtomicProperties
4.32Arrangethefollowingatomsinorderofdecreasingfirstionisationenergy(smallestlast):Ar,Cl,
CsandK.
4.33Oneelementhastheseionisationenergiesandelectronaffinity(allinkJmol1):E =376,E =
i1 i2
2420,Ei3=3400,Eea =45.5.Inwhichcolumnoftheperiodictableisthiselementfound?Give
yourreasoning.
4.34AccordingtoappendixG,eachofthefollowingelementshasapositiveelectronaffinity.Foreach
one,constructitsvalenceorbitalenergyleveldiagramanduseittoexplainwhytheanionis
unstable.
(a)N,
(b)Mg,
(c)Zn
4.35Fromthefollowinglist,selecttheelementsthatformioniccompounds:Ca,C,Cu,Cs,ClandCr.
Indicatewhethereachformsastablecationorastableanion.
IonsandChemicalPeriodicity
4.36Classifyeachoftheelementsfromgroup16oftheperiodictableasametal,anonmetalora
metalloid.
4.37Classifyeachoftheelementslistedinquestion4.35asametal,anonmetalorametalloid.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWPROBLEMS
4.38Listthepropertiesofelectronsandofphotons,includingtheequationsusedtodescribeeach.
4.39Writeashortdescriptionof:
(a)thephotoelectriceffect,
(b)particlewaveduality,
(c)electronspinand
(d)theuncertaintyprinciple.
4.40Describeanatomicenergyleveldiagramandtheinformationitincorporates.
4.41Redrawthefirstlightwaveinfigure4.3toshowawavewhosefrequencyistwiceaslargeasthat
showninthefigure,butwhoseamplitudeisthesame.
4.42Aminimumof216.4kJmol1isrequiredtoremoveanelectronfromapotassiummetalsurface.
Whatisthelongestwavelengthoflightthatcandothis?
4.43Inaphotoelectriceffectexperiment,theminimumfrequencyneededtoejectelectronsfroma
metalis7.510 14s1.Supposethata366nmphotonfromamercurydischargelampstrikesthe
metal.Calculate:
(a)thebindingenergyoftheelectronsinthemetal,
(b)themaximumkineticenergyoftheejectedelectronsand
(c)thewavelengthassociatedwiththoseelectrons.
4.44Microwaveovensuseradiationwithawavelengthof12.5cm.Whatisthefrequency,andenergy
inkJmol1,ofthisradiation?
4.45Bariumsaltsinfireworksgenerateayellowgreencolour.Ba2+ionsemitlightwith=487,514,
543,553and578nm.ConvertthesewavelengthsintofrequenciesandintoenergiesinkJmol1.
4.46Ahydrogenatomemitsaphotonasitselectronchangesfromn=5ton=1.Whatisthe
wavelengthofthephoton?Inwhatregionoftheelectromagneticspectrumisthisphotonfound?
4.47Writebriefexplanationsof:
(a)shielding,
(b)thePauliexclusionprinciple,
(c)theAufbauprinciple,
(d)Hund'sruleand
(e)valenceelectrons.
4.48Constructanorbitalenergyleveldiagramforallorbitalswithn<8andl<4.Usetheperiodic
tabletohelpdeterminethecorrectorderoftheenergylevels.
4.49Describeperiodicvariationsinelectronconfigurationsexplainhowtheyaffectionisationenergy
andelectronaffinity.
4.50WritetheelectronconfigurationfortheMn 2+groundstate,andgiveasetofquantumnumbersfor
allelectronsintheleaststableoccupiedorbital.
4.51Arrangethefollowinginorderofdecreasingsize(radius):Cl,K+,ClandBr.Explainyour
rankingsintermsofquantumnumbersandelectricalinteractions.
4.52DrawenergyleveldiagramsthatshowthegroundstatevalenceelectronconfigurationsforCu +,
Mn 2+andAu 3+.
4.53Writeabriefexplanationforeachofthefollowing.
(a)Inahydrogenatom,the2sand2p2orbitalshaveidenticalenergy.
(b)Inaheliumatom,the2sand2porbitalshavedifferentenergies.
4.54Refertofigure4.50toanswerthefollowingquestionsaboutfirstionisationenergies.
(a)WhichelementshowsthegreatestdecreasefromitsneighbourofnextlowerZ?
(b)Whatistheatomicnumberoftheelementwiththelowestvalue?
(c)IdentifythreerangesofZacrosswhichthevaluechangestheleast.
(d)Listtheatomicnumbersofallelementswhosevaluesarebetween925and1050kJmol1.
4.55Whichhasthemostunpairedelectrons,S+,SorS?Useelectronconfigurationstosupportyour
answer.
4.56Noneofthefollowingelectronenergydiagramsdescribesthegroundstateofasulfuratom.For
each,statethereasonwhyitisnotcorrect.
(a)

(b)

(c)

(d)
4.57Identifytheioniccompoundsthatbestfitthefollowingdescriptions:
(a)thegroup2cationwiththesecondsmallestradiuscombinedwithagroup16anionthatis
isoelectronicwiththenoblegasfromrow3
(b)a+1ionthatisisoelectronicwiththenoblegasfromrow3,combinedwiththeanion
formedfromtherow2elementwiththehighestelectronaffinity
(c)thegroup2metalwiththehighestsecondionisationenergythatcombinesina1:2ratio
withanelementfromrow3.

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ADDITIONALEXERCISES
4.58Thephotoelectriceffectformagnesiummetalhasathresholdfrequencyof8.9510 14s1.Can
Mgbeusedinphotoelectricdevicesthatsensevisiblelight?Doacalculationtosupportyour
answer.
4.59Energeticfreeelectronscantransfertheirenergytoboundelectronsinatoms.In1913,James
FranckandGustavHertzpassedelectronsthroughmercuryvapouratlowpressuretodetermine
theminimumkineticenergyrequiredtoproducetheexcitedstatethatemitsultravioletlightat
253.7nm.Whatisthatminimumkineticenergy?Whatwavelengthisassociatedwithelectronsof
thisenergy?
4.60Thediameterofatypicalatomis10 10m,andthediameterofatypicalnucleusis10 15m.
Calculatetypicalatomicandnuclearvolumesanddeterminewhatfractionofthevolumeofa
typicalatomisoccupiedbyitsnucleus.
4.61Neutrons,likeelectronsandphotons,areparticlewaveswithdiffractionpatternsthatcanbeused
todeterminethestructuresofmolecules.Calculatethekineticenergyofaneutronwitha
wavelengthof75pm.
4.62Thehumaneyecandetectaslittleas2.3510 18Jofgreenlightwithawavelengthof510nm.
Calculatetheminimumnumberofphotonsofgreenlightthatcanbedetectedbythehumaneye.
4.63Gaseouslithiumatomsabsorblightwithawavelengthof323nm.Theresultingexcitedlithium
atomslosesomeenergythroughcollisionswithotheratoms.Theatomsthenreturntotheirground
statebyemittingtwophotonswith=812.7and670.8nm.Drawanenergyleveldiagramthat
showsthisprocess.Whatfractionoftheenergyoftheabsorbedphotonislostincollisions?
4.64Calculatethewavelengthsassociatedwithanelectronandaproton,eachtravellingat5.000%of
thespeedoflight.
4.65Onehydrogenemissionlinehasawavelengthof486nm.Identifythevaluesforn finalandn initial
forthetransitiongivingrisetothisline.
4.66Anatomicenergyleveldiagram,showntoscale,follows.

Anexcitedstateatomemitsphotonswhentheelectronmovesinsuccessionfromleveldtolevel
c,fromlevelctolevelb,andfromlevelbtothegroundstate(levela).Thewavelengthsofthe
emittedphotonsare565nm,152nmand121nm(notnecessarilyinthepropersequence).Match
eachemissionwiththeappropriatewavelengthandcalculatetheenergiesoflevelsb,candd
relativetolevela.
4.67Smallheliumneonlasersemit1.0mJs1oflightat634nm.Howmanyphotonsdoessuchalaser
emitinoneminute?
4.68Theargonionlaserhasmajoremissionlinesat488and514nm.Eachoftheseemissionsleaves
theAr+ioninanenergylevelthatis2.7610 18Jabovethegroundstate.
(a)Calculatetheenergiesofthetwoemissionwavelengthsinjoules.
(b)Drawanenergyleveldiagram(injoulesperatom)thatillustratesthesefacts.
(c) WhatfrequencyandwavelengthradiationisemittedwhentheAr+ionreturnstoitslowest
energylevel?
4.69Theseriesofemissionlinesthatresultsfromexcitedhydrogenatomsundergoingtransitionstothe
n=3leveliscalledthePaschenseries.Calculatetheenergiesofthefirstfivelinesinthisseriesof
transitions,anddrawanenergyleveldiagramthatshowsthemtoscale.
4.70Ittakes486kJmol1toremoveelectronscompletelyfromsodiumatoms.Sodiumatomsabsorb
andemitlightofwavelengths589.6and590.0nm.
(a) CalculatetheenergiesofthesetwowavelengthsinkJmol1.
(b)Drawanenergyleveldiagramforsodiumatomsthatshowsthelevelsinvolvedinthese
transitionsandtheionisationenergy.
(c)Ifasodiumatomhasalreadyabsorbeda590.0nmphoton,whatisthewavelengthofthe
secondphotonasodiumatommustabsorbinordertoremoveanelectroncompletely?
4.71Thegraphbelowshowstheresultsofphotoelectronexperimentsontwometals,usinglightofthe
sameenergy.

(a)Calculatethebindingenergyofeachmetal.Whichhasthehigherbindingenergy?Explain.
(b)Calculatethekineticenergiesofelectronsejectedfromeachmetalbyphotonswith
wavelengthof125nm.
(c)Calculatethewavelengthrangeoverwhichphotonscanejectelectronsfromonemetalbut
notfromtheother.
4.72Writetheelectronconfigurationforthelowestenergyexcitedstateofeachofthefollowing:Be,
O2,Br,Ca2+andSb 3+.
4.73WritethegroundstateconfigurationsfortheisoelectronicspeciesCe2+,La+andBa.Aretheythe
same?Whatfeaturesoforbitalenergiesaccountforthis?
4.74Theionisationenergyoflithiumatomsinthegasphaseisabouthalfaslargeastheionisation
energyofberylliumatomsinthegasphase.Incontrast,theionisationenergyofLi+isaboutfour
timeslargerthantheionisationenergyofBe+.Explainthedifferencebetweentheatomsandthe
ions.
4.75ThefiguresbelowshowCl,Ar,andK+drawntoscale.Decidewhichfigurecorrespondstowhich
speciesandexplainyourreasoning.
(a)

(b)

(c)

4.76Makeanelectrondensityplotthatshowshowthe3sand3porbitalsareshieldedeffectivelybythe
2porbitals.Provideabriefexplanationofyourplot.
4.77UsethedatainappendixGtoexplainwhythenoblegasesseldomtakepartinchemicalreactions.
4.78Fromitslocationintheperiodictable,predictsomeofthephysicalandchemicalpropertiesof
francium.Whatelementdoesitmostcloselyresemble?
4.79Whatwouldbethenexttwoorbitalstofillafterthe7porbital?
4.80Whichhasthemorestable2sorbital,alithiumatomoraLi2+cation?Explainyourreasoning.
4.81Thefirstfourionisationenergiesofaluminiumareasfollows:E =577kJmol1,E =1817kJ
i1 i2
mol1,Ei3=2745kJmol1andEi4=11578kJmol1.
(a)Explainthetrendinionisationenergies.
(b)Rankionsofaluminiuminorderofionicradius,fromlargesttosmallest.
(c)Whichionofaluminiumhasthelargestelectronaffinity?
4.82Theideaofanatomicradiusisinherentlyambiguous.Explainwhythisisso.
4.83Useelectronelectronrepulsionandorbitalenergiestoexplainthefollowingirregularitiesinfirst
ionisationenergies:
(a)Boronhasalowerionisationenergythanberyllium.
(b)Sulfurhasalowerionisationenergythanphosphorus.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYTERMS
absorptionspectrum energyleveldiagram Pauliexclusionprinciple
amplitude excitedstate phase
atomicradius frequency() photoelectriceffect
Aufbauprinciple groundstate photons
azimuthalquantumnumber(l) groundstateconfiguration Planck'sconstant(h)
coreelectrons Hund'srule principalquantumnumber(n)
degenerate intensity quantised
diamagnetic ionisationenergy(Ei) quantumnumber
effectivenuclearcharge(Zeff) isoelectronic shielding
electromagneticradiation light spin
electronaffinity(Eea ) magneticquantumnumber spinquantumnumber(ms)
electronconfiguration (ml) uncertaintyprinciple
electrondensitypicture noblegasconfiguration valenceelectrons
electrondensityplot node wavelength()
emissionspectrum orbital
paramagnetic

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CHAPTER

5 ChemicalBondingand
MolecularStructure
Australia'sSamanthaStosurreturnsavolley.Thehightechfibresinhertennisracquetthatareresponsible
forsomeofthepowerareheldtogetherbychemicalbonds.Producingsuchhightechfibresrequiresa
thoroughunderstandingofchemicalbonding,becausethefibresareconstructedofpolymers,large
moleculesthatareheldtogetherbycovalentbondsinwhichelectronsaresharedbetweenatoms.Theways
inwhichchemicalbondsareformeddependonthenatureoftheelementsinvolved,andchemicalbonds
showavarietyofformsandstrengths.

Thischapterdescribeschemicalbondinganditsrelationshiptomolecularstructure.Wediscussthetwo
extremesofchemicalbonding:ionic,inwhichelectrostaticforcesholdionicarrangementstogether,and
covalent,wheresharedelectronpairsdictatethebondingandgeometryofindividualmolecules.Weshow
howsimpleLewistheorygivesagoodapproximationofthedistributionofelectronswithinmolecules,and
howwecanusethistopredictmoleculargeometryusingvalenceshellelectronpairrepulsiontheory.We
thenconsiderindetailthetwopredominanttheoriesusedtodescribecovalentbonding:valencebondtheory
andmolecularorbitaltheory.
KEYTOPICS

5.1Fundamentalsofbonding
5.2Ionicbonding
5.3Lewisstructures
5.4Valenceshellelectronpairrepulsion(VSEPR)theory
5.5Propertiesofcovalentbonds
5.6Valencebondtheory
5.7Molecularorbitaltheory:diatomicmolecules

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.1FundamentalsofBonding
Welearnedinchapter4thatthesize,energylevelsandelectronconfigurationofanatomdetermineits
chemicalproperties.Inmolecularcompounds,electronsonatomsinteractandaresharedbetweenatoms.In
ioniccompounds,electronsaretransferredcompletelybetweenatomstoformpositivelyandnegatively
chargedions.Sinceelectronshavebothparticleandwavelikeproperties,bondinginteractionscanbe
describedfromeitherviewpoint.Keepinmind,though,thatthesemodelsdonotnecessarilyreflectreality
exactly.

Theelectrostaticenergybetweentwochargedspeciesisproportionaltothemagnitudesofthechargesand
inverselyproportionaltothedistancebetweenthem.Chargesofoppositesignattractoneanother,butlike
chargesrepel.TherelationshipisgivenbyCoulomb'slawas:

where:

Theequationdescribesthepotentialenergyofonepairofcharges.Molecules,however,containtwoor
morenucleiandtwoormoreelectrons.Toobtainthetotalpotentialenergyofamolecule,theequationmust
beappliedtoeverypossiblepairofchargedspecies.Thesepairwiseinteractionsareofthreetypes(see
figure5.1):
1.Electronsandnucleiattractoneanother.Attractiveinteractionsareenergeticallyfavourable,soan
electronattractedtoanucleusisatalowerenergythanafreeelectron.
2.Electronsrepeleachother,raisingtheenergyandreducingthestabilityofamolecule.
3.Nucleirepeleachother,sotheseinteractionsalsoreducethestabilityofamolecule.

FIGURE5.1Whenelectronsareintheregionbetweentwohydrogennuclei,attractiveelectrostaticforcesexceed
repulsiveelectrostaticforces,leadingtothestablearrangementofachemicalbond.

Inanymolecule,thesethreeinteractionsarebalancedtogivethemoleculeitsgreatestpossiblestability.This
balanceisachievedwhentheelectrondensityissituatedbetweenthenucleiofbondedatoms.Weviewthe
electronsasbeingsharedbetweenthenucleiandcallthissharedelectrondensityacovalentbond.Inany
covalentbond,theattractiveenergybetweennucleiandelectronsexceedstherepulsiveenergyarisingfrom
nuclearnuclearandelectronelectroninteractions.
TheHydrogenMolecule
Theseconceptsaredemonstratedbelowforthesimpleststableneutralmolecule,molecularhydrogen.A
hydrogenmoleculecontainsjusttwonucleiandtwoelectrons.

Considerwhathappenswhentwohydrogenatomscometogetherandformacovalentbond.Astheatoms
approach,eachnucleusattractstheoppositeelectron,pullingthetwoatomsclosertogether.Atthesame
time,thetwonucleirepeleachother,asdothetwoelectrons.Theserepulsiveinteractionstendtodrivethe
atomsapart.

ForH2tobeastablemolecule,thesumoftheattractiveenergiesmustexceedthesumoftherepulsive
energies.Figure5.1showsastaticarrangementofelectronsandnucleiinwhichtheelectronnucleus
distancesareshorterthantheelectronelectronandnucleusnucleusdistances.Asthechargesonthe
hydrogennucleiandelectronsare1+and1respectively,thedistancesbetweenthembecomecrucialin
determiningtheenergyofthisarrangement.Inthiscase,attractiveinteractionsexceedrepulsiveinteractions,
leadingtoastablemolecule.Noticethatthetwoelectronsoccupytheregionbetweenthetwonucleiwhere
theycaninteractwithbothnucleiatoncethatis,theatomssharetheelectronsinacovalentbond.

Anactualmoleculeisdynamic,notstatic,andboththeelectronsandnucleimovecontinuously.Ina
covalentbond,themostprobableelectronlocationsarebetweenthenuclei,where,inthismodel,theycan
beviewedasbeingsharedbetweenthebondedatoms.

BondLengthandBondEnergy
Astwohydrogenatomscometogethertoformamolecule,attractiveforcesbetweennucleiandelectrons
makethehydrogenmoleculemorestablethantheindividualhydrogenatoms.Theamountofincreased
stabilitydependsonthedistancebetweenthenuclei,asshowninfigure5.2.Atdistancesgreaterthan300
pm(30010 12m),thereisalmostnointeractionbetweentheatoms,sothetotalenergyisthesumofthe
energiesofthetwoindividualatoms.Atcloserdistances,theattractionbetweentheelectronofoneatomand
thenucleusoftheotheratomincreases,andthecombinedatomsbecomemorestable.Movingtheatoms
closertogethergeneratesgreaterstabilityuntilthenucleiare74pmapart.Atthisdistance,weobtainthebest
possiblebalancebetweentheattractiveandrepulsiveforcesinthemolecule.Atdistancescloserthan74pm,
thenucleusnucleusrepulsionbeginstodominateandtheenergyofthesystemincreasesrapidly.Thus,ata
separationdistanceof74pm,thehydrogenmoleculehasthemaximumenergeticadvantage(7.2210 19J)
overtwoseparatedhydrogenatoms.Experimentalstudiesofmolecularmotionrevealthatnucleiwithin
moleculesmovecontinuously,oscillatingabouttheirlowestenergyseparationdistanceliketwospheres
attachedtooppositeendsofaspring.
FIGURE5.2Theinteractionenergyoftwohydrogenatomsdependsonthedistancebetweenthenuclei.

Figure5.2showstwocharacteristicfeaturesofcovalentbonds.Theseparationdistanceatwhichthe
moleculehasthemaximumenergeticadvantageovertheseparatedatoms(74pmforH2)isknownasthe
bondlength.Theenergydifferencebetweenthemoleculeandtheseparatedatomsatthisseparationdistance
iscalledthebondenergy.Bondenergyisdefinedastheenergyrequiredtobreakthebondandthereforeis
alwayspositive.Bondlengthsandenergiesareimportantpropertiesofchemicalbondsand,aswewillsee,
theyarerelated.ItisusualtoquotebondenergiesinunitsofkJmol1.Wecanobtainthisvalueforthe
hydrogenmoleculebymultiplyingtheenergyofasingleHHbond(7.2210 19J)byNA(6.02210 23
mol1).ThisgivesaHHbondenergyof435kJmol1.Eachdifferentchemicalbondhasacharacteristic
bondlengthandbondenergy.

Themostprobablepositionoftheelectronsinthehydrogenmoleculeisbetweenthenuclei.Ifwerotatethe
moleculeaboutitsinternuclearaxis(animaginarylinejoiningthetwonuclei)wefindthattheelectron
distributionbetweenthenucleilooksexactlythesame,regardlessoftheanglethroughwhichitwasrotated.
Inotherwords,thebondissymmetricwithrespecttorotationabouttheinternuclearaxis.Bondsforwhich
thisistruearecalledsigma()bonds.

OtherDiatomicMolecules:F2

BondformationinH2isrelativelyeasytodescribebecauseweneedtoconsiderjusttwoelectrons.
However,evenwhentheatomswithinamoleculecontainmanyelectrons,wecanstillconsiderbond
formationasthesharingofonlytwoelectrons.Wewillillustratethiswiththefluorinemolecule,F2.

Astwofluorineatomsapproacheachother,theelectronsofeachatomfeeltheattractionofthenucleusof
theotheratom,justasinH2.Inthiscase,thevalence2pelectronsareclosesttotheneighbouringnucleus
andexperiencethestrongestattraction.Thesingleelectroninoneofthe2porbitalsapproachestheopposite
nucleus.Consequently,wecandescribetheFFbondasthesharingoftwoelectronsfromthefluorine2p
orbitalsthatpointdirectlytowardseachother(seefigure5.3).Notethattheresultingbondisabond.

FIGURE5.3ThechemicalbondinF2 formsfromstrongelectrostaticattractionoftheelectroninthefluorine2p
orbitalthatpointsdirectlyattheneighbouringnucleus.
UnequalElectronSharing
Eachnucleuswithinahydrogenmoleculeandeachwithinafluorinemoleculehasthesamecharge.
Consequently,bothnucleiattractelectronsequally.Theresultisasymmetricaldistributionoftheelectron
densityaroundtheatoms.Inachemicalbondbetweenanytwoidenticalatoms,thenucleisharethebonding
electronsequally.

IncontrasttothesymmetricalforcesinH2andF2,thebondingelectronsinHFexperienceunsymmetrical
attractiveforces.Theeffectivenuclearchargeofafluorineatomissignificantlygreaterthantheeffective
chargeofahydrogenatomduetothegreaternumberofprotons,sotheelectronssharedbetweenHandF
feelastrongerattractiontotheFatom.Unequalattractiveforcesleadtoanunsymmetricaldistributionofthe
bondingelectrons.TheHFmoleculeismoststablewhenitsbondingelectronsareconcentratedclosertothe
fluorineatomandawayfromthehydrogenatom.Thisunequaldistributionofelectrondensitygivesthe
fluorineendofthemoleculeasmallnegativechargeandthehydrogenendasmallpositivecharge
however,themoleculeasawholeremainselectricallyneutral.Thesepartialchargesarelessthanonecharge
unitandareequalinmagnitude.Toindicatesuchpartialcharges,weusethesymbols+and(isthe
lowercaseGreekletterdelta)oranarrowpointingfromthenegativeendtowardsthepositiveendofthe
molecule,oranelectrondensitysurface,whichshowsthespreadofchargeusingcolours,withbluebeing
positiveandredbeingnegativeasshownforHFinfigure5.4.Thisunequalsharingofelectronsresultsina
polarcovalentbond.Wedescribebondpolarityanditsconsequencesinsection5.5.

FIGURE5.4UnequalsharingofelectrondensityinHFresultsinapolarcovalentbond.Thecolourgradient
representsthevariationinelectrondensitysharedbetweentheatoms.

Notethat,despitebeingpolar,theHFbondisstillabond,becauseitremainsunchangedaswerotate
themoleculeabouttheHFbondaxis.

Aselementsdifferintheireffectivenuclearcharges,atomsofeachelementhaveacharacteristicabilityto
attractelectronswithinacovalentbond.Thisabilityiscalledelectronegativityandissymbolisedby(the
lowercaseGreekletterchi).Abondbetweentwoelementsofdifferentelectronegativitieswillbepolar,and
thegreaterthedifference(),themorepolarthebond.

Electronegativitygivesanumericalvaluetohowstronglyanatomattractstheelectronsinachemicalbond.
Thispropertyofanatominvolvedinabondisrelatedto,butdistinctfrom,ionisationenergyandelectron
affinity.(Asdescribedinchapter4,ionisationenergymeasureshowstronglyanatomattractsoneofitsown
electrons.Electronaffinityspecifieshowstronglyanatomattractsafreeelectron.)

Electronegativities,whichhavenounits,areestimatedbyusingcombinationsofatomicandmolecular
properties.Theperiodictableshowninfigure5.5presentscommonlyusedvalues,developedbytheUS
scientistLinusPauling(figure5.6),basedonbondenergies.ThesevaluesareoftencalledthePaulingscale.
FIGURE5.5Electronegativitiesoftheelementsvaryperiodically.Whiletherearesomeexceptions,thegeneraltrend
isthatelectronegativityincreasesfromlefttorightanddecreasesfromtoptobottomoftheperiodic
table.ThePaulingscaleomitsgroup18elements(thenoblegases)becausetheyareveryunreactive
and,withveryfewexceptions,donotformcovalentbonds.Someotherelectronegativityscalesdo
assignvaluestotheseelements.
FIGURE5.6LinusPauling(19011994)wasoneofthemostinfluentialthinkersoftwentiethcenturychemistryand
wasawardedtheNobelPrizeinchemistryin1954forhisresearchintothenatureofthechemical
bond.HewasalsooneofthefewpeopletobeawardedtwoNobelPrizes,receivingthepeaceprize
in1962forhisstandagainstnuclearweapons,whichledtheUSgovernmenttorevokehispassportin
1952.

Figure5.5showsthatelectronegativityisaperiodicproperty.Electronegativitiesgenerallyincreasefromthe
lowerlefttotheupperrightoftheperiodictable.Theelementsfranciumandcaesium(=0.7)havethe
lowestvalue,andfluorine(=4.0)hasthehighestvalue.Electronegativitiesalsogenerallydecreasedown
mostgroupsandincreasefromlefttorightacrossthesandpblocks.Aswithionisationenergiesand
electronaffinities,variationsineffectivenuclearchargeandprincipalquantumnumberexplain
electronegativitytrends.Metalsgenerallyhavelowelectronegativities(=0.7to2.4)andnonmetalshave
highelectronegativities(=2.1to4.0).Asexpectedfromtheirintermediatecharacterbetweenmetalsand
nonmetals,metalloidshaveelectronegativitiesthatarelargerthanthevaluesformostmetalsandsmaller
thanthoseformostnonmetals.

Electronegativitydifferences()betweenbondedatomsindicatewhereaparticularbondliesonthe
continuumofbondpolarities.Threefluorinecontainingsubstances,F2,HFandCsF,representtherangeof
variation.(Notethat,asnoweighablequantityoffranciumhaseverbeenisolated,thecompoundFrFis
unknown.)Atoneendofthecontinuum,thebondingelectronsinF2aresharedequallybetweenthetwo
fluorineatoms(=4.04.0=0).Attheotherlimit,CsF(=4.00.7=3.3)isacompoundinwhich
electronshavebeenfullytransferredtogiveCs+cationsandFanions.Wecallsuchcompoundsionic
compounds,andtheywillbediscussedinmoredetailinthenextsection.Mostbonds,includingthebondin
HF(=4.02.1=1.9),fallbetweentheseextremes.Thesearepolarcovalentbonds,inwhichtwoatoms
shareelectronsunequally.

ChemicalConnections

ElectromagneticRadiationandCancer

Theabilityoflighttoprovidetheenergyforchemicalreactionsenableslifetoexistonourplanet.
Greenplantsabsorbsunlightand,withthehelpofchlorophyll,convertcarbondioxideandwater
intocarbohydrates(e.g.sugarsandcellulose),whichareessentialconstituentsofthefoodchain.
However,notalleffectsofsunlightaresobeneficial.

Aswesawinchapter4,lighthasenergythatisproportionaltoitsfrequency,and,ifthephotons
thatareabsorbedbyasubstancehaveenoughenergy,theycanrupturechemicalbondsandinitiate
chemicalreactions.Thecarboncarbonandcarbonhydrogencovalentbondsfoundinorganic
moleculestypicallyhaveenergiesofatleast350kJmol1.Visiblelight,whichrangesfrom780nm
to380nminwavelength,hasacorrespondingenergyrangeofapproximately153to315kJmol1,
andthereforephotonsofvisiblelightarenotsufficientlyenergetictobreaksuchbonds.However,
ultravioletradiation,whichhasshorterwavelengthsandhencehigherenergies,canbedangerous
inthisrespect,particularlylightofwavelengthlessthan340nm,whichhasenergygreaterthan
350kJmol1.ThesunlightilluminatingtheEarthcontainssubstantialamountsofUVradiation.
Fortunately,alayerofozone(O3)inthestratosphere,aregionoftheatmosphereextendingfrom
about45to55kmaltitude,absorbsmostoftheincomingUV,protectinglifeonthesurface.
However,someUVradiationdoesgetthrough,andthepartofthespectrumofmostconcernis
calledUVBwithwavelengthsbetween280and320nm.

WhatmakesUVBsodangerousisitsabilitytoaffecttheDNAinourcells.(ThestructureofDNA
anditsreplicationisdiscussedinchapter25.)AbsorptionofUVradiationcausesconstituentsof
theDNA,calledpyrimidinebases,toundergoreactionsthatformbondsbetweenthem.Thiscauses
transcriptionerrorswhentheDNAreplicatesduringcelldivision,givingrisetogeneticmutations
thatcanleadtoskincancers.Theseskincancersfallintothreeclasses:basalcellcarcinomas,
squamouscellcarcinomas,andmelanomas,thelastbeingthemostdangerous.Eachyearmore
than1millioncasesofskincancerarediagnosedworldwide.Itisestimatedthatmorethan90%of
skincancersareduetoabsorptionofUVBradiation(figure5.7).

FIGURE5.7Dawnofanewdaybringstheriskofskincancertothoseparticularlysusceptible.
Fortunately,understandingtheriskallowsustoprotectourselveswithclothingand
sunblockcreams.

Inrecentyears,concernhasbeenexpressedinsomesectionsofthemediaoverapossiblelink
betweentheuseofmobilephonesandbraincancerithasbeenproposedbysomethatradiation
frommobilephones(figure5.8)cancausebraintumours,althoughalargenumberofstudieshave
failedtofindacausalrelationship.Thisisnotsurprising,giventhatmobilephonesusemicrowave
radiation,whichisofmuchlongerwavelengththanultravioletlight,andhenceinsufficiently
energetictocausemutationofDNAbybreakingcovalentbonds.
FIGURE5.8Alargenumberofstudieshavefailedtofindacausalrelationshipbetweenmicrowave
radiationandbraintumours.MicrowaveradiationisnotenergeticenoughtomutateDNA.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.2IonicBonding
Compoundsformedbetweenelementsofverydifferentelectronegativitiesareoftenpredominantlyionic
incharacter.Forexample,ioniccompoundstendtoformbetweencationsfromgroups1and2and
anionsfromgroups16and17.Mostioniccompoundsaresolidswithrelativelyhighmeltingpoints,
particularlyiftheionicsolidsarecomposedofatomicorsmallmolecularions.Apartfromthesehigh
meltingpointionicsolids,thereisalsoaclassofcompoundscalledionicliquids,compoundsoflarge
molecularions.Theseare,bydefinition,ioniccompoundsthathavemeltingpointbelow100C.There
aresomeionicliquidsthatareliquidevenatroomtemperature,andthosehaveimportantapplications.

Thebondinginioniccompoundsdiffersfundamentallyfromthatincovalentcompoundsitdoesnot
involvethesharingofpairsofelectrons.Instead,ioniccompoundsareheldtogetherbythenon
directionalattractiveforcesbetweenoppositelychargedions,leadingtothreedimensionalarrangements
ratherthandistinctmolecules.

Consider,sodiumchloride,NaCl.ThestructureofthiscompoundhaseachNa+cationsurroundedby
sixClanionsandeachClanionsurroundedbysixNa+cations,asshowninfigure5.9.

FIGURE5.9Representationofpartofthestructureofsodiumchloride,NaCl.NotethateachNa+cationis
surroundedbysixClanions,andeachClanionissurroundedbysixNa+cations.

ThisarrangementofNa+cationsandClanionswasfirstdeterminedin1913byAustralianbornSir
WilliamLawrenceBragg,usingXrayequipmentdesignedbyhisfather,SirWilliamHenryBragg
(figure5.10).NaClwasthefirstcompoundwhosestructurewasdeterminedbyXraycrystallography
(seechapter7),afieldinwhichtheBraggswerepioneers.TheywerejointlyawardedtheNobelPrizein
physicsin1915,andWilliamLawrenceBraggbecametheyoungesteverawardeeattheageof25.
CrystalstructuresdeterminedthroughanalysisofXraydiffractiondatashowthepreciselocationsof
atomswithinachemicalspeciesandgiveatomicseparationsaccuratetoabout110 12m.Xray
crystallographyisavitalpartofmodernchemistryandisthesourceofmuchofthestructural
informationthatyouwillencounterinlaterchapters.
FIGURE5.10SirWilliamLawrenceBragg(left)andhisfatherSirWilliamHenryBraggwereawardedthe
NobelPrizeinphysicsin1915fortheirworkonXraycrystallography.

ThedistancebetweentheionsinNaClisdeterminedbyabalanceoftheCoulombic(electrostatic)
attractionsandrepulsionsandtheshortrangerepulsiveinteractionsbetweenboththeelectrondensities
andnucleiofneighbouringions.Atroomtemperature,thedistancebetweenthecentresofneighbouring
ionsis2.8210 10m.Usingthisnumber,wecancalculatethemagnitudeoftheattractiveforces
betweentwoneighbouringNa+andClionsusingtheequationintroducedatthestartofthischapter.

Giventhatq 1is+1.6010 19C,q 2is1.6010 19C(1.6010 19Cisthefundamentalchargeofa


singleelectron)andk=9.0010 9Nm2C2,weobtainavalueof8.1710 19J,whichequatesto492
kJmol1whenmultipliedbytheAvogadroconstant.Thiscorrespondstotheenergyreleased(hencethe
negativesign)when1moleofgaseousNa+andgaseousClionsarebroughtfromaninfinitedistance
toaseparationof2.8210 10m.However,thisvaluetakesintoaccountonlytheattractiveforcesto
onenearestneighbour,whereaseachioninthecrystalhassix.Ifwetakeallsixinteractionsinto
account,aswellasrepulsiveinteractionsbetweenionsofthesamechargeinthestructure,weobtaina
valueof769kJmol1.Thisisasubstantialamountofenergy,andmeansthat,inordertobreak1mole
ofthecompoundintoitsconstituentgaseousions,wewouldhavetosupply769kJofenergy.Thisis
calledthelatticeenergyofthecompound.Amongotherfactors,thelatticeenergyofacompoundis
dependentonthechargesoftheionsasthechargesincrease,thelatticeenergybecomesmorepositive
andtheionsbecomehardertoseparatefromoneanother.Wealsoexpectlatticeenergyvaluesto
decreaseastheionsgetlarger,becauser,thedistancebetweenthem,willincrease.Thesetrendsare
illustratedintable5.1,whichgivessomelatticeenergyvaluesforionicspecies.
TABLE5.1 Latticeenergiesforanumberofioniccompounds.AllvaluesareinkJmol1
Anion
Cation F Cl Br I O2

Li+ 1030 834 788 730 2799

Na + 910 769 732 682 2481

K+ 808 701 671 632 2238

Rb+ 774 680 651 617 2163


Mg 2+ 2913 2326 2097 1944 3795

Ca 2+ 2609 2223 2132 1905 3414

Sr2+ 2476 2127 2008 1937 3217

Ba 2+ 2341 2033 1950 1831 3029

Theeffectofionicsizeonlatticeenergyisshownbythefactthatthelatticeenergiesofthegroup1
chloridesdecreaseasthesizeofthecationincreasesfromLi+toRb +,andthelatticeenergiesofthe
sodiumhalidesdecreaseasthesizeoftheanionincreasesfromFtoI.Theeffectofionicchargeis
seenbycomparingthelatticeenergiesofthecompoundsformedfromthe2+ionswithhalideanions.In
allcases,theselatticeenergiesaremuchlargerthanthoseforthe1+/1combinations.Thevaluesfor
compoundscontaining2+and2ionsareevenlarger,withthelatticeenergyofMgObeingalmostfour
timesthelatticeenergyofLiF.However,itisimportanttonotethatmeaningfulcomparisonsoflattice
energyvaluescanbemadeonlybetweencompoundswiththesamestructuretype.

Whiletheionicmodeldescribesanumberofmetalhalides,oxidesandsulfideswell,itdoesnotdescribe
mostotherchemicalsubstancesadequately.CompoundssuchasCaO,NaClandMgF2behavelike
simplecationsandanionsheldtogetherbyelectrostaticattraction,butcompoundssuchasCO,Cl2and
HFdonot.Wemustdescribethebondingintheselattercompoundsintermsofthesharingofelectrons
betweenatoms.Therearetwopredominanttheoriesofbondingwhichdothis.Beforewestudythese,
wewilllookatasimplewayofdeterminingtheelectrondistributioninmoleculesandhowwecanuse
thistopredicttheshapeofaparticularmolecule.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.3LewisStructures
Inthissection,wedevelopaprocessformakingschematicdrawingsthatshowhowtheatomsina
moleculearebonded.Inaddition,thesedrawings,knownasLewisstructures,differentiatebetween
bondingandnonbondingvalenceelectronsinamolecule.Fromthisperspective,writingaLewis
structureisthefirststepindevelopingabondingdescriptionofamolecule.Lewisstructuresarenamed
aftertheiroriginator,GilbertNewtonLewis(18751946),formerProfessorofChemistryatthe
UniversityofCalifornia,Berkeley,USA.

TheConventions
Lewisstructuresaredrawnaccordingtothefollowingconventions:
1.Eachatomisrepresentedbyitselementalsymbol.Inthisrespect,aLewisstructureisan
extensionofthechemicalformula.
2.OnlythevalenceelectronsappearinaLewisstructure.Recallfromchapter4thatonlyvalence
electronsareaccessibleforbonding.
3.Alinejoiningtwoelementalsymbolsrepresentsonepairofelectronsthatissharedbetweentwo
atoms.Twoatomsmayshareuptothreepairsofelectronsinsinglebonds(2sharedelectrons,1
line),doublebonds(4sharedelectrons,2lines)andtriplebonds(6sharedelectrons,3lines).
4.Dotsplacednexttoanelementalsymbolrepresentnonbondingelectronsonthatatom.
Nonbondingelectronsusuallyoccurinpairswithopposingspins(seechapter4).

TheuseoftheseconventionsisshownfortheHFmoleculeinfigure5.11.

FIGURE5.11TheLewisstructureconventionsforhydrogenfluoride.

Theseconventionsdivideelectronsinmoleculesintothreegroups.Coreelectronsdonotappearin
Lewisstructures.Bondingvalenceelectronsaresharedbetweenatomsandappearaslines.Nonbonding
valenceelectronsarelocalisedonatomsandappearasdots.

WeuseafivestepproceduretodrawLewisstructures:
Step1:Countthevalenceelectrons.
Step2:Assemblethebondingframeworkusingsinglebonds.
Step3:PlacethreenonbondingpairsofelectronsoneachouteratomexceptH.(Note:Outeratoms
arethosethatarebondedtoonlyoneotheratom,whileinneratomsarethosebondedtomorethan
oneotheratom.)
Step4:Assigntheremainingvalenceelectronstoinneratoms.
Step5:Minimiseformalchargesonallatoms.

BuildingLewisStructures
LearninghowtodrawLewisstructuresisbestdonethroughexamples.Wewillworkthroughthefive
stepsusingthesulfurdioxidemolecule,SO2.

Step1:Countthevalenceelectrons.Ifthespeciesisanion,addorsubtractoneelectronforeach
negativeorpositivecharge,respectively.Sulfur(group16)hasthevalenceelectronconfiguration
3s23p 4,whiletheconfigurationofoxygen(alsogroup16)is2s22p 4.Hence,thereisatotalof(6+[2
6])=18valenceelectronsfromtheatomsthemselves.Themoleculeisuncharged,sothetotalnumber
ofvalenceelectronsis18.

Step2:Assemblethebondingframeworkusingsinglebonds.Thisstepisstraightforwardfororganic
molecules,whichconsistpredominantlyofCandHatoms,asthereisnoambiguityastothepossible
placementofatoms.However,caremustbetakenwhendrawingstructuresofinorganicmolecules.
Structureswillgenerallyconsistofaninner(central)atomconnectedtotwoormoreother(outer)atoms.
Theouteratomswillgenerallybeeitherhydrogen,orthemostelectronegativeoftheatomspresent,and
willbebondedonlytotheinneratom.Inthecaseofsulfurdioxide,oxygenisthemostelectronegative
elementpresent,sosulfurwillbetheinneratom.Thebondingframeworkwillthereforebeasfollows.

Aseachsinglebondintheframeworkconsistsoftwoelectrons,wehaveusedfouroftheoriginal18
valenceelectronssofar.

Step3:PlacethreenonbondingpairsofelectronsoneachouteratomexceptH.Withtheexceptionof
hydrogen,allouteratomsareassociatedwitheightelectrons(fourpairsinthevalencesandporbitals),
whichmaybebondingornonbonding.Suchasetoffourpairsofelectronsassociatedwithanatomis
oftencalledanoctet.

Thenonbondingpairsarecalledlonepairs.EachOatomisassociatedwiththreelonepairsandone
bondingpairandthereforehasacompleteoctet.Weused(26)=12electronsinthisstep.Combined
withthefourusedinthepreviousstep,thismeans16oftheoriginal18electronshavebeenused.

Step4:Assigntheremainingvalenceelectronstoinneratoms.Therearetworemainingvalence
electrons.TheseareplacedontheinnerSatomasalonepairasfollows.

WehavenowaccountedforallthevalenceelectronsofSO2.

Step5:Minimiseformalchargesonallatoms.Atthispoint,weneedtoanalysethestructureobtained
andcheckthatitmakeschemicalsense.Todothis,calculatetheformalchargeoneachatom,andthen
minimiseitbyadjustingtheelectrondistribution.Formalchargeisdefinedasthedifferencebetweenthe
numberofvalenceelectronsinthefreeatomandthenumberofelectronsassignedtothatatominthe
Lewisstructure.
Assumethatlonepairelectronsbelongtotheatomonwhichtheyarelocated,whileelectronsinbonds
aresharedequallybetweenthetwoatoms.Ausefulfeatureofformalchargesisthatthesumofthe
formalchargesonallatomsequalsthechargeofthespecies.Foraneutralmolecule,thesumofthe
formalchargesmustbezero.Foracationoranion,thesumoftheformalchargesequalsthechargeon
theion.

Theformalchargesoftheatomsinthestructureobtainedinstep4arecalculatedasfollows:

S Valenceelectronsoffreeatom 6
Lonepairelectrons 2
Sharedelectrons 4
Formalcharge

O Valenceelectronsoffreeatom 6
Lonepairelectrons 6
Sharedelectrons 2
Formalcharge

WecanminimisetheformalchargesbyconvertingalonepairofelectronsoneachOatomtoabonding
pair.Wecanrepresentthisprocessdiagrammaticallyasfollows.

Ifweanalysetheformalchargesontherighthandstructure,wefindthattheyareallzero.Therefore,
therighthandstructureisthebestLewisstructuralrepresentationoftheSO2molecule.

Inthisstructureeachoxygenatomissurroundedbyeightelectrons,andthereforehasanoctet,while
theinnersulfuratomissurroundedby10electrons.Wegenerallyfindoctetssurroundingatomsfrom
thesecondperiodoftheperiodictable,especiallyC,N,OandF,assuchatomscanaccommodatea
maximumofeightelectronsintheavailableorbitals.However,thelargeratomsfromthethirdand
subsequentperiodsoftenaccommodatemorethaneightelectrons,asobservedforthesulfuratom.This
isduetothefactthattheseatomshavemorethanfourorbitalsavailableforvalenceelectrons.

WORKEDEXAMPLE5.1

LewisStructureofClf3

Chlorinetrifluoride,ClF3,isusedtorecoveruraniumfromnuclearfuelrodsinahigh
temperaturereactionthatproducesgaseousuraniumhexafluoride.

DeterminetheLewisstructureofClF3.
Analysis

WefollowthefivestepsoutlinedpreviouslyfordrawingaLewisstructure.

Solution
1.Allfouratomsarehalogens(group17,ns2np 5),soClF has28valenceelectrons.
3
2.Chlorine,withlowerelectronegativitythanfluorine,istheinneratom.Makeasingle
bondtoeachofthethreefluorineatoms.

3.Addthreenonbondingpairstoeachfluorineatom.

4.Fourelectronsremainunassigned.Placetwoelectronpairsonthechlorineatom.

5.Determinetheformalchargesonalltheatomsandadjusttheelectrondistributionif
necessary.Inthiscase,eachatomhasaformalchargeofzero,andsonoredistribution
ofelectronsisrequired.

Isouranswerreasonable?

Step4resultsin10electronsaroundthechlorineatom.However,chlorineisathirdrow
elementandisthereforeabletoaccommodatemorethaneightelectrons.Wehavefollowed
therulesandobtainedthestructurewithformalchargesofzerooneveryatom,soouranswer
isreasonable.

PRACTICEEXERCISE5.1
DeterminetheLewisstructureofsulfur
tetrafluoride,SF4.

NotethatsomemoleculesandallionswillhavepreferredLewisstructuresinwhichtheformalcharges
arenotallzero.Inthesecases,ensurethatnegativeformalchargesaresituatedonthemostelectro
negativeatomsandpositiveformalchargesontheleastelectronegativeatoms(forexample,thenitrate
ioninfigure5.12,wherethemoreelectronegativeOatoms,ratherthantheNatom,haveanegative
formalcharge).Itisalsoimportanttorealisethatformalchargesarenotthesameasthepartialcharges
inducedasaresultofbondpolarity.Forexample,inClF3,thechlorineatomwouldhavea+charge,
despitethefactthatitsformalchargeiszero.
FIGURE5.12Therearethreepossiblewaystominimisetheformalchargesinthenitrateionanyofthethree
oxygenatomscansupplyapairofelectrons.

ResonanceStructures
Incompletingstep5oftheLewisstructureprocedure,theremightbemorethanonewaytominimise
theformalchargesontheatomsthatis,morethanoneLewisstructureispossibleforaparticular
moleculeorion.Thisisshownbelowwiththenitrateanion,NO3.

Theanionhas24valenceelectrons,andnitrogenistheinneratom.ThreeNObondsusesixelectrons,
andassigningsixelectronstoeachofthethreeouteroxygenatomsusestheremaining18electrons.
ThisgivesaLewisstructureinwhichtheOatomshaveformalchargesof1andtheNatomhasa
formalchargeof+2.Wecanminimisetheformalchargesbyconvertingthelonepairononeoxygen
atomtoabondingpair.However,asfigure5.12shows,alonepairfromanyofthethreeoxygenatoms
canbemovedtoformthisdoublebond.

WhichoftheseoptionsisthecorrectLewisstructure?Actually,nosingleLewisstructureisanaccurate
representationofNO3.AnysinglestructureoftheanionshowsnitratewithoneN Odoublebond
andtwoNOsinglebonds.Experiments,however,showthatallthreeNObondsareidentical(we
cannotformtwodoublebondssincenitrogencanaccommodateonlyeightelectronsinitsorbitals).To
showthatthenitrateNObondsareallalike,weuseacompositeofthethreeequivalentLewis
structures.Thesearethencalledresonancestructures.Resonancestructuresareconnectedbydouble
headedarrowstoemphasisethatacompletedepictionrequiresallofthem.

Itisessentialtorealisethatelectronsinthenitrateaniondonotflipbackandforthamongthethree
bonds,asimpliedbyseparatestructures.Noneofthesestructuresactuallyexist.Thetruecharacterof
theanionisablendofthethree,inwhichallthreenitrogenoxygenbondsareequivalent.Notealsothat
resonancestructuresdifferonlyinthepositionoftheelectronsyoucannotmoveatomswhendrawing
resonancestructures.Theneedtoshowseveralequivalentstructuresforspeciessuchasthenitrateion
reflectsthefactthatLewisstructuresareapproximaterepresentationsofstructureswithdelocalised
electrons.Whiletheyrevealmuchabouthowelectronsaredistributedinamoleculeorion,theycannot
describetheentirestoryofchemicalbonding.

WORKEDEXAMPLE5.2

ResonanceStructuresofanOxoanion

Determinethepossibleresonancestructuresofthephosphateanion,PO43.

Analysis

WemustfirstdeterminetheLewisstructurebyfollowingthefivestepprocedureoutlined
previously.Instep5,wedeterminethedifferentwayswecanminimisetheformalcharges
withintheion,therebyobtainingtheresonancestructures.

Solution

Wehave32electronstobeused(rememberthattheionhasa3charge).Followingtherules
outlinedpreviously,wearriveatthefollowingstructure,inwhichalltheelectronsareused
afterstep4.

Inthisstructure,theOatomsallhaveformalchargesof1,whilethePatomhasaformal
chargeof+1.Turningonelonepairfromanoxygenatomintoabondingpairmakesthe
formalchargeonthePatomzeroandalsomakestheformalchargeontheOatominvolved
equaltozero,therebyminimisingtheformalchargesintheion.Wecanshiftelectronsfrom
anyoftheouterOatoms,sotherearefourpossibleresonancestructuresasshownbelow.
(Notethatwehaveomittedthe3chargeoneachstructureforclarity.)

Isouranswerreasonable?
Therearefourpossiblewaystominimisetheformalcharges,sowemusthavefour
resonancestructures.Thefourstructuresdifferonlyinthepositionofadoublebond,and
thereforewecanbeconfidentthatouransweriscorrect.

PRACTICEEXERCISE5.2
DeterminetheLewisstructureoftheacetate
anion,CH3COO.

Intheexamplespresentedsofar,alltheresonancestructuresareequivalentinenergy,butresonance
structuresarenotalwaysequivalent.Resonancestructuresthatarenotequivalentoccurwhenstep5
requiresshiftingelectronsfromatomsofdifferentelements.Insuchcases,differentpossiblestructures
mayhavedifferentformalchargedistributions,andtheoptimalsetofresonancestructuresincludes
thoseformswiththelowestpossibleformalchargeoneachatom.

WORKEDEXAMPLE5.3

ResonanceStructuresofN2O

Determinethepossibleresonancestructuresofdinitrogenoxide,N2O,agasusedasan
anaesthetic,afoamingagentandapropellantforwhippedcream.

Analysis

Onceagain,wefirstdeterminetheLewisstructure,andtheninspectanypossibleresonance
structures.

Solution

WemustfirstchoosewhetherNorOwillbetheinneratom.AsOismoreelectronegative
thanN,thestructurewillhaveaninnerNatombondedtoanOatomandanotherNatom.
Thestructureweobtainfollowingthefirstfourstepsis:

Thisstructurehasformalchargesof2ontheouterNatom,+3ontheinnerNatomand1
ontheOatom.WecanconvertlonepairsontheendNatomortheOatomintobonding
pairstoreducetheformalcharges,butwemustensurethattheinnerNatomhasnomore
thanfourelectronpairs.Thisleavesuswiththefollowingpossibilities,inwhichthenumbers
denotetheformalcharges.
Theformalchargesofthefirsttwostructuresareidentical,andlessthanthoseonthethird
structure.Thus,theoptimalLewisstructureoftheN2Omoleculeisacompositeofthefirst
twostructures,whichareformallyinequivalent,butnotthethird.

Isouranswerreasonable?

Wehavechosenthetwostructuresinwhichtheformalchargesareminimised,andsoour
answershouldbecorrect.Infact,experimentalstudiesshowthatthenitrogenoxygenbond
inN2OissomewherebetweenanNOsingleandanN Odoublebond.

PRACTICEEXERCISE5.3
DeterminetheLewisstructureofozone,O3,
inwhichthethreeoxygenatomsarelinked
inarow.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.4ValenceshellelectronpairRepulsion(VSEPR)
Theory
TheLewisstructureofamoleculeshowshowthevalenceelectronsaredistributedamongtheatoms.Itdoes
not,however,showthethreedimensionalstructure,whichplaysanessentialroleindeterminingchemical
reactivity.However,wecanusetheLewisstructureasastartingpointtodeterminetheshapeofamolecule
orion.Thevalenceshellelectronpairrepulsion(VSEPR)theoryconsidersthatmolecularshapeis
determinedprimarilybytherepulsionsbetweenpairsofelectronsinthemoleculeormolecularion,bethey
bondingpairsorlonepairs.Therefore,tominimisetheserepulsions,electronpairsaroundaninneratom
withinamoleculewillbesituatedasfarapartaspossibleinthepreferredthreedimensionalstructure.

TodeterminetheshapeofamoleculeusingVSEPRtheory,weusethefollowingprocedure:
1.DetermineanddrawtheLewisstructureofthemolecule.
2.Countthenumberofsetsofbondingpairsandlonepairsofelectronsaroundanyinneratom,anduse
table5.2todeterminetheoptimumgeometryofthesesets.
NotethatVSEPRtheorymakesnodistinctionbetweenelectronpairsinsingle,doubleandtriple
bonds.Eachistreatedasbeingoneset.
TABLE5.2 Optimumgeometryofsetsofelectronpairs
Numberofsetsofelectronpairs Geometryofsetsofelectronpairs
2 linear
3 trigonalplanar
4 tetrahedral
5 trigonalbipyramidal
6 octahedral

3.Modifythegeometry,ifnecessary,totakeaccountofthefactthatthemagnitudesofrepulsions
betweensetsofelectronpairsdependonwhethertheelectronpairsinvolvedarebondingpairs(BP)or
lonepairs(LP).Therepulsionsareintheorder:

Therefore,twoneighbouringlonepairsonaninneratomwillrepeleachothertoagreaterextentthanwill
twoneighbouringbondingpairs.Thisisbecauselonepairsoccupyalargervolumethanbondingpairs.Note
thatdoublebondsoccupyalargervolumethansinglebonds,andsomestructuresmayhavetobemodified
forthis.

Itisimportanttomakethedistinctionbetweenthegeometryofthesetsofelectronpairs,andtheshapeof
themolecule.Theformerreferstothewayinwhichsetsofelectronpairsarearrangedaroundaninneratom
ofthemolecule,whilethelatterreferstothearrangementoftheatomsbondedtothatinneratom.Aswewill
see,whenlonepairsarepresent,thetwoarenotthesame.

WewillnowillustrateVSEPRusingexamplesofeachdifferentgeometryofsetsofelectronpairs.

TwoSetsofElectronPairs:LinearGeometry

BerylliumHydride,BeH2

TheLewisstructureofBeH2is:
Inthiscase,wehavetwosetsofelectronpairsaroundtheinneratomthatweneedtosituateasfaraway
fromeachotheraspossible.Thisissatisfiedbyplacingthetwosetsinalineararrangement(table5.2)and
resultsinalinearshapeforthismolecule,withaHBeHbondangleof180.Notethatwedonotadjust
theoptimumgeometryoftheelectronpairs,sincethereareonlytwosinglebondingpairsandnolonepairs.

CarbonDioxide,CO2

TheLewisstructureofCO2showsaninnerCatombondedtotwoouterOatoms.

ThisissimilartoBeH2becausewehavetwosetsofelectronpairsagain.Eventhougheachsetcomprisesthe
twoelectronpairsofadoublebond,theprincipleisstillthesame.Weplacethetwosetsasfarapartas
possible,i.e.inalineararrangement,andthisleadstoalinearshape.NoticethatthelonepairsontheO
atomsdonotaffecttheoverallshapeofthemoleculeonlysetsofelectronsthatareeitherbondedto,orlie
completelyon,aninneratomdeterminemolecularshape.

ThreeSetsofElectronPairs:TrigonalPlanarGeometry

BoronTrifluoride,BF3

TheLewisstructureofBF3showsaninnerBatomsinglybondedtothreeFatoms.Wehavethreesetsof
electronpairsabouttheinneratom.

Theoptimalgeometryforthreesetsofelectronpairsistrigonalplanar(table5.2).Inthisarrangement,the
setsareorientedat120toeachotherandarecoplanar.ThisleadstoatrigonalplanarshapefortheBF3
molecule,withallatomscoplanarandallFBFbondanglesof120.Notethat,again,asallthesetsof
electronpairsinvolvedareequivalent,wedonothavetoadjusttheiroptimalgeometry.

TheNitriteIon,NO2

Twopossibleresonancestructurescanbedrawnforthenitriteion,whichareasfollows.

Thisisthefirstexamplewehaveencounteredinwhichtheinneratombearsalonepair,andthishas
importantimplicationswhenapplyingVSEPRtheory.Notethatwecanchooseeitherresonancestructure
andendupwiththesameresult.Therearethreesetsofelectronpairs,twosetsofbondingpairsandalone
pair.Theidealisedgeometryistrigonalplanar.However,inthiscase,notalltherepulsionsbetweenthesets
ofelectronpairsarethesamethereareBPBPrepulsionsandBPLPrepulsions.TheBPLPrepulsionsare
stronger,whichmeansthatthetwobondingpairswillbepushedslightlyclosertogetherthananexact
trigonalplanararrangement.TheresultisthattheONObondangleisabout115,ratherthan120.This
examplealsoillustratesthedifferencebetweengeometryandshape.Thesetsofelectronpairshavean
approximatelytrigonalplanargeometry,butwewoulddescribetheshapeoftheNO2ionasbent,because
shaperefersonlytothepositionsoftheatomsandnottheelectrons.

FourSetsofElectronPairs:TetrahedralGeometry

Methane,CH4

TheLewisstructureofmethane,CH4,showsthatthemoleculecontainsfourCHsinglecovalentbonds,
andthereforefoursetsofequivalentelectronpairs.

Theoptimalgeometryforfoursetsofelectronpairsistetrahedral(table5.2).Thismeansthatthemethane
moleculeistetrahedralinshape,withHCHbondanglesof109.5,andtheHatomssituatedatthefour
verticesofatetrahedron.

Ammonia,NH3

TheLewisstructureofammonia,NH3,showsatotaloffoursetsofelectronpairs,threebondingpairsanda
lonepair.

Theidealisedarrangementoffoursetsofelectronpairsistetrahedral.ButwenowhaveBPBPandBPLP
repulsionstoconsider.ThesinglelonepairontheNatomtakesupmorespacethaneachofthethree
bondingpairs,andthisdistortstheidealisedarrangementsuchthattheHNHanglesinammoniaare
about107.Ammoniaadoptsatrigonalpyramidalshape,withtheNatomlyingoutoftheplaneofthethree
Hatoms.
Water,H2O

Likemethaneandammonia,waterhasfoursetsofelectronpairs,asshowninitsLewisstructure,andthe
idealisedarrangementisagaintetrahedral.

However,inthiscasewehavetwosetsofbondingpairsand,significantly,twolonepairs.TheLPLP
repulsiondominates,andtherearealsoBPLPrepulsionstoconsider.Theresultisthattheidealised
tetrahedralgeometryofthefoursetsofelectronpairsissignificantlydistorted,suchthattheHOHbond
angleinwaterisabout104.5.Wateradoptsabentshape.

Figure5.13showsthedifferentshapesofmethane,ammoniaandwater.Theimportanteffectoflonepairs
ontheshapesofthemoleculesisevidentinthesethreediagrams.

FIGURE5.13Representationsofthedifferentshapesofmethane,ammoniaandwatermolecules,eachwithfour
setsofelectronpairs.

WORKEDEXAMPLE5.4

ShapeoftheHydroniumIon

Determinetheshapeofthehydroniumion,H3O+,usingVSEPRtheory.Makeasketchoftheion
thatshowsthethreedimensionalshape,includinganylonepairsthatmaybepresent.

Analysis

Followthethreestepprocessdescribedpreviously.BeginwiththeLewisstructure,andthenuse
thistodeterminethenumberofsetsofelectronpairsandthereforethegeometryofthese.Finally,
takeintoaccountanylonepairstodeducethemolecularshape.

Solution
1.DeterminetheLewisstructure.Ahydroniumionhaseightvalenceelectrons.Sixareused
tomakethreeOHsinglebonds,andtwoareplacedasalonepairontheoxygenatom.
2.Therearefoursetsofelectronpairs,threebondingpairsandonelonepair.Theidealised
geometryisthereforetetrahedral.
3.Thepresenceofalonepairmeansthattheidealisedtetrahedralgeometryofthesetsof
electronpairswillbedistorted,owingtoLPBPrepulsions.Wewouldthereforeexpectthe
HOHbondanglestobesomewhatlessthanthe109.5.Theshapeofthehydronium
ionistrigonalpyramidal,asoutlinedinthefollowingdiagram.

Isouranswerreasonable?

Thehydroniumionhasthesamenumberofelectronsandatomsastheammoniamolecule,soit
isreasonableforthesespeciestohaveasimilarshape.

PRACTICEEXERCISE5.4
Determinetheshapeofchloromethane,CH3Cl.
Makeasketchofthemoleculethatshowsits
threedimensionalshape.

FiveSetsofElectronPairs:TrigonalBipyramidalGeometry

PhosphorusPentachloride,Pcl5

TheLewisstructureofPCl5showsfivesetsofequivalentelectronpairsaroundaphosphorusatom.

Thegeometrywhichplacestheseasfarapartaspossibleistrigonalbipyramidal(table5.2).Atrigonal
bipyramidissocalledbecauseitcanbeviewedastwopyramidsthatshareatriangularbase,asshownin
figure5.14a.Incontrasttothegeometriesencounteredsofar,thefivepositionsinatrigonalbipyramidare
notallequivalent.Threepositionslieatthecornersofanequilateraltrianglearoundtheinneratom,
separatedby120bondangles.Atomsinthetrigonalplaneareinequatorialpositions.Theothertwo
positionsliealonganaxisaboveandbelowthetrigonalplane,separatedfromequatorialpositionsby90
bondangles.Atomsinthesesitesareinaxialpositions.Thesedifferencesareoutlinedinfigure5.14b.
FIGURE5.14 (a)Modelrepresentingtheequatorialplaneandopposingpyramidsthatmakeupatrigonal
bipyramid.PCl5 adoptsaregulartrigonalbipyramidalshape.
(b)Ballandstickmodelrepresentingatrigonalbipyramidwithaxialandequatorialsites
labelled.

AsPCl5containsonlybondingpairsofelectrons,wewouldexpectittoadoptaregulartrigonalbipyramidal
shape,asshowninfigure5.14.

Whenlonepairsarepresentinmoleculeswithfivesetsofelectronpairs,theconsequencesofthe
inequivalenceoftheaxialandequatorialsitesbecomemoreapparent.WewillillustratethiswithSF4.

SulfurTetrafluoride,SF4

TheLewisstructureofSF4(figure5.15)showsfourSFbondsandonelonepairofelectronsonthesulfur
atom.Wewouldexpectatrigonalbipyramidalgeometryforthesefivesetsofelectronpairs,butthe
presenceofthelonepairmeanstherewillbesomeslightdistortion.

FIGURE5.15 Viewsofsulfurtetrafluoride:
(a)Lewisstructure
(b)ballandstickmodelofthetrigonalpyramidand
(c)ballandstickmodelshowingtheseesawform.

Inaddition,becausetheequatorialandaxialpositionsofatrigonalbipyramiddiffer,wecandrawtwo
possiblestructuresforSF4withthelonepairineitheraxialorequatorialposition.Asfigure5.15shows,
placingthelonepairinanaxialpositiongivesatrigonalpyramidalshape,whereasplacingthelonepairin
anequatorialpositiongivesaseesawshape.

ExperimentsshowthatSF4hastheseesawshape,whichmeansthatthisismorestablethanthetrigonal
pyramid.ThiscanbeexplainedbynotingthatthetrigonalpyramidstructurehasthreeLPBPrepulsionsat
90,whiletheseesawhastwoat90andtwoat120.Minimisingthenumberoflowestanglerepulsive
interactionsinvolvinglonepairsgivesthelowestenergystructureandconsequentlytheseesawshapeis
preferred.Notethat,becauseoftheLPBPrepulsionsbetweenthelonepairandtheaxialbondpairs,the
axialFSFbondangleisslightlylessthan180.

Chlorinetrifluoride,ClF3

TheLewisstructureofClF3showsfivesetsofelectronpairs:threebondingpairsandtwolonepairs.

Weagainexpectadistortedtrigonalbipyramidalgeometryofthefivesetsofelectronpairs,butnowwe
mustdeterminewhetherthetwolonepairsoccupyaxialorequatorialpositions.

Wecanimmediatelydiscountplacingonelonepairaxialandtheotherequatorial,asthiswouldleadtoa
LPLPrepulsion,thelargestpossible,at90.Youmightimaginethatplacingthelonepairsintheaxial
positionswouldbepreferred,asitplacesthemfurthestaway,butitalsoleadstoatotalofsixLPBP
repulsionsat90.Infact,experimentsshowthatthetwolonepairsareequatorialthisleadstofourLPBP
repulsionsat90andisenergeticallypreferred,despitethefactthatthereisaLPLPrepulsionat120.Thus,
ClF3isTshapedwithtwoequatoriallonepairs.

ItissometimesdifficulttodeterminewhichofthepossiblestructuresiscorrectusingsimpleVSEPRtheory,
andwemustthenresorttoexperimentalresultsfordefinitiveanswers.

TheTriiodideIon,I3

TheLewisstructureshowsfivesetsofelectronpairsaroundtheinnerIatom:twobondingandthreelone
pairs.

Wehaveseeninthepreviousexamplesthatlonepairsprefertobeinequatorialpositionsintrigonal
bipyramidalgeometries,andthesameprincipleapplieshere.Allthreelonepairsareequatorial,asthisisthe
onlywaytoavoidanyhighlydestabilisingLPLPrepulsionsat90.
Figure5.16summarisesthedifferentpossibleshapesofspecieswithfivesetsofelectronpairs.

FIGURE5.16Thedifferentpossibleshapesofspecieswithfivesetsofelectronpairs.

SixSetsofElectronPairs:OctahedralGeometry

SulfurHexafluoride,SF6

TheLewisstructureofSF6,showninfigure5.17a,indicatesthatsulfurhassixSFbondsandnolone
pairs,andthereforehassixsetsofelectronpairsaroundtheinnerSatom.Anoctahedralgeometryofthesix
sets(table5.2)placesthemasfarapartaspossible,asshowninfigure5.17b.Thisgivesanoctahedral
shapeeachFatomliesatoneofthesixverticesofanoctahedron,withpossibleFSFbondanglesof
90and180.Anoctahedronissocalledbecauseithaseighttriangularfaces,asshowninfigure5.17c.

FIGURE5.17 Viewsofsulfurhexafluoride:
(a)Lewisstructure
(b)ballandstickmodeland
(c)ballandstickmodelshowingthetriangularfacesoftheoctahedron.
Allsixpositionsaroundanoctahedronareequivalent,asfigure5.18demonstrates.Replacingonefluorine
atominSF6withachlorineatomgivesSF5Cl.Nomatterwhichfluorineisreplaced,theSF5Clmoleculehas
fourfluorineatomsinasquare,withthefifthfluorineandthechlorineatomonoppositesides,atright
anglestotheplaneofthesquare.

FIGURE5.18ReplacinganyofthefluorineatomsofSF6 withachlorineatomgivesamoleculewithasquareof
fluorineatomscappedbyonefluorineandonechlorine.Thisshowsthatallsixpositionsofthe
octahedronareequivalent.

ChlorinePentafluoride,ClF5

TheLewisstructureofClF5showsatotalofsixsetsofelectronpairs:fivebondingpairsandonelonepair.

Weagainexpectanoctahedralgeometryofthesixsetsofelectronpairs,and,inthiscase,allsixpossible
positionsofthelonepairareequivalent.Therefore,ClF5adoptsasquarepyramidalshape.

XenonTetrafluoride,XeF4

TheLewisstructureofthismoleculeshowssixsetsofelectronpairs:fourbondingpairsandtwolonepairs.
Wethereforeexpectanoctahedralgeometryofthesetsofelectronpairs,but,asalways,wemustdetermine
howtoarrangethelonepairs.InXeF4,bothlonepairsmustbeoppositeeachtotherbecauseanyother
arrangementwouldleadtohighlydestabilisingLPLPrepulsionsat90.Thisleavesthefourfluorineatoms
inasquareplanearoundxenon.

Figure5.19summarisestheshapesofmoleculeswithsixsetsofelectronpairs.Thiscompletesourinventory
ofmolecularshapes.

FIGURE5.19Thedifferentpossibleshapesofsomemoleculeswithsixsetsofelectronpairs.

ThemostcommonmistakemadewhendeterminingamolecularshapeusingVSEPRtheoryistocountthe
numberofatomssurroundinganinneratom,ratherthanthenumberofsetsofelectronpairs.Forexample,a
moleculesuchasSF4maybeeasilymistakenastetrahedral,byanalogywithtetrahedralCH4,asboth
moleculeshavefourouteratomssurroundinganinneratom.However,wehaveshownpreviouslythatSF4
hasfivesetsofelectronpairsanditsshapeisbasedonatrigonalbipyramidalarrangementofthese.While
VSEPRtheoryoftengivesremarkablyaccurateresults,itdoesnotnecessarilyworkforallmolecules.In
caseswhererepulsionbetweentheelectronpairsisnotthedominantfactorindeterminingmolecular
geometry,VSEPRtheoryfails.Youwillencountersomeexamplesofthisinchapter13.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.5PropertiesofCovalentBonds
HavingdevelopedideasaboutLewisstructuresandshapesofmolecules,wecannowexploresomeofthe
importantfeaturesofcovalentbonds.Thesefeaturesproviderevealinginformationaboutmolecular
shapes.

DipoleMoments
Asdescribedinsection5.1,mostchemicalbondsarepolar,meaningthatoneendofthebondisslightly
negative,andtheotherisslightlypositive.Bondpolaritiescanleadtomoleculeswithnegativeendsand
positiveends.Amoleculewiththistypeofelectrondensitydistributionissaidtohaveadipolemoment,
(thelowercaseGreeklettermu).

Thedipolemomentofapolarmoleculecanbemeasuredbyplacingasampleinanelectricfield.For
example,figure5.20showsaschematicdiagramofhydrogenfluoride,HF,moleculesbetweenapairof
metalplates.Intheabsenceofanappliedfield,themoleculesareorientedrandomlythroughoutthe
volumeofthedevice.Whenanelectricpotentialisappliedacrosstheplates,theHFmoleculesalign
spontaneouslyaccordingtotheprinciplesofelectrostaticforce.Thepositiveendsofthemolecules(the
hydrogenatoms)pointtowardsthenegativeplate,andthenegativeends(thefluorineatoms)point
towardsthepositiveplate.Theextentofalignmentdependsonthemagnitudeofthedipolemoment.The
SIunitforthedipolemomentisthecoulombmetre(Cm).Bonddipolemomentsspantherangefrom0to
about710 30Cm.Hydrogenfluoridehas=5.9510 30Cm,whileanonpolarmoleculelikeF2has
nodipolemoment,=0Cm.Experimentalvaluesarealsooftenreportedinunitsofdebyes,D(1D=
3.3410 30Cm).

FIGURE5.20AnappliedelectricfieldcausesanalignmentofpolarHFmolecules.Theextentofalignment
dependsonthemagnitudeofthedipolemoment.

Dipolemomentsdependonbondpolarities.Forexample,thetrendindipolemomentsforthehydrogen
halidesfollowsthetrendinelectronegativitydifferencesthemorepolarthebond(indicatedbythe
differenceinelectronegativity,,thelargerthedipolemoment,.
Dipolemomentsalsodependonmolecularshape.Anydiatomicmoleculecomposedofatomswith
differentelectronegativitieshasadipolemoment.Formorecomplexmolecules,wemustevaluatedipole
momentsusingbothbondpolarityandmolecularshape.Amoleculewithpolarbondswillhavenodipole
momentifitsshapecausesthedipolemomentsofindividualbondstocanceloneanother,whichismore
likelyforsmallsymmetricalmolecules.

Figure5.21illustratesthedramaticeffectofshapeonthedipolemomentsoftriatomicmolecules.Recall
fromsection5.1thatanarrowcanbeusedtorepresentadipolemoment.Theheadofthearrowpointsto
thepartialpositiveend(+)ofthepolarbond.Figure5.21ashowsthat,althoughbothbondsinlinearCO2
arepolar(=1.0),thetwoarrowsindicatingindividualbondpolaritiespointinexactlyopposite
directions.Thus,theeffectofonepolarbondexactlycancelstheeffectoftheother.ForbentH2O,in
contrast,figure5.21bshowsthattheeffectsofthetwopolarbondsdonotcancel.Waterhasapartial
negativechargeonitsoxygenatomandpartialpositivechargesonitshydrogenatoms.Theresulting
dipolemomentofthemoleculeis=6.1810 30Cm,withthedirectionofthedipolemomentshownby
thecolouredarrowinfigure5.21b.

FIGURE5.21 (a)Whenidenticalpolarbondspointinoppositedirections,asinCO2 ,theirpolarityeffects


cancel,givingzeronetdipolemoment.
(b)Whentwoidenticalpolarbondsdonotpointinexactlyoppositedirections,asinH2 O,
thereisanetdipolemoment.

Moleculescontainingpolarbondswhosedipolemomentscanceleachotherdonothaveoveralldipole
moments.Suchmoleculestendtohavehighlysymmetricalgeometries.Phosphoruspentachloride,for
example,has=0Cm.ThetwoaxialPClbondspointinoppositedirections,and,althoughthreeP
Clbondsarrangedinatrigonalplanehavenocounterpartspointinginoppositedirections,trigonometric
analysisshowsthatthepolareffectsofthreeidenticalbondsinatrigonalplanecancelexactly.Likewise,
thebondsinatetrahedronarearrangedsothattheirpolaritiescancelexactlyi.e.thetetrahedralmolecule
CCl4hasnodipolemoment.

Theperfectsymmetryofthesegeometricformsisdisruptedwhenalonepairreplacesabond,givinga
moleculewithadipolemoment.ExamplesincludeSF4(seesaw),ClF3(Tshape),NH3(trigonalpyramid)
andH2O(bent),allofwhichhavedipolemoments.Replacingoneormorebondswithabondtoa
differentkindofatomalsointroducesadipolemomentbecausethesymmetryislowered.Thus,
chloroform,CHCl3,hasadipolemomentbutCCl4doesnot.Thecarbonatomofchloroformhasfour
bondsinanearregulartetrahedron,butthefourbondsarenotidentical.TheCClbondsaremorepolar
thantheCHbond,sothepolaritiesofthefourbondsdonotcancel.Figure5.22showsthemagnitude
anddirectionofthedipolemomentinchloroform(=3.4710 30Cm).

FIGURE5.22Carbontetrachloride,CCl4 ,isasymmetricaltetrahedralmolecule,sotheindividualbond
polaritiescancel.Chloroform,CHCl3 ,isalsoatetrahedralmolecule,butthefourbondsarenot
identical,sothebondpolaritiesdonotcancel.

InasymmetricaloctahedralsystemsuchasSF6,eachpolarSFbondhasacounterpartpointinginthe
oppositedirection.Thebondpolaritiescancelinpairs,leavingthismoleculewithoutadipolemoment.

WORKEDEXAMPLE5.5

PredictingDipoleMoments
DoeseitherClF5orXeF4haveadipolemoment?

Analysis

Moleculescomposedofatomswithdifferentelectronegativitieshavedipolemomentsunless
theirsymmetriesaresufficienttocanceltheirbondpolarities.Therefore,wemustexamineeach
molecularstructureandtheorientationofthebondsineachmolecule.

Solution

Themolecularstructuresofchlorinepentafluorideandxenontetrafluorideareshowninfigure
5.19.Eachhassixsetsofelectronpairsaroundaninneratom,buttheseincludelonepairs.As
aresult,ClF5hasasquarepyramidalshape,whereasXeF4hasasquareplanarshape.Pictures
canhelpusdeterminewhetherornotthebondpolaritiescancel.
Eachmoleculehasfourfluorineatomsatthecornersofasquare.TheXeFbondpolarities
cancelinpairs,leavingXeF4withoutadipolemoment.Fourbondpolaritiesalsocancelin
ClF5,butthefifthClFbondhasnocounterpartintheopposingdirection,soClF5hasa
dipolemomentthatpointsalongtheaxiscontainingthelonepairandthefifthClFbond.

Isouranswerreasonable?

Anymoleculeinwhichindividualdipolemomentsdonotcancelwillhaveanoveralldipole
moment.ItisthereforereasonablethatXeF4willhavenodipolemomentwhiletheless
symmetricClF5moleculewill.

PRACTICEEXERCISE5.5
Determinewhetherethane,C2H6,and
ethanol,C2H5OH,havedipolemoments.

BondLength
Aswedescribedinsection5.1,thebondlengthofacovalentbondisthenuclearseparationdistanceat
whichthemoleculeismoststable.TheHHbondlengthinmolecularhydrogenis74pm.Atthis
distance,attractiveinteractionsaremaximisedrelativetorepulsiveinteractions(seefigure5.2).Having
developedideasaboutLewisstructuresandmolecularshapes,wecannowexaminebondlengthsinmore
detail.

Table5.3listsaveragebondlengthsforthemostcommonchemicalbonds.Thetabledisplaysseveral
trends.Onetrendisthatbondsbecomelongerasatomsizeincreases,asshownbybondlengthsofthe
diatomichalogens.

TABLE5.3 Averagebondlengths(allvaluesareinpicometres,1pm=1012 m)

na(a) nb(a) Bondlengths


HXbonds
1 1 HH 74
1 2 HC 109 HN 101 HO 96 HF 92
1 3 HSi 148 HP 144 HS 134 HCl 127
1 4 HBr 141
Secondrowelements
2 2 CC 154 CN 147 CO 143 CF 135
2 2 NN 145 OO 148 FF 142
2 3 CSi 185 CP 184 CS 182 CCl 177
2 3 OSi 166 OP 163 OS 158 NCl 175
2 3 FSi 157 FP 157 FS 156
2 4,5 FXe 190 CBr 194 CI 214
Largerelements
3 3 SiSi 235 PP 221 SS 205 ClCl 199
3 3 SiCl 202 PCl 203 SCl 207
4 4 BrBr 228
5 5 II 267
Multiplebonds
C C 133 C N 138 C O 120 O O 121
P O 150 S O 143
C C 120 C N 116 C O 113 N N 110

(a)n a istheprincipalquantumnumberforthefirstnamedatomandistheprincipalquantum
numberforthefirstnamedatomandn bisforthesecondatom.isforthesecondatom.

Thetrendisconsistentwithourintroductiontoorbitaloverlap.Recallthatbondinginvolvesvalence
orbitals,anditistheoccupiedvalenceorbitalsthatdeterminethesizeofanatom.

Bondpolarityalsocontributestobondlengthbecausepartialchargesgenerateelectrostaticattractionthat
pullstheatomsclosertogether.Forexample,noticeinTable5.3thatCNbondsareslightlyshorterthan
theaverageofCCandNNbonds.ThisisaresultofthepolarityoftheCNbond.

ThebondlengthsinTable5.3showonefinalfeature:amultiplebondisshorterthanthesinglebond
betweenthesametwoatoms.Thisisbecauseplacingadditionalelectronsbetweenatomsdecreases
internuclearrepulsion,leadingtoanincreaseinnetattraction,therebyallowingtheatomstocomecloser
together.Thus,triplebondsaretheshortestofallbondsamongsecondrowelements.

Becausebondlengthsdependonthenumberofelectronsinvolvedinthebond,wecanusebondlengths
todecidewhichLewisstructurebestrepresentstheactualelectrondistributioninamolecule.Sulfur
oxygenbondsprovideagoodexample.Figure5.23showstwopossiblesetsofLewisstructuresfor
speciesthatcontainsulfuroxygenbonds.Oneset,theunoptimisedstructures,placesoctetsofelectrons
ontheinnersulfuratom,whiletheotherset,theoptimisedstructures,reducestheformalchargeonsulfur
tozeroattheexpenseofexceedingtheoctetontheSatom.Asthefigureshows,thetwosetsofstructures
predictdifferentbondtypes.
FIGURE5.23Unoptimisedstructuresandoptimisedstructurespredictdifferentbondtypesforsulfuroxygen
bonds.

WecanuseexperimentalbondlengthvaluestosupporttheoptimisedLewisstructures.Insulfuricacid,
therearetwodistinctlydifferentbondtypeswithbondlengthsof157pmand142pm.Inthesulfate
anion,allthebondlengthsare147pm,whilethebondlengthsinSO2andSO3are143pmand142pm,
respectively.Thesevaluesindicatethatabondlengthof157pmisconsistentwithanSOsinglebond,
and142pmwithanS Odoublebond.Abondlengthof147pmindicatesanintermediatebond
character(seeTable5.3).ThesevaluessupporttheoptimisedLewisstructures,asshowninfigure5.22,
whichpredictdoublebondsonlyforSO2andSO3,doubleandsinglebondsforH2SO4andintermediate
bondsforSO42.

Tosummarise,generallythefollowingfactorsinfluencebondlengths:
1.Foragivenpairofatoms,themoreelectronsinthebondbetweenthem,theshorterthebond.
2.Fortwoatomsjoinedbythesametypeofbond(single,doubleortriple),thelargerthe
electronegativitydifferencebetweenthebondedatoms,theshorterthebond.

WORKEDEXAMPLE5.6

BondLengths
Whatfactoraccountsforeachofthefollowingdifferencesinbondlength?
(a)I2hasalongerbondthanBr2.
(b)CNbondsareshorterthanCCbonds.
(c)HCbondsareshorterthantheC Obond.
(d)Thecarbonoxygenbondinformaldehyde,H2C O,islongerthanthebondincarbon
monoxide,C O.

Analysis

Bondlengthsarecontrolledbythreefactors,someofwhicharemoreinfluentialthanothers.
Toexplainadifferenceinbondlength,weneedtodeterminethewaythatthefactorsare
balanced.

Solution
(a)II>BrBr.Iodineisjustbelowbromineintheperiodictable,sothevalenceorbitals
ofiodinearelargerthanthevalenceorbitalsofbromine.Thus,theI2bondislonger
thantheBr2bondbecauseiodinehasalargeratomicradius.
(b)CN<CC.Carbonandnitrogenarebothsecondrowelements.However,nitrogen
hasahighereffectivenuclearchargethancarbon,sonitrogenhasthesmallerradius.
ThismakesCNbondsshorterthanCCbonds.Inaddition,aCNbondispolar,
whichcontributestotheshorteningoftheCNbond.
(c)HC<C O.Here,wearecomparingbondsinwhichtheatomicradiiandthe
amountofmultiplebondinginfluencebondlength.TheexperimentalfactthatHC
bondsareshorterthanthetripleC Obondindicatesthatthesizeofthehydrogen
orbitalisamoreimportantfactorthanthepresenceofmultiplebondinginthiscase.
(d)C O>C O.Bothbondsarebetweencarbonandoxygen,son(theprincipal
quantumnumber,whichdeterminessize),atomicnumber(Z)andelectronegativity
difference()arethesame.However,carbonmonoxidecontainsatriplebond,
whereasformaldehydehasadoublebond.ThetriplebondinCOisshorterthanthe
doublebondinH2CObecausemoresharedelectronsmeansashorterbond.

Isouranswerreasonable?

Whenfactorsworkinthesamedirection(effectivenuclearchargeandbondpolarityinthe
caseofCN<CC),wecanmakeconfidentpredictions.Whenfactorsworkintheopposite
direction(nvalueandbondmultiplicityinthecaseofHC<C O),wecanexplainthe
observedvaluesbutcannotconfidentlypredictthem.

PRACTICEEXERCISE5.6
Whatfactoraccountsforeachofthe
followingdifferencesinbondlength?(a)The
C CbondislongerthantheC Cbond.
(b)TheCClbondisshorterthantheSiCl
bond.(c)TheCCbondislongerthantheO
Obond.

BondEnergy
Bondenergiesaredefinedastheamountofenergythatmustbesuppliedtobreakaparticularchemical
bond.Bondenergies,likebondlengths,varyinwaysthatcanbetracedtoatomicproperties,andthere
arethreeconsistenttrendsinbondenergies:
1.Bondenergiesincreaseasmoreelectronsaresharedbetweentheatoms.Sharedelectronsarethe
glueofchemicalbonding,sosharingmoreelectronsstrengthensthebond.
2.Bondenergiesincreaseastheelectronegativitydifference()betweenbondedatomsincreases.
Polarbondsgainstabilityfromtheelectrostaticattractionbetweenthenegativeandpositivepartial
chargesaroundthebondedatoms.Bondsbetweenoxygenandothersecondperiodelements
exemplifythistrend(notethatthebondlengthsalsochangeslightly).

Bond Differenceinelectronegativity() Bondenergy(kJmol1)


OO 0.0 145
ON 0.5 200
OC 1.0 360

3.Bondenergiesdecreaseasbondsbecomelonger.Asatomsbecomelarger,theelectrondensityofa
bondisspreadoverawiderregion.Thisdecreasesthenetattractionbetweentheelectronsandthe
nuclei.Thefollowingtableofbondenergiesillustratesthiseffect(notethattheelectronegativity
differencealsochanges,strengtheningthetrend).

Bond Bondlength(pm) Bondenergy(kJmol1)


HF 92 565
HCl 127 430
HBr 141 360
HI 161 295

Likebondlengths,bondenergiesresultfromtheinterplayofseveralfactors,includingeffectivenuclear
charge,principalquantumnumber,electrostaticforcesandelectronegativity.Thus,itisnotsurprisingthat
therearenumerousexceptionstothesethreetrendsinbondenergiesas,inmostcases,morethanoneof
thedeterminingfactorschangesatthesametime(seetablesabove)andoftennotwiththesameinfluence
onbondenergies.Althoughitispossibletoexplainmanydifferencesinbondenergy,itfrequentlyisnot
possibletopredictdifferenceswithconfidence.t

SummaryofMolecularShapes
Table5.4summarisestherelationshipsbetweennumberofsetsofelectronpairs,thegeometryofthesets
ofelectronpairsandmolecularshape.Ifyourememberthegeometryassociatedwitheachnumberofsets
ofelectronpairs,youcandeducemolecularshapes,bondanglesandtheexistenceofdipolemoments.
TABLE5.4 Featuresofmoleculargeometries
Number
ofsets Geometry
of Number ofsetsof
electron ofouter Lone electron Molecular Bond Dipole
pairs atoms pairs pairs shape angles moment(a) Example
2 2 0 linear linear 180 no

CO2

3 3 0 trigonal trigonal 120 no


planar planar

BF3

2 1 trigonal bent <120 yes


planar

NO2(plusother
resonance
structures)
4 4 0 tetrahedral tetrahedral 109.5 no

CH4

3 1 tetrahedral trigonal <109.5 yes


pyramidal

NH3

2 2 tetrahedral bent <109.5 yes

H2O
5 5 0 trigonal trigonal 90, no
bipyramidal bipyramidal 120

PCl5
4 1 trigonal seesaw <90, yes
bipyramidal <120

SF4
3 2 trigonal Tshaped <90, yes
bipyramidal <120

ClF3
2 3 trigonal linear 180 no
bipyramidal
I3

6 6 0 octahedral octahedral 90 no

SF6
5 1 octahedral square <90 yes
pyramidal

ClF5

4 2 octahedral square 90 no
planar
XeF4

(a)Appliesonlytomoleculeswithidenticalouteratoms.

Thisrelativelysmallcatalogueofmolecularshapesaccountsforaremarkablenumberofmolecules.Even
complicatedmoleculessuchasproteinsandotherpolymershaveshapesthatcanbetracedbacktothese
relativelysimpletemplates.Theoverallshapeofalargemoleculeisacompositeoftheshapesassociated
withitsinneratoms,withtheshapearoundeachinneratomdeterminedbythenumberofsetsof
surroundingbondingelectronpairsandthenumberoflonepairs.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.6ValenceBondTheory
Lewisstructuresareblueprintsthatshowthedistributionofvalenceelectronsinmolecules.However,the
dotsandlinesofaLewisstructuredonotshowhowbondsform,howmoleculesreactortheshapeofa
molecule.Inthisrespect,aLewisstructureisliketheelectronconfigurationofanatombothtellusabout
electrondistributions,butneitherprovidesdetaileddescriptions.Justasweneedatomicorbitalsto
understandhowelectronsaredistributedinanatom,weneedanorbitalviewtounderstandhowelectrons
aredistributedinamolecule.

Intheremainderofthischapterwedescribetwowaystothinkaboutcovalentbonding:valencebond
theory,whichuseslocalisedbonds,andmolecularorbitaltheory,whichusesdelocalisedbonds.The
valencebondapproachtomoleculesassumesthatelectronsareeitherlocalisedinbondsbetweentwoatoms
orlocalisedonasingleatom,usuallyinpairs.Accordingly,thelocalisedbondingmodeldevelopsorbitals
oftwotypes.Onetypeisabondingorbitalthathashighelectrondensitybetweentwoatoms.Theothertype
isanorbitallocatedonasingleatom.Inotherwords,anyelectronisrestrictedtotheregionaroundasingle
atom,eitherinabondtoanotheratomorinanonbondingorbital.

Localisedbondsareeasytoapply,eventoverycomplexmolecules,andtheydoanexcellentjobof
explainingmuchchemicalbehaviour.Inmanyinstances,however,localisedbondsareinsufficientto
explainmolecularpropertiesandchemicalreactivity.Wethereforealsoshowhowtoconstructdelocalised
bondsthatspreadoverseveralatomsusingmolecularorbitaltheory.Delocalisationrequiresamore
complicatedanalysis,butitexplainschemicalpropertiesthatlocalisedbondscannot.

OrbitalOverlap
Asdescribedearlierinthischapter,theelectronsinahydrogenmoleculearelocatedbetweenthetwonuclei
inawaythatmaximiseselectronnucleusattraction.Tounderstandchemicalbonding,wemustdevelopa
neworbitalmodelthataccountsforsharedelectrons.Inotherwords,weneedtodevelopasetofbonding
orbitals.

Themodelofbondingusedbymostchemistsisanextensionoftheatomictheorythatincorporatesa
numberofimportantideasfromchapters1and4.Bondingorbitalsarecreatedbycombiningatomic
orbitals.Rememberthatorbitalshavewavelikeproperties.Wavesinteract,resultinginadditionoftheir
amplitudes.Twowavesthatoccupythesameregionofspacewillbesuperimposed,generatinganewwave
thatisacompositeoftheoriginalwaves.Inregionswheretheamplitudesofthesuperimposedwaveshave
thesamephase,additionoftheamplitudesofthewavesleadstoconstructiveoverlap.Thisgivesanew
waveamplitudethatislargerthaneitheroriginalwaveinthatregion,asfigure5.24ashows.Inregions
wheretheamplitudeshaveoppositephases,additionoftheamplitudesofthewavesleadstodestructive
overlap,givinganewwaveamplitudethatissmallerthaneitheroftheoriginalwaves,asillustratedinfigure
5.24b.
FIGURE5.24 (a)Whentwowaves(dashedlines)haveamplitudesofthesamephase,additiongivesanew
wave(solidline)withalargeamplitudeintheoverlapregion.
(b)Whentwowaves(dashedlines)haveamplitudesofoppositephases,additiongivesanew
wave(solidline)withasmallamplitudeintheoverlapregion.

Becauseelectronshavewavelikeproperties,orbitalinteractionsinvolvesimilaradditionorsubtractionof
wavefunctions.Whentwoorbitalsofthesamephasearesuperimposed,theresultisaneworbitalthatisa
compositeoftheoriginals,asshownformolecularhydrogeninfigure5.25.Thisinteractioniscalledorbital
overlap,andisthefoundationofthebondingmodelswewilldescribe.

FIGURE5.25Astwohydrogenatomsapproacheachother,theoverlapoftheir1satomicorbitalsincreases.The
waveamplitudesaddtogenerateaneworbitalwithhighelectrondensitybetweenthenuclei.

ConventionsoftheOrbitalOverlapModel
Orbitaloverlapmodelsproceedfromthefollowingassumptions:
1.Eachelectroninamoleculeisassignedtoaspecificorbital.
2.NotwoelectronsinamoleculehaveidenticaldescriptionsbecausethePauliexclusionprinciple
(chapter4)appliestoelectronsinmoleculesaswellasinatoms.
3.TheelectronsinmoleculesobeytheAufbauprinciple(chapter4),meaningthat,inthegroundstate,
theyoccupythelowestenergyorbitalsavailabletothem.
4.Onlythevalenceorbitalsareneededtodescribebonding.

Bondinginvolvesthevalenceorbitalsexclusivelyinthismodel,becausetheseorbitalshavetheappropriate
sizesandenergiestointeractstrongly.Wehavealreadyseenexamplesoftheoverlapofvalenceatomic
orbitalsintheH2andF2moleculesearlierinthischapter,andthissimpleapproachisperfectlyadequatefor
thesesmalldiatomicmolecules.Thereare,however,instanceswherethissimplemodeldoesnotreproduce
theexperimentallydeterminedstructuresofcertainmolecules.Forexample,ifweconsiderthebondingina
watermoleculetoarisefromoverlapofthevalenceatomicorbitalsonOandH,wefindthatwecannot
reproducethe104.5HOHbondangle.Thetwosinglyoccupiedporbitalsonoxygenlieat90toeach
other,andoverlapofthesewiththeH1sorbitalsshouldgiveabondangleof90.
Valencebondtheoryrecognisesthisproblem,andattemptstosolveitbyconstructinghybridorbitalsfrom
valenceatomicorbitals.Thisapproachgivesmuchbetteragreementwithexperiments,andisoutlinedin
detailonthefollowingpages,withparticularemphasisonthetetrahedralmoleculemethane.

HybridisationofAtomicOrbitals
Theexperimentallydeterminedstructureofmethaneisshowninfigure5.26.Methaneadoptsatetrahedral
moleculargeometrywithHCHbondanglesof109.5andtheHatomssituatedattheverticesofa
tetrahedron.Ifweconsiderthebondinginmethanesolelyintermsoftheoverlapofatomicvalenceorbitals,
wequicklycometotheconclusionthatsuchamodelcouldnotreproducethesebondanglesthethree2p
orbitalsonCareat90toeachother,whilethe2sorbitalhasnodirectionalpreference,andwewould
thereforeexpectastructurewiththreeofthefourCHbondsat90toeachother.Obviouslythissimple
modelisinadequatetodescribethebondinginmethane.Wecan,however,usetheindividualvalence
atomicorbitalsasastartingpointtoconstructhybridorbitals.Thesearecombinationsofatomicorbitals
andtheprocessbywhichwecombinethemiscalledhydridisation.Weillustratethiswithmethane.

FIGURE5.26Theexperimentallydeterminedstructureofmethane.Themoleculehasatetrahedralgeometrywith
109.5bondangles.

Methane:sp3HybridOrbitals
Toconstructhybridorbitals,wefirstneedtoidentifythevalenceatomicorbitalsthatwewilluse.Carbon
hastheelectronconfiguration1s22s22p 2,whichmeansthatthevalenceorbitalsofinterestaretheone2sand
three2porbitals.Wethenmixthesefouratomicorbitalstoformfournewhybridorbitalsthatarecalled
sp 3hybridorbitals.Recallfromchapter4thataporbitalhastwolobesofoppositephase(indicatedin
figure5.27aaspinkandbluelobes).Ifweimagineplacingansandaporbitalsuchthattheircentres
coincide,oneoftheselobeswillinteractconstructivelywiththesorbitalandwillthereforebeenhanced,
whiletheotherwillinteractdestructivelyandbediminished.Thenamesp 3referstothefactthatthefour
hybridorbitalsareconstructedfromonesandthreepatomicorbitals.Equally,andpossiblymore
instructively,itcanalsobeinterpretedaseachindividualsp 3hybridorbitalhaving characterand
character.Figure5.27ashowstheshapeofsp 3hybridorbitals,andalsoshowsdiagrammaticallythe
processbywhichtheyareformed.
FIGURE5.27 (a)Theformationoffoursp3 hybridorbitalsfromonesorbitalandthreeporbitals.
(b)Thetetrahedralarrangementofthefoursp3 hybridorbitals.Thesmallerlobesofopposite
phasehavebeenomittedforclarityastheyarenotsignificantlyinvolvedinanymajor
bondinginteractions.

Theenergyleveldiagramforthisprocessisshowninfigure5.28.

FIGURE5.28Energyleveldiagramfortheformationoffoursp3 hybridorbitalsfromone2sandthree2patomic
valenceorbitals.

Becausewecanneithercreatenordestroyenergy,thetotalenergyofthefouratomicorbitalsmustequalthe
totalenergyofthefourhybridorbitals.Thismeansthattheenergyofthesp 3hybridorbitalsmustlie
betweentheenergiesofthe2sand2patomicorbitals.Specifically,theenergyofeachsp 3hybridorbital
mustbe .Asthefourhybridorbitalsaredegenerate,eachofthemaccommodatesonevalence
electron.

Thefoursp 3hybridorbitalsarearrangedsuchthattheirelectronsundergotheminimumrepulsion.This
resultsinatetrahedralarrangementinwhicheachhybridorbitalpointstowardsadifferentcornerofa
tetrahedron.Everyhybridorbitalisdirectional,withalobeofhighelectrondensitypointinginonespecific
direction,asshowninfigure5.27b.

Wecannowcompleteourmodelofmethane.Weoverlapeachsinglyoccupiedsp 3hybridorbitalwithone
singlyoccupied1sorbitalofaHatom.Thisleadstotheformationoffouridenticalbondsandaregular
tetrahedralshapeforthemolecule,asshowninfigure5.29.
FIGURE5.29Methaneformsfromorbitaloverlapbetweenthehydrogen1sorbitalsandthesp3 hybridorbitalsofthe
carbonatom.Note:Thelargelobesofthesp3 orbitalsandthehydrogensorbitalsshownareofthe
samephase.Thedifferentcoloursareusedforclarityonly.Diminishedlobesofoppositephaseforthe
sp3 hybridorbitalshavebeenomitted.

Notethatsp 3hybridisationisnotlimitedtoCatoms.Infact,anyatomwhichexhibitsatetrahedral(ornearly
so)arrangementofelectronpairscanbeconsideredtobesp 3hybridised.Thisisillustratedinworked
example5.7forthehydroniumioninwhichtheOatomissp 3hybridised.

WORKEDEXAMPLE5.7

BondingintheHydroniumIon

Describethebondingofthehydroniumion,H3O+,intermsofhybridorbitals.

Analysis

DeterminetheLewisstructuretoconfirmthattheinnerOatomissurroundedbyfoursetsof
electronpairs,whichwilladoptanearlytetrahedralgeometry.Thissuggestssp 3hybridisationof
theOatom.Thenconstructthefoursp 3hybridorbitalsfromtheappropriateatomicorbitalson
theOatom.

Solution

WehavedeterminedtheLewisstructureofthehydroniumionbefore(workedexample5.4).
AstheinneratomisO,weusethe2sand2patomicorbitalstoconstructthesp 3hybridorbitals.
Thesewillcontainatotalofsixelectrons.

Wehavetwohalfoccupiedsp 3hybridorbitalsthatcanoverlapwithtwohalfoccupied1sorbitals
onHtoformtwoOHbonds.Weformthethirdbondbyoverlappingoneofthefullsp 3
orbitalswithanempty1sorbitalonanH+ion.Althoughbothelectronsinthisbondderive
formallyfromtheOatom,thebondisidenticaltotheothertwoOHbonds.Thisleavesansp 3
hybridorbitalnotinvolvedinbonding,whichcontainstwoelectrons.Theseelectronsconstitutea
lonepairontheOatom.Wecanvisualisethebondingsituationas:

Note:Thelargelobesofthesp 3orbitalsandthehydrogensorbitalsshownareofthesamephase.
Thedifferentcoloursareusedforclarityonly.Diminishedlobesofoppositephaseforthesp 3
hybridorbitalshavebeenomitted.

Isouranswerreasonable?

Ourbondingdescriptionaccountsforthetrigonalpyramidalshapeofthehydroniumion.This
exampleprovidesanexcellentillustrationofhowvalencebondtheorycanaccountforthe
presenceoflonepairsinamolecule.TheactualHOHbondanglesinthehydroniumionwill
beslightlylessthantheidealised109.5 oduetothepresenceofthelonepair.
PRACTICEEXERCISE5.7
Describethebondinginawatermoleculein
termsofhybridorbitals.

Notethat,inmethane,thenumberofhybridisedvalenceatomicorbitalsequalsthenumberofvalence
atomicorbitalsparticipatinginhybridisation.Thisisalwaysthecase,regardlessofthenatureofthe
hybridisation.Forexample,aswewillseelater,hybridisationofthreeatomicorbitalsgivesthreesp 2hybrid
orbitals,whilehybridisationoftwoatomicorbitalsgivestwosphybridorbitals.

Tothispoint,wehaveconsideredonlymoleculesinwhichhybridorbitalsontheinneratomoverlapwithH
1satomicorbitals.Incaseswheretheouteratomsarenothydrogen,wealsohybridisetheseatomstoobtain
abetterdescriptionofthegeometryofanylonepairspresent.Wecanillustratethiswithreferencetothe
dichloromethanemolecule,CH2Cl2,theLewisstructureofwhichis:

WehybridisetheinnerCatomtogeneratefoursinglyoccupiedsp 3hybridorbitals,andwecangeneratetwo
CHbondsbyoverlappingthesewithtwosinglyoccupiedH1sorbitals.WecouldalsoformtheCCl
bondsbyoverlappingtheremainingtwohybridorbitalswiththesinglyoccupiedporbitaloneachoftwoCl
atoms.However,theproblemwiththisapproachisthesameasthatwhichledustohybridiseatomicorbitals
inthefirstplaceitleadstoanincorrectgeometryofelectronpairs(inthiscase,thethreelonepairson
eachClatom).WecanhybridisethevalenceorbitalsonClinthesamewayaswehavedonepreviouslyfor
C,asshowninfigure5.30.

FIGURE5.30Energyleveldiagramfortheformationofsp3 hybridorbitalsonClfromthe3sand3pvalence
atomicorbitals.

Thishybridisationgivesonesinglyoccupiedsp 3hybridorbitaloneachClatom,whichcanoverlapwiththe
sp 3hybridorbitalsonthecarbonatomtoformtwoCClbonds.Giventhatthesp 3hybridorbitalsonthe
chlorineatomaretetrahedrallydisposed,thethreelonepairswillbeatapproximately109.5toeachother.
sp2hybridorbitals
Borontrifluorideappearsinsection5.4asanexampleofamoleculewheretheinneratomhasthreesetsof
electronpairsinatrigonalplanargeometry,with120anglesseparatingthethreeBFbonds.Ifwewereto
treatthebondinginBF3solelyintermsofoverlapofatomicvalenceorbitals,wewouldpredictbondangles
closeto90.Asetofsp 3hybridsisalsonotappropriate,becausethesewouldgiveFBFbondanglesof
109.5ratherthan120.Weneedadifferentsetofhybridorbitalstorepresentanatomwithtrigonalplanar
geometry.Inthiscasewecangenerateasetofthreesp 2hybridorbitalsbymixingthe2sorbitalwithtwo
2porbitalsontheboronatom.Werepresentthisprocessinfigure5.31,inwhicheachresultingsp 2hybrid
orbitalhas and character.

FIGURE5.31 (a)Theformationofthreesp2 hybridorbitalsfromonesorbitalandtwoporbitals.


(b)Theorientationofthethreesp2 hybridorbitals.Theylieinthesameplaneatanangleof
120toeachother.Thesmallerlobesofoppositephasehavebeenomittedforclarityasthey
arenotinvolvedinthemajorbondinginteraction.

Althoughanindividualsp 2hybridorbitallooksverymuchlikeitssp 3counterpart,theenergeticsofthe


hybridisationprocessarequitedifferent,asshowninfigure5.32.
FIGURE5.32Energyleveldiagramfortheformationofsp2 hybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonaBatom.

Thethreesp 2hybridorbitalsarecoplanar,andarepositionedatanglesof120toeachotheraroundtheB
atom.Asweuseonlytwoofthethree2porbitalsinconstructingthesp 2hybridorbitals,thisleavesone
orbital(byconvention,thep z)unhybridised.Figure5.33showsthearrangementofalltheorbitals.

FIGURE5.33Ansp2 hybridisedatomhasthreecoplanarhybridorbitalsseparatedby120angles.One
unchangedporbitalisperpendiculartotheplaneofthehybridorbitals.Note:Apartfromonehalf
(pinkorblue)oftheunhybridisedpzatomicorbital,allorbitalsareofthesamephase.Thedifferent
coloursareusedforclarityonly.Diminishedlobesofoppositephasehavebeenomitted.

WealsohybridisetheFatoms.EachFatomissurroundedbyfourelectronpairs,whichmeanstheatoms
willbesp 3hybridised,andtheprocessisentirelyanalogoustothatusedpreviouslyfortheClatomsin
CH2Cl2.Wenowoverlapeachofthethreesinglyoccupiedsp 2hybridorbitalswithasinglyoccupiedsp 3
hybridorbitalonafluorineatomtoformthethreeidenticalBFbonds.

Thepresenceoftheunoccupiedp zorbitalontheBatomhassignificantconsequencesforthereactivityof
BF3.BF3oftenreactsveryeasilywithmoleculesthathavealonepairofelectrons,suchasNH3.Thep z
orbitalservestoacceptthepairofelectronsfromsuchmolecules,therebygivingtheBatomanoctetand
convertingittosp 3hybridisationintheprocess.
spHybridOrbitals
Berylliumhydrideappearsinsection5.4asanexampleofamoleculewithlineargeometry.Therearetwo
bondstotheberylliumatomandaHBeHbondangleof180.Todescribelinearorbitalgeometry,we
needahybridisationschemethatgeneratestwoorbitalspointinginoppositedirections.Wedothisby
hybridisingthe2sorbitalofBewithoneofthe2porbitalstogenerateapairofsphybridorbitals.We
representthisprocessinfigure5.34,inwhicheachsphybridorbitalhas characterand character.

FIGURE5.34 (a)Theformationoftwosphybridorbitalsfromonesorbitalandoneporbital.
(b)Theorientationofthetwosphybridorbitals.Theylieatanangleof180toeachother.The
smallerlobeshavebeenomittedforclarityastheyarenotinvolvedinthemajorbonding
interaction.

Figure5.35showstheenergeticsofthehybridisationprocess.Inthiscase,weuseonlyoneoftheporbitals,
whichleavestwoofthemunhybridised.

FIGURE5.35Energyleveldiagramfortheformationofsphybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonBe.

Thetwosphybridorbitalsareorientedat180fromeachother,whichleadstoalinearshapeforthe
molecule.WeformtwoidenticalBeHbondsbyoverlappingeachhalffilledhybridorbitalwithone
halffilled1sorbitalonaHatom.NotethatwecannothybridisetheouterHatoms,astheyhaveonlya1s
orbitaleach.Figure5.36showsadiagramofthebondingforBeH2.Notethatthetwounoccupiedand
unhybridisedporbitalslieperpendiculartoeachother.Wewillseehowsuchorbitalscanparticipatein
bondingwhenweconsidertriplybondedmoleculeslaterinthischapter.
FIGURE5.36ThebondinginBeH2 .Note:Thelargelobesofthesp3 orbitalsandthehydrogensorbitalsshown
areofthesamephase.Thedifferentcoloursareusedforclarityonly.Diminishedlobesofopposite
phaseinthesphybridorbitalshavebeenomitted.

Table5.5summarisesthehybridisationschemeswehaveencounteredsofar.Whileotherhybridisation
schemesarerequiredtodescribethebondinginmoleculeswithcoordinationnumbershigherthan4,sp,sp 2
andsp 3arebyfarthemostuseful,particularlytodescribethebondinginorganicmolecules.Multiple
bondingisoneofthefeaturesofmanyorganicmolecules.Onthefollowingpages,wewilllookatthis
phenomenonfromavalencebondpointofview.
TABLE5.5 Asummaryofvalenceorbitalhybridisation
Numberof Numberof
Numberofsetsof Electrongroup hybrid unusedp
electronpairs geometry Hybridisation orbitals orbitals Diagram(a)
2 linear sp 2 2

3 trigonalplanar sp 2 3 1

4 tetrahedral sp 3 4 0

(a)Apartfromonehalf(pinkorblue)oftheunhybridisedp zatomicorbital,allorbitalsareofthe
samephase.Thedifferentcoloursareusedforclarityonly.Diminishedlobesofoppositephase
havealsobeenomitted.

MultipleBonds
ManyoftheLewisstructuresinthisbookrepresentmoleculesthatcontaindoubleandtriplebonds.From
simplemoleculessuchasetheneandethyne,tocomplexcompoundssuchaschlorophyllandvitaminB12,
multiplebondsareabundantinchemistry.Doubleandtriplebondscanbedescribedbyextendingthe
valencebondmodel.Webeginwithethene,asimplehydrocarbonwiththeformulaC2H4.

BondinginEthene
Ethene(ethylene)isacolourless,flammablegaswithaboilingpointof104Cthatispredominantlyusedin
themanufactureofplasticssuchaspolyethylene(seechapter26).Becauseethenestimulatesthebreakdown
ofcellwalls,itisusedcommerciallytospeeduptheripeningoffruit,particularlybananas.

EverydescriptionofbondingstartswithaLewisstructure.Ethenehas12valenceelectrons.Thebond
frameworkofthemoleculehasoneCCbondandfourCHbonds,requiring10oftheseelectrons.Ifwe
placethefinaltwoelectronsasalonepairononeofthecarbonatoms,thisgivesaformalchargeof1on
onecarbonatomand+1ontheother.Thesechargescanbeminimisedbyformingadoublebondbetween
thecarbonatoms,leavingthembothwithanoctetofelectrons.

Eachcarbonatomisthussurroundedbythreesetsofelectronpairs,whichimpliesthatthecarbonatomsare
sp 2hybridised,withatrigonalplanargeometry.(Recallfromp.176thatdoublebondsandtriplebondsare
treatedasbeingasinglesetofelectronpairs.)

Todevelopabondingpictureformoleculeswithmultiplebonds,westartbyconsideringonlythesingly
bondedframeworkofthemolecule,whichweconstructusinghybridorbitals.Theorbitaldiagramforan
sp 2hybridisedCatomisshowninfigure5.37andtheframeworkisshowninfigure5.38.Notethatthe
electronconfigurationontherighthandsideoffigure5.37violatestheAufbauprinciple.Thisisjustifiedas
theenergydifferencebetweenthesp 2orbitalsandthep zorbitalissmall,andthereforetheenergyrequired
topopulatethep zorbitalissmallerthanthespinpairingenergythatwouldotherwiseberequiredtooccupy
oneofthehybridorbitalswithtwoelectrons.Suchanelectronconfigurationprovidesuswithresultsthat
agreewithexperiments.

FIGURE5.37Energyleveldiagramfortheformationofsp2 hybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonC.

FIGURE5.38Theframeworkoftheethenemolecule.

Fortheframework,wemustformfourCHbondsandoneCCbond.Wecandothis,asshownin
figure5.39,byusingtwosp 2hybridorbitalsoneachcarbontoformtwoCHbonds,withtheCC
bondformedbyoverlapoftheremainingsp 2hybridorbitaloneachCatom.
FIGURE5.39Orbitaloverlapsusedtoformtheframeworkofethene.Notethatallorbitalsshownareofthesame
phaseandcoloursareusedforclarityonly.

Havingconstructedtheframework,weareleftwithonehalfoccupiedp zorbitaloneachCatom,whichis
usedtoconstructthedoublebond.Aswehaveseenearlier,abondhasitsmaximumelectrondensity
alongtheinternuclearaxisbetweenthetwonuclei.Toconstructthedoublebond,weoverlapthetwop z
orbitalsinasidebysidefashiontoformapi()bond,asshowninfigure5.40.Abondhasitsmaximum
electrondensityaboveandbelowtheplaneofthenuclei,andhaszeroelectrondensityalongtheinter
nuclearaxisbetweenthenuclei.Adoublebondalwaysconsistsofonebondandonebond.Thebond
formsfromtheendonoverlapoftwohybridorbitals,andthebondformsfromthesidebysideoverlapof
twoatomicporbitals.Asthesidebysideoverlapisnotasefficientastheendonoverlap,doublebondsare
nottwiceasstrongassinglebondsbetweenthesameatoms.Figure5.40showsthecompleteorbitalpicture
ofthebondinginethene.Etheneisthesimplestofaclassofmolecules,thealkenes,whichcontainC C
doublebonds.

FIGURE5.40 Orbitalpicturesofthebondinginethenefromthreeperspectives:
(a)viewofthepzatomicorbitalswhichoverlaptoformthebond,
(b)viewofthebondformedfromtheoverlapofthepzatomicorbitalsand
(c)thebondsuperimposedontheframework.Notethatthepinkandbluelobestogether
representasinglebond,whichisoccupiedbytwoelectrons.

Theavailabilityofanunhybridisedvalenceporbitaltoformbondsischaracteristicofsp 2hybridisation
andisnotrestrictedtocarbonatoms.ManyorganicmoleculescontainC NandC Odoublebondsand
wecandescribethebondinginsuchcompoundsinasimilarfashiontotheabovedescriptionofaC C
doublebond.

Tosummarise,wecanconstructthevalencebonddescriptionofanydoublebondusingthefollowingfour
stepprocedure:
1.DeterminetheLewisstructure.
2.UsetheLewisstructuretodeterminethetypeofhybridisation.
3.Constructthebondframework.
4.Addthebonds.
BondinginEthyne
Theethynemoleculemaybefamiliartoyoubyitsmorecommonnameacetylene,thegasusedin
oxyacetyleneweldingtorches.Ethynehas10valenceelectrons,andweusesixofthesetoformoneCC
bondandtwoCHbonds.ThisleaveseachCatominthemoleculewithashareofonlyfourelectrons.We
cancompletetheoctetofoneoftheCatomsbyallocatingtheremainingfourelectronstoitintheformof
twolonepairs.However,thisleadstoa2chargeonthisandaformalchargeof+2ontheotherCatom.
ConvertingthetwolonepairsontheCatomtotwobondingpairssituatedbetweenthetwoCatoms,we
obtainformalchargesofzeroforallatomsinthemolecule.ThisproducesthefollowingLewisstructurein
whichthecarbonatomsarejoinedbyatriplebond.

Eachcarbonatomissurroundedbytwosetsofelectronpairs,andwewouldpredictalineargeometryfor
thismolecule.Wecanthereforeusesphybridorbitalstodescribethebondinginethyne.

Aswedidforethene,wefirstconstructthesinglybondedframeworkusingthehybridorbitals.Theorbital
diagramforansphybridisedCatomisshowninfigure5.41,andtheframeworkofethyneisshownin
figure5.42.

FIGURE5.41Energyleveldiagramfortheformationofsphybridorbitalsfromthe2sand2pvalenceatomic
orbitalsonC.

FIGURE5.42Theframeworkoftheethynemolecule.

WeformtheframeworkbyformingtwoCHbondsandoneCCbondusingthesphybridorbitals,as
showninfigure5.43.

FIGURE5.43Orbitaloverlapsusedtoformtheframeworkofethyne.Allorbitalsareinthesamephasedifferent
coloursareusedforclarityonly.

ThisthenleavestwosinglyoccupiedporbitalsoneachCatom.Wecanformtwobondsbyoverlapping
thep y andp zorbitalsoneachCatominasidebysidefashion,asshowninfigure5.44.
FIGURE5.44Overlappingnonhybridisedporbitalsformtheframeworkofethyne.

Thus,eachtriplebondhasoneCCbondandtwoCCbondsperpendiculartoeachother,whichis
alwaysthecaseinanyalkyne.Workedexample5.8treatsanothermoleculewithbondingthatcanbe
describedbysphybridorbitals.

WORKEDEXAMPLE5.8

OrbitalOverlapinTripleBonds
Hydrogencyanide,HCN,isanextremelypoisonousgas.Approximatelyhalfamilliontonnesof
HCNisproducedeachyear,mostofwhichisusedtopreparestartingmaterialsforpolymers.
ConstructacompletebondingpictureforHCNandsketchthevariousorbitals.

Analysis

Usethefourstepproceduredescribedpreviously.BeginwiththeLewisstructureforthe
molecule,andthenidentifytheappropriatehybridorbitals.Constructabondframework,and
completethebondingpicturebyassemblingthebondsfromtheunhybridisedporbitals.

Solution

ThefivestepsofourprocedureforwritingLewisstructuresleadtoatriplebondbetweencarbon
andnitrogen.

TheinnerCatomissurroundedbytwosetsofelectronpairs,asistheNatom.Theseatomscan
thereforebeconsideredtobesphybridised.Wehavederivedtheorbitaldiagramforansp
hybridisedCatompreviously,whilethatforanspNatomisshownbelow.

Weformthelinearsinglybondedframeworkshownbelowbyoverlappingoneofthesphybrid
orbitalsonCwiththe1sorbitalontheHatomtogiveaCHbond.Similarly,weformaCN
bondbyoverlappingtheothersphybridorbitalontheCatomwiththesinglyoccupiedsp
hybridorbitalontheNatom.

ThisleavestwosinglyoccupiedporbitalsonCandtwosinglyoccupiedporbitalsontheNatom
withwhichwecanconstructtheC Ntriplebond,inthesamewayasdescribedpreviouslyfor
ethyne.WearethenleftwithansphybridorbitalcontainingtwoelectronssituatedontheN
atom.Thisisanonbondinglonepairandisshowninthediagrambelowingold,forclarity.

Isouranswerreasonable?

Wehavealreadyshownthatatriplebondconsistsofoneandtwobonds,whichiswhatwe
havederived.OurbondingschemealsoaccountsforthepresenceofalonepairontheNatom,
soitisconsistentwiththeexperimentallydeterminedstructure.

PRACTICEEXERCISE5.8
Describethebondinginthebut2yne
molecule,CH3C CCH3,usingvalencebond
theory,andsketchtheorbitalsinvolved.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
5.7MolecularOrbitalTheory:DiatomicMolecules
Hybridorbitalsandlocalisedbondsprovideamodelofbondingthatcanbeeasilyappliedtoawiderangeof
molecules.Usingthismodelwedoanexcellentjobofrationalisingandpredictingchemicalstructures,butlocalised
bondscannotpredictorinterpretallaspectsofbondingandreactivity.Forexample,whilevalencebondtheory
predictsthegeometryofthemethanemoleculeperfectly,itcannotexplainthefactthatthefourvalenceorbitalsinthis
moleculearenotdegenerate.ItalsofailstoexplainwhythereareunpairedelectronsinamoleculeofO2.Inthis
sectionweintroducemolecularorbitaltheory,apowerfultheoryofbondingthatismoresuccessfulthanvalence
bondtheoryinpredictingandexplainingmolecularproperties.Molecularorbitaltheorydiffersfundamentallyfrom
valencebondtheoryinthattheelectronswithinamoleculearenotlocalisedeitherononeatomorbetweentwoatoms
insteadtheyoccupymolecularorbitals(MOs)thatcancovertheentiremolecule.

Althoughmolecularorbitaltheoryismorecomplexthanthehybridorbitalapproach,wecanillustratethe
fundamentalsofthetheorywithreferencetosimplediatomicmolecules.

MolecularOrbitalsofH2andHe2

Molecularorbitaltheoryconsiderstheformationofmolecularorbitalsfromtheoverlapofatomicorbitalsonallofthe
individualatomsinthemolecule.TheoverlapofNatomicorbitalswillalwaysleadtotheformationofNmolecular
orbitals.Becauseofthelargenumberofpossibleoverlapsinevenquitesmallmolecules,wewillrestrictour
discussiontodiatomicmolecules,andwillfirstconsiderthemolecularorbitaltreatmentoftheH2molecule.

WecanconsidertheMOsofH2tobeformedfromtheoverlapofthe1sorbitalsontheHatoms.Aseachatomic
orbitalcanhaveeitherapositiveornegativephase,therearetwopossiblewaysinwhichtheseatomicorbitalscan
overlapbothorbitalscanhavethesamephase(inphaseoverlap)ortheycanhaveoppositephases(outofphase
overlap).Inphaseoverlapisconstructiveandresultsintheformationofamolecularorbitalwithalargeamplitude,
andconsequentlyhighelectrondensity,betweenthenuclei.Outofphaseoverlapisdestructiveandgivesamolecular
orbitalwithzeroamplitude,andthereforezeroelectrondensity,exactlyhalfwaybetweenthenuclei.Asforatomic
orbitals,thispositionwheretheamplitudechangesphaseiscalledanode.Theseoverlapsandtheresultingmolecular
orbitalsareshowninfigures5.24and5.45.

FIGURE5.45Whentwohydrogen1satomicorbitalsinteract,theygeneratetwomolecularorbitals,onebonding(1s)and
oneantibonding .

Constructiveoverlapgivesabondingmolecularorbital,inwhichelectrondensityismaximisedbetweenthetwo
nuclei.Suchanarrangementofelectronsminimisesinternuclearrepulsions.Theorbitaliscompletelysymmetricwith
respecttorotationaroundtheinternuclearaxisandisthereforeaorbital.Weusea1ssubscripttoshowthatit
derivesfromtheoverlapoftwo1satomicorbitals,andthecompletedescriptionofthisorbitalistherefore1s.

Destructiveoverlapgivesanantibondingmolecularorbitalinwhichelectrondensityisminimisedbetweenthe
nucleiandiszeroatthenodebetweenthenuclei(allantibondingorbitalshavemorenodesthanthecorresponding
bondingorbitalsandarethereforeofhigherenergy.).Internuclearrepulsionsarethereforesignificantastheyarenot
mediatedbytheelectrons.Astheorbitaliscompletelysymmetricwithrespecttorotationabouttheinternuclearaxis,it
isaorbital.Weuseasuperscriptasterisk(*)todenoteitsantibondingnatureandagainuseasubscript1stoshow
thatitisderivedfromtwo1satomicorbitals.Thecompletedescriptionofthisorbitalistherefore .
Therelativeenergiesofatomicorbitalsandthemolecularorbitalstheyformareshowninamolecularorbital
diagram.Figure5.46showsthemolecularorbitaldiagramforH2.Itshowsthatthebondingorbitalisoflowerenergy
thantheorbitalsfromwhichitisformed,whereastheantibondingorbitalisofhigherenergy.Whenahydrogen
moleculeforms,itstwoelectronsobeythesameprinciplesfordistributingelectronsasdescribedinchapter4.The
lowestenergyarrangementofelectronsrequiresadherencetotheAufbauprinciple,thePauliexclusionprincipleand
Hund'srule,nomatterwhattypesoforbitalstheyoccupy.Thetwovalenceelectronsofmolecularhydrogentherefore
fillthelowestenergyorbital,the1sorbital,withtheirspinspaired,leavingthe orbitalempty.

FIGURE5.46Molecularorbitaldiagramformolecularhydrogen.

Themolecularorbitaldiagramshowninfigure5.46appliestoalldiatomicspeciesfromthefirstrowoftheperiodic
table,exceptthattheelectronoccupancyandtheabsoluteenergiesinvolvedaredifferent.Wecan,forinstance,use
molecularorbitaltheorytorationalisewhytwoheliumatomsdonotcombinetoformamoleculeofHe2.Theelectron
configurationofHeis1s2andthereforethehypotheticalHe2moleculewouldhavefourelectrons.Twoofthesewould
populatethebonding1sorbital,whiletheremainingtwoelectronswouldhavetooccupytheantibonding orbital,
asshowninfigure5.47.ThetotalelectronicenergyoftheHe2moleculewouldthereforebeexactlythesameasthat
oftwoisolatedHeatoms,asthedestabilisingeffectoftheelectronsintheantibondingorbitalcancelsoutany
stabilisationduetotheelectronsinthebondingorbital.Asthereisnoenergeticadvantage,amoleculeisnotformed
(seethediscussionofentropyinchapter8foranexplanation).Aconvenientwaytosummarisethisargumentisby
calculatingthebondorder,whichrepresentsthenetamountofbondingbetweentwoatoms.

FIGURE5.47DiatomicHe2 doesnotexistbecausethestabilityimpartedbytheelectronsinbondingorbitalsisoffsetbythe
destabilisationduetotheelectronsinantibondingorbitals.

Bondordersusuallyhaveintegerorhalfintegervalues:thelargerthebondorder,thestrongerthebond(forthesame
typeofatom).

Formolecularhydrogen,withtwobondingelectronsandnoelectronsintheantibondingorbitals,thebondorderis
.Abondorderof1correspondstoasinglebond,consistentwiththeLewisstructureofH2.Forthe

hypotheticalHe2molecule,twobondingandtwoantibondingelectronsgiveabondorderof ,sono
bondformsandheliumdoesnotformstablediatomicmolecules.

WORKEDEXAMPLE5.9

DoesHe2+Exist?

UseamolecularorbitaldiagramtopredictifitispossibletoformtheHe2+cation.

Analysis

TheschematicMOdiagramshowninfigure5.46canbeappliedtoanyofthepossiblediatomicmolecules
orionsformedfromthefirstrowelements,hydrogenandhelium.CounttheelectronsofHe2+,placethe
electronsinthemolecularorbitaldiagramandcalculatethebondorder.Ifthebondorderisgreaterthan
zero,thespeciescanpotentiallyformundertherightconditions.

Solution

OneHeatomhastwoelectrons,soaHe2+cationhasthreeelectrons.FollowingtheAufbauprinciple,two
electronsfillthelowerenergy1sorbital,sothethirdmustbeplacedintheantibonding orbitalin
eitherspinorientation.

Thebondorderofthecationistherefore .Althoughabondorderof mightsoundunusual,

itisgreaterthanzeroandthereforewepredictthatHe2+,withanetbondorderof ,canbepreparedinthe
laboratoryunderappropriateconditions.

Isouranswerreasonable?

Upuntilthispoint,wehavediscussedonlysingle,doubleandtriplebonds,andhavenotencountered
bondswithnonintegerorders.Infact,suchbondsarequitecommoninchemistry.He2+canbeprepared
bypassinganelectricaldischargethroughasampleofheliumgas.TheHe2+ionisunstablebutsurvives
longenoughtoallowitsstudy.ThebonddissociationenergyofHe2+is250kJmol1,approximately60%
asstrongasthebondintheH2molecule,whichhasabondorderof1.
PRACTICEEXERCISE5.9

Whichspecieshasthestrongerbond,H2orH2?
Useamolecularorbitaldiagramtosupportyour
answer.

MolecularOrbitalsofO2

Thenextstepinthedevelopmentofmolecularorbitaltheoryistoconsiderthemolecularorbitalsformedby
constructiveanddestructiveoverlapofatomicporbitals.Weusemolecularoxygen,O2,asacasestudy.

TheLewisstructureofO2showsthetwoatomsconnectedbyadoublebond,withtwononbondingelectronpairson
eachatom.NotethattherearenounpairedelectronsintheLewisstructure.

WederivethemolecularorbitaldiagramfortheO2moleculebyconsideringoverlapofonlythevalenceatomic
orbitalsonthetwooxygenatomsanexacttreatmentwouldalsoincludethecore1sorbitals,butwewillignorethese
intheinterestsofclarity.Eachoxygenatomhasfourvalenceorbitals,sothemolecularorbitaldiagramforO2will
containeightmolecularorbitals.Thefirstinteractioninvolvesthe2satomicorbitals.Thispairinteractsinexactlythe
samewayasthe1sorbitalsdescribedpreviouslyforH2.Theconstructiveoverlapgeneratesabondingsorbital,and
thedestructiveoverlapformsanantibonding orbital.Becauseofthelargersizeofthe2satomicorbitals,thesetwo
molecularorbitalsarelargerthantheirhydrogen1sand counterparts,buttheiroverallappearancesaresimilar.

Figure5.48showstheconstructionofthe2pbasedmolecularorbitals.Onepairofmolecularorbitalsformsfromend
onconstructiveanddestructiveoverlapofthep zorbitalsthatpointtowardseachotheralongthebondaxis(by
convention,thebondaxisischosentobethezaxis).Theseendonoverlapsgiveapairoforbitals,thebondingp
andtheantibonding asshowninfigure5.48a.(Notethatherewehavesimplylabelledthemolecularorbitalsasp
and ,ratherthan2pand forreasonswewillexplainonp.203.)Theremainingsetsofporbitalsundergo
constructiveanddestructiveoverlapinasidebysidefashiontoformpairsofmolecularorbitalswithelectrondensity
locatedprimarilyaboveandbelowtheinternuclearaxis.Suchmolecularorbitalsarecalledorbitals.Constructive
overlapgivesabondingorbital,whiledestructiveoverlapgivesanantibonding*orbital.Oneofthesepairscomes
fromoverlapofthep y orbitals,whiletheothercomesfromoverlapofthep x orbitals.Figure5.48bshowsonlythep y
pairoforbitals,whichwelabely thex pairoforbitalsderivedfromthep x atomicorbitalshasthesame
appearance,butisperpendiculartothey orbitals.Notethattheantibonding*orbitalcontainsanodebetweenthe
twoOatoms.
FIGURE5.48 Constructiveanddestructiveoverlapofporbitalsleadtobondingandantibondingorbitals
(a)Endonoverlapofthepzorbitalsgivesorbitals.
(b)Sidebysideoverlapofthep atomicorbitalsgives and molecularorbitals.Similarcombinations
y y
ofpxorbitalswouldgivexand MOs.

TodrawthemolecularorbitaldiagramforO2,wemustfirstdeterminetherelativeenergiesofthemolecularorbitals.
Wecandothiswiththefollowingrules:
1.Thecoresand orbitalsderivedfromtheoverlapofthe1satomicorbitalsareoflowestenergyand
contributelittletobonding.Forthisreason,theyarenotshownexplicitly.
2.Thebondingsandantibonding orbitalsderivedfromtheoverlapofthe2sorbitalsareoflowerenergy
thananyofthesixmolecularorbitalsderivedfromthe2porbitals.Thisisbecausethe2sorbitalsthatgenerate
thesand orbitalsareoflowerenergythanthe2patomicorbitals.
3.Thex andy bondingorbitalsaredegenerate,becausethecorrespondingatomicporbitalsfromwhichtheyare
derivedaredegenerate.The and orbitalsaredegenerateforthesamereason.
4.Theantibondingorbitalsformedfromtheatomic2porbitalsarehighestinenergy,withthe orbitalhigher
thanthedegenerate and pairoforbitals.

Afterapplyingthesefeatures,weareleftwiththebondingpandmolecularorbitals.Thesemustbeplacedbetween
and*,butwhichofthemislowerinenergy?Itcanbeshownmathematicallythatendonoverlapismore
efficientthansidebysideoverlap,whichsuggeststhattheporbitalshouldbeoflowerenergythantheorbitals.
ThisisthecasefortheO2moleculeandfigure5.49showsthecompletediagram.Toobtainthegroundstateelectron
configuration,weplacethe12valenceelectronsinthemolecularorbitalsinaccordancewiththePauliandAufbau
principlesandHund'srule.Wecandescribetheresultingelectronconfigurationbynamingtheorbitals(s,x etc.),
andusingsuperscriptstoshowhowmanyelectronseachorbitalcontains.Therefore,theconfigurationfortheground
stateofO2is:

FIGURE5.49ThemolecularorbitaldiagramforO2 .TheenergyorderingoftheMOsappliestosecondrowdiatomic
moleculeswithZ>7.

Notethat,tosatisfyHund'srule,wemustplaceoneelectronineachofthetwo*orbitalswithparallelspins.
Therefore,thismodelofbondingpredictsthatO2shouldcontaintwounpairedelectrons,incontrasttoboththeLewis
structureandthevalencebondtheory.Whichmodelagreeswithexperiment?

Figure5.50showsthatliquidoxygenadherestothepolesofamagnet.Attractiontoamagneticfieldshowsthat
molecularoxygenisparamagnetic.Recallfromchapter4thatparamagnetismariseswhentheelectronconfiguration
includesunpairedelectrons.NeithertheLewisstructureofO2northevalencebondmodelpredictsthepresenceof
unpairedelectrons.However,themolecularorbitaldescriptionshowsthatthetwohighestenergyelectronsofthe
oxygenmoleculeoccupythetwodegenerate and antibondingorbitals(figure5.50).So,molecularorbital
theorygivesusamoreappropriatemodelofthebondinginO2thaneithertheLewisorthevalencebondtheories.
Thisdoesnotnecessarilymeanthatthemolecularorbitaltheoryiscorrect,justthatitgivesbetteragreementwith
experimentthantheothermodels.

FIGURE5.50Molecularoxygenisparamagnetic,soitclingstothepolesofamagnet.

Bondlengthandbondenergymeasurementsonoxygenanditscationprovideevidencethatthe*orbitalsareindeed
antibonding.ThebondorderoftheO2moleculeis .IfweremoveanelectronfromO2,weformtheO2+
cation.ExperimentalmeasurementsshowthatthisspecieshasalargerbondenergyandshorterbondlengththanO2,
bothobservationsconsistentwithanincreasedbondorder.Thisindicatesthattheelectronremovedmustbe
antibondingincharacter,asitsremovalhasreducedtheamountofantibondingandstrengthenedthebond.

Species Bondlength Bondenergy Configuration Bondorder


O2 121pm 496kJmol1 (p)2(x )2(*x )1(*y )1 2

O2+ 112pm 643kJmol1 (p)2(x )2(y )2(*x,y )1 2.5

Molecularorbitaltheorypredictstheobservedincreaseinbondorder,withthecalculatedbondorderofO2+being
.TheexperimentaldatashowthatthehighestenergyorbitalofO2isantibondingincharacterandthe
theoreticalmolecularorbitalpredictionsareingoodagreement.

OurtreatmentofO2showsthattheextracomplexityofthemolecularorbitalapproachexplainsfeaturesthatasimpler
descriptionofbondingcannot.TheLewisstructureofO2doesnotrevealitstwounpairedelectrons,butamolecular
orbitalapproachdoes.ThesimpledescriptionofthedoublebondinO2doesnotpredictthatthebondinO2+is
strongerthanthatinO2,butamolecularorbitalapproachdoes.Wenowextendourdiscussiontoincludeallofthe
homonucleardiatomicmoleculesformedbyelementsinthesecondrowoftheperiodictable.

HomonuclearDiatomicMolecules

WesawpreviouslythatverysimilarmolecularorbitaldiagramscandescribethebondinginH2,He2+andHe2.Can
weusethemolecularorbitaldiagramforO2toexplainthebondinginallofthesecondrowdiatomicmolecules(Li2,
Be2,B2,C2,N2,O2,F2andNe2)?ConsidertheB2molecule,whichcanbeformedinthegasphasebystrongheating
ofsolidboron.IfweusethemolecularorbitaldiagramforO2andinsertthesixvalenceelectronsofB2,wewould
predicttheelectronconfiguration(s)2(s*)2(p)2forthismolecule.Withallitselectronspaired,B2shouldbe
diamagnetic.However,experimentsshowthatB2moleculesareparamagnetic,withtwounpairedelectrons.When
theoryandexperimentconflict,theorymustberevised.ThemolecularorbitaldiagramweusedforO2mustberevised
toaccountfortheparamagnetismofB2.

Theviewofmolecularorbitaltheorythatleadstothemolecularorbitaldiagraminfigure5.49assumesthatthe2sand
2porbitalsactindependently.Amorerefinedtreatmentconsidersinteractionsbetweenthe2sand2porbitals.Recall
fromchapter4thatthe2sand2porbitalshavesimilarradii.Consequently,whentwoatomsapproacheachother,the
2sorbitalononeatomwilloverlapnotonlywiththe2sorbital,butalsowiththe2p2zorbitaloftheotheratom.This
mixedinteractionof2sand2p2zstabilisesthesmolecularorbitalanddestabilisesthepmolecularorbital.Inother
words,orbitalmixingcausesthesandpmolecularorbitalstomovefurtherapartinenergy.Inthismorerefined
treatment,theresultingmolecularorbitalsarethereforenotderivedsolelyfromtwoatomicorbitals,andhencewedo
notusespecificlabels,suchas1s,aswedidforthehydrogenandheliumcases.Labelsofthetypesandy show
thepredominanttypeofoverlapthatcontributestothetmolecularorbital.Theamountofmixingdependsonthe
differenceinenergybetweenthe2sand2patomicorbitals.Mixingislargestwhentheenergiesoftheorbitalsare
nearlythesame.Asfigure5.51shows,theenergiesofthe2sand2patomicorbitalsdivergeasZincreasesacrossthe
secondrow,somixingislargeforB2butsmallforF2.Figure5.52showshowmixingaffectstheenergiesofthes
andpmolecularorbitals.

FIGURE5.51Energiesofthen=2valenceorbitalsasafunctionofZ.
FIGURE5.52Mixingofthe2sand2pzorbitalscausesthesMOstobecomelowerinenergyandthep MOstoincreasein
energy.Theamountofmixingdecreasesacrossthesecondrowoftheperiodictable.ForB2 ,C2 andN2 ,the
MOsareoflowerenergythanthep orbitals.ForO2 andF2 ,theoppositeistrue.

Themaineffectofmixingistomakethepmolecularorbitalofhigherenergythanthedegenerateorbitalsforthe
B2,C2andN2molecules.Therefore,accordingtotheAufbauprinciple,wefirstfilltheorbitalsandthenthep
orbitalforthesemolecules.FollowingHund'srule,thismeansthatB2isparamagnetic,asithastheelectron
configuration ,inagreementwithexperiment.Noticethatcrossoverofthepandenergy
levelstakesplacebetweenmolecularnitrogenandmolecularoxygen.Becauseoforbitalmixing,wethereforerequire
twogeneralisedmolecularorbitaldiagramsfordiatomicmolecules,oneforB2,C2andN2,andtheotherforO2and
F2.Figure5.52showsbothdiagrams.

Thesemolecularorbitaldiagramshelptorationaliseexperimentalobservationsaboutmolecules.

WORKEDEXAMPLE5.10

TrendsinBondEnergy

Usemolecularorbitaldiagramstoexplainthetrendinthefollowingbondenergies:B2=290kJmol1,C2=
600kJmol1andN2=942kJmol1.

Analysis

Thedatashowthatbondenergiesforthesethreediatomicmoleculesincreaseaswemoveacrossthe
secondrowoftheperiodictable.Wemustconstructmolecularorbitaldiagramsforthethreemoleculesand
usetheresultstointerpretthetrend.

Solution

Thecrossoverpointforthep/energylevelstakesplacebetweenN2andO2,sothegeneraldiagramforZ
7infigure5.52appliestoallthreemolecules.ThevalenceelectroncountsareB2=6e,C2=8e,andN2
=10e.PlacetheseelectronsintheMOdiagramfollowingthePauliexclusionandAufbauprinciplesand
Hund'srule.Herearetheresults.
Thediagramsshowthattheincreasingelectroncountsasweprogressfromborontocarbontonitrogen
resultinthefillingofbondingmolecularorbitals.Thisisrevealedmostclearlybycalculatingthebond
ordersforthethreemolecules: , and .
Increasingbondordercorrespondstostrongerbondingbetweentheatomsandthereforegreaterbond
energies.

Isouranswerreasonable?

Ourpredictedbondorderscorrelateperfectlywiththeexperimentalbondenergies,andthereforeour
answerisreasonable.Ofthesethreediatomicmolecules,onlyN2existsundernormalconditions.Boron
andcarbonformnonmolecularsolidsratherthanisolateddiatomicmolecules.However,molecularorbital
theorypredictsthatB2andC2mayexistundertherightconditions,andinfactbothmoleculescanbe
generatedinthegasphasebyvaporisingsolidboronorsolidcarbon.

PRACTICEEXERCISE5.10
Usemolecularorbitaldiagramstoexplainthetrend
inbondenergiesforthefollowingdiatomic
molecules:N2=942kJmol1,O2=495kJmol1
andF2=155kJmol1.

HeteronuclearDiatomicMolecules
Nitrogenoxide(NO)isanexampleofaheteronucleardiatomicmolecule.Thisinterestingmoleculehasbeeninthe
newsinrecentyearsbecauseofimportantdiscoveriesabouttheroleofNOasabiologicalmessenger.Amolecular
orbitaldiagramofNOisshowninfigure5.53.

FIGURE5.53MolecularorbitaldiagramofNO.
Becausethequalitativefeaturesoforbitaloverlapdonotdependontheidentityoftheatoms,thebondinginNOcan
bedescribedbythesamesetsoforbitalsthatdescribehomonucleardiatomicmolecules.WhichofthetwogeneralMO
diagramsfordiatomicmoleculesappliestonitrogenoxide?Thecrossoverpointfortheenergyrankingsofthepand
molecularorbitalsfallsbetweenNandO,soweexpecttheorbitalenergiestobenearlyequal.Experimentshave
shownthatthepMOisslightlymorestablethantheMO.Consequently,theMOconfigurationforthe11valence
electronsofNOmirrorsthatforthe12valenceelectronsofO2,exceptthatthereisasingleelectroninthe*orbital:

Thereareeightbondingelectronsandthreeantibondingelectrons,sothebondorderofNOis2.5.Thisbondis
strongerandshorterthanthedoublebondofO2butweakerandlongerthanthetriplebondofN2.

Species Bondlength Bondenergy Configuration Bondorder


O2 121pm 495kJmol1 2

NO 115pm 605kJmol1 2.5

N2 110pm 945kJmol1 (x )2(y )2(p)2 3

Electronconfigurationsforthesemoleculesleadtoaguidelineformolecularorbitalconfigurationsbasedonaverage
nuclearcharge,Zaverage :

Forsecondrowdiatomicmoleculesandions:
pislowerinenergythan x , y whenZaverage >7
x , y islowerinenergythanpwhenZaverage 7.

Workedexample5.11comparestheionisationenergiesofthreediatomicmoleculesandusesMOtheorytoexplain
thedifferences.

WORKEDEXAMPLE5.11

ComparingIonisationEnergies

ThefirstionisationenergyofNOis891kJmol1,thatofN2is1500kJmol1,andthatofCOis1350kJ
mol1.UseelectronconfigurationstoexplainwhyNOionisesmoreeasilythaneitherN2orCO.

Analysis

Recallfromchapter4thationisationenergyreferstotheremovalofanelectronfromanatom,or,inthis
case,fromamolecule.Wemustcountthevalenceelectrons,choosethecorrectMOdiagram,followthe
Aufbauprincipleinplacingtheelectrons,andthenusetheconfigurationstoexplaintheionisationenergy
data.

Solution

Beginwithasummaryoftheimportantinformationforeachmolecule:NOhas11valenceelectronsand
Zaverage =7.5N2has10valenceelectronsandZaverage =7COhas10valenceelectronsandZaverage =7.
ApplyingthegeneraldiatomicMOdiagramsoffigure5.52givesthefollowingconfigurations:
COandN2areisoelectronicspecies,meaningtheyhavethesamenumberofelectrons(seep.145),and
eachhasabondorderof3.Itmakessensethatthesetwomoleculeshavecomparableionisationenergies.
NOhasoneelectronmorethanN2andCO,andthiselectronoccupiesoneoftheantibonding*orbitals.It
ismucheasiertoremovethisantibondingelectronfromNOthanitistoremoveabondingelectronfrom
eitheroftheothertwospecies.

PRACTICEEXERCISE5.11
Useelectronconfigurationstopredictwhichofthe
followingisthemoststablediatomiccombination
ofcarbonandnitrogen:CN,CNorCN+.

Fordiatomicmoleculescomposedofatomsthathaveverydifferentenergiesoftheiratomicorbitals,theMOdiagram
becomesslightlymorecomplicated.WewilluseHFasanexampleandshowtheenergylevelsforbothatomic
orbitalsandmolecularorbitalsinfigure5.54.

FIGURE5.54ThemolecularorbitaldiagramofHF.

Generally,orbitalsareoflowerenergyinamoreelectronegativeatomandorbitalswiththesamedesignationare
lowerinenergyifthenuclearchargeislarger.Armedwiththeseruleswecanunderstandthatthe1sorbitalintheF
atomismuchlowerinenergythanthe1sorbitalofH.

Molecularorbitalscanformonlywhenthereisnetoverlapbetweentheconstituentatomicorbitalsandwhenthe
atomicorbitalsarerelativelycloseinenergy.Wecanillustratethisbyconsideringtheapproachofthehydrogen1s
orbitalwitheitherthe2p x or2p y orbitalofthefluorineatom.
Astheseorbitalsapproacheachotherinasideonmanner,therewillbeconstructiveinterference,andhencea
bondinginteraction,betweenthesorbitalandthesamephasedlobeoftheporbital,buttherewillbeanequaland
oppositedestructiveinterference,andhenceanantibondinginteraction,betweenthesorbitalandtheoppositephased
lobeoftheporbital(figure5.54).Therefore,thereisnonetoverlapbetweenansorbitalandap x orp y orbitalwhen
theyapproachinthismanner,andnomolecularorbitalsareformed.Instead,the2p x and2p y orbitalsarelocated
primarilyonthefluorineatomasessentiallynonbondingmolecularorbitals.Whileoverlapofthehydrogen1sand
fluorine2sorbitalscan,intheory,occur,theenergiesoftheorbitalsaretoodifferenttopermiteffectiveoverlap,and
forthisreason,thefluorine2sorbitalremainsessentiallynonbonding.The1sorbitalofhydrogenandthe2p zorbital
offluorineoverlapeffectivelyandformtwoMOs.The3orbitalismuchcloserinenergytothe2p y orbitaloffluorine
andthereforehasmore2p y characterandisclosertothefluorinenucleus,whiletheantibonding4orbitalhasmore
hydrogen1scharacter.TheMOdiagraminfigure5.54showsthesequenceofthevalencemolecularorbitals.

TheCOmoleculeisanotherheteronucleardiatomicmoleculethatcanservetoillustratefeaturesofMOtheory.BothC
andOhave2sand2pvalenceorbitalsandthereforecanformbonds.GiventhatOismoreelectronegativethanC,
thevalenceorbitalsonOwillbeoflowerenergythanthecorrespondingorbitalsonC.

Figure5.55showstheenergyleveldiagramforCO.The2sandthe2p zorbitalsonbothCandOoverlaptoformfour
molecularorbitals,whiletheothertwoporbitalsonCandOoverlaptoformtwobondingandtwoantibonding
orbitals.Thebondingorbitalsarelowerinenergythanthebondingorbitalwithmainlypcharacterduetosp
mixing,whichisgenerallylargeinheteronucleardiatomicmolecules.
FIGURE5.55ThemolecularorbitaldiagramofCO.

Wehavebarelyscratchedthesurfaceofmolecularorbitaltheory.Morecomplicatedsystems(threeormoreatoms)
requiretheuseofpowerfulcomputerstoadequatelytreatthebonding.Indeed,eventhesimplediatomicsystemswe
havediscussedhaveinvolvedhugesimplificationsitis,infact,currentlyimpossibletoexactlydescribeamolecule
containingmorethanoneelectron,asthemathematicsofsuchasystemhavesofardefiedsolution.Wehave
discussedanumberofwaystodescribethebondinginmoleculesalthougheachofthemhasparticularshortcomings,
ifappliedappropriately,wecanusethemtosatisfactorilyexplainthebondinginvirtuallyallchemicalsystems.

ChemistryResearch

AsymmetricOrganocatalysisacomputationalapproach

Professor(Richard)MingWahWong,NationalUniversityofSingapore

Inthischapterwehavediscussedhowtheelectronsonatomsinmolecularcompoundscaninteractandbe
sharedbetweenatomstoformbonds.Understandinghowelectronsinspecificorbitalsinagroupofatoms
interactwithotherelectronsfromanothergroupofatomscanassistusindeterminingmethodsbywhich
complexmoleculesmightbesyntesised.Thiscanbecarriedoutusingtheprinciplesofquantummechanics
andsolutionsoftheSchrdingerequation(seechapter4).However,practicalmeanstoachievethishave
onlyrecentlybecomeavailablethroughthedevelopmentofsophisticatedcomputersandintelligent
programs.Withthelatestadvancesincomputerhardwareandcomputationalmethodologies,highlyaccurate
theoreticalcalculationsofchemicalprocessescannowbecarriedoutroutinely.

Professor(Richard)MingWahWongisoneresearcherwhousescomputationalmethodstostudyhow
moleculesreact.Histheoreticalstudiesshowedforthefirsttimethatargonandheliumarecapableofforming
chemicalbondsandpredictedthattheircompoundscanexistinthegasphase.Thesepredictionshave
subsequentlybeenconfirmedbyexperimentalchemistsandthisshowshowusingacomputercanguide
practicalresearchtowardsnewdiscoveries.

ProfessorWong'srecentresearchhasfocusedonunderstandingthedetailedpathwaysinvolvedinreactions
wheretwosmallermoleculesjointomakemorecomplicatedstructures.Importantly,someofthesereactions
canbeinfluencedbythepresenceofothersmallmolecules.Theseadditivescancontrolthespeedofthe
reactionandinfluencetheorientationofthereactants.Forinstance,Wongandcoworkershaveinvestigated
theuseofBF3asacatalystforareactionbetweentwoalkenemoleculesthatcreatesanewcyclicstructure.
Figure5.56isarepresentationofhowBF3bindstopropenaltocontroltheorientationoftheorbitaloverlap
betweenpropenalandbuta1,3diene,whichleadsultimatelytothecyclicproduct.Thediagramalsoshows
thetransitionstate,whichisthemomentaryarrangementofbondsandatomsthatexistsasreactantsare
convertedtoproducts.Youwillseeinchapter15thattransitionstateshavenomeasurablelifetimeand
consequentlytheirnaturecannotbedeterminedexperimentallybutmustbeinferredfromotherobservations.
Wong'stheoreticalcalculationsalsogiveinsightintothenatureofthetransitionstateandallowusto
understandhowthereactionoccursandpredictthenatureoftheobservedproduct.
FIGURE5.56Agraphicaldescriptionofthemannerbywhichbuta1,3dieneandpropenalareconvertedintoa
cyclicalkene.Thetransformationgoesthroughanenergypeak,whichiscalledthetransitionstate,
wheretheorbitalsinthealkenesbegintooverlaptoformthenewcarboncarbonbondsfoundinthe
product.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
SUMMARY
FundamentalsofBonding
Covalentbondsareformedasaresultofthesharingofelectronsbetweennucleiinawaythatbalances
attractiveandrepulsiveforces.Inthehydrogenmolecule,H2,thisleadstoalowestenergyinternuclear
separationof74pm.Thisdistanceiscalledthebondlength,andtheenergydifferencebetweenthe
moleculeatthisdistanceandtheseparatedatomsiscalledthebondenergy.ThesinglebondinH2isan
exampleofabond,abondthatistotallysymmetricwithrespecttorotationabouttheinternuclearaxis.
InsimplediatomicmoleculessuchasH2andF2wecandescribebondingintermsofoverlapofatomic
orbitalscontainingsingleelectrons.Whenthetwoatomsinadiatomicmoleculearedifferent,the
electronpairwilltendtobeattractedmoretooneatom,resultinginunequalsharingoftheelectronsand
apolarcovalentbond.Theunequalsharingisaconsequenceofthedifferentelectronegativityvaluesof
theatomsinthemoleculethegreatertheelectronegativitydifferencebetweentheatoms,themorepolar
thebond.Electronegativitiesgenerallyincreaseacrossaperiodanddecreasedownagroupinthe
periodictable.

IonicBonding
Compoundsformedbetweenelementswithverydifferentelectronegativitiesareoftenionicin
character.Ioniccompoundsgenerallyconsistofalternatingpositivelyandnegativelychargedionsthat
areheldtogetherbyattractiveelectrostaticforcesbetweentheoppositelychargedions.Themagnitude
oftheattractiveforcesisdependentonthechargeoftheionsandtheseparationbetweenthem,aswell
asanumberofotherfactors.Thetotalenergythatmustbesuppliedtobreakthecrystallatticeintoits
gaseousionsiscalledthelatticeenergy.Trendsinlatticeenergyvaluesforioniccompoundscanbe
explainedintermsofionicchargeandseparation.

LewisStructures
Lewisstructuresshowthedistributionofvalenceelectronswithinamolecule.Bondingelectronsare
foundinsinglebonds(1electronpair),doublebonds(2electronpairs)ortriplebonds(3electronpairs)
andthesearerepresentedas1,2and3linesrespectivelybetweenthebondedatoms.Nonbonding
electrons,calledlonepairs,areindicatedasdotsnexttotheelementalsymbolfortheatomonwhich
theyarelocated.Lewisstructuresmaybedrawnusingthefollowingfivestepprocedure:
Step1:Countthevalenceelectrons.
Step2:Assemblethebondingframeworkusingsinglebonds.
Step3:Placethreenonbondingpairsofelectronsoneachouteratom,exceptH.
Step4:Assigntheremainingvalenceelectronstoinneratoms.
Step5:Minimiseformalchargesonallatoms.

Anatomhasanoctetifitissurroundedbyfourpairsofelectrons.Thisarrangementisoftenfoundfor
elementsinthesecondperiodoftheperiodictable.Whenthereisachoiceofelectronarrangement,the
onewhichminimisestheformalchargeonallatomswillbepreferred.Insomecases,twoormore
energeticallyequivalentLewisstructuresforamoleculecanbedrawnwhichdifferonlyintheposition
ofoneelectronpair.Suchstructuresarecalledresonancestructures.Wecanalsohaveenergetically
inequivalentresonancestructuresinthesecases,thepreferredstructurewillagainbethatwiththe
lowestpossibleformalchargeoneachatom.

ValenceShellElectronPairRepulsion(Vsepr)Theory
VSEPRtheorystatesthatamoleculewilladoptashapeinwhichelectronpairrepulsionsareminimised.
Thisisachievedbyplacingelectronpairsasfarapartaspossible.Wecanpredictthestructureofa
moleculebyusingthefollowingthreestepprocedure:
1.DrawtheLewisstructureofthemolecule.
2.Countthenumberofsetsofbondingpairsandlonepairsofelectronsaroundanyinneratom,and
usethefollowingtabletodeterminetheoptimumgeometryofthesesets.

Numberofsetsofelectronpairs Geometryofsetsofelectronpairs
2 linear
3 trigonalplanar
4 tetrahedral
5 trigonalbipyramidal
6 octahedral

3.Modifythegeometry,ifnecessary,totakeaccountofthefactthatthemagnitudesofrepulsions
betweensetsofelectronpairsdependonwhethertheelectronpairsinvolvedarebondingpairs
(BP)orlonepairs(LP).Therepulsionsareintheorder:

Theidealisedelectronpairgeometrieswillbeslightlydistortedwheneverlonepairsarepresent,because
lonepairsoccupymorespacethanbondingpairs.

PropertiesofCovalentBonds
Moleculeswherethecentresofpartialnegativeandpartialpositivechangesdonotcoincidehavea
dipolemoment.ThemagnitudesofdipolemomentsaremeasuredinCm(coulombmetres).Molecules
containingpolarbondsdonotnecessarilyhaveadipolemoment,asthepolaritiesofsuchbondscan
canceleachother.Carbondioxideprovidessuchanexample.

Bondlengthsinmoleculesaredependentontheatomicradiiofthebondedatoms,whichthemselvesare
dependentoneffectivenuclearcharge.Amultiplebondbetweentwoatomsisshorterthanasinglebond
betweenthesameatoms.Bondenergiesincreaseasthenumberofelectronsinthebondincreases,and
alsoastheelectronegativitydifferencebetweenthebondedatomsincreases.Thelengthofabondis
inverselyproportionaltoitsbondenergyasabondlengthens,itsenergybecomesless.

ValenceBondTheory
Valencebondtheorydescribesbondinginmoleculesusinglocalisedbondsformedfromorbitaloverlap
ofhybridorbitals.Asthenamesuggests,valencebondtheoryconsidersonlyvalenceorbitalsinthe
formationofbonds.Valenceatomicorbitalsundergohybridisationtoformhybridorbitals,withthe
orbitalsinvolveddependingonthetypeofhybridorbitalrequired.Hybridisationofonesandthreep
orbitalsgivesfoursp 3hybridorbitals,hybridisingonesandtwoporbitalsgivesthreesp 2hybrid
orbitals,andhybridisingonesandoneporbitalgivestwosphybridorbitals.Theseprocessesleave
zero,oneandtwoporbitals,respectively,unhybridised.Thesp 3hybridorbitalsarepositioned
tetrahedrally,sp 2hybridorbitalsarearrangedinatrigonalplane,andsphybridorbitalsadoptalinear
arrangement.Thehybridorbitalsformbondsbyoverlappingwitheitheratomicorbitalsorhybrid
orbitalsonadjacentatoms.Multiplebondscanbedescribedintermsofonebondplusonebond
(doublebond)oronebondplustwobonds(triplebond)bondsareformedbyoverlapofthe
unhybridisedporbitalsonadjacentsp 2orsphybridisedatoms.

MolecularOrbitalTheory:DiatomicMolecules
Molecularorbitaltheoryconsidersallpossibleoverlapsbetweenatomicorbitalsinamoleculeand
describesbondingintermsofdelocalisedbonds.Overlapoftwoatomicorbitalsgivestheformationof
molecularorbitalsthatcancovertheentiremolecule.Atomicorbitalscanoverlapinphase(constructive
overlap)togivealowenergybondingmolecularorbital,oroutofphase(destructiveoverlap)togivea
highenergyantibondingmolecularorbital.Electrondensityismaximisedbetweenthenucleiinbonding
MOs,whileantibondingMOscontainanode,apositionwheretheamplitudechangessign,betweenthe
nuclei.Therelativeenergiesoftheresultingorbitalsareshownonamolecularorbitaldiagram.
Electronsareplacedintoamolecularorbitaldiagramfollowingthesamerulesasusedinanatomic
energyleveldiagram.Thebondorderofasimplediatomicmoleculecanbecalculatedfromthe
expression:

Whilebondordersaregenerally1,2or3,itispossibletohavenonintegerbondorders.Molecular
orbitaltheorycanaccountfortheobservedparamagnetismofO2whilevalencebondtheorycannot.
However,toaccountfortheobservedpropertiesofotherdiatomicmolecules,orbitalmixing,the
overlapofsatomicorbitalswithp zatomicorbitals,mustbeconsidered.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYCONCEPTSANDEQUATIONS
Periodictrendsinelectronegativity(section5.1)
Thesetrendsallowustousethepositionsofelementsintheperiodictabletoestimatethedegreeof
bondpolarityandtoestimatewhichatominabondisthemostelectronegative.

MethodfordrawingLewisstructures(section5.3)
Lewisstructuresshowthedistributionofvalenceelectronsinamoleculeorionandaredrawnaccording
tothefollowingconventions.
1.Eachatomisrepresentedbyitselementalsymbol.
2.OnlythevalenceelectronsappearinaLewisstructure.
3.Alinejoiningtwoelementalsymbolsrepresentsonepairofelectronssharedbetweentwoatoms.
4.Dotsplacednexttoanelementalsymbolrepresentnonbondingelectronsonthatatom.

Formalcharges(section5.3)
Byassigningformalcharges,wecanselectthebestLewisstructureforamoleculeorpolyatomicion.

Methodfordeterminingresonancestructures(section5.3)
Bydistributingmultiplebondsoveratomsinamolecule,weobtainabetterdescriptionofthebonding.

VSEPRtheory(section5.4)
ThistheoryenablesustopredicttheshapeofamoleculeorpolyatomicionwhenitsLewisstructureis
known.
1.DrawtheLewisstructureofthemolecule.
2.Countthenumberofsetsofbondingpairsandlonepairsofelectronsaroundanyinneratom,and
usethefollowingtabletodeterminetheoptimumgeometryofthesesets.

Numberofsetsofelectronpairs Geometryofsetsofelectronpairs
2 linear
3 trigonalplanar
4 tetrahedral
5 trigonalbipyramidal
6 octahedral

3.Modifythegeometry,ifnecessary,totakeaccountofthefactthatthemagnitudesofrepulsions
betweensetsofelectronpairsdependonwhethertheelectronpairsinvolvedarebondingpairs
(BP)orlonepairs(LP).Therepulsionsareintheorder:

Hybridorbitals(section5.6)
Hybridorbitalshelptoexplainthebondinginmolecules,andinparticularcanbeusedtorationalisethe
shapesofmolecules.

Molecularorbitaldiagrams(section5.7)
Byplacingelectronsinmolecularorbitaldiagramsweareabletoobtainbondordersthatagreewith
experimentsforsimplediatomicmolecules.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWQUESTIONS
FundamentalsofBonding
5.1Forthefollowingatoms,writethecompleteelectronconfigurationandidentifywhichofthe
electronswillbeinvolvedinbondformation:
(a)O
(b)P
(c)B
(d)Br.
5.2DescribebondformationbetweenahydrogenatomandaniodineatomtoformamoleculeofHI,
andincludeadiagramoftheoverlappingorbitals.
5.3Givethegroupnumberandthenumberofvalenceelectronsforthefollowingelements:
(a)aluminium
(b)arsenic
(c)fluorine
(d)tin.
5.4Hydrogenformsdiatomicmoleculeswithelementsfromgroup1oftheperiodictable.Describethe
bondinginLiHandincludeadiagramoftheoverlappingorbitals.
5.5Foreachofthefollowingpairs,identifywhichelementtendstoattractelectrondensityfromthe
otherinacovalentbond:
(a)CandN
(b)SandH
(c)ZnandI
(d)SandAs.
5.6Showthedirectionofbondpolarityforthefollowingbondsusing+/notation:
(a)SiO
(b)NC
(c)ClF
(d)BrC.
5.7Arrangethefollowingmoleculesinorderofincreasingbondpolarity:H2O,NH3,PH3andH2S.
IonicBonding
5.8Fromthefollowinglist,selecttheelementsthatformioniccompounds:Ca,C,Cu,Cs,ClandCr.
Indicatewhethereachformsastablecationorastableanion.
5.9Fromthefollowinglist,selecttheelementsthatformioniccompounds:B,Ba,Be,BiandBr.
Indicatewhethereachformsastablecationorastableanion.
5.10Considerthreepossibleioniccompoundsformedbybariumandoxygen:Ba+O,Ba2+O2and
Ba3+O3.
(a)Whichwouldhavethegreatestlatticeenergy?
(b)Whichwouldrequiretheleastenergytoformtheions?
(c)Whichcompoundactuallyexists,andwhy?
LewisStructures
5.11Countthetotalnumberofvalenceelectronsinthefollowingspecies:
(a)H3PO4
(b)(C H ) C+
6 53
(c)(NH2)2CO
(d)SO 2.
4
5.12Convertthefollowingformulaeintomolecularframeworks.Foreachmolecule,calculatehow
manyvalenceelectronsarerequiredtoconstructtheframework:
(a)(CH3)3CBr
(b)(CH3CH2CH2)2NH
(c)HClO3
(d)OP(OCH3)3.
5.13DeterminetheLewisstructuresof:
(a)NH3
(b)NH +
4
(c) H N.
2
5.14DeterminetheLewisstructuresof:
(a)PBr3
(b)SiF4
(c) BF .
4
5.15UsethestandardprocedurestodeterminetheLewisstructuresof:
(a)H3CNH2
(b)CF2Cl2
(c)OF2.
5.16DeterminetheLewisstructuresof:
(a)IF5
(b)SO3
(c)OPCl3
(d)XeF2.
5.17DeterminetheLewisstructureofeachofthefollowingpolyatomicions.Includeallresonance
structuresandformalchargeswhereappropriate.
(a) NO
3
(b)HSO
4
(c) CO 2
3
(d)ClO
2
ValenceshellelectronpairRepulsion(VSEPR)Theory
5.18Sketchthefollowingmolecularshapesandgivethevariousbondanglesinthestructures:
(a)trigonalplanar,
(b)tetrahedral,
(c)octahedral.
5.19Sketchandnametheshapesofthefollowingmolecules:
(a)CF2Cl2
(b)SiF4
(c)PBr3.
5.20Drawaballandstickmodelthatshowsthegeometryof1,2dichloroethane,ClH2CCH2Cl.
5.21WritetheLewisstructureofdimethylamine,(CH3)2NH.Determineitsgeometry,anddrawaball
andstickmodelofthemoleculeshowitasanammoniamoleculewiththetwohydrogenatoms
replacedbyCH3groups.
5.22Iodineformsthreecompoundswithchlorine:
(a)ICl
(b)ICl3
(c)ICl5.
DeterminetheLewisstructure,describetheshapeanddrawaballandstickmodelofeach
compound.
5.23Determinethemolecularshapeandtheidealbondanglesforeachofthefollowing:
(a)SO2
(b)SbF5
(c) ClF +
4
(d)ICl .
4
PropertiesofCovalentBonds
5.24DeterminetheLewisstructuresofthefollowingcompounds,anddeterminewhichhavedipole
moments.Foreachmoleculethathasadipolemoment,drawaballandstickmodelandinclude
anarrowtoindicatethedirectionofthedipolemoment.
(a)SiF4
(b)H2S
(c)XeF2
(d)GaCl3
(e)NF3
5.25Carbondioxidehasnodipolemoment,butsulfurdioxidehas=5.4410 30Cm.UseLewis
structurestoaccountforthisdifferenceindipolemoments.
5.26Whichofthefollowingmoleculeswouldyouexpecttohavebondanglesthatdeviatefromthe
idealVSEPRvalues?Forthemoleculesthatdo,makesketchesthatillustratethedeviations.
(a)PF5
(b)CH3I
(c)BrF5
5.27UseTable5.3toarrangethefollowingbondsinorderofincreasingbondstrength(weakestfirst).
Listthesinglemostimportantfactorforeachsuccessiveincreaseinstrength.

C C,HN,C O,N NandCC


ValenceBondTheory
5.28DescribethebondingbetweenfluorineandchlorineatomsinthemixedhalogenFCl.
5.29DescribethebondingbetweenhydrogenandchlorineatomsinHClandincludeapictureofthe
overlappingorbitals.
5.30Thebondanglesinantimonytrifluorideare87.DescribethebondinginSbF3,includingapicture
oftheorbitaloverlapinteractionthatcreatestheSbFbonds.
5.31Determinethehybridisationofaninneratominamoleculethathaseachofthefollowing
characteristics:
(a)2lonepairsand2ligands
(b)3ligandsand1lonepair
(c)3ligandsandnolonepairs.
5.32Namethehybridorbitalsformedbycombiningeachofthefollowingsetsofatomicorbitals:
(a)3sandthree3porbitals
(b)2sandone2porbital.
5.33Identifythehybridisationoftheboldedatomineachofthefollowingspecies:
(a)(CH3)2NH
(b)SO2
(c)CS2.
5.34Describethebondinginthechloroformmolecule,CHCl3.Sketchanorbitaloverlapdiagramofthe
molecule.
5.35Describethebondinginthehydrazinemolecule,H2NNH2.Sketchanorbitaloverlapdiagramof
themolecule.
5.36Describethebondinginthecommonsolventacetone,(CH3)2CO,andincludesketchesofallthe
bondingorbitals.

5.37Thecarboncompoundspenta1,4diene,pent1yneandcyclopenteneallhavethemolecular
formulaC5H8.Usethenumberofsetsofelectronpairsandhybridisationtodevelopbonding
picturesofthesethreemolecules.
(a)

(b)

(c)

5.38Decideifthefollowingpairsoforbitalsoverlaptoformabond,bond,ornobondatall.
Explainyourreasoningineachcase,includingasketchoftheorbitals.Assumethebondlies
alongthezaxis.
(a)2p zand2p z
(b)2p y and2 px
(c) sp 3and2p
z
(d)2p y and2p y
MolecularOrbitalTheory:DiatomicMolecules
5.39Usemolecularorbitaldiagramstorankthebondenergiesofthefollowingdiatomicspeciesfrom
weakesttostrongest:H2,H2andH22.
5.40WhichofN orN +hasthestrongerbond?Useorbitalconfigurationstojustifyyourselection.
2 2
5.41Foreachofthefollowinginteractionsbetweenorbitalsoftwodifferentatoms,sketchtheresulting
molecularorbitals.Assumethatthenucleiliealongthezaxis,andincludeatleasttwocoordinate
axesinyourdrawing.LabeleachMOasbondingorantibondingandor.
(a)2sand2p z
(b)2p x and2p x
5.42Belowisanillustrationshowingtwo3dorbitalsabouttooverlap.Thedrawingsalsoshowthe
algebraicsignsofthewavefunctionsforbothorbitalsinthiscombination.Willthiscombinationof
orbitalsproduceabondingoranantibondingMO?

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWPROBLEMS
5.43Determinethemoleculargeometriesofthefollowingmolecules:
(a)SiCl4,
(b)SeF4and
(c)CI4.
5.44Determinethemoleculargeometriesofthefollowingions:
(a) ClF ,
2
(b)BF and
4
(c) PF +.
4
5.45Howmanydifferentstructuralisomersarethereforoctahedralmoleculeswiththegeneralformula
AX3Y3?Drawthreedimensionalstructuresofeach.
5.46UsinginformationinTable5.1,determinetheaveragedifferenceinlatticeenergybetweengroup
1fluoridesandgroup1chlorides,andtheaveragedifferenceinlatticeenergybetweengroup1
bromidesandgroup1iodides.Isthereatrendintheindividualvalues?Ifso,describeandexplain
it.
5.47Carbon,nitrogenandoxygenformtwodifferentpolyatomicions:thecyanateion,NCO,andthe
isocyanateion,CNO.WriteLewisstructuresforeachanionincludenearequivalentresonance
structuresandindicateformalcharges.
5.48SpecieswiththegeneralchemicalformulaXY4canhavetheshapesshowninthefollowing
diagrams.Foreach,namethemoleculargeometry,identifytheidealVSEPRbondangles,givethe
numberoflonepairspresentinthestructureandprovideaspecificexample.
(a)

(b)

(c)

5.49SpecieswiththegeneralchemicalformulaXY3Ycanhavetheshapesshowninthefollowing
diagrams.Foreach,namethemoleculargeometry,identifytheidealVSEPRbondangles,givethe
numberoflonepairspresentinthestructureandprovideaspecificexample.
(a)
(b)

(c)

5.50Intheloweratmosphere,NO2participatesinaseriesofreactionsinairthatisalsocontaminated
withunburnedhydrocarbons.Oneproductofthesereactionsisperoxyacetylnitrate(PAN).The
skeletalarrangementoftheatomsinPANappearsbelow.

(a)CompletetheLewisstructureofthiscompound.
(b)Determinethegeometryaroundeachatommarkedwithanasterisk.
(c)Givetheapproximatevaluesofthebondanglesindicatedwitharrows.
5.51TheHOHbondangleinawatermoleculeis104.5.TheHSHbondangleinhydrogen
sulfideisonly92.2.Explainthesevariationsinbondanglesusingorbitalsizesandelectron
electronrepulsionarguments.Drawspacefillingmodelstoillustrateyourexplanation.
5.52ListthefollowingXHbondsfromsmallestbondpolaritytolargestbondpolarity:CH,FH,
NH,OHandSiH.
5.53Sulfurformstwostableoxides,SO2andSO3.Describethebondingandgeometryofthese
compounds.
5.54Capsaicinisthemoleculeresponsibleforthehotspicinessofchillies:

(a)Howmanybondsdoescapsaicinhave?
(b)Whichorbitalsareusedforbondingbyeachofthelabelledatoms?
(c)Whatarethebondanglesaroundeachofthelabelledatoms?
(d)Redrawthestructureofcapsaicinaddingthelonepairs.
5.55Useelectronconfigurationstodecideifthefollowingspeciesareparamagneticordiamagnetic:
(a) N +
2
(b)O +.
2
5.56Determinethetypeoforbitals(atomic,sp 3orsp 2)usedbyeachatominthemoleculesshown
below.
(a)

(b)H3CNH2
(c)

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
ADDITIONALEXERCISES
5.57DeterminetheLewisstructuresforthetwopossiblearrangementsoftheN2Omolecule:NNO
andNON.Experimentsshowthatthemoleculeislinearandhasadipolemoment.Whatisthe
arrangementofatoms?Justifyyourchoice.
5.58Theinneratomofatriatomicmoleculecanhaveanyoffourdifferentgeometriesforthe
surroundingsetsofelectronpairs.Identifythefour,describetheshapeassociatedwitheachand
giveaspecificexampleofeach.
5.59BothPF3andPF5areknowncompounds.NF3alsoexists,butNF5doesnot.Whyisthereno
moleculewiththeformulaNF5?
5.60Phosphorusacid,H3PO3,isanexceptiontotherulethathydrogenalwaysbondstooxygenin
oxoacids.Inthiscompound,oneofthehydrogenatomsbondstophosphorus.Determinethe
Lewisstructureofphosphorusacidanddeterminethegeometryaroundthephosphorusatom.
Drawaballandstickmodelofthemolecule.
5.61Nitrogenmoleculescanabsorbphotonstogenerateexcitedstatemolecules.Constructanenergy
leveldiagramandplacethevalenceelectronssothatitdescribesthemoststableexcitedstateofan
N2molecule.IstheNNbondinthisexcitedstateN2moleculestrongerorweakerthantheN
Nbondingroundstatenitrogen?Explainyouranswer.
5.62Chlorineformsoneneutraloxide,ClO2.Describethebondinginthisunusualcompound.Explain
whyitisconsideredunusual.
5.63Dilithiummoleculescanbegeneratedbyvaporisinglithiummetalatverylowpressure.Doyou
thinkitispossibletopreparediberyllium?ExplainyourreasoningusingMOdiagramsforLi2and
Be2.
5.64Whenanoxalateanion,C O 2,addstwoprotonstoformoxalicacid,twoCObondsbecome
2 4
longerandtwobecomeshorterthanthebondsinoxalateanions.Whichbondsgetlongerand
whichshorter?Usebondingprinciplestoexplainthechanges.
5.65Considerthebondlengthsofthefollowingdiatomicmolecules:N2,110pmO2,121pmF2,143
pm.Explainthevariationinlengthintermsofthemolecularorbitaldescriptionsofthese
molecules.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYTERMS
antibondingmolecularorbital ioniccompounds polarcovalentbond
bondenergy latticeenergy resonancestructure
bondlength Lewisstructure seesawshape
bondorder linear sigma()bond
bondingmolecularorbital localisedbond singlebond
bondingorbital lonepair sphybridorbitals
covalentbond molecularorbitaldiagram sp 2hybridorbitals
delocalisedbond molecularorbitaltheory
sp 3hybridorbitals
dipolemoment molecularorbital(MO)
tetrahedral
doublebond node
trigonalbipyramidal
electronegativity octahedral
trigonalplanar
formalcharge orbitalmixing
triplebond
hybridorbital orbitaloverlap
valenceshellelectronpair
hydration pi()bond
repulsion(VSEPR)

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CHAPTER

6 Gases
Weareallfamiliarwiththethreecommonstatesofmattergas,liquidandsolidin,forexample,theair
webreathe,thewateroftheoceanandthesandofthebeach.Allthreestatesarecomposedofatoms,ionsor
molecules.Thestrengthoftheattractiveforcesbetweentheseconstituentsinfluenceswhichparticularstateof
matteracompounddisplays.Inthischapterwewillfocusonthecharacteristicsandbehaviourofgases,and
inchapter7wewilldealwithliquidsandsolids.

Althoughfewchemicalelementsoccurnaturallyasgases,wespendalmostallofourtimeimmersedinthem.
TheEarth'satmosphereismadeupmainlyofnitrogen,N2,(78%)andoxygen,O2,(21%)withsomeother
speciesintraceamounts.Theexactcompositionandtemperatureofthisgasmixtureisresponsibleforour
weather.ThephotoonthispageshowshotairballoonsovertheMelbourneCricketGround(MCG)and
remindsusthathotairballoonistsexploitthefactthathotairrises.

Webeginthischapterwithadiscussionofthevariablesthatcharacterisegases.Thenwedevelopamolecular
descriptionthatexplainsgasbehaviour.Next,weexploreadditionalgaspropertiesandshowhowtocarryout
stoichiometriccalculationsforreactionsinvolvinggasphasespecies.Wethenexplorethekindsofattractions
thatexistbetweenmoleculesandhowtheseattractionsaffectthephysicalpropertiesofgases.

KEYTOPICS

6.1Thestatesofmatter
6.2Describinggases
6.3Molecularviewofgases
6.4Gasmixtures
6.5Applicationsoftheidealgasequation
6.6Gasstoichiometry
6.7Realgases
6.8Intermolecularforces

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.1TheStatesofMatter
Itisremarkablethatessentiallyallofthematterintheuniverseexistsinonlythreestates:solid,liquidor
gas.Afourthstateofmatter,plasma,existsonlyunderextremeconditionssuchasthosefoundinthe
interiorsofstars,whiletheBoseEinsteincondensate,arecentlydiscoveredstateofmatter,isfound
onlyattemperaturesapproachingabsolutezero.Wewillalsoencountersupercriticalfluids,whichhave
propertiesofbothliquidsandgases,inchapter7.

Itisalsointerestingthatmostsubstancescanexistinanyofthesethreestates,andwecanchangethe
moststablestateofaparticularsubstancebyvaryingthetemperatureand/orpressureforexample,
coolingliquidwatertobelow0Catambientpressurewillproducesolidwater(ice).

Why,at25Candatmosphericpressure,doeswaterexistasaliquid,whileoxygenisagasandgoldis
asolid?Theanswerliesintheforcesthatoccurbetweenindividualatoms,moleculesorionsina
substance.Solidsareheldtogetherbyrelativelystrongforcesbetweentheircomponents,whilethe
correspondingforcesingasesarerelativelyweak.Thischapterandchapter7focusonthedifferent
possiblestatesofmatter.Inthischapter,weconcentrateonthegaseousstateofmatter,andinvestigate
thedifferenttypesofforcesthatcanoccurbetweenatoms,ionsandmolecules.Chapter7isprimarily
concernedwithliquidsandsolids(thesocalledcondensedphases),andalsolooksattheprocesses
involvedwhensubstancesundergochangesofstate.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.2DescribingGases
Gasesarecharacterisedbythefactthat,incontrasttoliquidsandsolids,theyexpandtooccupyallthe
spaceoftheircontainer.Forexample,gaseouswater(watervapour)willbefoundinallpartsofany
flaskitisin,but,ifthetemperatureislowered,theresultingliquidwateroccupiesonlythebottomofthe
flask.Loweringthetemperaturefurthertobelowthefreezingpointproducesice,whichalsooccupies
onlythebottomoftheflask.Thefactthatgasesfillallavailablespaceimpliesthattheindividualgas
atomsormoleculesarefreetomoveanywherewithintheircontainer(figure6.1),andthereforethe
forcesbetweenthemmustbeveryweak.Oneofthedefiningcharacteristicsofgasesisthepressurethey
exert.Thisresultsfromtherapidmotionofindividualgasatomsormoleculesandtheircollisionswith
thewallsofthecontainer.Thepressure(p)exertedbyagasisdependentontheamountofgaspresent
(n),thevolumeinwhichitiscontained(V!)anditstemperature(T).Onthefollowingpages,wederivea
relationshiprelatingallofthesevariables.

FIGURE6.1Moleculesoratomsofagasmovefreelythroughouttheentirevolumeofacontainer,changing
directionwhenevertheycollidewithothermoleculesoratomsorwithawall.Thelinetracesa
possiblepathofasinglemoleculeoratom.

Pressure(p)
Anyobjectthatstrikesasurfaceexertsaforceagainstthatsurface.Inthesamewaythataballexertsa
forceagainstthegroundwhenitstrikesit,thegasmoleculesinsidetheballalsoexertpressurethrough
collisionswiththewallsoftheball.Atanytemperatureaboveabsolutezero,atomsandmoleculesare
alwaysinmotion.Atthemolecularlevel,atomsandmoleculesexertforcesthroughneverending
collisionswitheachotherandwiththewallsoftheircontainer(e.g.theinsidesurfaceoftheball).The
collectiveresultofthesecollisionsiswhatwecallpressure.Weexperiencepressureasamacroscopic
property.

WecangetafeelforthemacroscopiccharacteristicsofgaspressurebyexaminingtheEarth's
atmosphere.Theatmosphereisahugereservoirofgasthat,duetoEarth'sgravity,exertspressureonthe
Earth'ssurface.Thepressureoftheatmospherecanbemeasuredwithaninstrumentcalleda
barometer.Figure6.2showsaschematicviewofasimplemercurybarometer.Alongglasstube,
closedatoneend,isfilledwithliquidmercury.Thefilledtubeisinvertedcarefullyintoadishthatis
partiallyfilledwithmoremercury.Theforceofgravitypullsdownwardsonthemercuryinthetube.
Withnoopposingforce,allthemercurywouldrunoutofthetubeandmixwiththemercuryinthedish.
Themercurydoesfall,buttheflowstopsatacertainheight.Thecolumnofmercurystopsfalling
becausetheatmosphereexertspressureonthemercuryinthedish,pushingthecolumnupthetube.
Whentheheightofthemercurycolumngeneratesadownwardforceontheinsideofthetubethat
exactlybalancestheforceexertedbytheatmosphereontheoutsideofthetube,thecolumnofmercury
willremainsteady.
FIGURE6.2Amercurybarometer.Thepressureoftheatmosphereonthesurfaceofthemercurybalances
thepressureofthecolumnofmercury.

Atsealevel,atmosphericpressuresupportsamercurycolumnapproximately760mmhigh.Changesin
altitudeandweathercausefluctuationsinatmosphericpressure.Atsealeveltheheightofthemercury
columnseldomvariesbymorethan10mm,exceptunderextremeconditions,suchasintheeyeofa
cyclone,whenitmayfallbelow740mm.

Amanometerissimilartoabarometer,butinamanometergasesexertpressureonbothliquid
surfaces.Consequently,amanometermeasuresthedifferenceinpressuresexertedbytwogases.A
simplemanometer,showninfigure6.3,isaUshapedglasstubecontainingmercury.Onesideofthe
tubeisexposedtotheatmosphereandtheothertoagaswhosepressurewewanttomeasure.Infigure
6.3,thepressureexertedbytheatmosphere(p atm)islessthanthepressureexertedbythegasinthebulb
(p gas).Thedifferenceinheightsofmercurybetweenthetwosidesofthemanometerdependsonthe
differenceinthepressuresexertedbythegasandtheatmosphere(equaltop Hg).

FIGURE6.3Thedifferenceinheightsofliquidonthetwosidesofamanometerisameasureofthedifference
ingaspressuresappliedtothetwosides.

Aswelearnedinchapter2,theSIunitforpressureisthepascal(Pa).Pressureisdefinedasforceper
unitarea,sothepascalisexpressedbycombiningtheSIunitsforthesetwovariables.TheSIunitof
forceisthenewton(N),andtheunitofareaissquaremetres(m2).Thus1Pa=1Nm2=1kgm1s2=
1Jm3(with1N=1kgms2and1J=1kgm2s2).

AnumberofnonSIunitsforpressurearealsocommonlyused:
Onestandardatmosphere(1atm)isthepressurethatwillsupportacolumnofmercury760mmin
height(i.e.averageatmosphericpressureatsealevel)1atm=1.0132510 5Pa.
Onetorristhepressureexertedbyacolumnofmercury1mminheight1atm=760torr.
1bar=110 5Pa.
InthistextbookwewillalwaysexpresspressureintheSIunit:thepascal(Pa).Inchapter8,wewill
encounterstandardpressure, ,whichis110 5Pa,veryslightlydifferentfromonestandard
atmosphere.Itisimportantnottoconfusethetwo.

TheGasLaws
Thevolumeoccupiedbyagaschangesinresponsetochangesinpressure,temperatureandamountof
gas.Therelationshipsamongtheseareknownasthegaslaws.

Boyle'SLaw:theRelationshipBetweenVolumeandPressure
Figure6.4aillustratesexperimentsconductedatconstanttemperaturebytheEnglishscientistRobert
Boyleinabout1660.BoyleaddedliquidmercurytotheopenendofaJshapedglasstube,trappinga
fixedamountofairontheclosedside.WhenBoyleaddedadditionalmercurytotheopenendofthe
tube,thepressureexertedbytheweightoftheadditionalmercurycompressedthetrappedgasintoa
smallervolume.Forexample,asshowninfigure6.4a,Boylefoundthatdoublingthetotalpressureon
thetrappedairbytheadditionofmercuryhalveditsvolume.Inmoregeneralterms,Boyle's
experimentsshowedthatthevolumeofthetrappedairwasinverselyproportionaltothetotalpressure
appliedbythemercuryplustheatmosphere.

or,alternatively:

wherekisaconstant.Thisisshowngraphicallyinfigure6.4b.

FIGURE6.4 (a)SchematicillustrationofBoyle'sexperimentsonairtrappedinJshapedtubes.The
pressureontheenclosedgasintherighthandtubeistwicethatinthelefthandtube,
andthevolumeoftheenclosedgasishalved.
(b)
GraphshowingthelinearvariationofVversus .
Charles'Law:theRelationshipBetweenVolumeandTemperature
Boylealsoobservedthatheatingagascausesittoexpandinvolume,butmorethanacenturypassed
beforeJacquesAlexandreCsarCharlesreportedthefirstquantitativestudiesofgasvolumeasa
functionoftemperature.Charlesfoundthat,forafixedamountofgas,agraphofgasvolumeversus
temperaturegivesastraightline,asshowninfigure6.5.Inotherwords,thevolumeofagasisdirectly
proportionaltoitstemperature.

FIGURE6.5Plotsofvolumeversustemperaturefor1moleofairatthreeconstantpressures.Thedots
representexperimentaldata,withdashedlinesofbestfitextrapolatedto0K.

or,alternatively:

wherekisaconstant.

Avogadro'sLaw:theRelationshipBetweenVolumeandAmount
Thevolumeofagasalsochangeswhentheamountofthegaschanges.Ifwedoubletheamountofa
gaswhilekeepingthetemperatureandpressurefixed,thegasvolumedoubles.Inotherwords,gas
volumeisproportionaltotheamountofgas.

or,alternatively:

wherekisaconstant.

TheIdealGasEquation
TheworkofBoyle,Charles,Avogadroandotherearlyscientistsshowedthatthevolumeofanygasis
proportionaltothetemperatureandamountofthegas,andinverselyproportionaltothepressureofthe
gas.Combiningtheseobservations,wefindthat:

Thisproportionalityisconvertedintoanequalitybyintroducingthegasconstant,representedbythe
symbolR.IntroducingRandmultiplyingbothsidesoftheequationbypgives:

Thisisknownastheidealgasequation,becauseitdescribesthebehaviourofanidealgas.Whileno
gasistrulyideal,theidealgasequationisadequatetodescribemostrealgasesprovidedthattheir
pressureisrelativelylow.Thetemperatureintheidealgasequationisexpressedinkelvin,withT(K)=
T(C)+273.15.ThegasconstantisdefinedinSIunitsasR=8.314Jmol1K1.Pressureisexpressed
inPa,volumeisexpressedinm3(1m3=110 3L)andamount(n)isexpressedinmoles.Thereisa
secondversionofthegasconstantthatisexpressedinnonSIunits:R=0.08206Latm1K1mol1.
Thisisusedfrequentlyandsoitisimportanttoalwaysconfirmthatthevalueandunitsofthegas
constantarechosenappropriatelyforagivenproblem.Workedexample6.1showsthecalculationsfor
bothgasconstants.

Itfollowsnaturallyfromtheidealgasequationthatallidealgaseshavethesamemolarvolumeundera
givensetofstandardconditions.Inchemistry,thegenerallyacceptedstandardconditionsare0Cand1
10 5Pa,leadingtoamolarvolumeundertheseconditionsof22.71L.

WORKEDEXAMPLE6.1

CalculationofGasPressure

A1.00010 3Lsteelstoragetankcontains88.5kgofmethane,CH4.Ifthetemperatureis25
C,whatisthepressureinsidethetank?

Analysis

Theproblemasksforthepressureexertedbyagas.Thegasisstoredinasteeltank,sothe
volumeofthegascannotchange.Nochemicalchangesaredescribedintheproblem.We
canthereforesolvethisproblemusingtheidealgasequation.

Solution

Wearetoldthat:

Wecancalculatethepressureofthegasusingtheidealgasequation,butweneedtomake
sureallthevariablesareexpressedinappropriateunits.Temperaturemustbeinkelvin,
amountofmethaneinmoles,andvolumeinm3.

WerearrangetheidealgasequationbydividingbothsidesbyV,thusmakingpressurethe
subjectoftheequation.

Add273.15tothetemperatureinCtoconverttokelvin.
Notethat,whenweaddnumbers,theresulthasthesamenumberofdecimalplacesasthe
numberwiththefewestdecimalplaces(zerointhisexample).

Usethemolarmassofmethanetocalculatetheamountofgas.

Nowsubstitutethisintotherearrangedidealgasequationandcalculatethepressure.

IfweusethenonSIversionofthegasconstant,0.08206LatmK1mol1,weneedto
expressthevolumeinlitres(L):

Isouranswerreasonable?

Itisimportanttocheckthattheunitscancelproperly,givingaresultinpressureunits(recall
that1Pa=1Jm3).Theproblemdescribesalargeamountofmethaneinarelativelysmall
volume,soahighpressure(over100timesatmosphericpressure)isreasonable.Thishigh
valueindicateswhygasesmustbestoredintanksmadeofmaterialssuchassteelthatcan
withstandhighpressures.

PRACTICEEXERCISE6.1
Determinethenewpressureifthetankin
workedexample6.1isstoredinahotshed
wherethetemperaturereaches42C.

Duringchemicalandphysicaltransformations,anyofthefourvariablesintheidealgasequation(p,V,
n,T)maychange,andanyofthemmayremainconstant.Theidealgasequationcanberearrangedas:

Then,fordifferentinitialandfinalconditions,wehave:

WORKEDEXAMPLE6.2

PressureVolumeVariations
Asampleofheliumgasisheldatconstanttemperatureinsideacylinderwithavolumeof
0.80Lwhenapistonexertsapressureof1.510 5Pa.Iftheexternalpressureonthepiston
isincreasedto2.110 5Pa,whatwillthenewvolumebe?

Analysis

Wecanvisualisetheconditionsbydrawingaschematicdiagramoftheinitialandfinal
conditions(p=initialpressure,p f=finalpressure,Vi=initialvolume,Vf=finalvolume).

Solution

Gasbehaviourisinvolved,sotheequationthatappliesistheidealgasequation,pV=nRT.
RearrangingthegasequationtosolveforVwillnothelpbecausewedonotknown,the
amountofHepresent,orT,thetemperatureofthegas.Wedoknow,however,thatnandT
remainunchangedasthepressureincreases.

Todeterminethefinalvolumeoftheheliumgas,applytheidealgasequationtotheinitial
andfinalconditions(shownwithsubscriptsiandf,respectively).

Inthisproblem,thequantityofHeinsidethecylinderandthetemperatureofthegasare
constant:

Therefore:

NoticethatwecansolvethisforVfwithoutknowingthevaluesofnandT.

Nowwerearrangetheaboveequation,substitutetheappropriatevaluesandcalculatethe
finalvolume.

Isouranswerreasonable?
Thisanswerisreasonablebecauseanexternalpressureincreasehascausedavolume
decrease.

PRACTICEEXERCISE6.2
Thepistoninworkedexample6.2is
withdrawnuntilthegasvolumeis2.55L.
Calculatethefinalpressureofthegas.

Inworkedexample6.2,thequantitiesontherighthandsideoftheidealgasequation(pV=nRT)are
fixed,whereasthequantitiesontheleftarechanging.Ausefulstrategyfororganisinggascalculationsis
torearrangethegasequationtoplaceallvariablesthatdonotchangeononeside.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.3MolecularViewofGases
Tounderstandwhyallgasescanbedescribedbyasingleequation,weneedtoexplorehowgases
behaveatthemolecularlevel.Asgasesarecharacterisedbyrapidmotionoftheirconstituentatomsor
molecules,themostimportantenergycomponenttoconsideristheirkineticenergy,Ekinetic .Thekinetic
energyofanobjectisgivenbytheequation:

wheremisthemassoftheobject(inthiscaseanindividualgasatomormolecule)anduisitsspeed.
Wecaneasilyobtainthemassofasingleatomormoleculefromthemolarmassofthegas,butinorder
tocalculateEkinetic wemustmeasurethespeedwithwhichanatomormoleculeismoving.Astheatoms
ormoleculesinanysampleofgasareconstantlyundergoingcollisionswithotheratomsormolecules
andwiththewallsofthecontainer,theymightnotnecessarilyallbemovingatthesamespeed.Onthe
followingpages,wedescribeamethodofmeasuringthespeedsofgasatomsormoleculestogivean
overalldistributionofspeedsforagassample.Thisallowsustodeterminethekineticenergy
distributionoftheatomsormoleculesinasampleofgas.

MolecularSpeeds
Thespeedsofmoleculesinagascanbemeasuredusingamolecularbeamapparatus,whichisshown
schematicallyinfigure6.6.Gasmoleculesinanovenescapethroughasmallholeintoachamberwith
verylowmoleculardensity:thatis,highvacuum.Asetofslitsblocksthepassageofallmolecules
exceptthosemovingintheforwarddirection.Theresultisabeamofmolecules,allmovinginthesame
direction.Arotatingdiscblocksthebeampathexceptforasmallslitthatallowsapacketofmolecules
topassthrough.Eachmoleculemovesdownthebeamaxisatitsownspeedundergoingminimal
collisionswithothermoleculesinthepacket.Thefasteramoleculemoves,thelesstimeittakestotravel
thelengthofthechamber.Adetectorattheendofthechambermeasuresthenumberofmolecules
arrivingasafunctionoftime,givingaprofileofspeeds.
FIGURE6.6 (a)Schematicdiagramofamolecularbeamapparatusdesignedtomeasurethespeedsof
gasmolecules.
(b)Distributionofmoleculesobservedbythedetectorasafunctionofthetimeafterapacket
ofmoleculesreachestheslitinthedisc.

Whenthespeedprofileofagasismeasuredinthisway,theresultsgiveadistributionliketheone
showninfigure6.6b.Ifallthemoleculestravelledatthesamespeed,theywouldallreachthedetector
atthesametime,inasingleclump.Instead,fastermoleculesmoveaheadofthemainpacket,and
slowermoleculesfallbehind.Thisexperimentshowsthatmoleculesinagashaveadistributionof
speeds.

Apatternemergeswhenthismolecularbeamexperimentisrepeatedforvariousgasesatacommon
temperaturemoleculeswithsmallmassesmove,onaverage,fasterthanthosewithlargemasses.Figure
6.7showsthisforH2,CH4andCO2.Ofthesemolecules,H2hasthesmallestmassandCO2thelargest.
Theverticallinedrawnforeachgasshowsthespeedatwhichthereisthelargestnumberofmolecules.
Moremoleculeshavethisspeedthananyother,sothisisthemostprobablespeedformoleculesofthat
gas.Themostprobablespeedforamoleculeofhydrogenat300Kis1.5710 3ms1or5.6510 3km
h 1.
FIGURE6.7GraphshowingmolecularspeeddistributionsforCO2 ,CH4 andH2 atatemperatureof300K.

WORKEDEXAMPLE6.3

AMolecularBeamExperiment
Thefiguresbelowrepresentmixturesofneonatomsandhydrogenmolecules.

Oneofthegasmixtureswasusedinamolecularbeamexperiment.Theresultofthe
experimentisshownbelow.Whichofthetwogassamples,AorB,wasusedforthis
experiment?

Analysis

Examinethetwosamples,andthendecidehoweachofthemwouldbehaveinabeam
experiment.

Solution

SampleAcontainseightH2moleculesandfourNeatoms,andsampleBcontainsfourH2
moleculesandeightNeatoms.Inamolecularbeamexperiment,bothsampleswouldgive
twopeaksinrelativeareasof2:1.Atomsormoleculeswithasmallmassmovefasterthan
thosewithalargemass,soweexpectH2(M=2.02gmol1)toreachthedetectorbeforeNe
(M=20.2gmol1).Thedatashowthatthefirstsubstancetoreachthedetectorispresentin
thesmalleramount.Consequently,thesampleusedinthebeamexperimentistheonewith
thesmalleramountofhydrogenmoleculessampleB.

Isouranswerreasonable?

H2movesfasterthanother,heaviersubstances,soitmakessensethattheH2molecules,
whicharelighterthanNeatoms,gettothedetectorfaster.H2moleculesarepresentina
smalleramountthanNeatoms,andtheexperimentaldataareconsistentwiththat.

PRACTICEEXERCISE6.3
Supposethat,inworkedexample6.3,
sampleAisusedandthatthesecondgasis
heliuminsteadofneon.Sketchagraph,
similartotheoneinworkedexample6.3,
showingthenumberofmolecules/atoms
versustime.

ChemicalConnections

MetalOrganicFrameworksforGreenhouseGasSeparationandHydrogen
StorageApplications

DeannaMD'Alessandro,UniversityofSydney

Theprospectofaworseningclimaticsituationduetoglobalwarmingisoneofthemost
pressingenvironmentalconcernsforourgeneration.Theurgentneedforstrategiestoreduce
atmosphericconcentrationsofgreenhousegaseshaspromptedactionfrommany
governmentsandindustries,andanumberofhighprofilecollaborativeprogramshavebeen
establishedtotackletheissue.Twoofthecentralstrategiesintheseinitiativesincludethe
captureandsequestrationofcarbondioxide,thepredominantgreenhousegas,fromlarge
stationarysourcessuchaspowerplants,andtheintroductionofhydrogenasacleanburning
alternativetofossilfuelsinmobileapplicationssuchascars.

Amongseveralcandidategroupsofmaterialsforgasstorageandseparation,highlyporous
threedimensionalsolidsknownasmetalorganicframeworks(MOFs,whicharealsoknown
asporouscoordinationpolymers,figure6.8)showexceptionalpromise.Believeitornot,one
teaspoonofoneofthesematerialscanhaveasurfaceareathatisequivalenttoafootball
field!Thesemicroporouscrystallinesolidsarecomposedoforganicbridgingligandsor
strutscoordinatedtometalbasednodestoformathreedimensionalextendednetworkwith
uniformporediameterstypicallyintherangeof3to20.Thenodesgenerallyconsistofone
ormoremetalions(e.g.Al3+,Cr3+,Cu 2+,Zn 2+)towhichtheorganicbridgingligands
coordinateviaaspecificfunctionalgroup(e.g.carboxylate,pyridyl).

FIGURE6.8RepresentationofCO2 diffusingthroughamicroporousMOFstructure.

TheintensecurrentresearchefforttowardsindustrialapplicationsofMOFsingasstorage,
separationandcatalysisisattributedtotheiruniquestructuralproperties,including:
robustness,highthermalandchemicalstabilities,unprecedentedinternalsurfaceareas(upto
6000m2g 1),highvoidvolumes(5590%)andlowdensities(from0.21to1.00gcm3),
whichcanbemaintainedevenuponevacuationoftheguestmoleculesfromthepores.The
regularmonodispersenatureofthecrystallinearrayofmicroporesisakeyfeaturethat
distinguishesMOFsfromotherporousmaterials(e.g.polymers,mesoporoussilicas,activated
carbon).Inaddition,theabilitytosystematicallymodulatetheporedimensionsandsurface
chemistrywithinMOFsisafeaturethatwaspreviouslylargelyabsentinzeolitematerials.

TheCO2captureproblem:GasstreamsfrompowerstationchimneysconsistprimarilyofN2,
H2OandCO2ina13:2:2ratiobymass.Usingconventionaltechnologies,theseparationof
CO2fromthishighvolumeofeffluentgas,whichisatapproximatelyatmosphericpressure,
wouldrequireapproximately2535%oftheenergygeneratedbyapowerstation.Itisthere
foreobviouswhysofewlargescalepowerstationsworldwide(andnoneinAustraliaorNew
Zealand)performpostcombustioncarboncapture.Clearly,thereisanurgentneedforcheaper
alternativestotheconventionalwetscrubbingmethodsthatarebasedontheabsorptionof
CO2byaqueousaminesolutions.

MOFsofferapotentialsolutiontothisgasseparationproblemastheirporevolumesand
surfacefunctionalitiescanbetunedtopreferentiallyseparateonegasfromanother(figure
6.9).ThereareotherapplicationswhereCO2captureusingMOFscanalsobeenvisagedfor
example,thesweeteningofnaturalgasrequirestheseparationofmixturesofN2,CO2and
CH4fromgasfields.

FIGURE6.9RepresentationofpartofthecrystalstructureofamagnesiumbasedMOFalongthe
onedimensionalchannels.Theinsetshowsthechargeinducedinteractionbetween
oneoftheopenMg2+coordinationsitesandaCO2 molecule.

TheH2storageproblem:Hydrogenisanidealenergycarrierfortransportationbecauseitis
lightweight,canbeproducedusingrenewableresourcessuchassunlight,andtheonly
byproductiswater.Commercialapplicationisproblematic,though,ashydrogenishardto
storewithouttakingupaverylargeamountofspace.Onesolutiontothisstorageissueisto
useMOFswhich,byvirtueoftheirextraordinarilyhighsurfaceareas,couldonedaystore
enoughhydrogenatnormaloperatingtemperaturesandpressuresinfuelcellstodrivemore
than1000kilometres.

SpeedandEnergy
Theenergyofamoleculeisrelatedtoitsspeed.Aswelearnedonp.218,anymovingobjecthaskinetic
energy(Ekinetic )withamagnitudegivenby:

wheremistheobject'smassanduisitsspeed.Themostprobablespeedofhydrogenmoleculesat300
Kis1.5710 3ms1(seep.219).WeneedthemassofoneH2moleculetobeabletocalculateitsmost
probablekineticenergy.TheSIunitofenergyisthejoule(J),whichequals1kgm2s2.Thus,weneed
themass(m)inkilograms.Themolarmassgivesthemassof1moleofmolecules,sodividingmolar
massbytheAvogadroconstant(NA)givesthemassof1molecule.
Nowapply:

Themostprobablespeedsofmethaneandcarbondioxideareslowerthanthemostprobablespeedof
hydrogen(seefigure6.7),butCH4andCO2moleculeshavelargermassesthanH2.Whenkinetic
energycalculationsarerepeatedforthesegases,theyshowthatthemostprobablekineticenergyisthe
sameforallthreegases.

ForaCH4molecule(m=2.66410 26kg):

ForaCO2molecule(m=7.30810 26kg)

Eventhoughthespeeddistributionsforthesethreegasespeakatdifferentvalues,themostprobable
kineticenergiesareidentical.Wecanalsoshowthat,atagiventemperature,allgaseshavethesame
molecularkineticenergydistribution.

Molecularbeamexperimentsshowthatmoleculesmovefasterasthetemperatureincreases.Molecules
escapingfromtheovenat900Ktakelesstimetoreachthedetectorthanmoleculesescapingat300K.
Asthemolecularspeedincreases,sodoesthekineticenergy.Figure6.10showsthemolecularkinetic
energydistributionsat300Kand900K.Bycomparingthisfigurewithfigure6.7,weseethatthe
molecularenergiesshowawidedistributionthatissimilartothedistributioninmolecularspeeds.
Unlikespeeds,however,themolecularenergydistributionsarethesameforallgasesatanyparticular
temperature.Thedistributionsshowninfigure6.10applytoanygas.

FIGURE6.10Graphofdistributionofmolecularenergiesforanygasat300Kand900K.
AverageKineticEnergyandTemperature
Themostprobablekineticenergyisnotthesameastheaveragekineticenergy.Tofindtheaverage
kineticenergypermolecule( ,thebaroveravariableindicatesthatitisanaveragevalue),we
mustaddalltheindividualmolecularenergiesanddividebythetotalnumberofmolecules.Theresult
describeshowtheaveragekineticenergyofgasmoleculesisrelatedtothetemperatureofthegas.

Inthisequation,Tisthetemperatureinkelvin,NAistheAvogadroconstantandRisthegasconstant
(8.314Jmol1K1).

Theaveragekineticenergyexpressedbytheequationiskineticenergypermolecule.Wefindthetotal
kineticenergyof1mole(Ekinetic,molar)ofgasmoleculesbymultiplyingbytheAvogadroconstant.

Thus,1moleofagashasatotalmolecularkineticenergyof RTindependentofthenatureofthatgas.
Whiletheequationisusuallystatedinthisway,itisworthwhiletonotethatitisthetemperaturethatisa
measureofaveragekineticenergy.

WORKEDEXAMPLE6.4

MolecularKineticEnergies
Determinetheaveragemolecularkineticenergyandmolarkineticenergyofgaseoussulfur
hexafluoride,SF6,at150C.

Analysis

Theproblemasksforacalculationofkineticenergiesandprovidesatemperature.Wehave
twoequationsforthekineticenergyofagas.

Tocarryoutthecalculations,weneedtoknowtheconstantsR(8.314Jmol1K1)andNA
(6.02210 23mol1)aswellasTinkelvin.

Solution

ConvertthetemperaturefromCtoKbyadding273.15.

Nowsubstitutethisintothekineticenergyequationandcalculate.

Forasinglemolecule:
For1moleofmolecules:

Isouranswerreasonable?

Wehaveshownthattheaveragekineticenergyisindependentofthenatureofthegas.
Figure6.10showsthemolecularenergydistributionsforatemperatureof300Kand900K.
Thetemperatureof423Kisinbetweentheseandthemolecularenergythatwecalculatedis
alsobetweenthevaluesat300Kand900K.Thisanswer,therefore,seemsreasonable.

PRACTICEEXERCISE6.4
Theatmospherictemperatureatthealtitudes
wherecommercialjetsflyisaround35C.
Calculatetheaveragemolecularandmolar
kineticenergiesofN2atthistemperature.

RatesofGasMovement
Theaveragespeedofthemoleculesinagasdeterminesitstemperature.Tostatethisdependence
quantitatively,westartwith:

and:

Wesetthetwoexpressionsforkineticenergyequaltoeachother.

Nowsolvethisequalityforu,notingthattheproductmNANisequaltothemolarmassofthegasinkg
mol1.

Thisspeediscalledtherootmeansquarespeedbecauseitisfoundbytakingthesquarerootof .
Theaveragespeedofgasmoleculesisdirectlyproportionaltothesquarerootofthetemperatureandis
inverselyproportionaltothesquarerootofthemolarmassofthegasinkgmol1.Thisequationcanbe
applieddirectlytothemovementofmoleculesescapingfromacontainerintoavacuum.Thisprocessis
oneexampleofeffusion(moregenerally,effusionistheflowofmoleculesthroughanopeningwithout
collisionsbetweenmolecules).Effusionisexemplifiedbytheescapeofmoleculesfromtheovenshown
infigure6.6a.
Asecondtypeofgasmovementisdiffusion,themovementofonetypeofmoleculethroughmolecules
ofthesameoranothertype.Diffusionisexemplifiedbyairescapingfromapuncturedtyre.The
escapingmoleculesmustdiffuseamongthemoleculesalreadypresentintheatmosphere.Diffusing
moleculesundergofrequentcollisions,sotheirpathsaresimilartothatshowninfigure6.1.
Nevertheless,theiraveragerateofmovementdependsontemperatureandmolarmass.Figure6.11
showsamolecularlevelcomparisonofeffusionanddiffusion.

FIGURE6.11Effusionisthemovementofagasintoavacuum.Diffusionisthemixingoftwoormoregases.

Anexampleofdiffusionisshowninfigure6.12,inwhichconcentratedaqueoussolutionsof
hydrochloricacid,HCl,andammonia,NH3,areplacedatoppositeendsofaglasstube.Moleculesof
HClgasandNH3gasescapefromthesolutionsanddiffusethroughtheairinthetube.Whenthetwo
gasesmeet,theyundergoareactionthatproducesammoniumchloride,awhitesolidsalt.

ThelighterNH3moleculesdiffusemorerapidlythantheheavierHClmolecules,sothewhitebandof
saltformsclosertotheHClendofthetube,ascanbeseeninfigure6.12.
FIGURE6.12NH3 diffusesthroughaglasstubefasterthanHCl.Whenthetwogasesmeet,theyformsolid
ammoniumchloride,NH4 Cl(s),whichappearsasawhitebandclosertotheendofthetubethat
containsHCl.

Fromthediscussionofrootmeansquarespeedonthepreviouspage,itfollowsthattheratioof
distancesthatHClandNH3travel,respectively,isinverselyrelatedtothesquarerootofthemolar
masses:

Ratesofmolecularmotionaredirectlyproportionaltomolecularspeeds,so,foranygas,ratesof
effusionanddiffusionincreasewiththesquarerootofthetemperatureinkelvin.Also,atanyparticular
temperature,ratiosofeffusionanddiffusionarefasterformoleculeswithsmallmolarmasses.

IdealGases
Aswehaveseeninthischapter,gasescanconsistofeitheratomsormolecules.Inwhatfollows,wewill
usethetermmoleculesexclusivelyforbrevity'ssake,butyoumustrememberthateverythingsaid
aboutmoleculesinthissectionappliesequallytoatoms.

Thebehaviourofgasessuggeststhatgasmoleculeshavelittleeffectononeanother.Gasesareeasyto
compress,showingthatthereislotsofemptyspacebetweenmolecules.Gasesalsoescapeeasily
throughanyopening,indicatingthattheirmoleculesarenotstronglyattractedtooneanother.Anideal
gasisdefinedasagasforwhichboththevolumeofmoleculesandtheforcesbetweenthemolecules
aresosmallthattheyhavenoeffectonthebehaviourofthegas.Wecanassumethatthisisthecase
whenmolecularsizesarenegligiblecomparedwiththevolumeofthecontainer,andtheenergies
generatedbyforcesbetweenmoleculesarenegligiblecomparedwithmolecularkineticenergies.

Aswedescribelaterinthischapter,smallmoleculesusuallyhavesmallattractiveforceswithrespectto
theirkineticenergies,orwithrespecttoRT,oftencalledthethermalenergy.Table6.1liststhe
substancesthatexistasgasesunderambientconditions(notethatabinarygasisonethatcontains
moleculesformedfromtwoelements).Thesegasesaremostlysmallmoleculeswithmolarmassesless
than50gmol1.Therearesomenotableexceptionstothis,however.Tungstenhexafluoride,WF6(M=
297.8gmol1),andtheelementradon,Rn(M=222gmol1),areexamplesofgaseshavingmolar
massesgreaterthan200gmol1.Uraniumhexafluoride,UF6(M=334gmol1),asolidcompoundused
intheseparationofthefissionableuraniumisotope235Ufromthemoreabundant238Uisotope(see
chapter27),sublimes(changesdirectlyfromasolidtoagas)at56.5CtogiveUF6(g)atatmospheric
pressure.
TABLE6.1 Molarmassesofsomegaseoussubstances(at298Kand1.013105 Pa)
Elementalgases Binarygases
Substance Formula M(gmol1) Substance Formula M(gmol1)
hydrogen H2 2.016 methane CH4 16.04

helium He 4.003 ammonia NH3 17.03

neon Ne 20.18 carbonmonoxide CO 28.01


nitrogen N2 28.02 nitrogenoxide NO 30.01

oxygen O2 32.00 ethane C2H6 30.07

fluorine F2 38.00 hydrogensulfide H2S 34.09

argon Ar 39.95 hydrogenchloride HCl 36.46


ozone O3 48.00 carbondioxide CO2 44.01

chlorine Cl2 70.90 nitrogendioxide NO2 46.01

Howdoesanidealgasbehave?Wecananswerthisquestionbyconsidering,forexample,howchanges
inV,Tornaffectthepressure,p.Eachtimeamoleculestrikesawall,itexertsaforceonthewall.
Duringeachsecond,manycollisionsexertmanysuchforces.Pressureisthesumofalltheseforcesper
unitareaandunittime.Inanidealgas,eachmoleculeisindependentofallothers.Thisindependence
meansthatthetotalpressureisthesumofthepressurecreatedbyeachindividualmolecule.

ToseehowpressuredependsonV,Torn,weconsidertheeffectofchangingonepropertywhile
holdingtheotherpropertiesconstant.Weanalysewhathappenstothemolecularcollisionsaseach
propertychanges.

First,considerincreasingtheamountofgaswhilekeepingthetemperatureandvolumefixed.Doubling
theamountofgasinafixedvolume(figure6.13)doublesthenumberofcollisionswiththewalls.Thus,
aspressureisessentiallyameasureofthenumberofcollisionsofthemoleculeswiththewallsofthe
container,pressureisdirectlyproportionaltotheamountofgas.Thisagreeswiththeidealgasequation.
FIGURE6.13Schematicviewoftheeffectofdoublingthenumberofgasmoleculesinafixedvolume.The
containerin(b)hastwiceasmanymoleculesasitdoesin
(a)Consequently,themoleculardensityistwiceaslargein
(b)withtwiceasmanycollisionspersecondwiththewalls.

Next,considerkeepingthetemperatureandamountfixedandchangingthevolumeofthegas.Figure
6.14showsthatcompressingagasintoasmallervolumehasthesameeffectasaddingmoremolecules.
Theresultismorecollisionswiththewalls.Ifthemoleculesactindependently,cuttingthevolumein
halfwilldoublethepressure.Inotherwords,pressureisinverselyproportionaltovolume,againin
agreementwiththeidealgasequation.

FIGURE6.14Schematicviewoftheeffectofcompressingafixedquantityofgasintoasmallervolumeat
constantT.Decreasingthevolumeincreasesthemoleculardensity,whichincreasesthe
numberofcollisionspersecondwiththewalls.

Tocompleteouranalysis,wemustdeterminetheeffectofachangeintemperature,keepingvolumeand
amountfixed.Recallthatkineticenergyisproportionaltothesquareofthemolecularspeed(a
microscopicvariable),andtemperature(amacroscopicvariable)isameasureofaveragemolecular
kineticenergy.Thus,thesquareofthemolecularspeedisproportionaltotemperature.Wecan
summarisetheserelationshipsby:

Molecularspeedaffectspressureintwoways,whichareillustratedinfigure6.15.First,fastermoving
moleculeshitthewallsmoreoftenthanslowermovingmolecules.Thenumberofcollisionseach
moleculemakeswiththewallisproportionaltothemolecule'sspeed.Second,theforceexertedwhena
moleculestrikesthewallalsodependsonthemolecule'sspeed.Afastmovingmoleculeexertsalarger
forcethanthesamemoleculemovingmoreslowly.Forcepercollisionandnumberofcollisions
increasewithspeed,sothetotaleffectofasinglemoleculeonthepressureofagasisproportionaltothe
squareofitsspeed.

FIGURE6.15Schematicviewoftheeffectofincreasingmolecularspeeds(asmeasuredbyanincreasein
temperature),resultinginmorewallcollisionsandmoreforcepercollision,andthereforean
increaseinpressure.

Pressureisproportionaltomolecularspeedsquared,whichinturnisproportionaltotemperature.Foran
idealgas,then,thepressureisdirectlyproportionaltotemperature,andaplotofpversusTyieldsa
straightline.Again,thisagreeswiththeidealgasequation.

Agaswillobeytheidealgasequationifitsmolecularsizesarenegligiblecomparedwiththevolumeof
thecontainer,andtheenergiesgeneratedbyforcesbetweenmoleculesarenegligiblecomparedwith
molecularkineticenergies.Thebehaviourofanyrealgasdepartssomewhatfromidealitybecausereal
moleculesoccupyvolumeandexertforcesononeanother.Nevertheless,departuresfromidealityare
smallenoughtoneglectundermanycircumstances,andrealgasesapproximateidealbehaviourunder
conditionsoflowpressureandhightemperature.Weconsiderdeparturesfromidealgasbehaviourlater
inthischapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.4GasMixtures
Theatmosphere,whichcontainsnitrogen,oxygenandvarioustracegases,isanobviousexampleofa
gasmixture.Anotherexampleisthegasusedbydeepseadivers,whichcontainsamixtureofhelium
andoxygen(figure6.16).Theidealgasmodelprovidesguidanceastohowtodescribemixturesof
gases.

FIGURE6.16Deepseadiversusemixturesofheliumandmolecularoxygenintheirbreathingtanks.

Allconstituentsofanidealgas,whetheratomsormolecules,actindependently.Thisnotionappliesto
gasmixturesaswellastopuregases.Gasbehaviourdependsonthenumberofgasatomsormolecules
butnotontheiridentity.Theidealgasequationappliestoeachgasinthemixture,aswellastothe
entirecollectionofatomsormolecules.

Supposeweintroduce0.1molofheliumintoanevacuated20Lflask.Ifweaddanother0.1molofHe,
thecontainernowcontains0.2molofgas.Thepressurecanbecalculatedusingtheidealgasequation,
withn=0.1mol+0.1mol=0.2mol.Supposethatweadd0.1molofmolecularoxygen.Nowthe
containerholdsatotalof0.3molofgas.Accordingtotheidealgasmodel,itdoesnotmatterwhether
weaddthesamegasoradifferentgasbecauseallatomsormoleculesinasampleofanidealgas
behaveindependently.Thepressureincreasesinproportiontotheincreaseinthetotalamountofgas.
Thus,wecancalculatethetotalpressurefromtheidealgasequation,usingn=0.2mol+0.1mol=0.3
mol.

Howdoesa1:2mixtureofO2andHeappearonthemolecularlevel?AsO2isaddedtothecontainer,
itsmoleculesmovethroughoutthevolumeandbecomedistributeduniformly.Diffusioncausesgas
mixturestobecomehomogeneous.Figure6.17illustratesthis.
FIGURE6.17 (a)0.2molofHeareaddedtoacontainer.
(b)Theatomsquicklybecomedistributeduniformlythroughoutthecontainer.
(c)0.1molofO2 areaddedtothiscontainer.
(d)ThemoleculesmoveaboutindependentlyoftheHeatoms,causingthegasestomix
uniformly.

Dalton'sLawofPartialPressures
Thepressureexertedbyanidealgasmixtureisdeterminedbythetotalamount(n total)ofgas.

Wecanexpressthetotalamountofgasasthesumoftheamountsoftheindividualgases.FortheHe
andO2mixture:

Substitutiongivesatwotermequationforthetotalpressure.
Noticethateachtermontherightresemblestheidealgasequationrearrangedtoexpresspressure.Each
termthereforerepresentsthepartialpressureofoneofthegases.Asfigure6.18illustrates,partial
pressureisthepressurethatwouldbepresentinagascontainerifonegaswerepresentbyitself.

FIGURE6.18SchematicrepresentationofasampleofO2 ,asampleofHeandamixtureofthetwogases.
Bothcomponentsaredistributeduniformlythroughoutthegasvolume.Eachgasexertsthe
samepressure,whetheritispureorpartofamixture.

Thetotalpressureinthecontaineristhesumofthepartialpressures.

WehaveusedHeandO2toillustratethebehaviourofamixtureofidealgases,butthisrelationshipcan
beextendedfromamixtureoftwoidealgasestomixtureswiththreeormoresubstancesbehavingas
idealgases.Inamixtureofgasesinwhichnochemicalreactionoccurs,eachgascontributestothe
totalpressuretheamountthatitwouldexertifthegaswerepresentinthecontainerbyitself.Thisis
Dalton'slawofpartialpressures.Toobtainatotalpressure,simplyaddthecontributionsfromall
gasespresent.

Whendoingcalculationsonamixtureofgases,wecanapplytheidealgasequationtoeachcomponent
tofinditspartialpressure(p i).Alternatively,wecantreattheentiregasasaunit,usingthetotalamount
todeterminethetotalpressureofthemixture(p).

DescribingGasMixtures
Thereareseveralwaystodescribethechemicalcompositionofamixtureofgases.Thesimplestmethod
istolisteachcomponentwithitspartialpressureoramount.Twootherdescriptions,molefractionsand
partspermillion,arealsousedfrequently.

Chemistsoftenexpresschemicalcompositioninfractionalterms,statingtheamountofasubstanceasa
fractionoftheamountofallsubstancesinthemixture.Thiswayofstatingcompositionisthemole
fraction(x).
Molefractionsprovideasimplewaytorelatethepartialpressureofonecomponenttothetotalpressure
ofthegasmixture.

Dividingp Abyp totalgives:

or:

Thepartialpressureofacomponentinagasmixtureisitsmolefractionmultipliedbythetotalpressure.

WORKEDEXAMPLE6.5

GasMixtures
Exactly8.00gofO2and2.00gofHewasplacedina5.00Ltankat298K.Determinethe
totalpressureofthemixture,andfindthepartialpressuresandmolefractionsofthetwo
gases.

Analysis

Wehaveamixtureoftwogasesinacontainerwithknownvolumeandtemperature.The
problemasksforpressuresandmolefractions.Assumingthatmolecularinteractionsare
negligible,eachgascanbedescribedindependentlybytheidealgasequation.Asusual,we
needmolaramountsforthecalculations.

Solution

Beginwiththedataprovided.

Convertthemassofeachgasintoanamountinmoles.

Next,usetheidealgasequationtocalculatethepartialpressureofeachgas.

ThesamecalculationforO2gives Pa.

Thetotalpressureisthesumofthepartialpressures.
Molefractionscanbecalculatedfromamountsorpartialpressures.

Isouranswerreasonable?

Themolefractionscalculatedfromthepartialpressuresmustsumto1.00.Theydointhis
case,suggestingthatouranswerisreasonable.

PRACTICEEXERCISE6.5
A5.00Ltankischargedwith7.50gofO2
and2.50gofHe.Calculatethemole
fractionsandthepartialpressuresofthe
gasesat25C.

Whenreferringtolowerconcentrationsinagasmixture,scientiststypicallyusepartspermillion(ppm)
orpartsperbillion(ppb).Molefractions,partspermillionandpartsperbillioncanalldescriberatiosof
amountofaparticularsubstancetototalamountofasample.Molefractionismolesperamounts,ppm
ismolespermillionmolesandppbismolesperbillionmoles.Aconcentrationof1ppmisamole
fractionof10 6,and1ppbisamolefractionof10 9.

WORKEDEXAMPLE6.6

WorkingWithPartsPerMillion(ppm)
Theexhaustgasfromanaveragecarcontains206ppmofthepollutantnitrogenoxide,NO.
Ifacaremits0.125m3ofexhaustgasat1.0010 5Paandexactly350K,whatmassofNO
hasbeenaddedtotheatmosphere?

Analysis

ThequestionasksforthemassofNO.Informationaboutconcentrationinppmtellsusthe
amountofNOpresentin1moleofexhaustgas.Wecanusetheidealgasequationto
determinethetotalamountofgasemitted,thenusetheconcentrationinformationtofindthe
amountofNO,andusethemolarmassofNOtoobtaintherequiredmass.

Solution
Isouranswerreasonable?

ThemassofNOisrathersmall,only27mg,butthemolefractionisalsosmall,sothisisa
reasonableresult.

PRACTICEEXERCISE6.6
IfthemaximumNOemissionallowedin
workedexample6.6is762ppm,whatmass
ofNOisallowedperlitreofexhaustemitted
atatemperatureofexactly50C?

Thedescriptionpresentedinthissectionappliestoagasmixturethatisnotundergoingchemical
reactions.Aslongasreactionsdonotoccur,theamountofeachgasisdeterminedbytheamountofthat
substanceinitiallypresent.Whenreactionsoccur,theamountsofreactantsandproductschangeas
predictedbytheprinciplesofstoichiometry.Changesincompositionmustbetakenintoaccountbefore
thepropertiesofthegasmixturecanbecalculated.Gasstoichiometryisdescribedinsection6.6.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.5ApplicationsoftheIdealGasEquation
Theidealgasequationandthemolecularviewofgasesleadtoseveralusefulapplications.Wehavealready
describedhowtocarryoutcalculationsinvolvingpVnTrelationships.Inthissection,weexaminetheuse
ofthegasequationtodeterminemolarmassesandgasdensity.

DeterminationofMolarMass

Theidealgasequationcanbecombinedwiththeequation (fromchapter3)tofindthemolarmassof
anunknowngas.

Ifweknowthepressure,volumeandtemperatureofagassample,wecanusethisinformationtocalculatethe
amountinmolesoftheunknowngasinthesample.

Ifwealsoknowthemassofthegassample,wecanusethatinformationtodeterminethemolarmassofthe
gas.

WORKEDEXAMPLE6.7

MolarMassDetermination
Purecalciumcarbide,CaC2,isahard,colourlesssolidthatwasusedincavinglamps.Ithasa
meltingpointof2160C,anditreactsvigorouslywithwatertoproduceagasandasolution
containingOHions.

A12.8gsampleofCaC2wastreatedwithexcesswaterandtheresultinggaswascollectedinan
evacuated5.00Lglassbulbwithamassof1254.49g.Thefilledbulbhadamassof1259.70gand
thepressureofthegasinsidewas1.0010 5Pawhenthetemperaturewas26.8C.Calculatethe
molarmassofthegasanddetermineitsformula.(Assumethattheproductgasisinsolubleinwater
andthatthevapourpressureofwaterisnegligibleinrelationtothepressureoftheproductgas.)

Analysis

Wecanusetheidealgasequationtocalculatethemolarmass.Thenwecanusethemolarmassto
identifythecorrectmolecularformulafromagroupofpossiblecandidates,astheproductsmay
containonlythesameelementsasthereactants.Theprobleminvolvesachemicalreaction,sowe
mustmakeaconnectionbetweenthegasmeasurementsandthechemistrythattakesplace.Because
thereactantsandoneproductareknown,wecanwriteapartialequationthatdescribesthechemical
reaction.

Inanychemicalreaction,atomsmustbeconserved,sothegasmoleculescancontainonlyH,O,C
and/orCaatoms.Todeterminethechemicalformulaofthegas,wemustfindthecombinationof
theseelementsthatgivestheobservedmolarmass.
theseelementsthatgivestheobservedmolarmass.

Solution

Usethedatatodeterminethemolarmass.Theproblemgivesthefollowingdataabouttheunknown
gas.

WeuseV,T,pandtheidealgasequationtofindtheamountofgasinmoles.Then,withthemassof
thegassample,wecandeterminethemolarmass.

WecouldrearrangethisexpressionandsolvetheequalityforMdirectly,but,inproblemslikethis,it
isoftenbettertocarryouteachstepexplicitly.Therefore,wewillfirstdeterminenandthensolvefor
M.

Toidentifythegas,weexaminetheformulaeandmolarmassesofknowncompoundsthatcontain
onlyH,O,CorCa.

Formula M Comment
Ca 40 AgaswithM=26.0gmol1cannotcontainCa.

CO 28 Thisisclosebuttoohigh.
O2 32 Thisisalsotoohigh.
H2O 18 Thisistoolow,andH2Oisareactantnotaproduct.
CH4 16 Thisistoolow.
C2H2 26 Thissubstancehastheobservedmolarmass.

ConsiderationofthesepossibilitiesleadstothemolecularformulaC2H2,ethyne(commonlyknown
asacetylene).

Isouranswerreasonable?

KnowingtheformulaofthegaseousproductandthatOHisanotherproduct,wecanwritea
balancedequationforthegenerationofethyne.

Thebalancedequationsuggeststhattheresultisreasonable.Asystematicevaluationofallpossible
gasesfromthereagentsthatinvolveonlyoneortwoatomsotherthanhydrogenshowsthatthereare
nootherpossibilitiesformolarmass26gmol1.

PRACTICEEXERCISE6.7
Theglassbulbinworkedexample6.7isfilled
withanunknowngasuntilthepressureis1.03
10 5Paatatemperatureof24.5C.Themass
ofthebulbpluscontentsis1260.33g.
Determinethemolarmassoftheunknowngas.

DeterminationofGasDensity
Onecharacteristicofgasesisthatthedensityofagasvariessignificantlywiththeconditions.Toseethis,we
combinetheidealgasequationand andrearrangetoobtainanequationfordensity .

Setthetwoexpressionsfornequaltoeachother.

Now,multiplybothsidesoftheequalitybyManddividebothsidesbyV.

Thisequationrevealsthreefeaturesofgasdensity:
1.Thedensityofanidealgasincreaseslinearlywithincreasingpressureatfixedtemperature.Thereason
isthatincreasingthepressurecompressesthegasintoasmallervolumewithoutchangingitsmass.

2.Thedensityofanidealgasdecreaseslinearlywithincreasingtemperatureatfixedpressure.Thereason
isthatincreasingthetemperaturecausesthegastoexpandwithoutchangingitsmass.

3.Thedensityofidealgasesincreaseslinearlywithincreasingmolarmassatagiventemperatureand
pressure.Thereasonisthatequalamountsofdifferentgasesoccupyequalvolumesatagiven
temperatureandpressure.

Therearepracticalapplicationsofallthesefeatures:
SCUBAdiversusehighpressurecylinders,wherethehighdensityofthegasgivesthemmoredivetime
pervolume(figure6.19).
FIGURE6.19ThehighdensityofairinsideaSCUBAtankincreasesthetimethatadivercanremainunder
water.

Balloonsinflatedwithheliumriseintheatmospherebecausethemolarmassofheliumissubstantially
lowerthantheaveragemolarmassofair(figure6.20).Consequently,thedensityofaheliumfilled
balloonislessthanthedensityofair,andtheballoonrises,justasacorkreleasedunderwaterrisesto
thesurface.

FIGURE6.20Aheliumfilledballoonfloatsbecauseheliumislessdensethanair.
Whentheairwithinahotairballoonisheated,itsdensitydecreasesbelowthatoftheoutsideair.With
sufficientheating,theballoonrisesandfloats(figure6.21).Incontrast,coldairisdenserthanwarmair,
socoldairsinks.Forthisreason,valleysoftenarecolderthanthesurroundinghillsides.
FIGURE6.21Ahotairballoonrisesbecausetheairinsideisheatedtoreduceitsdensity,sothatitisless
densethantheoutsideair.

Whenagasisreleasedintotheatmosphere,whetheritrisesorsinksdependsonitsmolarmass.Ifthemolar
massofthegasisgreaterthantheaveragemolarmassofair,thegasremainsneartheground.Carbondioxide
fireextinguishersareeffectiveforcertainfiresbecauseofthisfeature.ThemolarmassofCO2(44.0gmol1)
isgreaterthanthatofN2(28.0gmol1)orO2(32.0gmol1),andsoaCO2fireextinguisherlaysdowna
blanketofthisgasthatexcludesoxygenfromthefire.

WORKEDEXAMPLE6.8

GasDensity
Acertainhotairballoonwillrisewhenthedensityofitsairis15.0%lowerthanthatofthe
surroundingatmosphericair.Calculatethedensityofairat295Kand1.0010 5Pa(assumethat
dryairis78.0%N2and22.0%O2),anddeterminetheminimumtemperatureofairinsidethe
balloonthatwillcausetheballoontorise.

Analysis

Theproblemhastwoparts.First,wemustcalculatethedensityofatmosphericair.Todothis,we
needtodeterminethemolarmassofdryair,whichistheweightedaverageofthemolarmassesof
itscomponents.Thenwemustcalculatethetemperatureneededtoreducethedensityby15.0%.
Forbothcalculations,weusetheidealgasequationasrearrangedtogivegasdensity.

Solution

Beginbycalculatingthemolarmassofdryair.Multiplythefractionofeachcomponentbyits
molarmass.

Theotherconditionsarestatedintheproblem.
Recallthat,becausetheunitPaisdefinedintermsofNm2,andthat1N=1kgms2,wemustuse
amolarmassinkgmol1inthisequation.Substitutingtheseintotheequationforgasdensity
gives:

Theballoonwillrisewhenthedensityofitscontentsis15%lessthanthedensityofthe
surroundingair.

Rearrangethedensityequationtosolvefortemperature,thensubstituteandcalculate.

Isouranswerreasonable?

Atemperatureof348Kor75Cisareasonableresultasitishigherthanthetemperatureofthe
surroundingair.Noticethatthemolarmassandgasconstantappearinbothcalculations,sowecan
alsofindthetemperaturerequirementbysimpleproportions(comparingtheairinsideandoutside
theballoon).

PRACTICEEXERCISE6.8
Heliumisusedforlighterthanairblimps,
whereasargonisusedtoexcludeairfrom
flasksinwhichairsensitivesynthesesare
performed.Calculatethedensitiesofthesetwo
group18gasesat295Kand1.0010 5Pa,
andexplainwhythetwogaseshavedifferent
uses.

Gasdensityhasasignificanteffectontheinteractionsbetweenmoleculesofagas.Asmoleculesmoveabout,
theycollideregularlywithoneanotherandwiththewallsoftheircontainer.Figure6.22showsthatthe
frequencyofcollisionsdependsonthedensityofthegas.Atlowdensity,amoleculemaymoveasignificant
distancebeforeitencountersanothermolecule.Athighdensity,amoleculetravelsonlyashortdistance
beforeitcollideswithanothermolecule.
FIGURE6.22Asthemoleculardensitydecreases,theaveragedistancetravelledbetweenmolecularcollisions
increases.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.6GasStoichiometry
Theprinciplesofstoichiometryapplyequallytosolids,liquidsandgases.Nomatterwhatphase
substancesarein,theirchemicalbehaviourcanbedescribedinmolecularterms,andtheir
transformationsmustbevisualisedandbalancedusingmoleculesandmoles.

Theidealgasequationrelatestheamountofgastothephysicalpropertiesofthatgas.Whenachemical
reactioninvolvesagas,theidealgasequationprovidesthelinkbetweenpVTdataandmolar
amounts.

Stoichiometriccalculationsalwaysrequireamountsand,forgases,theseareusuallycalculatedfromthe
idealgasequation.

WORKEDEXAMPLE6.9

GasStoichiometry
Workedexample6.7describedtheformationofethyne,C2H2,fromcalciumcarbide,CaC2.
Modernindustrialproductionofethyneisbasedonareactionofmethane,CH4,undercare
fullycontrolledconditions.Attemperaturesgreaterthan1600K,twomethanemolecules
rearrangetogivethreemoleculesofhydrogenandonemoleculeofethyne.

A50.0Lsteelvessel,filledwithCH4toapressureof10.010 5Paat298K,isheatedto
exactly1600KtoconvertCH4intoC2H2.WhatisthemaximumpossiblemassofC2H2that
canbeproduced?Whatpressuredoesthereactorreachat1600K?AssumethatbothCH4
andC2H2behaveasidealgasesundertheconditionsofthereaction.

Analysis

Thisisastoichiometryprobleminvolvinggases.Themassofaproductandthefinalpres
suremustbecalculated.Wecandrawadiagramshowingtheprocessandlistingthedata.

Solution

Inanystoichiometryproblem,weworkwithamounts.Thisprobleminvolvesgases,sowe
usetheidealgasequationtoobtainamountsinmolesfromthepVTinformation.Usethe
idealgasequationtocalculatetheamountofCH4presentinitially.
Fromthestoichiometryofthebalancedchemicalequation,wecandeterminethatcomplete
conversionof20.18molofCH4intoC2H2andH2willgive molC2H2

and molH2.

Nowwedeterminethemassofethyneformed.

Usingtheidealgasequationandthetotalamountpresentattheendofthereaction,and
assumingalltheCH4hasreacted,wecancalculatethefinalpressure.

Isouranswerreasonable?

Fromtheinitialamountofmethane,wecancalculatetheinitialmassofmethane,whichis
323g.Themassofethyne,263g,islessthanthis,areasonableresultgiventhatH2isalso
produced.Thefinalpressure,1.0710 7Pa,seemshigh,butthetemperatureofthereactor
hasincreasedsubstantiallyandtheamountofproductsistwicetheamountofreactants,soa
largepressureincreaseistobeexpected.

PRACTICEEXERCISE6.9
Calculatethevolumeofhydrogengas
generatedwhen1.52gofMgreactswithan
excessofaqueousHCl,ifthegasis
collectedat1.0010 5Paand22.5C.The
balancedchemicalequationforthereaction
is:

Anyofthetypesofproblemsdiscussedinchapter3caninvolvegases.Thestrategyfordoing
stoichiometriccalculationsisthesamewhetherthespeciesinvolvedaresolids,liquidsorgases.Inthis
chapter,weaddtheidealgasequationtoourequationsforrelatingmeasuredquantitiestoamounts.

WORKEDEXAMPLE6.10
LimitingReagentsinaGasMixture
Margarinecanbemadefromnaturaloilssuchascoconutoilbyhydrogenation.

Ahydrogenator(figure6.23)withavolumeof2.5010 2Lischargedwith12.0kgofoil.
Theremainingvolumeisthenfilledwith7.0010 5Paofhydrogen,H2,at473K.The
reactionproducesthemaximumamountofmargarine.WhatisthefinalpressureofH2,and
whatmassofmargarinewillbeproduced?AssumethatH2doesnotdissolveincoconutoil
ormargarine,thatitbehavesasanidealgasunderthereactionconditionsandthatthe
coconutoilandmargarineoccupyanegligiblevolumeinthehydrogenator.

FIGURE6.23Ahydrogenatoravailablecommerciallyforsmallscaleuse,e.g.inaresearch
laboratory.

Analysis

Wehavedatafromwhichwecancalculatetheamountsofbothstartingmaterials.Giventhe
chemicalequation,thefirststepinastoichiometryproblemistodeterminetheinitialamount
ofeachstartingmaterial.Next,calculateratiosofamountstocoefficientstoidentifythe
limitingreagent.Afterthat,usetheidealgasequationandthestoichiometricprincipleswe
learnedinchapter3toobtainthefinalanswers.

Solution

Theidealgasequationisusedforthegaseousstartingmaterial.

Weobtaintheamountofoilfromthemassandthemolarmass.
Nowwedivideeachamountbythestoichiometriccoefficienttoidentifythelimitingreagent.

Thereactantwiththesmallerratio,oil,islimiting.(Excesshydrogeniseasilyrecoveredfrom
agasphasereactor,somargarinemanufacturersmaketheoilthelimitingreagenttoensure
completeconversionofoilintomargarine.TheexcessH2gasisrecoveredandreused.)

Fromthebalancedchemicalequation,13.55molofoilwillreactwith40.65mol(313.55)
ofH2togive13.55molofmargarine.Therefore,theamountofunreactedH2willbe(44.50
40.65)=3.85mol.Notethatwehavecarriedanextrafigurethroughthecalculation.We
thereforeneedtoroundtothecorrectnumberofsignificantfiguresatthispoint,so13.6mol
ofmargarinewillbeproducedand3.9molofH2willremainunreacted.

Usingtheidealgasequation,wecalculatethepressureofhydrogenattheendofthereaction.

Nowwecalculatethemassofmargarine.

Isouranswerreasonable?

Inthisexample,oilisthelimitingreagentandnotalltheH2willreact.Therefore,someH2
willbeleft,butweexpectthepressureofH2attheendofthereactiontobelowerthanatthe
start,whichitis.Noticethatthemassofmargarineproduced(12.1kg)isonlyslightlygreater
thanthemassofoilwestartedwith(12.0kg).Thisistobeexpected,asthemolarmassesof
coconutoilandmargarineareverysimilar.

PRACTICEEXERCISE6.10
Intheindustrialproductionofnitricacid,
onestepistheoxidationofnitrogenoxide:
2NO(g)+O2(g)2NO2(g).Areaction
chamberischargedwith5.0010 5Paeach
ofNOandO2.Ifthereactiongivesthe
maximumpossibleamountofNO2(g)
withoutachangeintemperatureorvolume,
calculatethefinalpressuresofeachreagent.

SummaryofMoleConversions
Onthemicroscopiclevel,molesarethecurrencyofchemistrytherefore,allstoichiometriccalculations
requireamounts.Onthemacroscopiclevel,wemeasuremass,volume,temperatureandpressure.Table
6.2liststhreeequationsthatcanbeusedtoconvertbetweenthemicroscopicandmacroscopiclevels.
Eachoftheseequationsappliestoaparticularcategoryofchemicalsubstances.Youshouldhavea
workingknowledgeofthesethreeequations,alongwiththecategoryofsubstancestowhichtheyapply.
TABLE6.2 Summaryofstoichiometricrelationships
Substance Relationship Equation
puresolid,liquid
orgas

solution

gas

Workedexample6.11usesallthreerelationships.Viewedasawhole,theexamplemayseem
complicated.However,asthesolutionillustrates,breakingtheproblemintoseparatepartsallowseach
parttobesolvedusingsimplechemicalandstoichiometricprinciples.Complicatedproblemsareoften
simplifiedconsiderablybylookingatthemonepieceatatime.

WORKEDEXAMPLE6.11

GeneralStoichiometry
Reactionofmagnesiummetalwithacid(figure6.24)generateshydrogengasandanaqueous
solutionofions.Supposethat3.50gofmagnesiummetalisdroppedinto0.150Lof6.00M
HClina5.00Lcylinderat25.0C.Theinitialgaspressureofthecylinderis1.0010 5Pa,
anditisimmediatelysealed.Findthefinalpartialpressureofhydrogen,thetotalpressurein
thecontainerandtheconcentrationofMg 2+insolution.
FIGURE6.24MagnesiumreactingwithaqueousHCl.

Analysis

Dataaregivenforallreactants.Wemustfirstwriteabalancedchemicalequationandthen
usetheequationsintable6.2,alongwiththestoichiometryofthereaction,tocalculatethe
requiredpressuresandconcentrations.

Solution

Webeginbywritingthebalancedchemicalequation,whichwehaveseenpreviouslyin
practiceexercise6.9.

Theproblemasksforpressuresandionconcentrations.Thefinalpressurecanbedetermined
frompVTdataandn H2.Theamountofhydrogencanbefoundfromthemassof
magnesiumandthestoichiometricratio.Hereisasummaryofthedata.

Nowweanalysethestoichiometryofthereaction.ThestartingmassofMgandthevolume
andconcentrationofHClaregiven,andwecanusethesedatatofindthelimitingreactant.

Wedividebythestoichiometriccoefficientstoshowthatmagnesiumisthelimitingreagent.

Fromthestoichiometryofthebalancedchemicalequation,wecanshowthat0.144molof
Mgwillform0.144molH2.WethereforeusethisamounttocalculatethepressureofH2.
However,beforedoingthis,wemustvisualisethereactionvessel.Thecontainer'stotal
volumeis5.0010 3m3,but0.15010 3m3isoccupiedbytheaqueoussolution.This
leaves4.8510 3m3forthegasmixture.Thepartialpressureofhydrogeniscalculated
usingtheidealgasequationandassumingthatnoH2remainsinsolutionthisisagood
assumptionbecausehydrogengasisnotverysolubleinwater.

Assumingthattheamountofairoriginallypresentdoesnotchangeinthereaction,the
pressureexertedbytheairremainsconstantat1.0010 5Pa.Thefinaltotalpressureisthe
sumofthepartialpressures.

WecancalculatethefinalconcentrationofMg 2+usingtheinitialamountofMgandthe
volumeofthesolution.

PRACTICEEXERCISE6.11
Repeatthecalculationsfromworked
example6.11withallconditionsthesame
exceptthat14.0gofMgisaddedtotheHCl
solution.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.7RealGases
Inchapter5welookedatwhatholdsatomsandionstogether,andwelistedthreetypesofbonding
forces:ionic,covalentandmetallic.Inadditiontotheserelativelystrongbondingforces,therearemuch
weakerforcesthatexistbetweenatoms,ionsandmolecules.Intheprevioussectionsofthischapterwe
lookedatidealgases,assumingthattherearenoattractiveforcesbetweeneitheratomsormolecules.
However,weakattractiveforcesdooccurinrealgases,andmuchstrongerforcesarepresentinliquids
andsolids.Intheabsenceoftheseintermolecularforces,allmoleculeswouldmoveindependently,
andallmolecularsubstanceswouldbegases.Theseintermolecularforcesareessentiallydueto
attractionsbetweenpolarisedmolecules,buttheyalsoincludepolarinteractionsbetweenionsand
moleculesaswellasatoms.Thename,intermolecularforces,isthereforesomewhatinaccurate,butit
canbejustifiedbythefactthatanoverwhelmingnumberofallchemicalcompoundsaremolecules.

TheHalogens
Thehalogens,theelementsfromgroup17oftheperiodictable,provideanintroductiontointer
molecularforces.Theseelementsexistasdiatomicmolecules:F2,Cl2,Br2andI2.Eachmolecule
containstwoatomsheldtogetherbyasinglecovalentbondthatcanbedescribedbyendonoverlapof
valenceporbitals.

Althoughtheyhavesimilarcovalentbonding,bromineandiodinedifferfromchlorineandfluorinein
theirmacroscopicphysicalappearanceandintheirmolecularbehaviour.Asfigure6.25shows,atroom
temperatureandpressure,chlorine(likefluorine)isagas,bromineisaliquidandiodineisasolid.

Undernormalconditions,chlorineisapaleyellowgreengas,bromineisadarkredliquid,and
FIGURE6.25iodineisadarkcrystallinesolid.

Gasesandcondensedphases(atermusedtocollectivelydescribeliquidsandsolids)lookverydifferent
atthemolecularlevel.MoleculesofF2orCl2movefreelythroughouttheirgaseousvolume,travelling
manymoleculardiametersbeforecollidingwithoneanotherorwiththewallsoftheircontainer.
Becausemuchofthevolumeofagasisemptyspace,samplesofgaseousF2andCl2readilyexpandor
contractinresponsetochangesinpressure.Thisfreedomofmotionexistsbecausetheintermolecular
forcesbetweenthesemoleculesaresmallwithrespecttotheirkineticenergy.

Moleculesofliquidbrominealsomoveaboutrelativelyfreely,butthereisnotmuchemptyspace
betweenmolecules.Aliquidcannotbecompressedsignificantlybyincreasingthepressure,becauseits
moleculesarealreadyinclosecontactwithoneanother.Neitherdoesaliquidexpandsignificantlyifthe
pressureisreduced,becausetheintermolecularforcesinaliquidarestrongenoughtopreventthe
moleculesfrombreakingawayfromoneanother.

Solidiodine,likeliquidbromine,haslittleemptyspacebetweenmolecules.Likeliquids,solidshave
sufficientlystrongintermolecularforcesthattheyneitherexpandnorcontractsignificantlywhenthe
pressurechanges.Insolids,theintermolecularforcesarestrongenoughtopreventmoleculesfrom
movingfreelypastoneanother.Instead,theI2moleculesinthesolidphasearearrangedinordered
arrays.Eachmoleculevibratesbackandfortharoundasinglemoststableposition,butitcannotslide
easilypastitsneighbours.

Thebalancebetweenmolecularkineticenergiesandintermolecularattractiveforcesaccountsforthese
strikingdifferences(figure6.26).Recallfromsection6.2thatmoleculesarealwaysmoving.
Intermolecularattractiveforcestendtoholdmoleculestogetherinacondensedphase,butmolecules
thataremovingfastenoughcanovercometheseforcesandmovefreelyinthegasphase.Whenthe
averagekineticenergyislargeenough,moleculesremainseparatedfromoneanother,andthe
substanceisagas.Conversely,whenintermolecularattractiveforcesarelargeenough,molecules
remainclosetooneanother,andthesubstanceisaliquidorsolid.

FIGURE6.26Asubstanceexistsinacondensedphasewhenitsmoleculeshavetoolittleaveragekinetic
energytoovercomeintermolecularforcesofattraction.

Thebarsinfigure6.27comparetheattractiveenergiesarisingfromintermolecularforcesactingonthe
halogens.Thefigurealsoshowstheaveragemolecularkineticenergyatroomtemperature.Forfluorine
andchlorine,theattractiveenergygeneratedbyintermolecularforcesissmallerthantheaverage
molecularkineticenergyatroomtemperature.Thus,theseelementsaregasesundertheseconditions.In
contrast,brominemoleculeshaveenoughkineticenergytomovefreelyabout,buttheirenergyis
insufficienttoovercometheintermolecularforcesoftheliquidphase.Finally,attractiveforcesiniodine
arestrongenoughtolocktheI2moleculesinpositioninthesolidstate.
FIGURE6.27Thebalanceofaveragekineticenergy(redline)andintermolecularenergiesofattraction
favoursthegasphaseforF2 andCl2 ,andthecondensedphasesforBr2 andI2 .

PropertiesofRealGases
Aswedescribedinsection6.3,theidealgasmodelmakestwoassumptions:agashasnegligibleforces
betweenitsconstituentatomsormolecules,andgasatomsormoleculeshavenegligiblevolumes.
Neitheroftheseassumptionsistrueforarealgas.Atsufficientlyhighpressuresandsufficientlylow
temperatures,allgasescanbeliquefied.

Howclosedorealgasescometoidealbehaviour?Toanswerthisquestion,werearrangetheidealgas
equationtoexaminetheratio .Figure6.28showshowthe ratiovarieswithpressurefor

chlorinegasatroomtemperature.Ifchlorinewereanidealgas,the ratiowouldalwaysbe1,as
shownbytheredlineonthegraph.Instead,chlorineshowsdeviationsfrom1asthepressureincreases.
FIGURE6.28Thevariationin withpressureshowsthatchlorineisnotanidealgas.

Noticeintheinsetoffigure6.28thatchlorineisnearlyidealatpressuresaround110 5Pa.Infact,
deviatesfrom1.0bylessthan4%atpressuresbelow410 5Pa.Asthepressureincreases,

however,thedeviationsbecomeincreasinglysignificant.Withincreasingpressure,the ratiofor
chlorinedropsbelow1.Thisisbecausethechlorinemoleculesarecloseenoughtogetherforattractive
forcestoplayasignificantrole.Theseintermolecularattractionsholdmoleculestogetherandreducethe
forcesexertedwhenthemoleculesstrikethewallsofthecontainer.Intermolecularattractionstendto
makethepressureofarealgaslowerthantheidealvalue.

Figure6.28alsoshowsthatatpressuresgreaterthan37510 5Pa, becomeslargerthan1.Thisis


duetotheeffectofmolecularsize.Athighenoughpressure,themoleculesarepackedsoclosetogether
thatthetotalvolumeofthemoleculesisnolongernegligiblecomparedwiththeoverallvolumeofthe
container.Theresultisthatthecontainervolumeiseffectivelydecreasedbythemolecules'volumeand
thepressureoftherealgastendstobegreaterthanthatoftheidealgas.

Everygasshowsdeviationsfromidealbehaviourathighpressure.Figure6.29shows forHe,F2,

CH4andN2,allofwhicharegasesatroomtemperature.Noticethat forheliumincreasessteadily
aspressureincreases.Interatomicforcesforheliumaretoosmalltoreducetheratiobelow1,butthe
finitesizeoftheheliumatomgeneratesdeviationsfromidealbehaviourthatbecomesignificantat
pressuresabove10010 5Pa.

FIGURE6.29Variationsin forHe,N2 ,F2 andCH4 at300K.

Giventhateverygasdeviatesfromidealbehaviourtosomedegree,canweusetheidealgasmodelto
discussthepropertiesofrealgases?Theanswerisyes,aslongasconditionsdonotbecometoo
extreme.Thegaseswithwhichchemistsoftenwork,suchaschlorine,heliumandnitrogen,arenearly
idealatroomtemperatureatpressuresbelowabout1010 5Pa,but,atveryhighpressuresornearthe
condensationpointsofsubstances,deviationsfromtheidealgasequationbecomelarge.

TheVanDerWaalsEquation
Itwouldbeusefultohaveanequationthatdescribestherelationshipbetweenpressureandvolumefora
realgas,justas describesanidealgas.Onewaytoapproachrealgasbehaviouristomodifythe
idealgasequationtoaccountforattractiveforcesandmolecularvolumes.Theresultisthevander
Waalsequation,namedafterthescientistwhofirstproposeditin1873,JohannesvanderWaals(1837
1923,NobelPrizeinphysics,1910).

ThevanderWaalsequationaddstwocorrectiontermstotheidealgasequation.Eachcorrectionterm
includesaconstantthathasaspecificvalueforeverygas.Thefirstcorrectionterm, ,adjustsfor
attractiveintermolecularforces.ThevanderWaalsconstantareflectsthestrengthofintermolecular
forcesforthegasthestrongertheforces,thelargerthevalueofa.Thesecondcorrectionterm,nb,
adjustsformolecularsizes.ThevanderWaalsconstantbreflectsthesizeofgasatomsormoleculesthe
largertheyare,thelargerthevalueofb.

ThevanderWaalsconstantsforanumberofgasesappearintable6.3,andthemagnitudeofvander
Waalscorrectionsisexploredinworkedexample6.12.
TABLE6.3 ValuesofvanderWaalsconstantsforavarietyofgases
a b

Substance (m6Pamol2) (m3mol1)


He 3.45710 3 2.3710 5
Ne 2.13510 2 1.70910 5
Ar 1.36310 1 3.21910 5
H2 2.47610 2 2.66110 5
N2 1.40810 1 3.91310 5
O2 1.37810 1 3.18310 5
CO 1.50510 1 3.98510 5
F2 1.15610 1 2.9010 5
Cl2 6.57910 1 5.62210 5
CO2 3.64010 1 4.26710 5
H2O 5.53610 1 3.04910 5
NH3 4.22510 1 3.70710 5
CH4 2.28310 1 4.27810 5
C2H6 5.56210 1 6.380 5
C6H6 1.82410 1 1.15410 5

WORKEDEXAMPLE6.12

MagnitudesofVanDerWaalsCorrections
Gasessuchasmethanearesoldandshippedincompressedgascylinders(figure6.30).A
typicalcylinderhasavolumeof15.0Land,whenfull,contains62.0molofCH4.After
prolongeduse,0.620molofCH4remainsinthecylinder.

FIGURE6.30Gasessuchasmethane,butaneandpropanearesoldincompressedgas
cylinders.

UsethevanderWaalsequationtocalculatethepressuresinthecylinderwhenfullandafter
use,andcomparethevalueswiththoseobtainedfromtheidealgasequation.Assumea
constanttemperatureof25C.

Analysis

WeareaskedtocalculateandcomparethepressuresofmethanegasusingthevanderWaals
equationandtheidealgasequation.VanderWaalsconstantsaandbmustbelookedupina
datatablesuchastable6.3.Tocalculatepressures,werearrangethevanderWaalsequation
andtheidealgasequation.

Solution
ThevanderWaalsconstantsforCH4are:

Whenthetankisfull,n=62.0mol.

Afteruse,n=0.620mol.

Organisetheresultstomakeacomparison.

NoticethatthevanderWaalscorrectionisappreciable(15.4%)athighpressure,butis
negligibleatatmosphericpressure(1.01310 5Pa).

Isouranswerreasonable?

Weknowthatmethaneisnormallyagasat298Kandatmosphericpressure,soitmakes
sensethatthegasbehavesideallyundertheseconditions.Apressureabove10010 5Pais
substantiallyhigherthannormalconditions,soweexpecttoseedeviationsfromideal
behaviour.

PRACTICEEXERCISE6.12
Methaneboilsat164C.Usetheidealgas
equationtocalculatethemolarvolumeof
methanegasatthistemperatureat1.013
10 5Papressure.ThenusethevanderWaals
equationtocalculatethepressureexertedby
1.00moleofthegasifitoccupiesthis
volumeat164C.

MeltingandBoilingPoints
Meltingpointsandboilingpointscanbeusedasindicatorsofthestrengthsofintermolecularforces.
Rememberthatthetemperatureincreaseswiththeaveragekineticenergyofmolecularmotion.The
boilingpointofasubstanceisthetemperatureatwhichtheaveragekineticenergyofmolecularmotion
balancestheattractiveenergyofintermolecularattractions.Whenthepressureis1.01310 5Pa,that
temperatureisthenormalboilingpoint.Forexample,thenormalboilingpointofbromineis332K(59
C).Abovethistemperature,theaveragekineticenergyexceedstheattractiveenergiescreatedby
intermolecularforcesofattraction,andbromineexistsasvapour.Underatmosphericpressure,bromine
isaliquidattemperaturesbelow332K.Notethat,becauseboilingpointsaredeterminedprimarilyby
intermolecularattractiveforces,factorsotherthanthemolarmassofthemoleculemaybeimportant.For
example,carbontetrachloride,CCl4,(M=153.81gmol1)hasalowerboilingpoint(77C)thanthe
lightermoleculephenol,C6H5OH,(M=94.12gmol1,bp=182C)becauseofthemuchstronger
intermolecularforcesinphenol.

Theconversionofaliquidintoagasiscalledvaporisation.Aliquidvaporiseswhenmoleculesleave
theliquidphasefasterthantheyarecapturedfromthegas.Condensationisthereverseprocess.Agas
condenseswhenmoleculesleavethegasphasemorerapidlythantheyescapefromtheliquid.We
exploretheseprocessesinmoredetailinchapter7.

Themoleculesinaliquidareabletomoveaboutfreely.Whenaliquidiscooled,however,thekinetic
energiesdecrease.Attemperaturesbelowthefreezingpoint,themoleculesbecomelockedinplaceand
theliquidsolidifies.Whenthepressureis1.01310 5Pa,thattemperatureisthenormalfreezingpoint.
Aliquidfreezeswhenliquidmoleculeshavetoolittlekineticenergytoslidepastoneanother.
Conversely,asolidmeltswhenitsmoleculeshaveenoughkineticenergytomovefreelypastone
another.Justasintermolecularforcesdeterminethenormalboilingpoint,theseforcesalsodeterminethe
freezingpoint.Thestrongertheintermolecularforces,thehigherthefreezingpointfluorinefreezesat
53.5K,chlorineat172Kandbromineat266K.

Boilingpointsandmeltingpointsdependonthestrengthsofintermolecularforces.Thisisbecausethe
ratesofescapeandcapturefromaphasedependonthebalancebetweenmolecularkineticenergiesand
intermolecularforcesofattraction.Asubstancewithlargeintermolecularforcesmustberaisedtoahigh
temperaturebeforeitsmoleculeshavesufficientkineticenergiestoovercomethoseforces.Asubstance
withsmallintermolecularforcesmustbecooledtoalowtemperaturebeforeitsmoleculeshavesmall
enoughkineticenergiestocoalesceintoacondensedphase.Table6.4liststheboilingandmelting
pointsofsomeelementalsubstances.
TABLE6.4 Normalmeltingandboilingpointsofselectedelements
Substance mp(K) bp(K)
He 0.95 (a) 4.2

H2 14.0 20.3
N2 63.3 77.4
F2 53.5 85.0

Ar 83.8 87.3
O2 54.8 90.2

Cl2 172 239

Br2 266 332

I2 387 458

P4 317 553

Na 371 1156
Mg 922 1363
Si 1683 2628
Fe 1808 3023

(a)Underhighpressure,asheliumcannotbesolidifiedatatmosphericpressure.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
6.8IntermolecularForces
Inchapter5weencounteredionic,covalentandmetallicbondingthatholdatomsandionstogether.In
addition,socalledintermolecularforcesexistbetweenallmolecules(hencethename),buttheyalsoinclude
attractiveforcesbetweenatoms,ionsandmoleculesotherthanbondingforces.Intermolecularforcesare
typicallymuchweakerthanbondingforcesandgenerallyinfluencephysicalpropertiesofcompounds(e.g.
whethertheyaregaseous,liquidorsolidatambientconditions)ratherthantheirchemicalproperties.As
statedearlierinthischapter,intermolecularforcesarecausedbydifferencesinpolarity(permanentor
temporary)betweenentities(seebelow).Inthissection,wewilltalkonlyaboutmolecules,butthe
discussionalsoencompassesionsandatoms.

Differentintermolecularforcescanbethoughtofaspointsalongabondingcontinuumallofthemrelyon
theattractionbetweenpositivelyandnegativelychargedpartsofneighbouringmolecules(i.e.electron
cloudsandnuclei),andthedistinctionbetweenthemisinsomecasesratherfluid.Forcesinorderof
increasingstrengthare:
instantaneousdipoleinduceddipoleforces(alsocalleddispersionforces)
dipoleinduceddipoleforces
dipoledipoleforces(includinghydrogenbonds,whicharetypicallyrelativelystrongdipoledipole
interactions).Thesearealsocalleddipolarforces.

Analogousforcesalsoexistbetweenionsandbothdipolesandinduceddipoles.Iondipoleforcesandion
induceddipoleforcesarestrongerthantheintermolecularforcesabove.

Dispersionforcesaretheattractionsbetweenthenegativelychargedelectroncloudofonemoleculeand
thepositivelychargednucleiofneighbouringmolecules.Allsubstancesdisplaydispersionforces.Theyare
causedbytheusuallysymmetricalelectrondistributionaroundamoleculenotbeingsymmetricalatevery
instantoftime.Thiscreatesaninstantaneousdipole,whichinturncaninduceadipoleinaneighbouring
molecule.

Dipoleinduceddipoleforcesaresomewhatstrongerthandispersionforcesthedifferenceisthat,inthis
case,amoleculewithapermanentdipoleinducesadipoleinaneighbouringmolecule.

Dipoledipoleforcesaretheattractionsbetweenthenegativelychargedendofapolarmoleculeandthe
positivelychargedendsofneighbouringpolarmolecules.Dipoledipoleforcesexistonlyforcompounds
thatpossesspermanentdipolemoments(seesection5.5).

Ifthesedipoledipoleforcesinvolveahydrogenatom,theyarecalledhydrogenbonds.Theyoccurmainly
betweenalonepairofelectronsonasmall,highlyelectronegativeatom(usuallyN,OorF)andahydrogen
atombondedtoahighlyelectronegativeatom.Stronghydrogenbondsoccurprimarilywithmoleculesthat
containOH,NHandFHcovalentbonds.

Dispersionforces,dipoledipoleforcesandhydrogenbondsareallmuchweakerthanintramolecular
covalentbonds.Forexample,theaverageCCbondenergyis345kJmol1,whereasdispersionforcesare
just0.1to5kJmol1forsmallalkanessuchaspropane.Dipoledipoleforcesbetweenpolarmoleculessuch
asacetonerangebetween5and20kJmol1,andhydrogenbondsrangebetween5and50kJmol1.This
generalisation,however,needstobetreatedwithcare.Inalargemolecule,thesumofalltheweak
dispersionforcesmaybemuchstrongerthanadipoledipoleinteractioninadifferentmolecule,leadingto
ahighermeltingorboilingpoint.

DispersionForces
Dispersionforcesexistbecausetheelectroncloudsofmoleculescanbedistorted.Forexample,consider
whathappenswhentwohalogenmoleculesapproacheachother.Eachmoleculecontainspositivenuclei
surroundedbyacloudofnegativeelectrons.Astwomoleculesapproach,thenucleusofonemolecule
attractstheelectroncloudoftheother.Electronsarehighlymobile,sotheelectroncloudschangeshapein
responsetothisattraction.Atthesametime,thetwoelectroncloudsrepeleachother,whichleadstofurther
distortiontominimiseelectronelectronrepulsion.Asfigure6.31indicates,thisdistortionoftheelectron
cloudcreatesachargeimbalance,givingthemoleculeaslightpositivechargeatoneendandaslight
negativechargeattheother.Dispersionforcesarethenetattractiveforcesbetweenmoleculesgeneratedby
alltheseinducedchargeimbalances.

FIGURE6.31Exaggeratedviewofhowdispersionforcesarise.

Themagnitudeofdispersionforcesdependsonhoweasyitistodistorttheelectroncloudofamolecule.
Thiseaseofdistortioniscalledthepolarisabilitybecausedistortionofanelectroncloudgeneratesa
temporarypolarity,calledaninstantaneousdipole,withinthemolecule.Wecanexplorehowpolarisability
variesbyexaminingboilingpointsofthehalogens,asshowninfigure6.32.Thedatarevealthatboiling
pointsincreasewiththetotalnumberofelectrons.Fluorine,with18totalelectrons,hasthelowestboiling
point(85K).Iodine,with106electrons,hasthehighestboilingpoint(458K).Thelargeelectroncloudof
I2distortsmorereadilythanthesmallelectroncloudofF2.Figure6.33showsschematicallyhowalarge
electronclouddistortsmorethanasmallone,generatinglargerdispersionforcesandleadingtoahigher
boilingpoint.

FIGURE6.32Boilingpointsofthehalogensincreasewiththenumberofelectrons.
FIGURE6.33Withmanymoreelectrons,theelectroncloudofiodineismuchlargerandmorepolarisablethan
thatoffluorine.

Molecularsizeincreaseswiththenumberaswellaswiththesizeofindividualatoms.Figure6.34shows
howtheboilingpointsofalkanesincreaseasthecarbonchaingetslonger.Asalkanesgetlonger,their
electroncloudsbecomelargerandmorepolarisable,makingdispersionforceslargerandraisingtheboiling
point.Asexamples,methane(CH4,10electrons)isagasat298K,pentane(C5H12,42electrons)isalow
boilingpointliquid,decane(C10H22,82electrons)isahighboilingpointliquidandicosane(C20H42,162
electrons)isawaxysolid.Theboilingpointincreasesprogressivelyasmoleculesbecomelargerandmore
polarisable.

FIGURE6.34Theboilingpointsofalkanesincreasewiththelengthofthecarbonchain,becausealargeelectron
cloudismorepolarisablethanasmallone.

Dispersionforcesincreaseinstrengthwiththenumberofelectronsbecauselargerelectroncloudsaremore
polarisablethansmallerelectronclouds.Formoleculeswithcomparablenumbersofelectrons,theshapeof
themoleculemakesanimportantsecondarycontributiontothemagnitudeofdispersionforces.For
example,figure6.35showstheshapesofpentaneand2,2dimethylpropane.Bothofthesemoleculeshave
theformulaC5H12,with72totalelectrons.Noticethat2,2dimethylpropanehasamorecompactstructure
thanpentane.Thiscompactnessresultsinalesspolarisableelectroncloudandsmallerdispersionforces.
Accordingly,pentanehasaboilingpointof309K,while2,2dimethylpropaneboilsat283K.
FIGURE6.35Theboilingpointofpentaneishigherthantheboilingpointof2,2dimethylpropanebecausean
extendedelectroncloudismorepolarisablethanacompactone.

DipolarForces
Dispersionforcesexistbetweenallmolecules,butsomesubstancesremainliquidatmuchhigher
temperaturesthancanbeaccountedforbydispersionforcesalone.Consider2methylpropaneand
propanone(acetone),whosestructuresareshowninfigure6.36.Thesemoleculeshavesimilarshapesand
nearlythesamenumberofelectrons(34versus32).Theyaresosimilarthatwemightexpectthetwoto
havenearlyequalboilingpoints,butacetoneisaliquidatroomtemperature,whereas2methylpropaneisa
gas.

FIGURE6.36Acetoneand2methylpropanehavesimilarmolecularshapes,butacetonehasalargedipole
momentresultingfromitspolarC Obond.

Whydoesacetoneremainaliquidattemperatureswellabovetheboilingpointof2methylpropane?The
reasonisthatacetonehasalargedipolemoment.Rememberfromchapter5thatchemicalbondsare
polarisedtowardthemoreelectronegativeatom.Thus,theC Obondofacetoneishighlypolarised,with
apartialnegativechargeontheOatom(=3.5)andapartialpositivechargeontheCatom(=2.5).The
CHbondsinthesemolecules,incontrast,areonlyveryslightlypolar,becausetheelectronegativityof
hydrogen(=2.1)isonlyslightlysmallerthanthatofcarbon.

Whentwopolaracetonemoleculesapproacheachother,theyalignsothatthe+endofonemoleculeis
closetotheendoftheother(figure6.36).Inaliquidarray,thisrepeatingpatternofheadtotail
alignmentcreatessignificantnetattractivedipolarforcesbetweenthemolecules.

Thesedipolarforcesinadditiontodispersionforces,whicharenearlythesameinacetoneand2
methylpropane,makethetotalamountofintermolecularattractionbetweenacetonemoleculessubstantially
greaterthanbetweenmoleculesof2methylpropane.Consequently,acetoneboilsataconsiderablyhigher
temperaturethan2methylpropane.

WORKEDEXAMPLE6.13

BoilingPointsandStructure
Thelinestructuresofbutane,methoxyethaneandacetoneareshownbelow.Explainthetrendin
boilingpoints:butane(273K),methoxyethane(281K)andacetone(329K).

Analysis

Theseboilingpointscanbeexplainedintermsofdispersionanddipolarforces.First,assessthe
magnitudesofdispersionforces,whicharepresentinallsubstances,andthenlookforpolarity
withinthemolecules.

Solution

Atablehelpstoorganisetheavailableinformation.

Substance Boilingpoint Totalelectrons


butane 273K 34
methoxyethane 281K 34
acetone 329K 32

Thetableshowsthatdispersionforcesalonecannotaccountfortherangeinboiling
temperatures.Methoxyethaneandbutanehavethesamenumberofelectronsandsimilarshapes
yettheirboilingpointsaredifferent.Acetone,whichhasfewerelectronsthantheother
compounds,hasslightlysmallerdispersionforces,yetitboilsatahighertemperature.Theorder
ofboilingpointsindicatesthatacetoneisamorepolarmoleculethanmethoxyethane,whichin
turnismorepolarthanbutane.

Weexpectbutanetobenonpolarbecauseofthesmallelectronegativitydifferencebetween
carbonandhydrogen.Acetoneandmethoxyethane,ontheotherhand,bothcontainpolar
carbonoxygenbonds.Moleculargeometryrevealswhyacetoneismorepolarthanmethoxy
ethane.Thefullstructuresofthesemoleculesshowthattheoxygenatomintheetherhasfour
setsofelectronpairsandabentgeometry.ThetwoCObonddipolesinmethoxyethane
partiallycanceleachother,leavingarelativelysmallmoleculardipolemoment.Ontheother
hand,thepolarC Obondinacetoneisunopposed,soacetonehasalargerdipolemomentand
ismorepolarthanmethoxyethane.

Isouranswerreasonable?

Forthemoleculesinthisexample,wewouldexpectthosecontainingelectronegativeoxygen
atomstohavehigherboilingpointsthanbutanebecauseofthepresenceofsignificantpermanent
dipoles.AnOatombondedtoonlyoneatomresultsinalargedipolemomentforthemolecule
asexplainedpreviously,andthereforeweexpectacetonetohaveahigherboilingpointthan
methoxyethane.Experimentalvaluesforthedipolemomentsare:butane,0Cmmethoxyethane,
3.7410 30Cmandacetone,9.6210 30Cm.

PRACTICEEXERCISE6.13
Acetaldehyde,CH3CHO,hasastructure
similartoacetonebutwithaCH3group
replacedbyH.Thissubstanceboilsat294K.
Explainitsboilingpointrelativetothethree
compoundsdescribedinworkedexample
6.13.

Althoughnotstrictlyclassedasanintermolecularforce,theinteractionbetweenanionandthepermanent
dipoleofamoleculecanbesignificant.Suchinteractionsarecallediondipoleinteractions,andthesecan
beviewedaslyingbetweendipoledipoleinteractionsandpureionicinteractions.Inaddition,ionspolarise
neighbouringmolecules,leadingtoinduceddipoleinteractions,whicharemuchweakerthaniondipole
interactions.

HydrogenBonds
Methoxyethaneisagasatroomtemperature(boilingpoint=281K),butpropan1ol,showninfigure6.37,
isaliquid(boilingpoint=370K).Thecompoundshavethesamemolecularformula,C3H8O,andeachhas
achainoffourinneratoms,COCCandOCCC.Consequently,theelectroncloudsofthese
twomoleculesareaboutthesamesize,andtheirdispersionforcesarecomparable.Eachmoleculehasan
sp 3hybridisedoxygenatomwithtwopolarsinglebonds,sotheirdipolarforcesshouldbesimilar.Thevery
differentboilingpointsofpropan1olandmethoxyethanemakeitclearthatdispersionanddipolarforces
donotrevealtheentirestoryofintermolecularattractions.
FIGURE6.37Thestructuralformulaandaballandstickmodelofpropan1ol.

Theforcesofattractionbetweenpropan1olmoleculesarestrongerthanthosebetweenmethoxyethane
moleculesbecauseofanintermolecularinteractioncalledahydrogenbond.Ahydrogenbondoccurs
betweenasmall,highlyelectronegativeatomwithalonepairofelectronsandapositivelypolarised
hydrogenatom.Theseinteractionscanbeconsideredaspecialexampleofdipoledipoleinteractions,and
theirstrengthsgenerallyliebetweenthoseofdispersionforcesandcovalentbonds.

Therearetworequirementsforhydrogenbondformation.First,theremustbeanelectrondeficient
hydrogenatomthatcanbeattractedtoanelectronpair.HydrogenatomsinOH,FHandNHbonds
meetthisrequirement.Second,theremustbeasmall,highlyelectronegativeatomwithanelectronpairthat
caninteractwiththeelectrondeficienthydrogenatom.Threesecondrowelements,O,NandF,meetthis
requirement,andthereisevidencethatSandClatomscanalsoformhydrogenbonds,butthesearemuch
weakerthanthoseinvolvingF,OandNatoms.Figure6.38showsrepresentativeexamplesofhydrogen
bonding.Thehydrogenbondsareshownasdottedlinestoindicatetheweakbondingnatureofthese
interactions.

FIGURE6.38Examplesofhydrogenbonding.

Noticefromtheexamplesshowninfigure6.38thathydrogenbondscanformbetweendifferentmolecules
(forexample,H3NH2O)orbetweenidenticalmolecules(forexample,HFHF).Alsonoticethat
moleculescanformmorethanonehydrogenbond(glycine,forexample)andthathydrogenbondscan
formbetweenmoleculesaswellaswithinamolecule(salicylicacid,forexample).

WORKEDEXAMPLE6.14

FormationofHydrogenBonds
Inwhichofthefollowingsystemswillhydrogenbondingplayanimportantrole:CH3F,
(CH3)2CO(acetone),CH3OH,andNH3dissolvedin(CH3)2CO?

Analysis

HydrogenbondsrequireelectrondeficienthydrogenatomsinpolarHXbondsandsmall,
highlyelectronegativeatomswithnonbondingpairsofelectrons.Uselinestructurestodetermine
whethertheserequirementsaremet.

Solution

Herearethestructuralformulaeofthefourmoleculeswithnonbondingelectronpairsindicated.

AcetoneandCH3Fcontainelectronegativeatomswithnonbondingpairs,butneitherhasany
highlypolarHXbonds.Thus,themagnitudeofanyhydrogenbondingbetweenmoleculesof
thesesubstanceswillbesmall.

TheOHbondinCH3OHmeetsbothoftherequirementsforhydrogenbonding.TheOH
hydrogenatomononemoleculeinteractswiththeoxygenatomofaneighbouringmolecule.

Forasolutionofammoniainacetone,wemustexaminebothcomponents.Acetonehasan
electronegativeoxygenatomwithnonbondingpairs,whereasNH3hasapolarNHbond.
Consequently,amixtureofthesetwocompoundsdisplayshydrogenbondingbetweenthe
hydrogenatomsofammoniaandoxygenatomsofacetone,and,dependingonthe
concentration,therewillalsobehydrogenbondsbetweenammoniamolecules.
Isouranswerreasonable?

Methanolhasaconsiderablyhigherboilingpointthanthealkanes,methaneandethane,
consistentwithsignificantintermolecularforces.Ammoniadissolvesreadilyinacetone,also
consistentwithsignificantintermolecularforces.

PRACTICEEXERCISE6.14
Drawapicturethatshowsthehydrogen
bondinginteractionsofanacetonemolecule
dissolvedinwater.

Hydrogenbondingisparticularlyimportantinbiochemicalsystems,becausebiomoleculescontainmany
oxygenandnitrogenatomsthatparticipateinhydrogenbonding.Themostimportantexampleofbiological
hydrogenbondingisseeninDNA,wherehydrogenbondsholdthetwostrandsofDNAtogetherina
doublehelixgeometry.Likewise,theaminoacidsfromwhichproteinsaremadecontainNH2(amino)and
CO2H(carboxylicacid)groups,andfourdifferenttypesofhydrogenbondsexistinthesesystems:OH
N,NHO,OHOandNHN.WhenbiologicalmoleculescontainSatoms,SHOandSH
Nhydrogenbondscanalsoform.Figure6.38includesaviewofhydrogenbondingbetweenmolecules
oftheaminoacidglycine.Moredetailsofhydrogenbondinginbiomoleculesareexaminedinchapters24
and25.

chemicalConnections

MethaneHydrates

Youareallprobablyawareofthepotentialdangerthatcarbondioxideposesasagreenhousegas
intheEarth'satmosphere.However,youmightbelessfamiliarwiththefactthatmethane,CH4,
is,onamassbasis,amuchmorepotentgreenhousegasthancarbondioxide,andlargescale
emissionsofthisgascouldhaveasignificantwarmingeffect.TheNewZealandgovernmentwas
oneofthefirstintheworldtoattempttotakeactiontolimitmethaneemissionsfromfarm
animalshowever,theirsocalledfarttax,whichwouldhaveleviedataxoneveryNewZealand
farmanimal,wasneverimplemented,owingtosubstantialpublicopposition.

Whilefarmanimalsdoindeedemitsignificantquantitiesofmethane,theEarth'soceans,
somewhatsurprisingly,provideafarlargerandpotentiallydevastatingstoreofmethaneinthe
formofanunusualchemicalspeciescalledmethanehydrate.Whenmethanedissolvedinwateris
subjectedtothehighpressuresand(relatively)lowtemperaturesfoundattheseabottom,itforms
methanehydrate,asolidspeciesthatlookslikeice,andcontainsbothmethaneandwater.There
arelargedepositsofmethanehydrateontheseafloorinmanypartsoftheworld,andonesuch
depositliesofftheeastcoastoftheNorthIslandofNewZealand.

Methanehydrateisanexampleofachemicalspeciescalledaclathrate,inwhichgasmolecules
aretrappedinsideanarrayofwatermoleculesthatareheldtogetherinahighlysymmetrical
arrangementbyhydrogenbonds.Figure6.39showsamodelofsuchahydrate,withthemethane
moleculerepresentedinthecentralcavity(theCatomisgrey,Oatomsareredandhydrogen
atomswhite).Methaneisnotaloneinformingsuchclathratesgroup18gasesinparticularare
knowntoformsimilarspecies.

FIGURE6.39Representationofthestructureofmethanehydrate.

Theformationofmethanehydraterequiresparticularconditionsoftemperatureandpressure.Itis
stableatdepthsgreaterthan300m,wherethewatertemperatureisaround2C.However,arise
inthetemperatureoftheEarth'soceansbyonlyafewdegreescouldleadtoconditionsunder
whichmethanehydrateisnolongerstable.Inthiscase,itwoulddecomposetoliquidwaterand
gaseousmethane,leadingtothereleaseofavastamountofgaseousmethane(someestimatesput
thefigureataround10 16kgofcarbon)intotheatmosphere.Thiswouldalmostcertainlyresultin
significantwarmingoftheatmosphere,and,indeed,suchascenariohasbeenpostulatedasthe
causeofpreviouswarmingeventsonplanetEarth.

Theminingofmethanehydrateasapotentialfuelforpowerstationshasbeenproposed,and,ifit
wasreleasedintotheatmosphere,theCO2formedfromburningtheevolvedmethanewouldhave
lessofaneffectasagreenhousegasthanwouldthegaseousmethaneitself.

BinaryHydrogenCompounds
Boilingpointsofbinaryhydrogencompoundsillustratetheinterplaybetweendifferenttypesof
intermolecularforces.Figure6.40showsthatthereareperiodictrendsintheboilingpointsofthese
compounds.Ingeneral,theboilingpointsofthebinaryhydrogencompoundsincreasefromtoptobottom
ofeachcolumnoftheperiodictable.Thistrendisduetoincreasingdispersionforcesthemoreelectrons
themoleculehas,thestrongerarethedispersionforcesandthehigheristheboilingpoint.Ingroup16,for
example,H2S(18electrons)boilsat213K,H2Se(36electrons)at232KandH2Te(54electrons)at269K.

FIGURE6.40Periodictrendsintheboilingpointsofbinaryhydrogencompounds.NoticethatH2 O,HFandNH3
areexceptionstothetrends.

Asfigure6.40shows,ammonia,waterandhydrogenfluoridedepartdramaticallyfromtheperiodic
behaviour.Thisisbecausetheirmoleculesexperienceparticularlylargeintermolecularforcesresultingfrom
hydrogenbonding.Inhydrogenfluoride,forinstance,hydrogenbondsformbetweenthehighly
electronegativefluorineatomofoneHFmoleculeandtheelectrondeficienthydrogenatomofanotherHF
molecule.SimilarinteractionsamongmanyHFmoleculesresultinchainsofhydrogenbondedHF
moleculesleadingtoaboilingpointmuchhigherthanthoseofHCl,HBrandHI.Note,however,thateven
theboilingpointofHClishigherthanifitwereonatrendlineparalleltothoseforgroups15and16,
indicatingthatweakhydrogenbondsmaybeformed.

Fluorinehasthehighestelectronegativityofanyelement,sothestrongestindividualhydrogenbondsare
thoseinHF.EveryhydrogenatominliquidHFisinvolvedinahydrogenbond,butthereisonlyonepolar
hydrogenatompermolecule.Thus,eachHFmoleculemayparticipateintwohydrogenbondswithtwo
otherHFpartners.Thereisonehydrogenbondinvolvingthepartiallypositivehydrogenatomandasecond
involvingthepartiallynegativefluorineatom,leadingtotheformationofHFchains.

Waterhasasubstantiallyhigherboilingpointthanhydrogenfluoride,whichindicatesthattheoverall
hydrogenbondinginH2OisstrongerthanthatinHF,eventhoughtheindividualhydrogenbondsinHFare
stronger.Thehigherboilingpointofwaterreflectsthefactthatitformsmorehydrogenbondsofsignificant
strengthpermoleculethanhydrogenfluoride.Awatermoleculehastwohydrogenatomsthatcanform
hydrogenbondsandtwononbondingelectronpairsoneachoxygenatom.Thispermitseverywater
moleculetobeinvolvedinfourhydrogenbondstofourotherH2Opartners,asshowninfigure6.41a.
FIGURE6.41Tworepresentationsofstructureofice.
(a)Eachoxygenatomisatthecentreofadistortedtetrahedronofhydrogenatoms.The
tetrahedroniscomposedoftwoshortcovalentOHbondsandtwolongHOhydrogen
bonds.
(b)Watermoleculesiniceareheldinanetworkofthesetetrahedra.

Hydrogenbondinginicecreatesathreedimensionalnetwork(figure6.41)thatputseachoxygenatomat
thecentreofadistortedtetrahedron.TwoarmsofthetetrahedronareregularcovalentOHbonds,
whereastheothertwoarmsofthetetrahedronarehydrogenbondstotwodifferentwatermolecules.

Therefore,boththestrengthandnumberofhydrogenbondsthatabinaryhydrogencompounddcanform
determineitsboilingpoint.Wewilldiscusstheroleofhydrogenbondinginsolidsinthenextchapter.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
SUMMARY
TheStatesofMatter
Thethreemostimportantstatesofmatteraresolid,liquidandgas.Mostsubstancescanexistinanyof
thesestates,andthestateadoptedbyaparticularsubstanceunderdefinedconditionsisdeterminedby
themagnitudeoftheforcesbetweenindividualatoms,moleculesorionsinthesubstance.

DescribingGases
Gasesoccupyallofthespaceinwhichtheyarecontained.Thepressureexertedbyagasisduetothe
collisionsofrapidlymovinggasatomsormoleculeswiththewallsofthecontainer.TheSIunitof
pressureisthepascal(Pa).Atmosphericpressureismeasuredwithabarometerinwhichapressureof1
standardatmosphere(1atm)willsupportacolumnofmercury760mmhigh.Thisisapressureof760
torr.Bydefinition,1atm=1.0132510 5pascals(Pa),andstandardpressure .
Manometersareusedtomeasurethepressureoftrappedgases.Boyle'sLaw,Charles'Lawand
Avogadro'sLawdescribetherelationshipsbetweenvolumeandpressure,volumeandtemperature,and
volumeandamountofagas,respectively.Thecombinationofthesethreelawsgivestheidealgas
equation:

wherep=pressure(Pa),V=volume(m3),n=amount(mol),R=thegasconstant(8.314Jmol1K1)
andTistemperature(K).

MolecularViewofGases
Inordertodeterminethekineticenergyofagasmolecule,itisnecessarytomeasurethespeedwith
whichitismoving.Thiscanbedoneusingamolecularbeamapparatus.Thisshowsthatallmolecules
withinaparticulargassampledonotmovewiththesamespeedandthatsmallmoleculesmove,on
average,fasterthanlargemolecules.However,themostprobablekineticenergyofagasmoleculeisthe
same,regardlessofitsmass,andallgaseshaveanidenticalmolecularkineticenergydistribution.The
averagekineticenergyofamoleofanygasisrelatedtothetemperatureinkelvinthroughtheequation:

Anidealgasisoneforwhichthevolumeofthemoleculesandtheforcesbetweenthemoleculesareso
smallastobeinsignificant.Anidealgasobeystheidealgasequationexactly.Realgasesapproximate
idealbehaviourunderconditionsoflowpressureandhightemperature.

Therootmeansquarespeedofagas canbefoundfromtheequation:

Themovementofgasmoleculescanbedescribedaseithereffusion(themovementofmoleculesintoa
vacuum)ordiffusion(themovementofonetypeofmoleculethroughmoleculesofthesameoranother
type).

GasMixtures
Eachgaseouscomponentinamixtureofidealgasesexertsapartialpressure.Thesumofpartial
pressuresofallgasesinamixtureequalsthetotalpressure.ThisisastatementofDalton'slawofpartial
pressures,whichcanalsobeexpressedas:
Themolefraction(xA)ofasubstanceAequalstheratiooftheamountofA(n A),tothetotalamount
(n total)ofallthecomponentsofamixture,i.e. .Intermsofmolefractions,p A=xAp total.The
compositionofagasmixturecanalsobeexpressedintermsofpartspermillionorpartsperbillion.

ApplicationsoftheIdealGasEquation
Combinationoftheidealgasequationwiththestoichiometricequation, ,allowsdeterminationof
themolarmassanddensityofanunknowngas.

GasStoichiometry
Theidealgasequationcanbeusedtodetermineamounts,throughrearrangementintotheform
,andcanthereforebeusedinstoichiometriccalculationsinvolvingpuregasesandgas
mixtures.

RealGases
Intermolecularforcesarepartiallyresponsibleforthefactthatrealgasesdonotexactlyobeytheideal
gaslaws.Thevariationfromidealbehaviourcanbeshownbyplotting versuspressureforan

idealgas, shouldalwaysequal1.Valueslessthan1arearesultofsignificantintermolecular
interactionsbetweenindividualgasmolecules,whilevaluesgreaterthan1arisefromthenonzero
volumeofthegasmolecules.Everygasshowsdeviationfromidealbehaviourathighpressuresandat
temperaturesnearthecondensationpoint.ThevanderWaalsequationforarealgas:

makescorrectionsforthevolumeofthegasmoleculesandfortheattractiveforcebetweenthem.The
vanderWaalsconstantareflectstheattractiveforcesbetweenmolecules,whereastheconstantb
reflectstherelativesizeofthegasmolecules.Meltingpointsand,especially,boilingpointsgivegood
indicationsofthestrengthsofintermolecularforces.Thenormalboilingpointisthetemperatureat
whichtheaveragekineticenergyofmolecularmotionbalancestheattractiveenergyofintermolecular
attractionsatapressureof1.01310 5Pa.Undertheseconditions,thesubstanceisconvertedfroma
liquidtoagasinaprocesscalledvaporisation.Thereverseprocessiscalledcondensation.Thenormal
freezingpointisthetemperatureatwhichaliquidsolidifiesatapressureof1.01310 5Pa.

IntermolecularForces
Therearethreegeneraltypesofintermolecularforces:dispersionforces,dipoleinduceddipoleforces
andhydrogenbonds.Theserangeinstrengthfrom0.15kJmol1,520kJmol1and550kJmol1
respectively.

Dispersionforcesresultfromtheasymmetricaldistributionofamolecule'selectronsatanyinstantof
time,leadingtotheformationofinstantaneousdipoleswithinthemolecule.Theeaseofdistortionofan
electroncloudiscalledthepolarisabilityofthemoleculemoleculeswithlargeelectroncloudshave
highpolarisabilitiesandconsequentlydisplaylargedispersionforces.Dispersionforcesoccurinall
molecules.

Polarmoleculesattracteachotherbydipolarforces,whicharisebecausethepositiveendofa
permanentdipoleattractsthenegativeendofadipoleinaneighbouringmolecule.
Hydrogenbonding,aspecialcaseofdipoledipoleattractions,occursbetweenmoleculesinwhich
hydrogeniscovalentlybondedtoasmall,veryelectronegativeatomprincipally,nitrogen,oxygenor
fluorineandmoleculescontainingatomsthathavelonepairsofelectrons(againmainlynitrogen,
oxygenorfluorine).Hydrogenbondingismuchstrongerthantheothertypesofintermolecular
attractionsandisthereasonfortheanomalousbehaviourofwater,ammoniaandhydrogenfluoride
whencomparedwithotherbinaryhydrogencompounds.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYCONCEPTSANDEQUATIONS
Idealgasequation(section6.2)
Thiscanbeusedwhenanythreeofthefourvariablesp,V,Torn,areknownandwewishtocalculate
thevalueofthefourth.

Dalton'slawofpartialpressures(section6.4)
Weusethislawtocalculatethepartialpressureofonegasinamixtureofgases.Thisrequiresthetotal
pressureandeitherthepartialpressuresoftheothergasesortheirmolefractions.Ifthepartialpressures
areknown,theirsumisthetotalpressure.

Molefractions(section6.4)
Giventhecompositionofagasmixture,wecancalculatethemolefractionofacomponent.Themole
fractioncanthenbeusedtofindthepartialpressureofthecomponentgiventhetotalpressure.Ifthe
totalpressureandpartialpressureofacomponentareknown,wecancalculatethemolefractionofthe
component.

Relationshipbetweenintermolecularforcesandmolecularstructure(section6.8)
Fromthemolecularstructure,wecandeterminewhetheramoleculeispolarandwhetherithasNHor
OHbonds.Thisletsuspredictandcomparethestrengthsofintermolecularattractions.Youshouldbe
abletoidentifywhendispersionforces,dipolarforcesorhydrogenbondingoccur.

vanderWaalsequation(section6.8)

Boilingpointsofsubstances(section6.8)
Theseallowustocomparethestrengthsofintermolecularforcesinsubstancesbasedontheirboiling
points.

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REVIEWQUESTIONS
DescribingGases
6.1Describewhatwouldhappentothebarometerinfigure6.2ifthetubeholdingthemercuryhada
pinholeatitstop.
6.2Describehowthedifferencebetweenaninflatedandaflatcartyreshowsthatagasexertspressure.
6.3Expressthefollowinginunitsofpascal:
(a)455torr
(b)2.45atm
(c)0.46torr
(d)1.3310 3atm.
6.4Asampleofairwascompressedtoavolumeof20.0L.Thetemperaturewas298Kandthe
pressurewas5.0010 5Pa.Whatamountofgaswasinthesample?Ifthesamplewascollected
fromairatapressureof1.0010 5Pawithatemperatureof298K,whatwastheoriginalvolume
ofthegas?
6.5Rearrangetheidealgasequationtogivethefollowingexpressions.
(a)Anequationthatrelatesp i,Ti,p fandTfwhennandVareconstant
(b)V=?
(c)Anequationthatrelatesp i,Vi,p fandVfwhennandTareconstant
6.6Itrequires0.255Lofairtofillametalfoilballoonto1.00010 5Papressureat25C.Theballoon
istiedoffandplacedinafreezerat15C.Whatisthenewvolumeofairintheballoon?
6.7Underwhichofthefollowingconditionscouldyouusetheequationp fVf=p iVi?
(a)AgasiscompressedatconstantT.
(b)Agasphasechemicalreactionoccurs.
(c)Acontainerofgasisheated.
(d)AcontainerofliquidiscompressedatconstantT.
MolecularViewofGases
6.8Redrawfigure6.6btoshowthedistributionofmoleculesifthetemperatureoftheovenisdoubled.
6.9DrawasinglegraphthatshowsthespeeddistributionsofN2at200K,N2at300KandHeat300
K.
6.10Calculatetherootmeansquarespeedandaveragekineticenergypermoleforeachofthe
following.
(a)Heat627C
(b)O2at27C
(c)SF6at627C
6.11Explaininmoleculartermswhyeachofthefollowingstatementsistrue.
(a)Atveryhighpressure,nogasbehavesideally.
(b)Atverylowtemperature,nogasbehavesideally.
6.12Thefigurebelowrepresentsanidealgasinacontainerwithamovablefrictionfreepiston.
(a) Theexternalpressureonthepistonexertedbytheatmosphereis1.01310 5Pa.Ifthe
pistonisnotmoving,whatisthepressureinsidethecontainer?Explainintermsof
molecularcollisions.
(b)Redrawthesketchtoshowwhatwouldhappenifthetemperatureofthegasinthe
containerisdoubled.Explainintermsofmolecularcollisions.
6.13Describethemolecularchangesthataccountfortheresultinquestion6.6
6.14DeterminetherootmeansquarespeedofSF moleculesat1.0110 5Paand27C.
6
6.15AstudentproposestoseparateCOfromN2byaneffusionprocess.Isthislikelytowork?Whyor
whynot?
GasMixtures
6.16TheconcentrationofNO2inasmoggyatmospherewasmeasuredas0.78ppm.Thebarometric
pressurewas1.01110 5Pa.CalculatethepartialpressureofNO2inPa.
6.17Indryatmosphericair,thefourmostabundantcomponentsareN2,x=0.7808O2,x=0.2095
Ar,x=9.3410 3andCO2,x=3.2510 4.Calculatethepartialpressuresofthesefourgases,in
Pa,understandardatmosphericconditions.
6.18Thefiguresshownbelowrepresentverysmallportionsofthreegasmixtures,allatthesame
volumeandtemperature.

(a)WhichsamplehasthehighestpartialpressureofgasA?
(b)WhichsamplehasthehighestmolefractionofgasB?
(c)InsampleIII,whatistheconcentrationofgasAinppm?
6.19Asampleofcarexhaustisanalysed.Thegascontains487.4ppmCO2,10.3ppbNOand4.2ppb
CO.Calculatethepartialpressuresofthesegasesiftheexhaustisemittedat113.1kPapressure.
ApplicationsoftheIdealGasEquation
6.20Whatisthedensity(gL1)ofSF gasat1.0110 5Paand27C?
6
GasStoichiometry
6.21Humansconsumeglucosetoproduceenergy.TheproductsofglucoseconsumptionareCO2and
H2O.

WhatvolumeofCO2isproducedunderbodyconditions(37C,1.01310 5Pa)duringthe
consumptionof4.65gofglucose?
6.22Sodiummetalreactswithmolecularchlorinegastoformsodiumchloride.Aclosedcontainerof
volume3.0010 3mLcontainschlorinegasat27Cand1.6710 5Pa.Then6.90gofsolid
sodiumisintroduced,andthereactiongoestocompletion.Whatisthefinalpressureifthe
temperaturerisesto47C?
6.23AmmoniaisproducedindustriallybyreactingN2withH2atelevatedpressureandtemperaturein
thepresenceofacatalyst.

Assuming100%yield,whatmassofammoniawouldbeproducedfroma1:1moleratiomixture
inareactorthathasavolumeof8.7510 3L,underatotalpressureof27510 5Paat455C?
6.24Inpractice,thereactionofquestion6.23givesayieldofonly13%.Repeatthecalculationtaking
thisintoaccount.
RealGases
6.25Predictwhethertheeffectsofmolecularvolumeandintermolecularattractionsbecomemoreor
lesssignificantwhenthefollowingchangesareimposed.
(a)Agasexpandsintoalargervolumeatconstanttemperature.
(b)Moregasisintroducedintoacontainerofconstantvolumeatconstanttemperature.
(c)Thetemperatureofagasincreasesatconstantpressure.
6.26Fromthefollowingexperimentaldata,calculatethepercentagedeviationfromidealbehaviour:
1.00molCO2ina1.20Lcontainerat40.0Cexerts19.710 5Papressure.
6.27Chlorinegasiscommerciallyproducedbyelectrolysisofseawaterandisstoredunderpressurein
metaltanks.Atypicaltankhasavolumeof15.0Landcontains1.25kgofCl2.Usethevander
Waalsequationtocalculatethepressureinthistankifthetemperatureis295K,andcomparethe
resultwiththeidealgasvalue.
IntermolecularForces
6.28Arrangethefollowinginorderofeaseofliquefaction:CCl4,CH4andCF4.Explainyourranking.
6.29Arrangethefollowinginorderofincreasingboilingpoint:Ar,He,NeandXe.Explainyour
ranking.
6.30Listethanol,CH3CH2OH,propane,CH3CH2CH3,andpentane,CH3CH2CH2CH2CH3,inorderof
increasingboilingpoint,andexplainwhatfeaturesdeterminethisorder.
6.31Whichofthefollowingwillformhydrogenbondswithanothermoleculeofthesamesubstance?
Drawmolecularpicturesillustratingthesehydrogenbonds.
(a)CH2Cl2
(b)H2SO4
(c)H3COCH3
(d)H2NCH2COOH
6.32Whichofthefollowingmoleculesformhydrogenbondswithwater?Drawmolecularpictures
illustratingthesehydrogenbonds.
(a)CH4
(b)I2
(c)HF
(d)H3COCH3
(e)(CH3)3COH

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
REVIEWPROBLEMS
6.33Nitrogengasisavailablecommerciallyinpressurised9.50Lsteelcylinders.Ifatankhasa
pressureof14510 5Paat298K,whatamountofN2isinthetank?WhatisthemassofN2inthe
tank?
6.34Thefigurebelowshowsthreechamberswithequalvolumes,allatthesametemperature,
connectedbyclosedvalves.Eachchambercontainsheliumgas,withamountsproportionaltothe
numberofatomsshown.

Answereachofthefollowingquestions,brieflystatingyourreasoning.
(a)Whichofthethreehasthehighestpressure?
(b)IfthepressureinBis1.010 5Pa,whatisthepressureinA?
(c) IfthepressureinAstartsat1.010 5Pa,andthenalloftheatomsfromBandCare
transferredtoA,whatwillbethenewpressure?
(d)IfthepressureinBis0.5010 5Pa,whatwillthepressurebeafterthevalvesareopened?
6.35Atanaltitudeof40kmabovetheEarth'ssurface,thetemperatureisabout25C,andthe
pressureisabout4.010 2Pa.Calculatetheaveragemolecularspeedofozone,O3,atthisaltitude.
6.36Molecularcloudscomposedmostlyofhydrogenmoleculeshavebeendetectedininterstellar
space.Themoleculardensityinthesecloudsisabout10 10moleculesperm3,andtheir
temperatureisaround25K.Whatisthepressureinsuchacloud?
6.37Describeagasexperimentthatwouldshowthattheelementoxygenexistsnaturallyasdiatomic
molecules.
6.38Amixtureofcyclopropanegas,C3H6,andoxygen,O2,ina1.00:4.00moleratioisusedasan
anaesthetic.Whatmassofeachofthesegasesispresentina2.00Lbulbat23.5Cifthetotal
pressureis1.0010 5Pa?
6.39Considertwogasbulbsofequalvolume,onefilledwithH gasat0Cand210 5Pa,theother
2
containingO2gasat25Cand110 5Pa.Whichbulbhas(a)moremolecules(b)agreatermass
(c)ahigheraveragekineticenergyofmoleculesand(d)ahigheraveragemolecularspeed?
6.40Molecularbeamexperimentsonammoniaat425Kgivethespeeddistributionshowninthefigure
below.
(a)Whatisthemostprobablespeed?
(b)Whatisthemostprobablekineticenergy?
6.41Asampleofgasisfoundtoexertapressureof7.0010 4Pawhenitisina3.00Lflaskat0.00
C.Calculate:
(a) thenewvolumeifpbecomes1.0110 5PaandTisunchanged
(b)thenewpressureifVbecomes2.00LandTisunchanged
(c)thenewpressureifthetemperatureisraisedto50.0CandVisunchanged.
6.42Determinewhethereachofthefollowingstatementsistrueorfalse.Iffalse,rewritethestatement
sothatitistrue.
(a)AtconstantTandV,pisinverselyproportionaltotheamountofgas.
(b)AtconstantV,thepressureofafixedamountofgasisdirectlyproportionaltoT.
(c)AtfixednandV,theproductofpandTisconstant.
6.43A3.00gsampleofanidealgasat22Cand0.96910 5Paoccupies0.963L.Whatisitsvolume
at15Cand1.0010 5Pa?
6.44Recently,carbondioxidelevelsattheSouthPolereached374.6partspermillionbyvolume.(The
1958readingwas314.6ppmbyvolume.)ConvertthisreadingtoapartialpressureinPa.Atthis
level,howmanyCO2moleculesaretherein1.0Lofdryairat45C?
6.45Listthedifferentkindsofforcesthatmustbeovercometoconverteachofthefollowingfroma
liquidtoagas.
(a)NH3
(b)CHCl3
(c)CCl4
(d)CO2
6.46Foreachofthefollowingpairs,identifywhichhasthehigherboilingpoint,andidentifythetype
offorcethatisresponsible.
(a)H3COCH3andCH3OH
(b)SO2andSiO2
(c)HFandHCl
(d)Br2andI2
6.47Whichgasdeviatesmorefromideal behaviour,F2orCl2?

Explainyourchoice.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
ADDITIONALEXERCISES
6.48Twochambersareconnectedbyavalve.Onechamberhasavolumeof15LandcontainsN2gas
atapressureof2.010 5Pa.Theotherhasavolumeof1.5LandcontainsO2gasat3.010 5Pa.
Thevalveisopened,andthetwogasesareallowedtomixthoroughly.Thetemperatureis
constantat300Kthroughoutthisprocess.
(a)WhatamountofeachofN2andO2ispresent?
(b)WhatarethefinalpressuresofN2andO2,andwhatisthetotalpressure?
(c)WhatfractionoftheO2isinthesmallerchamberaftermixing?
6.49Liquidoxygen,usedinsomelargerockets,isproducedbycoolingdryairto183C.Howmany
litresofdryairat25Cand1.0010 5Pahavetobeprocessedtoproduce150Lofliquid
oxygen(density=1.14gmL1)?Assumethatairis21%O2byvolume.
6.50Inanexplosion,acompoundthatisasolidoraliquiddecomposesveryrapidly,producinglarge
volumesofgas.Theforceoftheexplosionresultsfromtherapidexpansionofthehotgases.For
example,TNT(trinitrotoluene)explodesaccordingtothefollowingbalancedequation.

(a)Whatamountofgasisproducedintheexplosionof1.0kgofTNT?
(b)Whatvolumewillthesegasesoccupyiftheyexpandtoatotalpressureof1.010 5Paat
25C?
(c) Calculatethepartialpressureofeachgasat1.010 5Patotalpressure.
6.51TheHabersynthesisofammoniaoccursinthegasphaseathightemperature(400to500C)and
pressure(100to30010 5Pa).ThestartingmaterialsfortheHabersynthesisareplacedinsidea
container,inproportionsshowninthefigurebelow.

Assuming100%yield,sketchthesystemattheendofthereaction.
6.52Peopleoftenremarkthattheairisthinathigherelevation.Explainthiscommentinmolecular
termsusingthefactthattheatmosphericpressureatthetopofMountEverestisabout3.3310 4
Pa.
6.53Thefiguresshownbelowrepresentmixturesofargonatomsandhydrogenmolecules.Thevolume
ofcontainerBistwicethevolumeofcontainerA.

(a)Whichcontainerhasahighertotalgaspressure?Explain.
(b)Whichcontainerhasahigherpartialpressureofmolecularhydrogen?Explain.
(c)Oneofthetwogasmixtures(AorB)wasusedinapulsedmolecularbeamexperiment.
Theresultoftheexperimentisshownbelow.Whichofthetwogassamples,AorB,was
usedforthisexperiment?Explain.

6.54A0.1054gmixtureofKClO3andacatalystwasplacedinaquartztubeandheatedvigorouslyto
driveoffalltheoxygenasO2.TheO2wascollectedat25.17Candapressureof1.01210 5Pa.
Thevolumeofgascollectedwas22.96mL.
(a)WhatamountofO2wasproduced?
(b)WhatamountofKClO3wasintheoriginalmixture?
(c)WhatwasthemasspercentofKClO3intheoriginalmixture?
6.55DoestheboilingpointofHCl(seefigure6.40)suggestthatitmayformhydrogenbonds?Explain
youransweranddrawamolecularpicturethatshowsthepossiblehydrogenbondsbetweenHCl
molecules.
6.56Molecularhydrogenandatomicheliumbothhavetwoelectrons,butHeboilsat4.2K,whereas
H2boilsat20K.Neonboilsat27.1K,whereasmethane,whichhasthesamenumberof
electrons,boilsat114K.Explainwhymolecularsubstancesboilatahighertemperaturethan
atomicsubstanceswiththesamenumberofelectrons.
6.57Inthetwofiguresshownbelow,thegreenmoleculeisabouttostrikethewallofitscontainer.
Assumingallotherconditionsareidentical,whichcollisionwillexertgreaterpressureonthewall?
Explainintermsofintermolecularinteractions.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
KEYTERMS
barometer hydrogenbonding partsperbillion(ppb)
condensation idealgas partspermillion(ppm)
Dalton'slawofpartial idealgasequation pascal(Pa)
pressures intermolecularforces polarisability
diffusion manometer pressure
dipoleinduceddipoleforce molefraction(x) rootmeansquarespeed
dipoledipoleforce normalboilingpoint vanderWaalsequation
dispersionforce normalfreezingpoint vaporisation
effusion partialpressure
gasconstant

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CHAPTER

7 CondensedPhases:Liquids
andSolids
Inthepreviouschapter,welearnedaboutgases,oneofthethreecommonstatesofmatter.The
icebergsshownonthispage,picturedoffDunedinin2006,exemplifytheothertwocommonstates
ofmatter,liquidandsolid.Iceisextremelyunusualbecauseitislessdensethanitsliquidphaseand,
therefore,floatsonthesurfaceofwater.ThishaswiderangingconsequencesforlifeonEarthit
meansthaticewillaccumulateatthesurfaceofabodyofwater,ratherthanatthebottom,ensuring
thataquaticlifecansurviveevenincoldwinters.Italsomeansthatafullbottleofdrinkthatyouput
intothefreezermightcrackbecausewaterexpandswhenitchangesphasefromliquidtosolid.

Inthischapterwewillinvestigateliquidsandsolids,thetwocondensedphasesofmatter.Wewill
alsolookatwhathappenswhensubstanceschangephasebetweensolid,liquidandgas,andhow
thesephasechangesdependonbothtemperatureandpressure.Finallywewillexamineorderin
solidsandsomeapplicationsofmodernmaterials.
KEYTOPICS

7.1Liquids
7.2Solids
7.3Phasechanges
7.4Orderinsolids
7.5Xraydiffraction
7.6Amorphoussolids
7.7Crystalimperfections
7.8Modernceramics

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.1Liquids
Inthepreviouschapter,wesawthat,althoughmanygasesbehavelikeanidealgasunderambient
conditions,allofthemhaveintermolecularforceswhichmaycausedeviationsfromidealbehaviour.One
consequenceoftheseintermolecularforcesingasesisthatagascondensestoaliquidifitiscooled
sufficiently.Condensationoccurswhentheaveragekineticenergyofthemoleculesfallsbelowthevalue
neededforthemtomoveaboutindependently.Inaliquid,intermolecularforcesarestrongenoughto
confinethemoleculestoaspecificvolume,butnotstrongenoughtokeepmoleculesfrommovingfreely
withintheliquid.Asaconsequence,likegases,liquidsarefluid,andmostfloweasilyfromplacetoplace.
Unlikegases,however,liquidsarecompact,sotheycannotexpandorcontractmuch.

PropertiesofLiquids
Intermolecularforcesinliquidsleadtothreeimportantproperties:surfacetension,capillaryactionand
viscosity.

Surfacetensionisameasureoftheresistanceofaliquidtoanincreaseinitssurfacearea.Thispropertyis
causedbyattractiveintermolecularforcesbetweenthemoleculesinaliquid.Theseattractiveforcesare
knownascohesiveforces.

Figure7.1illustratesatthemolecularlevelwhyliquidsexhibitsurfacetension.Amoleculeintheinteriorof
aliquidiscompletelysurroundedbyothermolecules.Amoleculeataliquidsurface,ontheotherhand,has
othermoleculesbesideitandbeneathit,butveryfewaboveitinthegasphase.Thisdifferencemeansthat
thereisanetattractiveforceonmoleculesatthesurfacethatpullsthemtowardstheinterioroftheliquid,
resultinginasfewparticlesaspossibleatthesurface.Aliquidwillthereforeadoptashapewiththe
minimumpossiblesurfacearea.Smallamountsofaliquidwilladoptasphericalshapebecausesphereshave
lesssurfaceareaperunitvolumethananyothershape.Forexample,waterdripsfromatapinnearly
sphericalliquiddroplets.Largedropsaredistortedfromidealspheresbytheforceofgravity.

FIGURE7.1Intheinteriorofaliquid(bottom),eachmoleculeexperiencesequalforcesinalldirections
(representedbythearrows).Amoleculeatthesurfaceofaliquid(top)ispulledbackintotheliquidby
intermolecularforces.

Moleculesincontactwiththesurfaceoftheircontainerexperiencetwosetsofintermolecularforces.
Cohesiveforcesattractmoleculesintheliquidtooneanother.Adhesiveforcesattractmoleculesintheliquid
tothewallsofthecontainer.

Oneresultofadhesiveforcesisthecurvedsurfaceofaliquid,calledameniscus.Waterinaglasstube
formsaconcavemeniscusthatincreasesthenumberofwatermoleculesincontactwiththewallsofthe
tube.Thisisbecausetheadhesiveforcesbetweenwaterandglassarestrongerthanthecohesiveforces
betweenwatermolecules.

Figure7.2showsanotherresultofadhesiveforces.Inatubeofsmallenoughdiameter,wateractually
climbsthewallsbecausetheadhesiveforcesbetweenwaterandglassarestrongerthantheforceofgravity.
Thisupwardmovementofwateragainstthedownwardforceofgravityiscalledcapillaryactionandisdue
toattractionsbetweenpolarwatermoleculesandoxygenatomsinSiO2(glass).Similarly,capillaryaction
involvingsapandthecellulosewallsofwoodfibreplaysaroleinhowtreestransportsapfromtheirrootsto
theirhighestbranches.

FIGURE7.2Waterrisesinsideasmalldiametertubebecauseofcapillaryaction.Thewaterinthisphotohasbeen
colouredtoshowtheeffectofcapillaryactionmoreclearly.

Watercanbepouredveryquicklyfromonecontainertoanother,whileoilpoursmoreslowly,andhoney
sometimesseemstotakeforever.Aliquid'sresistancetoflowiscalleditsviscositythegreatertheviscosity,
themoredifficulttheliquidistopour.Viscosityisameasureofhoweasilymoleculesslidebyoneanother.
Viscosityis,therefore,affectedbyacombinationofmolecularshapeandthestrengthoftheintermolecular
forces.Thegreaterthecontactareaofeachmoleculeinaliquid,thehighertheviscosityoftheliquid.The
moleculesinliquidssuchaswater,acetoneandbenzenearesmallandcompacttheyhavesmallcontact
areasandthuslowviscosity.Incontrast,moleculeswithalargesurfacearea,suchasthesugarsinhoney
andthehydrocarbonsfoundinoils,havelargeareasofcontactandthushighviscosity.

Viscosityisaffectedbytemperature.Thisdependenceisquitenoticeableforhighlyviscoussubstancessuch
ashoneyandsyrup,whicharemucheasiertopourwhenhotthanwhencold.Athighertemperature,the
averagekineticenergyofthemoleculesintheliquidishigher,whichallowsthemtoovercomethe
intermolecularforcesmoreeasily.Thus,viscositydecreasesastemperatureincreases.

VapourPressure
Oursensestellusthatmoleculesescapefromaliquid.Forexample,boththesmellofpetrolaroundanopen
tankandtheevaporationofarainpuddleinthesunshinesuggestthatmoleculesescapefromtheliquidinto
thevapourphase.Theredvapourphasethatcanbeobservedaboveliquidbrominesuggeststhatbromine
moleculesarepresentinbothphases.
Recallfromsection6.3thatanycollectionofmoleculeshasadistributionofkineticenergies.Inaliquid,the
distributionofkineticenergiesissuchthatmoleculescanmoveaboutwithintheliquid,butonaveragethey
donothavesufficientkineticenergytoescapeintothegasphase.Nevertheless,thedistributionof
molecularenergiesguaranteesthatsomeofthemoleculesinanyliquidhaveenoughkineticenergyto
overcometheintermolecularforcesthatconfinetheliquid.Thesemoleculesescapeintothevapourphase
whenevertheyareatthesurfaceoftheliquid.Ifthesurfaceofaliquidisincontactwithagasphase,some
ofitsmoleculeswillescapeintothegasphase.

Thenumberofmoleculesofaliquidthathaveenoughenergytoescapeintothevapourphasedependsboth
onthestrengthofintermolecularforceswithintheliquidandthetemperature.Asfigure7.3shows,ata
particulartemperaturemoremoleculescanescapefromliquidbrominethanfromliquidwater.Thisis
becausetheintermolecularforcesbetweenwatermoleculesarestrongerthanthosebetweenbromine
molecules.Awatermoleculeneedsmorekineticenergytoescapetheliquidphase.Figure7.3billustrates
that,whenthetemperaturerises,thefractionofmoleculeshavingenoughenergytoescapeincreases.

FIGURE7.3 Thefractionofmoleculeswithenoughkineticenergytoescapealiquiddependsonthestrengthof
intermolecularforcesandtemperature.
(a)At300K,morebrominemoleculescanescapethanwatermoleculesbecausebrominehas
weakerintermolecularforcesthanwater.
(b)Morebrominemoleculescanescapeat320K(areaunderorangecurvetotherightofescape
energy)thanat300K(areaunderthebluecurvetotherightofescapeenergy)becausethere
aremoremoleculeswithatleasttheescapeenergy.

Aliquidinanopencontainercontinuallylosesmoleculesuntileventuallyithasevaporatedcompletely.
However,inaclosedcontainersuchastheoneshowninfigure7.4,thepartialpressureofthevapour
increasesasmoreandmoremoleculesenterthegasphase.Asthispartialpressurebuilds,increasing
numbersofmoleculesfromthevapourstriketheliquidsurfaceandreturntotheliquid.Eventually,asfigure
7.4illustrates,thenumberofmoleculesescapingfromtheliquidexactlymatchesthenumberofmolecules
beingcapturedbytheliquid.Thereisnonetchangeinthetotalnumberofmoleculesinthegasandthe
liquid,andwecallthisadynamicequilibrium.Thepressureatwhichthisequilibriumexistsisthevapour
pressureoftheliquid.Thevapourpressureofanyliquidriseswithincreasingtemperaturebecausemore
moleculeshavesufficientkineticenergytoescapetheliquidphaseintothegasphase.
FIGURE7.4Asthepartialpressureofasubstanceinthegasphaseabovealiquidinaclosedcontainerincreases
(asindicatedbythenumberofredarrows),thedifferencebetweenthenumberofmoleculesescaping
intothegasphaseandthenumberreenteringtheliquidphasedecreasesuntil,atthevapour
pressureofthesubstance,equilibriumisestablished.

Oncethevapourpressureoftheliquidinanopencontainerreachestheexternalpressure,theliquidstartsto
boil.Water,forinstance,boilsat100Cataverageatmosphericpressureatsealevel(1.01310 5Pa).As
welearnedinchapter6,thetemperatureatwhichaliquidboilsatthispressureisknownasthenormal
boilingpoint.Atlowerpressure,suchaswewouldfindontopofahighmountain,theboilingpointislower
becausetherequiredvapourpressureisreachedatalowertemperature.Forexample,ontopofNew
Zealand'sAoraki/MountCook,whichis3754mhigh,averageatmosphericpressureis0.63710 5Paand
waterboilsatabout85C.Conversely,apressurecookerworksontheprinciplethatifyouincreasethe
externalpressuretheboilingpointincreases.Forinstance,atnormalatmosphericpressure,youcannotheat
liquidwatertoabove100C,whereasinahouseholdpressurecookertemperaturesofupto120Ccanbe
reached.Figure7.5showsthedependenceofvapourpressureontemperatureforarangeofliquids.The
variationbetweenvapourpressuresofdifferentsubstancesisduetothedifferentstrengthsofintermolecular
forces.

FIGURE7.5Vapourpressureasafunctionoftemperaturefordiethylether,water,aceticacidandpropane1,3
diol.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.2Solids
Thevastmajorityofcompoundsaresolidsunderambientconditions.Asubstanceisasolidwhenitsions,atomsormoleculesareheldtogetherso
stronglythattheycannoteasilymovepasteachother.Unlikegasesandliquids,solidsarecharacterisedbyrigidity,whichgivesthemthestable
shapesthatweseeinstructuresrangingfrombonestoaeroplanewings.Oneofthemostactiveareasofresearchinchemistry,physicsand
engineeringisthedevelopmentofneworimprovedsolidmaterials.Solidscontinuetoplayalargeroleinsociety,fromcapacitorsandsolidstate
batterycomponentsinmobilephonesandlaptopstonewtissuecompatiblesolidsforsurgicalimplants.Inthissection,wedescribethevarioustypes
ofsolids.

MagnitudesofForces
Inchapter6,wesawthatthemeltingpointsofsolidsspananimmenserange,e.g.from0.95K(He)to1808K(Fe)forthosepresentedintable6.4(p.
240).Thesevaluesindicatethattheforcesinsolidsrangefromverysmalltoextremelylarge.Thisisbecausetheions,atomsormoleculesinsolids
canbeboundtogetherbyvariousattractiveforces:intermolecularforces,metallicbonding,covalentbondsandionicinteractions.

Themoleculesofamolecularsolidareheldinplacebyintermolecularforces:dispersionforcesanddipolarinteractions,includinghydrogenbonds.
Theatomsofametallicsolidareheldinplacebydelocalisedbondinginvolvingmobileelectrons(p.259).Anetworksolidcontainsanarrayof
covalentbondslinkingeveryatomtoitsneighbours.Anionicsolidcontainscationsandanions,attractedtooneanotherbyelectrostaticforcesas
describedinsection5.2.Table7.1contraststheforcesandenergiesassociatedwiththesefourtypesofsolids.
TABLE7.1 Characteristicsofdifferenttypesofsolids
Solidtype atomic/molecular molecular molecular metallic network ionic
Attractive dispersion dispersion+dipolar dispersion+dipolar delocalised covalent electrostatic
forces +hydrogen bonding
bonding
Energy 0.0540 525 550 751000 150500 4004000
(kJmol1)
Example Ar HCl H2O Cu SiO2 NaCl

Melting 189 114 0 1088 1713 801


point(C)
Schematic
diagram

MolecularSolids
Molecularsolidsareaggregatesofmoleculesboundtogetherbyintermolecularforces.Theforcescanbedispersionforces,dipolarforces,hydrogen
bondingoracombinationofthese.

Manylargermoleculeshavesufficientdispersionforcestoexistassolidsatroomtemperature.Oneexampleisnaphthalene,C10H8,theactive
substanceinmothballs.Naphthaleneisawhitesolidthatmeltsat80C.Naphthalenehasaplanarstructurewithacloudof10electronsdelocalised
aboveandbelowthemolecularplane(figure7.6).Naphthalenemoleculesareheldinthesolidstatebystrongdispersionforcesinvolvingthesehighly
polarisableelectrons.Themoleculesincrystallinenaphthalenearearrangedtomaximisethesedispersionforces,thusleadingtotheformationof
platelikemacroscopiccrystals.

FIGURE7.6 (a)Naphthalene,
(b)thelinestructureofnaphthaleneand
(c)aballandstickmodel,overlaidwiththelowestenergybondingmolecularorbital.

Dimethyloxalate,CH3OC(O)C(O)OCH3(figure7.7)isanexampleofamolecularsolid(mp=52C)inwhichneighbouringmoleculesareheld
togetherpredominantlybydipolarinteractions.ThetwocarbonylCatomshavesignificant+character,duetothefactthateachisbondedtotwo
electronegativeOatoms.The+CatomsareinvolvedinattractivedipolarinteractionswiththeOatomsofneighbouringmolecules.
FIGURE7.7Structuralformulaofdimethyloxalate.

Inadditiontodispersionanddipolarforces,molecularsolidsofteninvolvehydrogenbonding.Benzoicacid,C6H5COOH,whosesodiumsaltisa
commonfoodpreservative,providesagoodexample,asillustratedinfigure7.8.Moleculesofbenzoicacidareheldinplacebyacombinationof
dispersionforcesbetweentheelectronsandhydrogenbondingbetweentheCOOHgroups.Withfewerelectrons,benzoicacidhasweaker
dispersionforcesthannaphthalene,butitshydrogenbondinggivesbenzoicacidahighermeltingpointof122C.

FIGURE7.8 (a)Crystalsofbenzoicacidcontain
(b)pairsofmoleculesheldtogetherheadtoheadbyhydrogenbonds.Thesepairsthenstackinplanesthatareheldtogetherbydispersion
forces.

Theeffectofextensivehydrogenbondingisrevealedbytherelativelyhighmeltingpointofglucose,C6H12O6,thesugarfoundinbloodandhuman
tissue.Glucosemeltsat155CbecauseeachofitsmoleculeshasfiveOHgroupsthatformhydrogenbondstoneighbouringmolecules(figure
7.9).Althoughglucoselacksthehighlypolarisableelectronsfoundinnaphthaleneandbenzoicacid,itsextensivehydrogenbondinggivesthis
sugarthehighestmeltingpointofthesethreecompounds.

FIGURE7.9Thestructuralformulaofglucose,C6 H12 O6 .

NetworkSolids
Insharpcontrasttomolecularsolids,networksolidshaveveryhighmeltingpoints.Comparethebehaviourofphosphorusandsilicon,thirdrow
neighboursintheperiodictable.Whitephosphorusmeltsat44C,butsiliconmeltsat1410C.Whitephosphorusisamolecularsolidthatcontains
individualP4molecules(seefigure7.10),butsiliconisanetworksolidinwhichcovalentbondsconnecteverySiatomtoeachofitsfourneighbours
(seefigure7.11).
FIGURE7.10RepresentationofaP4 moleculeinwhitephosphorus.

FIGURE7.11Partofthestructuralmodelofsilicon,showingsiliconatomsconnectedtoeachothertoformathreedimensionalnetwork.

Thecauseofthegreatdifferenceinthemeltingpointsofthesetwoelementsisevidentfromtable7.1.Covalentbondsaremuchstrongerthan
intermolecularforces.Forsolidsilicontomelt,asignificantfractionofitsSiSicovalentbondsmustbreak.TheaverageSiSibondenergyis225
kJmol1,whereasattractiveenergiesduetointermolecularforcesinP4aremuchlower(asshownintable7.1,intermolecularforcesaregenerallyless
than50kJmol1)soittakesamuchhighertemperaturetomeltsiliconthanwhitephosphorus.

Bondingpatternsdeterminethepropertiesofnetworksolids.Diamondandgraphite,thetwoformsofelementalcarbonthatoccurnaturallyonEarth,
haveverydifferentphysicalandchemicalproperties.Diamondcontainsathreedimensionalarrayofbonds,witheachsp 3hybridisedcarbonatom
linkedtoeachofitsfourneighbouringcarbonatomsthroughcovalentbondsresultinginatetrahedralgeometryaroundeachcarbonatom(identical
totheSistructurementionedabove,seefigure7.12a).Itisthusanetworksolid.Itsthreedimensionalnetworkofstrongcovalentbondsmakes
diamondextremelystrongandabrasive.Covalentbondsconnectingatomsinthreedimensionsmakenetworksolidsextremelydurable.Thesp 2
hybridisedcarbonatomsingraphite,incontrast,areconnectedtoonlythreeneighbouringcarbonatomsviacovalentbondsinaplanararrangement.
Thebondingissupplementedbydelocalisedbondingaboveandbelowtheplaneofthebonds(seefigure7.12b).Eachtwodimensionallayeris
attractedtoitsneighbouringlayersonlybydispersionforcesbetweentheelectrons.Asaresult,planesofcarbonatomseasilyslidepastone
another,makinggraphiteabrittlelubricant.

FIGURE7.12 Partofthestructuralmodelsof
(a)diamondshowingcarbonatomsconnectedtoeachothertoformathreedimensionalnetwork,and
(b)graphite,showingthetwodimensionallayers.

Compoundssuchassilica(silicondioxide,SiO2)mayalsoexistasnetworksolids.Opalsarecomposedofnanosizedsilicaspheroids.Theirprized
colourisduetothewaytheydiffractlight,ratherthantheimpuritiesthatgivemostothergemstonestheircolour.Anotherexampleissiliconcarbide,
SiC,whichhasasimilarstructuretodiamondandisusedasanabrasiveinsandpaperandasanedgeoncuttingtoolsasitislessexpensiveto
produce.Thesesubstanceshaveveryhighmeltingpointsbecausetheiratomsareheldtogetherbynetworksofstrongcovalentbonds.

MetallicSolids
Thebondinginsolidmetalsdiffersfromthatinothertypesofsolidsbecauseitderivesprimarilyfromelectronsinhighlydelocalisedvalenceorbitals.
Recallfromthemolecularorbitaltheorydiscussedinchapter5thatoverlapofnvalenceatomicorbitalsgivesrisetonmolecularorbitals.Whennis
verylarge,asisthecasein1moleofasolidmetal,thenalargenumberofmolecularorbitalsareformed.Theenergiesofthesemolecularorbitalsare
soclosetogetherthattheyessentiallyformacontinuumofenergies,calledaband,whichextendsoveralloftheatomsinthemetal.Therefore,an
electroninapartiallyfilledorbitalisdelocalisedoveralltheatoms,andisconsequentlyabletomovethroughouttheentiremetal.Hence,wecanview
ametalasconsistingofaregulararrayofmetalatomcoresembeddedinaseaofmobilevalenceelectrons(seefigure7.13).Thepropertiesof
metals,suchaselectricalandthermalconductivity,canbeexplainedonthebasisofthismodel.

FIGURE7.13Adiagrammaticrepresentationofmetallicbonding.Themetalatomsareembeddedinaseaofmobilevalenceelectrons.

Metalsdisplayawiderangeofmeltingpoints,indicatingthatthestrengthofmetallicbondingisvariable.Thegroup1metalsarequitesoftandmeltat
relativelylowtemperatures(seefigures7.14a,c).Sodium,forexample,meltsat98Candcaesiummeltsat28.5C.Bondingisweakinthesemetals
becauseeachatomofagroup1metalcontributesonlyonevalenceelectrontothebondformingenergyband.Metalsnearthemiddleofthedblock,
ontheotherhand,areveryhardandhavesomeofthehighestknownmeltingpoints:tungstenmeltsat3407C(figure7.14b),rheniumat3180C
andchromiumat1857C.Atomsofthesemetalscontributeseveraldelectronstobondformation,leadingtoextremelystrongmetallicbonding.
FIGURE7.14 (a)Sodium,Na,canbecutwithaknife.
(b)Tungsten,W,canbeheatedtoincandescencewithoutmelting,whichiswhyitisusedasthefilamentinlightbulbs.
(c)Group1metalsmeltatrelativelylowtemperatureswhereasmetalsnearthemiddleofthedblockhavesomeofthehighestknownmelting
points.

Metalsareductile,meaningtheycanbedrawnintowires,andmalleable,meaningtheycanbehammeredintothinsheets.Whenapieceofmetal
formsanewshape,itsatomschangeposition.However,becausethebondingelectronsarefullydelocalised,changingthepositionsoftheatomsdoes
notcausecorrespondingchangesintheenergylevelsoftheelectrons.Theseaofelectronsislargelyunaffectedbythepatternofmetalatoms,as
figure7.15illustrates.Thus,metalscanbeforcedintomanyshapes,includingsheetsandwires,withoutdestroyingtheirbondingnature.

FIGURE7.15Whenametalchangesshape,itsatomsshiftposition.However,becausethevalenceelectronsarefullydelocalised,theenergyoftheseelectronsis
unaffected.

Thedblockmetalsdisplayarangeofproperties.Copperandsilveraremuchbetterelectricalconductorsthanchromium.Tungstenhasverylow
ductility.Mercuryisaliquidatroomtemperature.Thesedifferencesariseinpartbecauseofvariationsinthenumberofvalenceelectrons.Thed
blockmetalsvanadiumandchromiumhavefiveorsixvalenceelectronsperatomrespectively,allofwhichoccupybondingorbitalsinthemetal
atoms.Asaresult,therearestrongattractiveforcesbetweenthemetalatoms,andvanadiumandchromiumarestrongandhard.Beyondthemiddleof
thedblockseries,theadditionalvalenceelectronsoccupyantibondingorbitals,whichreducesthenetbonding.Thiseffectismostpronouncedatthe
endofthedblock,wherethenumberofantibondingelectronsnearlymatchesthenumberofbondingelectrons.Zinc,cadmiumandmercury,withs2
andd 10configurations,havemeltingtemperaturesthataremorethan600Clowerthanthoseoftheirimmediateneighbours.

IonicSolids
Asdescribedinchapter5,ionicsolidscontaincationsandanionsstronglyattractedtoeachotherbyelectrostaticforces.Ionicsolidsmustbe
electricallyneutral,sotheirstoichiometriesaredeterminedbythechargescarriedbythepositiveandnegativeions.

Manyionicsolidscontainmetalcationsandpolyatomicanions.Hereagain,thestoichiometryofthesolidisdictatedbythechargesontheionsand
theneedforthesolidtomaintainelectricalneutrality.Someexamplesof1:1ionicsolidscontainingpolyatomicanionsareNaOH,KNO3,CuSO4,
BaCO3andNaClO3.Somemetallicoreshave1:1stoichiometry,suchasscheelite,CaWO4(containsWO42),zircon,ZrSiO4(containsSiO44)and
ilmenite,FeTiO3(containsTiO32).IlmeniteisthesourceofTiO2,whichisusedasawhitepigmentinpaperandpaints.

Mineralsoftencontainmorethanonecationoranion.Forexample,apatite,Ca5(PO4)3OH,themainsubstanceintoothenamel,containsboth
phosphateandhydroxideanions.Beryl,Be3Al2Si6O18,containsberylliumandaluminiumcationsaswellastheSi6O1812polyatomicanion.Berylis
thesubstancethatmakesupemeralds.Anevenmorecomplicatedmineralisgarnierite,(Ni,Mg)6Si4O10(OH)2,whichhasavariablecompositionof
Ni2+andMg 2+cations.AlthoughtherelativeproportionsofMg 2+andNi2+vary,garnieritealwayshassixcationsandtwoanionsofOHforevery
anionofSi4O1010.

Somemixedoxidesthatcontainrareearthmetalsaresuperconductors.Belowacertaintemperature,asuperconductorcancarryanimmenseelectrical
currentwithoutincurringlossesfromresistance.Optimalsuperconductingbehaviouroftenrequiresaslightdeviationfromstoichiometric
composition,whichwewilllearnmoreaboutinsection7.8.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.3PhaseChanges
Inchapter6andthefirsttwosectionsofthischapter,wehaveexaminedthethreemostcommonphasesof
matter(gas,liquidandsolid)inisolation.Wewillnowinvestigatewhatgovernsaphasechangethe
transitionofasubstancefromonephasetoanother.Substancescanundergophasechangesgiventhe
appropriateconditions.Phasechangesdependontemperature,pressure,andthemagnitudesofbonding
andintermolecularforces.

Weareallfamiliarwiththephasechangesofwateratambientpressure,whichareillustratedinfigure
7.16.Considertakingicecubesfromthefreezerat18Candplacingtheminacontaineratroom
temperature.Atfirstthewaterisinthesolidphase(stage1).Outsidethefreezer,thetemperatureoftheice
cubesbeginstoincrease.Whenthetemperatureoftheicecubesreaches0C,theybegintomeltandwe
getamixtureofsolidandliquidwater(stage2).Thetemperatureofthismixturedoesnotincreaseuntilall
theicehasmelted.Oncetheicehascompletelymelted,thetemperatureoftheliquidwillstartincreasing
(stage3).Ifweapplyheattothecontainertheliquidwillincreaseintemperature(stage3)untilitreaches
100C.Thewaterthenstartstoboil(stage4)andwegetwatervapour.Thesystemremainsat100Cuntil
allofthewaterhasevaporated.Continuedheatingofthewatervapouronceallofthewaterhasevaporated
willresultinitstemperatureincreasingabove100C(stage5).Thetemperatureofthecontainerwillalso
increaseonceallthewaterhasevaporated,whichiswhyitisnotagoodideatoallowasaucepantoboil
dryonahotplate.

FIGURE7.16WhenheatissuppliedtoasampleofH2 Oataconstantpressureof1.013105 Pa,phasechanges


occurat0Cand100C.Thexaxisrepresentstheheatrequiredforeachindividualprocess.It
shouldbenotedthattherearemoleculesinthevapourphaseabovebothsolidandliquidwater,but
thesehavebeenomittedinstages1,2and3forclarity.
Adaptedfrom:Chemistry:Themolecularnatureofmatterandchange,3rdedition,MartinS
Silberberg,p.424,2003TheMcGrawHillCompanies,Inc.

Phasechangesrequirethatenergy(usuallyintheformofheat)beeithersuppliedtoorremovedfromthe
substanceundergoingthephasechange.Restrictingourselvestomolecularsubstances,butrecognising
thatsimilarargumentsholdforatomicandionicsubstances,amolecularperspectiverevealswhythisisso.
Anyphasechangethatresultsinincreasedmolecularmobilityrequiresthatintermolecularforcesbe
overcome.Forexample,hydrogenbondsinicemustbebrokentochangetheicetoliquidwater,and
hydrogenbondsinliquidwatermustbebrokentoconvertittowatervapour.About41kJofheatmustbe
suppliedtotransfer1moleofwatermoleculesfromtheliquidphaseintothevapourphase.Similarly,41
kJofheatmustberemovedtoliquefy1moleofwatervapour.Asfigure7.16indicates,theheatrequired
tochangebetweentheliquidandsolidphasesisconsiderablyless.

Asyouwillseeinmoredetailinchapter8,theamountofheattransferredatconstantpressureisequaltoa
quantitycalledtheenthalpychange(H).Themagnitudeofthechangedependsonthestrengthof
intermolecularforcesinthesubstanceundergoingthephasechange.

Theamountofheatrequiredtovaporiseasubstancealsodependsontheamountinthesample.The
energyrequiredtovaporise2molesofwateristwicethatneededfor1mole.Theheatneededtovaporise
1moleofasubstanceatitsnormalboilingpointiscalledthemolarenthalpyofvaporisation(vapH).For
example,vapHofwaterisabout41kJmol1.

Energymustalsobeprovidedtomeltasolidsubstance.Thisenergyisusedtoovercomethe
intermolecularforcesthatholdmoleculesinfixedpositionsinthesolidphase.Theheatneededtomelt1
moleofasubstanceatitsnormalmeltingpointiscalledthemolarenthalpyoffusion(fusH).For
example,fusHofwaterisabout6kJmol1.

Phasechangesbetweensolidandliquid,andbetweenliquidandgas,arethemostcommon,butaphase
changeinwhichasolidconvertsdirectlytoagaswithoutpassingthroughtheliquidphaseisalsopossible.
Thistransitionisknownassublimation(depositionistheoppositetransition).Dryice(solidCO2)
sublimesat195Kwiththemolarenthalpyofsublimation(subH)=25.2kJmol1.Mothballscontain
naphthalene,C10H8(sub=73kJmol1),acrystallinewhitesolidthatsublimestoproduceavapourthat
repelsmoths.Thepurplecolourofthegasaboveiodinecrystalsinaclosedcontainer(figure7.17)
providesvisibleevidencethatthissolidalsosublimesatroomtemperature(subH=62.4kJmol1).Both
naphthaleneandiodinemeltatambientpressure(at80Cand114C,respectively),indicatingthat,while
asmallamountcansublimeatambientpressure,itisnotathermodynamicequilibrium.

FIGURE7.17ThepurplecolourofthevapourabovesolidiodineisduetoI2 moleculesinthegasphase.

Phasechangescangoineitherdirectionicemeltsuponaddingheat,andliquidwaterfreezesonremoving
heatfromthesystem.Heatisabsorbedasasolidmeltstoaliquidandisreleasedasaliquidfreezestoa
solid.Tomakeicecubes,forinstance,waterisplacedinafreezerthatabsorbstheheatreleasedduringthe
formationofice.Theheatreleasedwhenliquidwaterchangestoiceisequalinmagnitudetotheheat
requiredtochangeicetoliquidwater.

Byconvention,tabulatedvaluesofenthalpiesofphasechangesarealwaysspecifiedintermsofthephase
changethatrequirestheadditionofheat.Thereverseprocesseshavethesamemagnitudebuttheopposite
sign.

Table7.2listsvaluesoffusH,vapH,meltingpointsandboilingpointsforselectedchemicalsubstances.

TABLE7.2 Phasechangedataforselectedchemicalsubstances

Substance Formula mp(K) fusH(kJmol1) bp(K) vapH(kJmol1)


argon Ar 83 1.3 87 6.3
oxygen O2 54 0.45 90 9.8

methane CH4 90 0.84 112 9.2

ethane C2H6 90 2.85 184 15.5


diethylether (C2H5)2O 157 6.90 308 26.0

bromine Br2 266 10.8 332 30.5

ethanol C2H5OH 156 7.61 351 39.3

benzene C6H6 278 10.9 353 31.0

water H2O 273 6.01 373 40.79


mercury Hg 234 23.4 630 59.0

WORKEDEXAMPLE7.1

EnthalpyofPhaseChange
Aswimmeremergingfromapooliscoveredwithafilmcontainingabout75gofwater.How
muchheatmustbesuppliedtoevaporatethiswater?

Analysis

Energyintheformofheatisrequiredtoevaporatethewaterfromtheswimmer'sskin.The
energyneededtovaporisethewatercanbefoundusingthemolarenthalpyofvaporisationand
theamountofwater.

Solution

vapHofwateris40.79kJmol1(seetable7.2).Themolarmassofwateris18.02gmol1,so
75gofwateris4.16mol.Therefore,theheatthatmustbesuppliedis:
Isouranswerreasonable?

Iftheswimmer'sbodymustsupplyallthisheat,asubstantialchillingeffectoccurs.Thus,
swimmersusuallytoweloff(toreducetheamountofwaterthatmustbeevaporated)orlieinthe
sun(toletthesunprovidemostoftheheatrequired).

PRACTICEEXERCISE7.1
Determinehowmuchheatisinvolvedin
freezing125gofwaterinanicecubetray.
Whatisthedirectionofheatflowinthis
process?

Recallfromourdiscussionoffigure7.16thataddingheattoboilingwaterdoesnotcausethetemperature
ofthewatertoincrease.Instead,theaddedenergyisusedtoovercomeintermolecularattractionsasmore
moleculesleavetheliquidphaseandenterthegasphase.Othertwophasesystemsshowsimilar
behaviour.Thiscanbeusedtoholdachemicalsystematafixedtemperature.Atemperatureof100C
canbemaintainedbyaboilingwaterbath,andanicebathholdsasystemat0C.Lowertemperaturescan
beachievedwithothersubstances.Dryice(solidCO2)suspendedinliquidacetonemaintainsa
temperatureof78C(195K)abathofliquidnitrogenhasaconstanttemperatureof196C(77K)and
liquidhelium,whichboilsat4.2K,isusedforresearchrequiringultracoldtemperatures.

Atthestartofthissectionwementionedthatpressureisalsoinvolvedinphasechanges.Theeffectof
pressureismainlyseenforphasetransitionsinvolvinggases.Recallfromchapter6thatgasdensity
increaseswithpressure.Agasatconstanttemperaturecanbeliquefiedbyincreasingthepressure.Thisis
importantinthestorageofliquefiedpetroleumgas(LPG),amixtureofpropaneandbutanethatisusedas
afuelforcars,barbecuesandheaters.Propaneandbutanearegasesatroomtemperatureandnormal
atmosphericpressure.Tomakethestorageandtransportofthefuelpracticable,itisliquefiedbyplacingit
underpressure.Thepressureatwhichagasliquefiesataspecifictemperatureisknownasthe
condensationpoint.

SupercriticalFluids
Wehavelearnedaboutthethreephaseswearefamiliarwithfromeverydaylife:solids,liquidsandgases.
Wehaveseenthatwecanliquefygasesbycoolingorincreasingthepressure.Asthepressureonagas
increases,thegasiscompressedintoaneversmallervolume.Ifthetemperatureislowenough,this
compressioneventuallyresultsinliquefaction.Athighenoughtemperature,however,noamountof
compressioncancauseliquefactionthatis,theliquidgastransitionisnolongerpossible.Instead,the
substancebecomesasupercriticalfluid.Asupercriticalfluidisafluidthathascertaincharacteristicsof
bothliquidsandgasesbutisneither.

Imaginethatyouhavealiquidinasealedcontainer.Onheating,thevapourpressureincreasesasmore
moleculesfromtheliquidescapeintothegasphase,thusincreasingthedensityinthegasphasewhilealso
decreasingthedensityintheliquidphase.Aswecontinueheatingthecontainer,thedensitiesinthegas
phaseandtheliquidphaseapproachthesamevalue.Atthepointwheretheybecomeequalwecanno
longerdistinguishbetweentheliquidandgasphases,i.e.wecannotobserveaphaseboundary.The
temperatureatwhichthisoccursiscalledthecriticaltemperature(Tc )theassociatedpressureiscalled
thecriticalpressure.Thecombinationofthecriticaltemperatureandthecriticalpressureiscalledthe
criticalpoint.Thesubstanceisnowinitssupercriticalstate(figure7.18).Ithastheviscositytypicalofa
liquid,butitisabletoexpandorcontractlikeagas.

FIGURE7.18 (a)BelowthecriticaltemperatureforCO2 youcanclearlyseethephaseboundarybetween


theliquidandthegasphase.
(b)Asthetemperaturerisestheliquidbecomeslessdense,thevapourphasebecomesmore
dense,andthephaseboundaryblurs.
(c)Abovethecriticaltemperaturethephaseboundaryhasdisappearedandonlya
supercriticalfluidexists.

ThecriticalpointofwaterisT=647K,p=22110 5Pa,thatofCO2isT=304K,p=73.910 5Pa,and


thatofN2isT=126K,p=33.910 5Pa.Althoughcriticalpressuresaremanytimesgreaterthan
atmosphericpressure,supercriticalfluidshaveimportantcommercialapplications.Themostimportantof
theseistheuseofsupercriticalcarbondioxideasasolvent.SupercriticalCO2diffusesthroughasolid
matrixrapidly,andittransportsmaterialswellbecauseithasalowerviscositythanliquids.Supercritical
CO2iscurrentlyusedasasolventfordrycleaning,forpetroleumextraction,fordecaffeinationandfor
polymersynthesis.Comparedwithsolventsusedpreviouslyforsomeoftheseprocesses,suchas
dichloromethane,CH2Cl2,andtetrachloromethane,CCl4,supercriticalCO2isamuchbetterchoice.

PhaseDiagrams
Thephasebehaviourofasubstancecanbeconvenientlysummarisedinaphasediagramasafunctionof
temperatureandpressure.Anexampleisprovidedinfigure7.19.Pressureisplottedalongtheyaxis,and
temperatureisplottedalongthexaxis.IntheregionoflowTandhighp,thesubstanceexistsasasolid.In
theregionofhighTandlowp,thesubstanceexistsasagas.InsomeintermediaterangeofTandp,the
substanceexistsasaliquid.
FIGURE7.19Thegeneralformofaphasediagram.Anypointonthediagramcorrespondstoaspecific
temperatureandpressure.Boundarylinestraceconditionswhereneighbouringphasesexistin
equilibrium,andthebluearrowsshowsixtypesofphasetransitions.Theredarrowshighlighta
sequenceofphasechangesonchangingtemperatureatconstantpressure,oronchanging
pressureatconstanttemperature.

Figure7.19illustratesmanyofthecharacteristicfeaturesofphasediagrams:
1. Boundarylinesbetweenphasesseparatetheregionswhereeachphaseisthermodynamically
stable.(Substancescanexistasametastablephaseoutsidetheirthermodynamicallydetermined
boundaries,e.g.carboncanexistasdiamond,ratherthangraphite,underambientconditions.
2. Movementacrossaboundarylinecorrespondstoaphasechange.Thebluearrowsonthefigure
showsixdifferentphasechanges:sublimationanditsreverse,depositionmeltinganditsreverse,
freezingandvaporisationanditsreverse,condensation.
3. Onaboundaryline,thetwoneighbouringphasescoexistinadynamicequilibrium.Inaddition,at
agivenpressure,forexample,whenheatisaddedorremoved,thetemperatureofthistwophase
systemdoesnotchangeuntilallofonephasehasconvertedtotheother.Thenormalmeltingpoint
andnormalboilingpointofasubstance(shownbyreddots)arethepointswherethephase
boundarylinesintersectthehorizontallinethatrepresentsp=1.01310 5Pa.
4. Threeboundarylinesmeetatasinglepoint(shownbyanotherreddot),calledatriplepoint.All
threephasesarepresentsimultaneouslyatthisuniquecombinationoftemperatureandpressure.
Noticethat,althoughtwophasesarestableunderanyoftheconditionsspecifiedbytheboundary
lines,threephasescanbesimultaneouslystableonlyatatriplepoint.
5. Abovethetemperaturespecifiedbythecriticalpoint(againshownbyareddot),thegascannotbe
liquefiedunderanypressure.Insteadifthepressureishighenoughasupercriticalfluidforms.It
hastheviscositytypicalofaliquid,butitisabletoexpandorcontractlikeagas.
6. Whathappenstoasubstanceastemperaturechangesatconstantpressurecanbedeterminedby
drawingahorizontallineattheappropriatepressureonthephasediagram(shownasahorizontal
redline).
7. Whathappenstoasubstanceaspressurechangesatconstanttemperaturecanbedeterminedby
drawingaverticallineattheappropriatetemperatureonthephasediagram(shownasaverticalred
line).
8. Thetemperatureforconversionbetweenthegasphaseandacondensedphasedependsstronglyon
pressure.Qualitatively,thisisbecausecompressingagasincreasesthecollisionrateandmakes
condensationmorefavourable.
9. Themeltingtemperatureisalmostindependentofpressure,makingtheboundarylinebetween
solidandliquidnearlyvertical.Qualitatively,thisisbecausemoderatepressurehashardlyany
effectonthecondensedliquidandsolidphases.
10.Thesolidgasboundarylineextrapolatestop=0PaandT=0K.Thisisaconsequenceofthe
directlinkbetweentemperatureandenergy.At0K,atoms,ionsandmoleculeshaveminimum
energy,sotheycannotescapefromthesolidlattice.At0K,thevapourpressureofeverysolid
substancewouldbe0Pa.

Thephasediagramforwater,showninfigure7.20,illustratesthesefeaturesforafamiliarsubstance.The
figureshowsthatliquidwaterandsolidicecoexistatthenormalmeltingpoint(mp),T=273.15Kandp=
1.01310 5Pa.Liquidwaterandwatervapourcoexistatthenormalboilingpoint(bp),T=373.15Kand
p=1.01310 5Pa.Thetriplepoint(tp)ofwateroccursatT=273.16Kandp=0.006110 5Pa.The
figureshowsthatwhenpislowerthan0.006110 5Pa,thereisnotemperatureatwhichwaterisstableas
aliquid.Atthoselowpressures,icesublimesbutdoesnotmelt.

FIGURE7.20Thephasediagramforwater.ThecriticalpointisatT=647K,p=221105 Pa,welloutsidethis
diagram.

Thedashedlinesonfigure7.20showtwopathsthatinvolvephasechangesforwater.Thehorizontal
dashedlineshowswhathappensasthetemperatureincreasesataconstantpressureof1.01310 5Pa.As
icewarmsfromalowtemperature,itremainsinthesolidphaseuntilthetemperaturereaches273.15K.At
thattemperature,solidicemeltstoliquidwater,andwaterremainsliquidasthetemperatureincreases,until
itreaches373.15K.At373.15K,liquidwaterchangestowatervapour.Whenthepressureis1.01310 5
Pa,waterexistsinthegasphaseatallhighertemperatures.Theverticaldashedlineshowswhathappensas
thepressureonwaterisreducedataconstanttemperatureof298K(approximatelyroomtemperature).
Waterremainsintheliquidphaseuntilthepressuredropsto3.0410 3Pa.At298K,waterexistsinthe
gasphaseatanypressurelowerthanthis.Noticethatat298Kthereisnopressureatwhichwaterexistsin
thesolidstate.

Giventhatthetemperatureofthetriplepointisslightlyhigherthanthetemperatureofthenormalmelting
point,wecanconcludethattheslopeoftheboundarylinebetweenthesolidandliquidphaseshastobe
negative.Asshowninthemagnifiedsectionoffigure7.20,ifyoustartwithsolidH2Oatatemperaturejust
belowthetriplepointandincreasethepressureatconstanttemperatureyouwilleffectaphasechange
fromsolidtoliquid(dashedline).Thisshows,aswediscussedintheopeningparagraphofthischapter,
thatthedensityoftheliquidishigherthanthedensityofthesolid,whichiswhyicefloatsonwater.Ice
skatersmakeuseofthispressureinducedphasetransition.Thethinbladesoftheiriceskatesputpressure
ontheice,changingittoliquidwaterwhichrefreezesoncethepressureisremoved.Thispropertyofwater
isrelativelyuncommonamongsubstances.Mostsolidshavehigherdensitythantheircorresponding
liquids.Forwater,thelowerdensityiscausedbythelargernumberofhydrogenbondsperwatermolecule
inicecomparedwithliquidwater.
Allphasediagramsofpuresubstancessharethe10commonfeatureslistedpreviously.However,the
detailedappearanceofaphasediagramisdifferentforeachsubstance,asdeterminedbythestrengthof
theinteractionsbetweenitsconstituents.Figure7.21showstwoexamples,thephasediagramsfornitrogen
andcarbondioxide.Bothofthesesubstancesaregasesundernormalconditions.IncontrasttoH2O,which
hasatriplepointcloseto298K,N2andCO2havetriplepointsthatarewellbelowroomtemperature.
Althoughbotharegasesatambienttemperatureandpressure,theybehavedifferentlywhencooledat
atmosphericpressure.Molecularnitrogenliquefiesat77.4Kandthensolidifiesat63.29K,whereas
carbondioxidecondensesdirectlytothesolidphaseat195K.Thisdifferenceinbehaviourarisesbecause
thetriplepointofCO2,incontrasttothetriplepointsofH2OandN2,occursatapressuregreaterthan
1.01310 5Pa.ThephasediagramofCO2showsthatatapressureof1.01310 5Pa,thereisno
temperatureatwhichCO2existsintheliquidphase.

FIGURE7.21Phasediagramsfornitrogenandcarbondioxide,twosubstancesthataregasesatroom
temperatureandpressure(sp=normalsublimationpoint).

Phasediagramsareconstructedbymeasuringthetemperaturesandpressuresatwhichphasechanges
occur.Approximatephasediagramssuchasthoseshowninfigures7.20and7.21canbeconstructedfrom
thetriplepoint,normalmeltingpointandnormalboilingpointofasubstance.

WORKEDEXAMPLE7.2

ConstructingaPhaseDiagram
Ammoniaisagasunderambientconditions.Itsnormalboilingpointis239.8K,anditsnormal
meltingpointis195.5K.ThetriplepointforNH3isp=0.061210 5PaandT=195.4K.Use
thisinformationtoconstructanapproximatephasediagramforNH3.

Analysis

Thenormalmeltingandboilingpointsandthetriplepointgivethreepointsonthephase
boundarycurves.Toconstructthecurvesfromknowledgeofthesethreepoints,usethe
commonfeaturesofphasediagrams:thegasliquidandgassolidboundariesofphase
diagramsslopeupwards,theliquidsolidlineisnearlyvertical,andthegassolidlinebeginsat
T=0Kandp=0Pa.

Solution

Beginbychoosingappropriatescales,drawingthep=1.01310 5Palineandlocatingthe
givendatapoints.Anuppertemperaturelimitof300Kencompassesallthedata.

Next,connectthepointsandlabelthedomains.

Isouranswerreasonable?

Checkthatpressureisontheyaxisandtemperatureisonthexaxisandthatyouhavenot
accidentallyinterchangedthesolid,liquidandgasphases.Alsocheckthattheslopeofthe
solidgasphaseboundaryislesssteepthanthatoftheliquidgasphaseboundarynearthetriple
pointandthatthesolidliquidphaseboundaryisnearlyvertical.
PRACTICEEXERCISE7.2
Molecularchlorinemeltsat172K,boilsat
239Kandhasitstriplepointat0.01410 5
Paand172K.Sketchthephasediagramfor
thiscompound.

Phasediagramscanbeusedtodeterminewhichphaseofasubstanceisstableatanyparticularpressure
andtemperature.Theyalsosummarisehowphasechangesoccuraseitherconditionisvaried.

WORKEDEXAMPLE7.3

InterpretingaPhaseDiagram

Achemistwantstoperformasynthesisinavesselatp=0.5010 5PausingliquidNH3asthe
solvent.Whattemperaturerangewouldbesuitable?Whenthesynthesisiscomplete,the
chemistwantstoboiloffthesolventwithoutraisingTabove220K.Isthispossible?

Analysis

ThephasediagramforNH3(refertoworkedexample7.2)showstheboundarylinesforthe
liquiddomain.Theseboundarylinescanbeusedtodeterminetheconditionsunderwhich
phasechangesoccur.

Solution

Becausethechemistwantstoworkatp=0.5010 5Pa,drawahorizontallineacrossthephase
diagramatp=0.5010 5Pa.Hereisanexpandedviewofthephasediagrambetween150and
300K.
Thehorizontallineintersectstheboundarylinesatabout235Kand195K.LiquidNH3is
stablebetweenthesetemperaturesatthispressure.

Atthecompletionofthesynthesis,thechemistwantstoremovethesolventwithoutraisingT
above220K.Averticallineat220Konthephasediagramrepresentsthiscondition.

Thelineintersectstheliquidgasboundaryatabout0.3510 5Pa.Avacuumpumpcapableof
reducingpbelow0.3510 5PacanbeusedtovaporiseandremovetheNH3whilekeepingthe
temperaturebelow220K.

Isouranswerreasonable?

Checkthatthelinesforpressureandtemperatureareenteredcorrectly.SinceNH3(l)boilsat
235Kand0.510 5Pa,forNH3(l)toboilatthelowertemperatureof220Kweneedareduced
pressure,aswehavedetermined.
PRACTICEEXERCISE7.3

AsampleofN2gasisatp=0.110 5Paand
T=63.1K.Usefigure7.21todeterminewhat
willhappentothissampleifthetemperature
remainsfixedwhilethepressureslowly
increasesto110 5Pa.

Thephasediagramswehavestudiedarethesimplestonesthatoccurforpuresubstances.However,many
substanceshavemorethanonesolidphase(thereare14differentknownformsofice!).Phasediagramsof
solidsareparticularlyusefulingeology,becausemanymineralsundergosolidsolidphasetransitionsat
thehightemperaturesandpressuresfounddeepintheEarth'scrust.Figure7.22isthephasediagramfor
silica(silicondioxide,SiO2),animportantgeologicalsubstance.Noticethatthescalereflectsgeological
pressuresandtemperatures.Noticealsothattherearesixdifferentformsofcrystallinesilica,eachstablein
adifferenttemperaturepressureregion.Ageologistwhoencountersasampleofstishovitecanbe
confidentthatitsolidifiedunderextremelyhighpressureconditions.

FIGURE7.22Thephasediagramforsilicashowssixdifferentformsofthesolid,eachstableunderdifferent
temperatureandpressureconditions.

Ifwehavemorethanonecomponentinamixture,phasediagramsbecomeevenmorecomplicated,and
treatmentoftheseisbeyondthescopeofthisbook.

ChemicalConnections

ChemistryandCoolJackets
ResearchersatRMITUniversityhavedevelopedanadvancedcoolingjackettohelpathletes
reducetheirbodytemperaturesbeforemajorevents.Coolingthebodypriortoanevent
enhancestheathlete'sperformanceanddelaystheonsetofexhaustionbyminimisingthestress
andstrainonthebody,whichreducestherelianceonthebody'sstoreofsugar.Athleteshave
longusedicejacketstoreducetheirbodytemperaturebeforebigracestotakeadvantageof
thesebenefits,buttheyhaveoftensufferedundesirablesideeffectssuchasshivering,iceburn
andheadaches.TheRMITteam,ledbyProfessorDavidMainwaring,andincludingProfessor
RobertShanks,developedajacketthatisfilledwithsolidphasechangematerial(PCM,figure
7.23).Inordertoeffectcooling,aPCMmustundergoanendothermicphasechange(onethat
requiresheatfromthesurroundingstooccur).Manycompoundsdoofcoursedothis,most
notablywater(theicejacketsmentionedaboveoperateonthisprinciple)butinorderforthe
wearertobecomfortable,thephasechangeneedstooccurataroundroomtemperature.The
PCMdevelopedbyRMITconsistsofamixtureoftwoormorestraightchainalkanes.While
lowmolarmassalkanesareeithergasesorliquids,thosewithmorethanabout12carbonatoms
havemeltingpointsabove0C.Theactualalkanesusedarechosensoastogivethemost
desirablethermalproperties,and,inthiscase,atleast90%ofthealkaneshavebetween14and
18carbonatoms.Attemperaturesbelowabout18C,thePCMexistsasawaxysemisolidin
whichthechainsofthealkanemoleculesarealigned.Whenthejacketisworn,thebodyheatof
thewearercausesaphasechangetooccurinthePCMfromasemisolidtoaliquidatabout20
C.Thisisanendothermicprocessthatremovesheatfromthesurroundings,therebyleadingto
acoolingeffectforthewearer.Thejacketcanberegeneratedforusesimplybycoolingittoa
temperaturebelowabout18Cin,forexample,anairconditionedroom.Thiscausesan
exothermicphasechange(onethatgivesoutheattothesurroundings)ofthePCMbacktoa
semisolidandthejacketisagainreadyforuse.
FIGURE7.23Anicejacketthatusessolidphasechangematerial(PCM)whichchangesfroma
semisolidtoafluidatabout20C.
2005RMITUniversity,EducationalTechnologyAdvancementGroup.Photographer
MargundSallowsky.

Becauseheatiswithdrawnfromthebodyatclosetonormalskintemperature,andnotatice
temperature,thecoolingprocessesaremorecomfortable,efficientandeffective.

ThejacketsweredevelopedinconjunctionwiththeAustralianInstituteofSportandareusedby
manyofAustralia'seliteathletesinpreparationformajorsportingeventssuchastheOlympic
Games.

Thevestsalsohavepotentialinthetreatmentofmedicalconditions.Applicationsmightinclude
controlofheatinducedhandtremorsanddizzinessinpeoplewithmultiplesclerosis,aswellas
theeffectiveandsafecoolingofpeoplewhohavesufferedbraininjuriesorcardiactrauma.
CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.4OrderinSolids
Incontrasttomoleculesingasesandliquids,whichcanmoverelativelyfreely,theatoms,moleculesorions
inasolidareinfixedpositions.Generally,theirmotionsarerestrictedtovibrationsaboutthesefixed
positions.Inthissection,weexaminetheprinciplesthatgoverntherelativearrangementsofatoms,
moleculesandionsinsolids.Tostartourexplorationoforderinsolidswewilllookatsomesimplecases.

ClosepackedStructures
Mostelementsintheperiodictablearemetalsand,apartfrommercury,allmetalsaresolidsatstandard
conditions.Inordertodevelopapictureofmetalstructures,wewillassumethatwecanapproximateametal
atomwithasphere.Figure7.24showsbothsquareandhexagonalarrangementsofidenticalspheres.We
canseethatthehexagonalarrangementisabletofitmorespheresintothesameareaeverysphereinthe
hexagonalarrangementhassixdirectneighbours,butonlyfourinthesquarearrangement.Thishexagonal
arrangementofidenticalspheresisthemostdensepackingthatyoucanachieveinonelayerofspheres.
Youcanseethiswhenyouplacepoolballsinthetriangleatthestartofthegame(figure7.25).Onlyifyou
arrangethemthiswaycanalloftheballsfitintothetriangle.

FIGURE7.24Comparisonof(a)squareand(b)hexagonalarrangementofidenticalspheres.Youcanseethatboth
squaresfit16spheres(movingthespheresoutsidethesquarein(b)intotheemptyspaceattheother
sideofthesquare(lightershadedspheres).In(b),thereisspaceleftoveratthetopofthesquare,
whilein(a)thereisnospaceleftover,indicatingthatthespheresinthehexagonalarrangementare
closertogether.
FIGURE7.25Poolballsfitintothetriangleinahexagonalarrangement.

Nowaddasecondlayerofspherestothehexagonalarrangement.Let'scallthefirstlayerlayerAandthe
secondlayerlayerB.Toachievethemostcompactarrangement,eachsphereinlayerBsitsinoneofthe
dimplesbetweenatrioofspheresinlayerA.TherearesixdimplesaroundanysphereinlayerA.Youcan
seethatthecentresoftwoneighbouringdimplesareclosertogetherthanthediameterofthespheres.Hence,
itisimpossibletoplaceasphereovereverydimple.Forexample,ifweplacespheresasindicatedbythered
ringsinfigure7.26,wecanseethatitisimpossibletoplacespheresinthepositionsindicatedbytheblue
ringsatthesametime.

FIGURE7.26Itisimpossibletoplaceasphereovereverydimple.Wecanplacespheresonlyintheredpositions
orbluepositions,notbothatthesametime.

Ifwefillallthedimplescorrespondingtotheredringsinfigure7.26a,wecreateasecondlayerasshownin
figure7.27b.ThisaddsthreemoreadjoiningspheresforeachsphereinlayerA,oneineachsetofthree
neighbouringdimples.Asadditionalspheresareadded,layerBeventuallylooksidenticaltolayerA,except
thatitisoffsetslightlytoallowthespherestonestleinthedimplesformedbythelayerbelow.Thereisno
differencebetweenfillingalldimplescorrespondingtotheredringsortheblueringstheresulting
arrangementsofspheresareindistinguishable.

Nowconsideraddingathirdlayerofspheres.Thisnewlayercanbeplacedintwodifferentwaysbecause
therearetwosetsofdimplesinlayerB.Figure7.28showsacloseupoffigure7.27b.Noticeinfigure7.28
thattheviewthroughonesetofdimples(highlightedinorange)revealstheorangespheresoflayerA.The
viewthroughtheothersetofdimples(highlightedinblue)revealstheunfilleddimplesoflayerA.
FIGURE7.27 (a)Spheresclosepackedinalayergenerateahexagonalpattern.
(b)Whenasecondlayerispackedontopofthefirst,eachsphereinthesecondlayernestlesin
thedimpleformedbetweenthreeadjacentspheresinthelowerlayer.

FIGURE7.28Athirdlayerofspherescanbeplacedintwodifferentways.

Ifspheresinthethirdlayerlieinthedimpleshighlightedinorange,thethirdlayerisdirectlyabovethefirst,
andthestructureiscalledhexagonalclosepacked(hcp).Ifthespheresofthethirdlayerlieinthedimples
highlightedinblue,thethirdlayerisoffsetfrombothofthelowerlayers.Thisarrangementiscalledcubic
closepacked(ccp).Figure7.29showsthatinthehexagonalclosepackedstructurethepositioningofthe
thirdlayercorrespondstothatoflayerAandthereforewealsolabelitA.Inthecubicclosepacked
structure,thepositioningisdifferentandsowelabelthethirdlayerlayerC.Comparingthetwodiagrams,
wecanseethatinthehexagonalclosepackedstructureonesetofdimplesisnevercovered,whileinthe
cubicclosepackedstructure,theyare.Ifwecontinuethislayeringpattern,wefindthatahexagonalclose
packedstructurehasthepatternABABetc.,whileacubicclosepackedstructurehasthepatternABCABC
etc.
FIGURE7.29 Topdownviewsofhexagonalandcubicclosepackedarrangements:
(a)ThehexagonalclosepackedstructurehasalayerrepeatingpatternABABetc.
(b)ThecubicclosepackedstructurehasalayerrepeatingpatternABCABCetc.

Thetwostructuretypesdescribedarecalledclosepackedstructuresbecausetheyachievemaximumspace
fillingforidenticalspheres.Ineitherofthesearrangements,74%ofthetotalspaceisfilled,andeachsphere
has12nearestneighbours(i.e.neighbourswiththesameshortestdistancetothatsphere):sixinthesame
plane,threeinthedimplesaboveandthreeinthedimplesbelow.Thisisshownforthehexagonalandcubic
closepackedstructuresinfigure7.30.Thenumberofnearestneighboursisalsocalledthecoordination
number,andthereforespheresinclosepackedstructureshaveacoordinationnumberof12.

FIGURE7.30Inclosepackedstructures,eachspherehas12nearestneighbours:sixinthesameplane,threein
thedimplesaboveandthreeinthedimplesbelow.

Manymetalsformcrystalswithhexagonalorcubicclosepackedgeometries,sincemetalbondingthat
involvessharingvalenceelectronsbenefitsfromclosecontactbetweenparticipatingmetalatoms.For
instance,magnesiumandzinccrystallisewiththeiratomsinahexagonalclosepackedarray,whilesilver,
aluminiumandgoldcrystalliseinthecubicclosepackedarrangement.Othersphericalentities,suchas
argonatoms,andmethaneandC60molecules,alsoformclosepackedarrangements.Argonsolidifiesatlow
temperatureasacubicclosepackedcrystal,andneoncansolidifyineitherthehcporccpform.
TheCrystalLatticeandtheUnitCell
Inasolid,thenumberofatoms,ionsormoleculesisenormous.Ifyoucouldimaginebeingatthecentreof
evenasmallsampleofasolid,youwouldfindthattheatoms,ionsormoleculesgoonasfarasyoucansee
ineverydirection.Describingalltheindividualpositionsisimpossibleand,fortunately,unnecessaryifwe
areabletoidentifyarepeatingpatternwithinthesolid.

Thereareanumberofrulestoconsiderwhendefiningsucharepeatingpattern,andtostartoffwewilllook
atexamplesintwodimensions.Wecanrecognisearepeatingmotifinthewallpaperdesignoffigure7.31a.
Howcanwedescribethispattern?Inordertoconcentrateontherepeatingfeaturesofthepattern,westart
byrandomlyselectingapointandthenmarkeveryotherpointonthewallpaperthathasanidentical
environment(tomakethateasiertoseewechoosetheeyeoftherearmostofthethreefish)asshownin
figure7.31b.

FIGURE7.31 Definingarepeatingpattern:
(a)Thereisarepeatingpatterninthewallpaperdesign.
(b)Thepatterncanbedescribedbyasetofpointswithidenticalenvironments.
(c)Theresultingpatternisalatticeandeachblackdotisalatticepoint.

Figure7.31bshowsthissetofpoints,whichhavebeenconnectedbylines.Infigure7.31cwetakeawaythe
wallpaper,leavingjusttheconnectedpoints.Wecallthispatternofpointsalattice,andeveryindividual
pointisalatticepoint.Sinceweselectedasetofpointsbyrequiringeachonetohaveanidentical
environment,thissetofpointsrepresentstherepeatingfeatureofourwallpaperdesign,andeverylattice
pointrepresentsonerepeatingmotif.

Inthenextstep,wemustfindthesmallestrepeatingunitwithinourlattice,whichinthiscaseisoneofthe
rectanglesinfigure7.31c.Wecallthesmallestuniquerepeatingunitofalatticetheunitcell(therearea
numberofrulesforthecorrectchoiceofunitcell,buttheyarebeyondthescopeofthisbook).Repeating
theunitcellintwodimensionswillcreatethelattice.Therefore,allweneedtodescribeanypatternisthe
latticeandthecontentoftheunitcell.

Animportantfactaboutlatticesisthatthesamelatticecanbeusedtodescribemanydifferentdesignsor
structures.Forexample,takethesquarelatticeandunitcellinfigure7.32a.Infigure7.32b,weseeadesign
formedbyassociatingablueheartwitheachlatticepoint.Usingasquarelattice,wecouldformanynumber
ofdesignsjustbyusingdifferentdesignelements(forexample,aroseoradiamond),orbychangingthe
lengthsoftheedgesoftheunitcell.Theonlyrequirementisthatthesamedesignelementmustbe
associatedwitheachlatticepointthatis,eachlatticepointmusthaveanidenticalenvironment.Thereisno
requirement,however,thatthelatticepointiscentredontheobject,asillustratedinfigure7.32c,d.Youare
allowedtoshifttheentirelatticeaslongasyoustillendupwithalllatticepointshavingidentical
environments.

FIGURE7.32 Atwodimensionallattice:
(a)asimplesquarelattice,forwhichtheunitcellisasquarewithlatticepointsatthecorners,
(b)awallpaperpatternformedbyassociatingadesignelement(blueheart)witheachlattice
point.Thexcentredoneachheartcorrespondstoalatticepoint.Noticethattheunitcell
containsportionsofaheartateachcorner.(Therestofeachheartliesinadjacentunitcells.)
(c)and
(d)Thereisnorequirementthatthelatticepointiscentredonanyobject.In(a),(b),(c)and(d),
alltheinformationneededtogeneratetheentirearrayispresentintheunitcell,whichis
repeatedoverandover.

AnotherexampleisshowninthepicturebytheDutchartistMCEscher(18981972)reproducedinfigure
7.33.Escheroftenusedsymmetricalpatternsalignedtogethertocreateanoveralldesign.Therepeating
unitscanbevisualisedastilesplacededgetoedge.Thefacesofunitcellscanbesquares,rectanglesor
parallelograms.Infigure7.33aeachtileisaparallelogram.Onceyouhavechosenthesizeandshapeofthe
unitcell,youcanmoveitsoriginandstillcreatethesameoverallpattern(figure7.33b).
FIGURE7.33AdrawingbyMCEscherthatcontainsarepeatingpattern.Atwodimensionalunitcellishighlighted
in(a).In(b),theunitcellhasbeenshiftedanditisshownhowrepeatingitintwodimensionswill
producetheentirepattern.(Source:M.C.Escher'sSymmetryDrawingE18,2007TheM.C.
EscherCompanyHolland.Allrightsreserved.www.mcescher.com)

Forthesakeofsimplicitywehavelookedatlatticesandunitcellsintwodimensions.Wecanalsoapply
theseconceptstothreedimensionalpatterns.Theions,atomsormoleculesinmanysolidsarearrangedin
regularthreedimensionalpatterns.Suchsolidsareclassifiedascrystallinesolids.Diamondsarean
example.Wecandescribecrystallinesolidsusingtheconceptsofacrystallattice,thatis,thelatticeofa
crystallinesolidandaunitcell.Itispossibletodescribelimitlessnumbersofdifferentcompoundswithjusta
limitedsetofthreedimensionallattices.Infact,ithasbeenshownmathematicallythatthereareonly14
differenttypesofthreedimensionallatticespossible,whichmeansthatessentiallyallcrystallinechemical
substancesmustformcrystalswithoneofthese14latticetypes,albeitwithdifferentunitcelldimensions.
Onthefollowingpages,wedescribesomemetalstructureswithcubicunitcells.Thesecrystalstructurescan
bedescribedsuchthatalltheatomsinaunitcellareassociatedwiththelatticepoints,i.e.thenumberof
atomsintheunitcellandthenumberoflatticepointswillbeidentical.Thisisbecauseallmetalatomsin
eachoftheseverysimplestructureshaveidenticalsurroundingsandthereforeallcanbeassociatedwith
latticepoints.Thisisnotsoformostothercrystallinesolidstructures.

CubicStructures
Theeasiestthreedimensionalstructuretovisualisehasasimplecubeastheunitcell.Inasimplecubic
crystal,layersofatomsstackonedirectlyaboveanother,sothatallatomsliealongstraightlinesatright
angles,asfigure7.34shows.Eachatominthisstructurehasacoordinationnumberof6therearefour
nearestneighbourswithinthesameplane,oneabovetheplaneandonebelowtheplane.Withinonelayerof
thecrystal,anysetoffouratomsformsasquare.Addingfouratomsdirectlyaboveorbelowthefirstfour
formsacube.Thisstructureiscalledtheprimitivecubicstructure,becauseithasaprimitivecubiclattice.
(Inthiscontext,primitivemeansthatthereisonlyonelatticepointperunitcell.Amethodfordetermining
thenumberoflatticepointsisdescribedbelow.)Theunitcelloftheprimitivecubicstructureisshowninthe
cutawayportionoffigure7.34.Tocalculatehowmanyatomsareintheunitcell,wecountonlythat
proportionoftheatomthatiswithintheunitcellboundaries.Anatomthatislocatedonthecornerofacube
issharedbyeightcubesintotal.Therefore,only ofthatatomcountsforanyoneofthosecubes.Theunit
cellcontains ofanatomateachoftheeightcornersofacube.Thetotalnumberofatomsintheunitcellis

thus .Thesameappliestocountinglatticepointsaunitcellwithlatticepointsonlyonthecorners
endsupwithonelatticepoint,i.e.aprimitivelattice.Thefractionofspacethatisfilledbytheatomsinthis
primitivecubicunitcellisonly52%.Thisismuchlessthanthemostefficientpacking,whichachieves74%
spacefilling(seep.270).Consequently,thisstructureisadoptedbyonlyonemetal:polonium.
FIGURE7.34Thesimplecubicstructureisbuiltfromsquarelayersofspheresstackedonedirectlyaboveanother.
Thecutawayviewshowsoneunitcell.

Wheneightatomsformacube,thereisacavityatthecentreofthecube.Thecavityisnotlargeenoughto
holdanadditionalatom,butmovingtheeightcorneratomsslightlyawayfromeachotherdoesallowthe
structuretoaccommodateanotheratomofthesametypeinthecentre.Theresultisthebodycentredcubic
structure,describedbyabodycentredcubiclattice(bcc),whichnowhastwolatticepoints:oneonacorner
andoneinthecentreofthecube.Eachatominabodycentredcubiclatticeisatthecentreofacubeand
contactseightneighbouringcorneratoms(seefigure7.35).Inotherwords,everyatominthestructurecan
beviewedasthecentreatomofonebodycentredcubeorasacorneratominanothercube.Theunitcellof
abodycentredcubecontainsatotalof atoms.Theviewsoftheironcrystalstructurein
figure7.35onthenextpageillustratethisarrangement.
FIGURE7.35 Viewsofthearrangementofatomsiniron:
(a)aviewofthebodycentredcrystallatticeand
(b)theunitcell.

Althoughthecorneratomsarefurtherapartinabodycentredcubethaninaprimitivecube,theextraatom
inthecentreofthestructuremakesthebodycentredcubicstructuremorecompactthantheprimitivecubic
structure.Itfills68%ofthetotalspace,whichisclosetothemaximumpossible.Allofthegroup1metals,
aswellasironandthetransitionmetalsfromgroups5and6,formcrystalswithbodycentredcubic
structures.

Anothercommoncubiccrystalstructureisthefacecentredcubicstructure(fcc),whichisthesameasthe
cubicclosepackedstructurethatweencounteredonp.270.Whenfouratomsformasquare,thereisopen
spaceatthecentreofthesquare.Afifthatomcanfitintothisspacebymovingtheotherfouratomsaway
fromoneanother.Additionalatomscanbeplacedinthecentresofallsixfacesofthesimplecube,asfigure
7.36shows.

FIGURE7.36 Thefacecentredcubiclatticecanbeviewedas:
(a)asimplecube,
(b)witheachfaceexpandedjustenoughtofitanadditionalatominthecentre,
(c)givingeightatomsatthecornersandsixatomsembeddedinthefaces.
(d)
Theunitcellhas ofanatomatthecentreofeachfaceand ofanatomateachcorner.
(Allatomsinthisarrangementarethesame.Differentcoloursareusedonlyforclarity.)

Theunitcellofthefacecentredcubeconsistsofsix atomsembeddedinthefacesofthecubeandeight

atthecornersofthecube.Thisunitcellcontains atoms.Eachatominaface
centredcubecontacts12neighbouringatoms.Consequently,thefacecentredcubeismorecompactthan
eitheroftheothercubicstructuresandfills74%ofthetotalspace.Thecubicclosepackedstructurethatwe
encounteredatthebeginningofsection7.4canbedescribedbythisfacecentredcubicunitcell.

Figure7.37showstherelationshipbetweenasetofhexagonallayersandafacecentredcubicunitcell.
Figure7.37ashowsatopdownviewofthehexagonallayers.Infigure7.37bwehaveremovedallbutone
oftheatomsfromthetopandbottomlayers,andhaveremovedallbutsixatomsineachofthetwomiddle
layers.Wecanseefromfigure7.37cthatalinedrawnbetweentheorangeatoms(fromthetopandbottom
layers)representsthebodydiagonalofacube.Eachfaceofthecubehasanatomateachcornerandone
atominthecentre,asshownbyfigure7.37c.Sincealltheatomsareidentical,thisisafacecentredcubic
arrangementasrevealedintheperspectivesoffigures7.37cand7.37d.

FIGURE7.37 Fourviewsofthehexagonallayerscontainedwithinafacecentredcubicarrangement:
(a)atopdownviewofthehexagonallayers,withanaxisshownasablackdot,
(b)asideviewshowingfourlayersalongtheaxis,
(c)tilting(b)leadstothearrangementshownhere,withtheverticalblacklinein(b)nowthe
bodydiagonalofthiscube,and
(d)theunitcell.(Allatomsinthisarrangementarethesame.Differentcoloursareusedforclarity
only.)

WecannowseethatthearrangementofhexagonallayersinanABCABCfashioniscalledacubicclose
packedstructure,becausethestructurecanbedescribedbyafacecentredcubicunitcell(thetermscubic
closepackedstructureandfacecentredcubicstructureareoftenusedsynonmously).Equally,the
hexagonalclosepackedstructuregetsitsnamebecauseitcanbedescribedbyahexagonalunitcellas
showninfigure7.38.
FIGURE7.38 Threeviewsofthehexagonallayerscontainedwithinahexagonalclosepackedstructure:
(a)atopdownviewofthehexagonallayerswiththeunitcellshown,
(b)asideviewshowingthreelayersand
(c)theunitcell.Thisunitcellcontainstwoatomsandfills74%ofthespace.(Allatomsinthis
arrangementareofthesametype.Differentcoloursareusedforclarityonly.)

Uptonow,wehavedescribedthecrystallinearrangementsfavouredbysphericalobjectssuchasatoms,but
mostmoleculesarefarfromspherical.Nonsphericalobjectsrequiredifferentarraystoachievemaximal
stability.Toillustrate,compareastackofbananaswithastackoforanges(figure7.39).Justasthestacking
patternforbananasislesssymmetricalthanthatfororanges,thestructuralpatternsformostmolecular
crystalsarelesssymmetricalthanthoseforcrystalsofsphericalatoms,reflectingthelowersymmetryofthe
molecules.
FIGURE7.39Nonsphericalbananasrequiredifferentpackingschemesfromsphericaloranges.

IonicSolids
Wewillnowshowhowtheprinciplesdiscussedpreviouslyrelatetotheactualstructuresofionicsolids.
Recallfromfigure7.28thattwosetsofdimplesarecreatedwhenweaddtwohexagonallayersofspheres.
Thisisshownagaininfigure7.40a.Onesetofdimpleshasanatomdirectlybelow(showninorange),while
theothersetdoesnot(showninblue).Theopenspacebetweenthetwolayersofspheresdirectlybelowthe
firstsetofdimplesissurroundedbyfourspheres(onebelowandthreeabove),whiletheopenspace
betweenthetwolayersofspheresdirectlybelowthesecondsetofdimplesissurroundedbysixspheres
(threebelowandthreeabove).Figure7.40bshowsthatthefourspheresassociatedwiththefirstsetof
dimplesformatetrahedron,whilefigure7.40cshowsthatthesixspheresassociatedwiththesecondset
formanoctahedron.Thespacebetweenthespheresiscalledaninterstitialhole.Theinterstitialholestake
upmuchlessspacethanthespheresthatsurroundthem.Ingeneral,themorespheresthatsurroundan
interstitialhole,thelargertheholeis,thatis,anoctahedralholeislargerthanatetrahedralhole.Thenumber
ofoctahedralholesequalsthenumberofspheresthatformthestructure,whilethenumberoftetrahedral
holesistwicethenumberofspheresthatformthestructure.
FIGURE7.40 (a)Twosetsofdimplesarecreatedwhentwohexagonallayersofspheresarecombined.
(b)Thefourspheresassociatedwitheachdimpleshowninorangesurroundatetrahedralhole.
(c)Thesixspheresassociatedwitheachdimpleshowninredsurroundanoctahedralhole.

Thepackinginioniccrystalsrequiresthationsofoppositechargealternatewithoneanothertomaximise
attractionsandminimiserepulsions.Thecationsandanionsareusuallydifferentsizes(oftenthecationsare
smaller).Wecanunderstandionicstructuresbyassumingthattheclosepackedstructureisformedbythe
largerions,whilethesmallerionsfilltheinterstitialsites.Wecanidentifyacrystallatticeforthelargerions,
andthendescribehowthesmallerionspackwithinthatlattice.Becausethecrystalismadeupofahuge
numberofidenticalunitcells,thestoichiometrywithintheunitcellmustmatchtheoverallstoichiometryof
thecompound.

Ioniccompoundsadoptavarietyofstructuresthatdependonthestoichiometryandrelativesizesofthe
ions.Formany1:1ioniccrystalssuchasNaCl,themoststablearrangementisafacecentredcubicarrayof
anions(Cl)withthecations(Na+)packedintotheoctahedralholesbetweentheanions.Thisstructure
appearsinfigure7.41a.Noticethateverycationissurroundedbysixanionsandeveryanionissurrounded
bysixcations.TheunitcellbasedonclosepackingofClisshown.Inadditiontothefacecentredcubic
arrangementofchlorideions,theunitcellinfigure7.41bshows ofasodiumcationalongeachedgeof
thecell,andthereisanadditionalsodiumcationinthecentreoftheunitcell.Summingthecomponents
revealsthateachunitcellcontainsfourcompleteNaClunits,thusgivingthecorrect1:1stoichiometry.

FIGURE7.41 (a)Thestructureofsodiumchloridecanbedescribedasafacecentredcubicarrangementof
Clanions(green),withtheNa+cations(orange)occupyingtheinterstitialoctahedralsites.
(b)BecauseClanionsareconsiderablylargerthanNa+cations,thecommonlyusedunitcell
placesanionsatthecorners.Thereisacationatthecentreofthisunitcell.

Manyionicsolidshavethesamestructuretypeassodiumchloride.ExamplesareallthehalidesofLi+,Na+,
K+andRb +,aswellastheoxidesofMg 2+,Ca2+,Sr2+andBa2+.

Caesiumchloride,inwhichtherelativesizeofthecationismuchlargerthaninsodiumchloride,formsa
differenttypeofstructure.Becauseitscationandanionareclosetothesamesize,caesiumchlorideismost
stableinaprimitivecubiclattice.ThereareClanionsatthecornersofthecube,withaCs+inthecentre,as
figure7.42shows.Theunitcellcontains chlorideionand1caesiumion.Thecaesiumchloride
structuretypeisalsofoundforCsBr,CsIandseveralother1:1ioniccrystalsinwhichthecationsand
anionshavesimilarsizes.

FIGURE7.42Thecaesiumchloridestructureconsistsofaprimitivecubicarrayofchlorideanionswithacaesium
cationatthecentreofeachunitcell.

Inzincsulfide,ZnS,therelativesizeratiosaresuchthatthezinccationistoosmallforoctahedralsitesand
insteadoccupiestetrahedralholesinthestructure.Sincetherearetwiceasmanytetrahedralsitesasspheres
thatformthestructure,onlyhalfwillbeoccupiedbyZn 2+cationsinaregularfashion.Wehaveseen
previouslythatafacecentredarrangementofanionsleadstofouranionsintheunitcell.Wecanseein
figure7.43thattherearealsofourcationswithintheunitcell,resultinginthecorrect1:1stoichiometry.In
thisstructure,asseeninfigure7.43b,everycationissurroundedbyfouranions,andeveryanionis
surroundedbyfourcationsinatetrahedralarrangement.

FIGURE7.43 Zincsulfide.
(a)Theunitcellofcubiczincsulfidehasanionsinafacecentredcubicarrangement.
(b)Eachcationissurroundedbyfouranionsintheformofatetrahedron.

Manyioniccompoundshavestoichiometriesthatdifferfrom1:1.Togiveanexample,thefluoritestructure
isnamedforthenaturallyoccurringformofCaF2andiscommonforsaltsofthegeneralformulaMX2X.Itis
easiesttodescribethisstructurebythinkingoftheCa2+cationsarrangedinafacecentredcubicstructure.In
thisarrangement,theFanionsfillallthetetrahedralholesinthelattice,formingasimplecubeofeight
anionsintheinteriorofthefacecentredcube.Thisisincontrasttozincsulfide,whereonlyhalfofthe
tetrahedralholeswerefilled.Figure7.44ashowstheunitcellofthefluoritestructure,whichcontainsatotal
offourCa2+cationsandeightFanions(consistentwiththenumberoftetrahedralholesbeingtwicethe
numberofspheresthatformthestructure).
FIGURE7.44 (a)Theunitcellofthefluoritestructurehascationsinafacecentredcubicarrangement,witha
simplecubeofanionswithintheunitcell.
(b)Allfluorideionsaresurroundedbyfourcalciumionsinatetrahedralarrangement.

Thisgivesthecorrect1:2stoichiometry,resultinginelectricalneutrality.

Thecalciumionsarearrangedinatetrahedronaboutthefluorideionsasshowninfigure7.44b.Wehave
brieflymentionedfoursimpleioniclattices,buttherearemanyothers.Moreover,thestructuresofmany
crystallinenetworksolidscanalsobedescribedbythemethodswehaveintroducedhereforNaCl,CsCl,
ZnSandCaF2.

CopyrightJohnWiley&SonsAustralia,Ltd.Allrightsreserved.
7.5XrayDiffraction
Xraydiffractioncanbeusedtodeterminethearrangementofatoms,moleculesorionsinacrystalline
structure.WhenatomsareexposedtoXrays,theyactliketinyXraysources.Ifwelookatradiationfrom
twosuchatoms(seefigure7.45),wefindthattheXraysareinphaseinsomedirectionsbutoutofphasein
others.Inchapter4youlearnedaboutconstructive(inphase)anddestructive(outofphase)interferencesof
waves,andthesecreateaphenomenoncalleddiffraction.Xraydiffractionbycrystalshasenabledscientists
todeterminethestructuresofextremelycomplexcompoundsinaparticularlyelegantway.

FIGURE7.45DiffractionofXraysfromatomsinacrystal.Xraysemittedfromatomsareinphaseinsome
directionsandoutofphaseinotherdirections.

Inacrystal,thereareenormousnumbersofatoms,andthesecanbedescribedbyalatticeandaunitcell.
WhenthecrystalisexposedtoXrays,diffractedbeamsduetoconstructiveinterferenceappearonlyin
specificdirections.Inotherdirections,noXraysappearbecauseofdestructiveinterference.TheXrays
comingfromthecrystalarerecordedandforma