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Walter D. Loveland

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ModernNuclearChemistry

SecondEdition

WalterD.Loveland

OregonStateUniversity

DavidJ.Morrissey

MichiganStateUniversity

GlennT.Seaborg

UniversityofCalifornia,Berkeley

Copyright©2017byJohnWiley&Sons,Inc.Allrightsreserved.

PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey. PublishedsimultaneouslyinCanada.

LibraryofCongressCataloging-in-PublicationData

Names:Loveland,WalterD.|Morrissey,DavidJ.|Seaborg,GlennT.(Glenn Theodore),1912–1999.

Title:Modernnuclearchemistry/WalterD.Loveland,DavidJ.Morrissey,GlennT.Seaborg.

Description:Secondedition.|Hoboken,NJ:JohnWiley&Sons,Inc.,2017.| Includesbibliographicalreferencesandindex.

Identifiers:LCCN2016045901|ISBN9780470906736(cloth)|ISBN9781119328483(epub)

Subjects:LCSH:Nuclearchemistry–Textbooks.|Chemistry,Physicaland theoretical–Textbooks.

Classification:LCCQD601.3.L682017|DDC541/.38–dc23

LCrecordavailableathttps://lccn.loc.gov/2016045901

CoverImage:Courtesyoftheauthor CoverDesign:Wiley

Setin10/12ptWarnockbySPiGlobal,Pondicherry,India PrintedintheUnitedStatesofAmerica

PrefacetotheSecondEdition xv

PrefacetotheFirstEdition xvii

1IntroductoryConcepts 1

1.1Introduction 1

1.2TheExcitementandRelevanceofNuclearChemistry 2

1.3TheAtom 3

1.4AtomicProcesses 4

1.4.1Ionization 5

1.4.2X-RayEmission 5

1.5TheNucleus:Nomenclature 7

1.6PropertiesoftheNucleus 8

1.7SurveyofNuclearDecayTypes 9

1.8ModernPhysicalConceptsNeededinNuclearChemistry 12

1.8.1ElementaryMechanics 13

1.8.2RelativisticMechanics 14

1.8.3deBroglieWavelength:Wave–ParticleDuality 16

1.8.4HeisenbergUncertaintyPrinciple 18

1.8.5UnitsandConversionFactors 19 Problems 19 Bibliography 21

2NuclearProperties 25

2.8.1NuclearAngularMomentum 43

2.9ElectricandMagneticMoments 45

2.9.1MagneticDipoleMoment 45

2.9.2ElectricQuadrupoleMoment 48 Problems 51 Bibliography 55

3RadioactiveDecayKinetics 57

3.1BasicDecayEquations 57

3.2MixtureofTwoIndependentlyDecayingRadionuclides 65

3.3RadioactiveDecayEquilibrium 66

3.4BranchingDecay 76

3.5RadiationDosage 77

3.6NaturalRadioactivity 79

3.6.1GeneralInformation 79

3.6.2PrimordialNucleiandtheUraniumDecaySeries 79

3.6.3CosmogenicNuclei 81

3.6.4AnthropogenicNuclei 83

3.6.5HealthEffectsofNaturalRadiation 83

3.7RadionuclideDating 84 Problems 90 Bibliography 92

4NuclearMedicine 93

4.1Introduction 93

4.2Radiopharmaceuticals 94

4.3Imaging 96

4.4 99 Tcm 98

4.5PET 101

4.6OtherImagingTechniques 103

4.7SomeRandomObservationsaboutthePhysicsofImaging 104 4.8Therapy 108 Problems 110 Bibliography 112

5ParticlePhysicsandtheNuclearForce 113

5.1ParticlePhysics 113

5.2TheNuclearForce 117

5.3CharacteristicsoftheStrongForce 119

5.4ChargeIndependenceofNuclearForces 120 Problems 124 Bibliography 124

6NuclearStructure 125

6.1Introduction 125

6.2NuclearPotentials 127

6.3SchematicShellModel 129

6.4IndependentParticleModel 141

6.5CollectiveModel 143

6.6NilssonModel 149

6.7FermiGasModel 152

Problems 161 Bibliography 164

7 ��-Decay 167

7.1Introduction 167

7.2Energeticsof α Decay 169

7.3Theoryof α Decay 173

7.4HindranceFactors 182

7.5HeavyParticleRadioactivity 183

7.6ProtonRadioactivity 185

Problems 186 Bibliography 188

8 ��-Decay 191

8.1Introduction 191

8.2NeutrinoHypothesis 192

8.3DerivationoftheSpectralShape 196

8.4KuriePlots 199

8.5 β DecayRateConstant 200

8.6ElectronCaptureDecay 206

8.7ParityNonconservation 207

8.8NeutrinosAgain 208

8.9 β-DelayedRadioactivities 209

8.10Double β Decay 211

Problems 213 Bibliography 214

9 ��-RayDecay 217

9.1Introduction 217

9.2Energeticsof γ-RayDecay 218

9.3ClassificationofDecayTypes 220

9.4ElectromagneticTransitionRates 223

9.5InternalConversion 229

9.6AngularCorrelations 232

9.7MössbauerEffect 238

10NuclearReactions 247

10.2EnergeticsofNuclearReactions 248

10.3ReactionTypesandMechanisms 252

10.4NuclearReactionCrossSections 253

10.5ReactionObservables 264

10.6RutherfordScattering 264

10.7Elastic(Diffractive)Scattering 268

10.8AsideontheOpticalModel 270

10.12.2ElasticScattering 284 10.12.3FusionReactions 284 10.12.4IncompleteFusion 288

10.12.5Deep-InelasticScattering 289 10.13High-EnergyNuclearReactions 291

10.13.1Spallation/FragmentationReactions 291

10.13.2ReactionsInducedbyRadioactiveProjectiles 295

10.13.3Multifragmentation 296

10.13.4Quark–GluonPlasma

11.2.4SpontaneouslyFissioningIsomers 315 11.2.5TheTransitionNucleus 316

11.3DynamicalPropertiesofFissionFragments 323

11.4FissionProductDistributions 327

11.4.1TotalKineticEnergy(TKE)Release 327

11.4.2FissionProductMassDistribution 327

11.4.3FissionProductChargeDistributions 330 11.5ExcitationEnergyofFissionFragments 334

Problems 337 Bibliography 338

12NuclearAstrophysics 339

12.1Introduction 339

12.2ElementalandIsotopicAbundances 340

12.3PrimordialNucleosynthesis 343

12.3.1StellarEvolution 347

12.4ThermonuclearReactionRates 351

12.5StellarNucleosynthesis 353

12.5.1Introduction 353

12.5.2HydrogenBurning 353

12.5.3HeliumBurning 357

12.5.4SynthesisofNucleiwith A < 60 359

12.5.5SynthesisofNucleiwith A > 60 360

12.6SolarNeutrinoProblem 366

12.6.1Introduction 366

12.6.2ExpectedSolarNeutrinoSources,Energies,andFluxes 367

12.6.3DetectionofSolarNeutrinos 369

12.6.4TheSolarNeutrinoProblem 371

12.6.5SolutiontotheProblem:NeutrinoOscillations 371

12.7SynthesisofLi,Be,andB 373 Problems 375 Bibliography 376

13ReactorsandAccelerators 379

13.1Introduction 379

13.2NuclearReactors 380

13.2.1Neutron-InducedReaction 380

13.2.2Neutron-InducedFission 383

13.2.3NeutronInventory 384

13.2.4LightWaterReactors 386

13.2.5TheOkloPhenomenon 391

13.3NeutronSources 392

13.4NeutronGenerators 392

13.5Accelerators 393

13.5.1IonSources 394

13.5.2ElectrostaticMachines 396

13.5.3LinearAccelerators 400

13.5.4Cyclotrons,Synchrotrons,andRings 403

13.6Charged-ParticleBeamTransportandAnalysis 410 13.7RadioactiveIonBeams 415

13.8NuclearWeapons 421

Problems 425

Bibliography 427

14TheTransuraniumElements 429

14.1Introduction 429

14.2LimitsofStability 429

14.3ElementSynthesis 434

14.4HistoryofTransuraniumElementDiscovery 437

14.5SuperheavyElements 449

14.6ChemistryoftheTransuraniumElements 453

14.7EnvironmentalChemistryoftheTransuraniumElements 461 Problems 468 Bibliography 469

15NuclearReactorChemistry 473

15.1Introduction 473

15.2FissionProductChemistry 475

15.3RadiochemistryofUranium 478

15.3.1UraniumIsotopes 478

15.3.2MetallicUranium 478

15.3.3UraniumCompounds 478

15.3.4UraniumSolutionChemistry 479

15.4TheNuclearFuelCycle:TheFrontEnd 480

15.4.1MiningandMilling 481

15.4.2RefiningandChemicalConversion 483

15.4.3IsotopicEnhancement 484

15.4.4FuelFabrication 487

15.5TheNuclearFuelCycle:TheBackEnd 488

15.5.1PropertiesofSpentFuel 488

15.5.2FuelReprocessing 490

15.6RadioactiveWasteDisposal 493

15.6.1ClassificationsofRadioactiveWaste 493

15.6.2WasteAmountsandAssociatedHazards 494

15.6.3StorageandDisposalofNuclearWaste 496

15.6.4SpentNuclearFuel 497

15.6.5HLW 498

15.6.6TransuranicWaste 499

15.6.7Low-LevelWaste 499

15.6.8MillTailings 500

15.6.9PartitioningofWaste 500

15.6.10TransmutationofWaste 501

15.7ChemistryofOperatingReactors 504

15.7.1RadiationChemistryofCoolants 504

15.7.2Corrosion 505

15.7.3CoolantActivities 505 Problems 506 Bibliography 507

16InteractionofRadiationwithMatter 509

16.1Introduction 509

16.2HeavyChargedParticles 512

16.2.1StoppingPower 512

16.2.2Range 521

16.3Electrons 526

16.4ElectromagneticRadiation 532

16.4.1PhotoelectricEffect 534

16.4.2ComptonScattering 536

16.4.3PairProduction 537

16.5Neutrons 540

16.6RadiationExposureandDosimetry 544 Problems 548 Bibliography 550

17RadiationDetectors 553

17.1Introduction 553

17.1.1GasIonization 554

17.1.2IonizationinaSolid(SemiconductorDetectors) 554

17.1.3SolidScintillators 555

17.1.4LiquidScintillators 555

17.1.5NuclearEmulsions 555

17.2DetectorsBasedonCollectingIonization 556

17.2.1GasIonizationDetectors 557

17.2.2SemiconductorDetectors(SolidStateIonizationChambers) 567

17.3ScintillationDetectors 578

17.4NuclearTrackDetectors 584

17.5NeutronDetectors 585

17.6NuclearElectronicsandDataCollection 587

17.7NuclearStatistics 589

17.7.1DistributionsofDataandUncertainty 591

17.7.2RejectionofAbnormalData 597

17.7.3SettingUpperLimitsWhenNoCountsAreObserved 598 Problems 599 Bibliography 600

18NuclearAnalyticalMethods 603

18.1Introduction 603

18.2ActivationAnalysis 603

18.2.1BasicDescriptionoftheMethod 603

18.2.2AdvantagesandDisadvantagesofActivationAnalysis 605

18.2.3PracticalConsiderationsinActivationAnalysis 607

18.2.4ApplicationsofActivationAnalysis 611

18.3PIXE 612

18.4RutherfordBackscattering 615

18.5AcceleratorMassSpectrometry(AMS) 619

18.6OtherMassSpectrometricTechniques 620 Problems 621

Bibliography 623

19RadiochemicalTechniques 625

19.1Introduction 625

19.2UniqueAspectsofRadiochemistry 626

19.3AvailabilityofRadioactiveMaterial 630

19.4Targetry 632

19.5MeasuringBeamIntensityandFluxes 637

19.6Recoils,EvaporationResidues,andHeavyResidues 639

19.7RadiochemicalSeparationTechniques 644

19.7.1Precipitation 644

19.7.2SolventExtraction 645

19.7.3IonExchange 648

19.7.4ExtractionChromatography 650

19.7.5RapidRadiochemicalSeparations 652

19.8Low-LevelMeasurementTechniques 653

19.8.1Blanks 654

19.8.2Low-LevelCounting:GeneralPrinciples 654

19.8.3Low-LevelCounting:Details 655

19.8.4LimitsofDetection 658 Problems 659 Bibliography 660

20NuclearForensics 663

20.1Introduction 663

20.1.1BasicPrinciplesofForensicAnalysis 666

20.2Chronometry 670

20.3NuclearWeaponsandTheirDebris 672

20.3.1RDDorDirtyBombs 672

20.3.2NuclearExplosions 674

20.4DeducingSourcesandRoutesofTransmission 678 Problems 680 Bibliography 681

AppendixB:NuclearWalletCards 687

AppendixC:PeriodicTableoftheElements 711

AppendixD:AlphabeticalListoftheElements 713

AppendixE:ElementsofQuantumMechanics 715

Index 737

PrefacetotheSecondEdition

Inthissecondeditionof ModernNuclearChemistry,wehaveaddednew chaptersonnuclearmedicine,particlephysics,andnuclearforensics.Wehave editedandupdatedallthechaptersinthefirsteditionreflectingthesubstantial progressthathasbeenmadeinthepast12years.Wehavedroppedthechapter onradiotracermethods.Wehavetriedtoremoveallthetypographicalerrors inthefirstedition,without,wehope,introducingnewerrors.Wecontinueto begratefultothemanycolleaguesandstudentswhohavetaughtusabouta widerangeofnuclearchemistry.Inadditiontoourcolleaguesacknowledgedin thefirsteditionofthisbook,wegratefullyacknowledgethehelpfulcomments ofJ.CernyandL.G.Sobotkaonvariousportionsofthebook.

PrefacetotheFirstEdition

Therearemanyfinetextbooksofnuclearphysicsandchemistryinprintatthis time.Sothequestioncanberaisedastowhywewouldwriteanothertextbook, especiallyonefocusingonthesmallerdisciplineofnuclearchemistry.When webeganthisprojectoverfiveyearsago,wefeltthatwewereauniquejuncture innuclearchemistryandtechnologyandthat,immodestly,wehadaunique perspectivetooffertostudents.

Muchofthemainstreamofnuclearchemistryisnowdeeplytiedtonuclear physics,inacooperativeendeavorcalled“nuclearscience.”Atthesametime, thereisalarge,growing,andvitalcommunityofpeoplewhousetheapplicationsofnuclearchemistrytotacklewide-rangingsetofproblemsinthephysical,biological,andenvironmentalsciences,medicine,engineering,andsoon. Wethoughtitwasimportanttobringtogether,inasinglevolume,arigorous, detailedperspectiveonboththe“pure”and“applied”aspectsofnuclearchemistry.Assuch,onemightfindmoredetailaboutanyparticularsubjectthanone mightlike.Wehopethisencouragesinstructorstosummarizethetextbook materialandpresentitinamannermostsuitabletoaparticularaudience.The amountofmaterialcontainedinthisbookistoomuchforaonequarterorone semestercourseandabittoolittleforayearlongcourse.Instructorscanpick andchoosewhichmaterialseemsmostsuitablefortheircourse.

Wehaveattemptedtopresentnuclearchemistryandtheassociatedapplicationsatalevelsuitableforanadvancedundergraduateorbeginninggraduate student.Wehaveassumedthatastudenthaspriororconcurrentinstructionin physicalchemistryormodernphysicsandhassomeskillsinhandlingdifferentialequations.Wehaveattemptedtosprinklesolvedproblemsthroughoutthe text,aswebelievethatonelearnsbyworkingproblems.Theend-of-the-chapter homeworkproblemsarelargelyexaminationquestionsusedatOregonState University.Theyshouldbeconsideredtobeintegralpartofthetextbookas theyareintendedtoillustrateoramplifythemainpointsofeachchapter.We havetakensomepainstousequantummechanicsinaschematicway,thatis, tousetheconclusionsofsuchconsiderationswithoutusingordemandinga rigorous,completeapproach.Theuseofhand-wavingquantummechanics,we

believe,isappropriateforourgeneralaudience.Wesummarize,intheappendices,somesalientfeaturesofquantummechanicsthatmaybeusefulforthose studentswithlimitedbackgrounds.

Ouraimistoconveytheessenceoftheideasandtheblendoftheoryand experimentthatcharacterizesnuclearandradiochemistry.Wehaveincluded somemoreadvancedmaterialforthosewhowouldlikeadeeperimmersionin thesubject.Ourhopeisthatthereadercanusethisbookforanintroductory treatmentofthesubjectofinterestandcanusetheend-of-chapterbibliographyasaguidetomoreadvancedanddetailedpresentations.Wealsohopethe practicingscientistmightseethisvolumeasaquickrefreshercourseforthe rudimentsofrelativelyunfamiliaraspectsofnuclearandradiochemistryand asaninformationboothfordirectionsformoredetailedinquiries.

Itiswiththedeepsenseoflossandsadnessthatthejuniorauthors(WDL, DJM)notethepassingofourdearfriend,colleague,andcoauthor,Prof.Glenn T.Seaborg,beforethecompletionofthiswork.Glennparticipatedinplanning anddevelopmentofthetextbook,wrotesomeofthetext,andreviewedmuch oftherest.Wedeeplymisshisguidanceandhisperspectiveaswehavebrought thisprojecttoconclusion.Weregretnotpayingcloserattentiontohisurging thatweworkharderandfasterashewouldremarktous,“YouknowI’mnot goingtoliveforever.”Wehopethatthethoughtsandideasthathetaughtusare reflectedinthesepages.

Wegratefullyacknowledgethemanycolleaguesandstudentswhohave taughtusaboutnuclearchemistryandotherthings.Specialthanksaredue toDarrahThomasandthelateTomSugiharaforpointingoutbetterwaysto discusssomematerial.WeacknowledgetheeffortsofEinarHagebwhoused anearlyversionofthisbookinhisclassesandgaveusimportantfeedback. WegratefullyacknowledgethehelpfulcommentsofD.Peterson,P.Mantica, A.Paulenova,andR.A.Schmittonvariousportionsofthebook.Oneofus (WDL)wishestoacknowledgethehospitalityoftheNationalSuperconducting CyclotronLaboratoryatMichiganStateUniversityfortheirhospitalityinthe fallof1999duringwhichtimeaportionofthisbookwaswritten.

IntroductoryConcepts

1.1Introduction

Nuclearchemistry consistsofafour-prongedendeavormadeupof(a)studies ofthechemicalandphysicalpropertiesoftheheaviestelementswheredetectionofradioactivedecayisanessentialpartofthework,(b)studiesofnuclear propertiessuchasstructure,reactions,andradioactivedecaybypeopletrained aschemists,(c)studiesofmacroscopicphenomena(suchasgeochronology orastrophysics)wherenuclearprocessesareintimatelyinvolved,and(d) applicationofmeasurementtechniquesbasedonnuclearphenomena(such asactivationanalysisorradiotracers)tostudyscientificproblemsinavariety offields.Theprincipalactivityor“mainstream”ofnuclearchemistryinvolves thoseactivitieslistedunder(b).

Asabranchofchemistry,theactivitiesofnuclearchemistsfrequentlyspan severaltraditionalareasofchemistrysuchasorganic,analytical,inorganic,and physicalchemistry.Nuclearchemistryhastiestoallbranchesofchemistry. Forexample,nuclearchemistsarefrequentlyinvolvedwiththesynthesisand preparationofradiolabeledmoleculesforuseinresearchormedicine.Nuclear analyticaltechniquesareanimportantpartofthearsenalofthemodernanalyticalchemist.Thestudyoftheactinideandtransactinideelementshasinvolved thejointeffortsofnuclearandinorganicchemistsinextendingknowledgeof theperiodictable.Certainlythephysicalconceptsandreasoningattheheart ofmodernnuclearchemistryarefamiliartophysicalchemists.Inthisbookwe willtouchonmanyoftheseinterdisciplinarytopicsandattempttobringin familiarchemicalconcepts.

Afrequentlyaskedquestionis“whatarethedifferencesbetween nuclear physics and nuclearchemistry?”Clearly,thetwoendeavorsoverlaptoalarge extent,andinrecognitionofthisoverlap,theyarecollectivelyreferredtoby thecatchallphrase“nuclearscience.”Butwebelievethattherearefundamental, importantdistinctionsbetweenthesetwofields.Besidesthecontinuingclose tiestotraditionalchemistrycitedpreviously,nuclearchemiststendtostudy nuclearproblemsindifferentwaysthannuclearphysicists.Muchofnuclear

physicsisfocusedondetailedstudiesofthefundamentalinteractionsoperatingbetweensubatomicparticlesandthebasicsymmetriesgoverningtheir behavior.Nuclearchemists,bycontrast,havetendedtofocusonstudiesof morecomplexphenomenawhere“statisticalbehavior”isimportant.Nuclear chemistsaremorelikelytobeinvolvedinapplicationsofnuclearphenomena thannuclearphysicists,althoughthereisclearlyaconsiderableoverlapintheir efforts.Someproblems,suchasthestudyofthenuclearfuelcycleinreactorsor themigrationofnuclidesintheenvironment,aresoinherentlychemicalthat theyinvolvechemistsalmostexclusively.

Onetermthatisfrequentlyassociatedwithnuclearchemistryis radiochemistry.Thetermradiochemistryreferstothechemicalmanipulationof radioactivityandassociatedphenomena.Allradiochemistsare,bydefinition, nuclearchemists,butnotallnuclearchemistsareradiochemists.Manynuclear chemistsusepurelynonchemicalandthereforephysicaltechniquestostudy nuclearphenomena,andthus,theirworkisnotradiochemistry.

1.2TheExcitementandRelevanceof NuclearChemistry

Whatdonuclearchemistsdo?Whydotheydoit?Whoarethenuclear chemists?Whatisexcitingandrelevantaboutnuclearchemistry?Theanswers tothesequestionsandmanymoresimilarquestionsarewhatwewilldiscuss inthisbook.

Nuclearchemistsaskquestionsaboutthesizesofthingslikenucleiandtheir constituents.Butbecausenuclearreactionsarewhatmakesthestarsshine,the laboratoryformanynuclearchemistsistheuniversewithattentionfocusingon supernovaandneutronstars(thelargestknown“nuclei”).Thesizescaleforthe nuclearchemistrylaboratoryrangesfromzeptometers(10 21 m)tozettameters (1021 m).Nuclearchemistsarealwaystryingtomake/discovernewthingsabout thenaturalworld.Fromusingradioactivitytomeasurethetemperatureofthe planetEarthtotracingtheflowofgroundwaterorthecirculationpatternsof theoceans,nuclearchemistsexplorethenaturalworld.Whatmakesthestars shineorhowdotheyshine?Anuclearchemist,RayDavis,wonthe2002Nobel PrizeinPhysicsforhispioneeringworkontheneutrinosemittedbythesun (seeChapter12).

SpeakingofNobelPrizes,thejuniorauthors(WDL,DJM)wouldberemiss nottomentionthatourcoauthor(GTS)wonthe1951NobelPrizeinChemistryforhisdiscoveriesinthechemistryofthetransuraniumelements.Intotal, nuclearchemistsandphysicistshavediscovered26newelements,expanding thefundamentalbuildingblocksofnaturebyabout30%.Theexpansionofthe nuclearlandscapefromthe3000knownnucleitothe7000possiblybound

nucleiremainsanagendaitemfornuclearscience.Understandingwhyonly about228ofthesenucleiarestableisalsoimportant.

Understandingthesizesandshapesofnucleiremainsanimportantitem. Shapessuchasspherical,oblate,prolate,andhexadecapoleareallobserved; sometimestherearecoexistingshapeseveninthedecayproductsofasingle nucleus,suchas 190 Po,whichdecaystospherical,oblateandprolate-shaped products.Somenucleilike 11 Liappeartohavespatiallyextendedstructures duetoweakbindingthatmakethemhuge.

Theapplicationsofnuclearchemistrytotheworldaroundusenrichourlives incountlessways.Oneofthesewaysistheapplicationofnuclearchemistry tothediagnosisandtreatmentofdisease(nuclearmedicine).Over400million nuclearmedicineproceduresareperformedeachyearforthediagnosisofdisease.Themostwidelyused(over10millionprocedures/year)radionuclideis 99 Tcm ,whichwasdiscoveredbyoneofus(GTS).Positronemissiontomography(PET)isusedinover1.5millionprocedures/yearintheUnitedStates.In PET,compoundsofshort-lived �� + emitters,like 18 F,areinjectedintoapatient, concentratinginparticularorgans.Whenthepositronemittersdecay,the �� + particlescontactordinaryelectrons,annihilatingtoproducetwo0.511MeV photonsmovinginoppositedirections.Whenenoughofthesephotonpairsare detected,onecanformanimageofthelocationofthedecay.Studiesofthese imagescanbeusedtounderstandthelocationoftumors,brainfunctions,and soon.Targetedradiopharmaceuticalscanbeusedtodeliveraradiationdoseto aspecificlocationinthebody.

Nuclearchemistryplaysaroleinournationalsecurity.IntheUnitedStates, 300portalmonitorsdetectthepossibleentryofclandestinenuclearmaterial. Severalofthesemonitorsemployadvancedtechnologiestocombatsophisticatedschemestoshieldtheclandestinematerial.Intheeventofanuclear radioactivityrelease,suchaswhatoccurredattheFukushimareactorcomplex inJapan,simplerayspectroscopyofexposedairfiltershasproventobeuseful.

Nuclearpowerremainsanimportantsourceofelectricityforseveralcountries.Nuclearchemistsplaykeyrolesinwasteremediationfromnuclearpower plantsandprovidingsolutionsfornuclearfuelcycleissues.Aschemists,they arealsoabletocontributetostudiesofmaterialdamageinreactorcomponents.

Thereisasignificantdemandforpeopletrainedasnuclearchemistsand radiochemists.IntheUnitedStates,thedemandfortrainednuclearchemistsat thePhDlevelexceedsthesupplybyafactorof10andhasdonesofordecades.

1.3TheAtom

Beforebeginningadiscussionofnucleiandtheirproperties,weneedtounderstandtheenvironmentinwhichmostnucleiexist,thatis,inthecenterofatoms. Inelementarychemistry,welearnthattheatomisthesmallestunitachemical

Figure1.1 Schematic representationoftherelative sizesofalithiumatomandits nucleus.Thenucleusistoo smalltoberepresentedinthe imageoftheatomevenwith thesmallestprintabledot. (Seeinsertforcolor representationofthefigure.) elementcanbedividedintothatretainsitschemicalproperties.Asweknow fromourstudyofchemistry,theradiiofatomsare ∼ 1to5 × 10 10 m,thatis, 1–5Å.Atthecenterofeachatom,wefindthe nucleus,asmallobject(r ≈ 1 to10 × 10 15 m)thatcontainsalmostallthemassoftheatom(Fig.1.1).The atomicnucleuscontains Z protonswhere Z isthe atomicnumber oftheelementunderstudy. Z isequaltothenumberofprotonsandthusthenumber ofpositivechargesinthenucleus.The chemistry oftheelementiscontrolled by Z inthatallnucleiwiththesame Z willhavesimilarchemicalbehavior.The nucleusalsocontains N neutronswhere N isthe neutronnumber.Neutrons areunchargedparticleswithmassesapproximatelyequaltothemassofaproton( ≈1u).Theprotonshaveapositivechargeequaltothatofanelectron.The overallchargeofanucleusis +Z electronicchargeunits.

Mostoftheatomisemptyspaceinwhichtheelectronssurroundthenucleus. (Electronsaresmall,negativelychargedparticleswithachargeof 1electronic chargeunitsandamassofabout1∕1840oftheprotonmass.)Thenegatively chargedelectronsareboundbyanelectrostatic(Coulombic)attractiontothe positivelychargednucleus.Inaneutralatom,thenumberofelectronsinthe atomequalsthenumberofprotonsinthenucleus.

Quantummechanicstellsusthatonlycertaindiscretevaluesof E ,thetotal electronenergy,and J ,theangularmomentumoftheelectrons,areallowed. Thesediscretestateshavebeendepictedinthefamiliarsemiclassicalpictureof theatom(Fig.1.1)asatinynucleuswithelectronsrotatingaboutitindiscrete orbits.Inthisbook,wewillexaminenuclearstructureandwilldevelopasimilar semiclassicalpictureofthenucleusthatwillallowustounderstandandpredict alargerangeofnuclearphenomena.

1.4AtomicProcesses

Thesizesandenergyscalesofatomicandnuclearprocessesareverydifferent. Thesedifferencesallowustoconsiderthemseparately.

Supposeoneatomcollideswithanotheratom.Ifthecollisionis inelastic,(the kineticenergiesofthecollidingnucleiarenotconserved),oneoftwothings mayhappen.Theyare(a) excitation ofoneorbothatomstoanexcitedstate involvingachangeinelectronconfigurationor(b) ionization ofatoms,that is,removalofoneormoreoftheatom’selectronstoformapositivelycharged ion.Forionizationtooccur,anatomicelectronmustreceiveanenergythatisat leastequivalenttoitsbindingenergy,which,fortheinnermostorKelectrons, is(Zeffective /137)2 (255.5)keV,where Zeffective istheeffectivenuclearchargefeltby theelectron(andincludestheeffectsofscreeningofthenuclearchargebyother electrons).ThiseffectivenuclearchargeforKelectronscanbeapproximatedby theexpression(Z –0.3).Asonecanseefromtheseexpressions,theenergynecessarytocauseionizationfarexceedsthekineticenergiesofgaseousatomsat roomtemperature.Thus,atomsmustbemovingwithhighspeeds(astheresult ofnucleardecayprocessesoracceleration)toejecttightlyboundelectronsfrom otheratoms.

1.4.2X-RayEmission

Theterm X-ray referstotheelectromagneticradiationproducedwhenanelectroninanouteratomicelectronshelldropsdowntofillavacancyinaninner atomicelectronshell(Fig.1.2),suchasgoingfromtheMshelltofillavacancy intheLshell.Theelectronlosespotentialenergyinthistransition(ingoing toamoretightlyboundshell)andradiatesthisenergyintheformofX-rays. (X-raysarenottobeconfusedwithgenerallymoreenergetic �� -raysthatresult fromtransitionsmadebytheneutronsandprotonsinthenucleusoftheatom,

Figure1.2 Schematic representationtoshow X-rayemissiontofillvacancy causedbynucleardecay.An Lshellelectron(A)isshown fillingaKshellvacancy(B). Indoingso,itemitsa characteristicKX-ray.

notintheatomicelectronshells.)TheenergyoftheX-rayisgivenbythedifferenceinthebindingenergiesoftheelectronsinthetwoshells,which,inturn, dependsontheatomicnumberoftheelement.ThusX-rayenergiescanbeused todeterminetheatomicnumberoftheelementalconstituentsofamaterialand arealsoregardedasconclusiveproofoftheidentificationofanewchemical element.

InX-rayterminology,X-raysduetotransitionsfromtheLtoKshellarecalled K�� X-rays;X-raysduetotransitionsfromtheMtoKshellsarecalledK�� X-rays. Inafurtherrefinement,thetermsK�� 1 andK�� 2 refertoX-raysoriginatingin differentsubshells(2p3∕2 ,2p1∕2 )oftheLshell.X-raysfromMtoLtransitions areL�� andsoon.Foreachtransition,thechangesinorbitalangularmomentum, Δ�� ,andtotalangularmomentum, Δj,arerequiredtobe

(1.1)

ThesimpleBohrmodelofthehydrogen-likeatom(oneelectrononly)predicts thattheX-rayenergyorthetransitionenergy, ΔE ,isgivenas

where R∞ , h, c,and n denotetheRydbergconstant,thePlanckconstant,the speedoflight,andtheprincipalquantumnumberfortheorbitalelectron, respectively.SincetheX-rayenergy, Ex ,isactually– ΔE ,wecanwrite(after substitutingvaluesforthephysicalconstants)

(1.4) where Ex isgiveninunitsofelectronvolts(eV). ForK�� X-raysfromionswithonlyoneelectron,

whileforL�� X-rays,wehave

Inreality,manyelectronswillsurroundthenucleus,andwemustreplace Z by Zeffective toreflectthescreeningofthenuclearchargebytheseotherelectrons. ThiscorrectionwasdonebyMoseleywhoshowedthatthefrequencies, �� ,of theK�� seriesX-rayscouldbeexpressedas

MoseleythusdemonstratedtheX-rayenergies(= h�� )dependonthesquare ofsomealteredform(duetoscreening)oftheatomicnumber.Also,therelativeintensitiesoftheK�� 1 ,K�� 2 ,etcX-rayswillbeproportionaltothenumber ofpossiblewaystomakethetransition.Thus,weexpecttheK�� 1 /K�� 2 intensity ratiotobe ∼2asthemaximumnumberofelectronsinthe2p3∕2 levelis4while themaximumnumberofelectronsinthe2p1∕2 levelis2.TherelativeintensitiesofdifferentX-raysdependonthechemicalstateoftheatom,itsoxidation state,bondingwithligands,andotherfactorsthataffectthelocalelectrondensity.Theserelativeintensitiesare,thus,usefulinchemicalspeciationstudies. Weshouldalsonote,asdiscussedextensivelyinChapters7–9,thatX-rayproductioncanaccompanyradioactivedecay.Radioactivedecaymodes,suchas electroncapture(EC)orinternalconversion(IC),directlyresultinvacancies intheatomicelectronshells.TheresultingX-raysaresignaturesthatcanbe usedtocharacterizethedecaymodesand/orthedecayingspecies.

1.5TheNucleus:Nomenclature

Anucleusissaidtobecomposedof nucleons.Therearetwo“kinds”ofnucleons, theneutronsandtheprotons.Anucleuswithagivennumberofprotonsand neutronsiscalleda nuclide.The atomicnumberZ isthenumberofprotonsin thenucleus,while N ,the neutronnumber,isusedtodesignatethenumberof neutronsinthenucleus.Thetotalnumberofnucleonsinthenucleusis A,the massnumber.Obviously A = N + Z .Notethat A,thenumberofnucleonsin thenucleus,isaninteger,whiletheactualmassofthatnucleus, m,isnotan integer.

Nuclideswiththesamenumberofprotonsinthenucleusbutwithdiffering numbersofneutronsarecalled isotopes.(ThiswordcomesfromtheGreek iso + topos,meaning“sameplace”andreferringtothepositionintheperiodictable.) Isotopeshaveverysimilarchemicalbehaviorbecausetheyhavethesameelectronconfigurations.Nuclideswiththesamenumberofneutronsinthenucleus, N ,butdifferingnumbersofprotons, Z ,arereferredtoas isotones.Isotones havesomenuclearpropertiesthataresimilarinanalogytothesimilarchemicalpropertiesofisotopes.Nuclideswiththesamemassnumber, A,butdiffering numbersofneutronsandprotonsarereferredtoas isobars.Isobarsareimportantinradioactivedecayprocesses.Finally,theterm isomer referstoanuclidein anexcitednuclearstatethathasameasurablelifetime(>10 9 s).Theselabels arestraightforward,butoneofthemisfrequentlymisused,thatis,theterm isotope.Forexample,radioactivenuclei(radionuclides)areoften incorrectly

referredtoasradioisotopes,eventhoughthenuclidesbeingreferenceddonot havethesameatomicnumbers.

Theconventionfordesignatingagivennuclide(with Z protons, N neutrons) istowrite A Z ChemicalSymbolN withtherelativepositionsindicatingaspecific featureofthenuclide.Thus,thenucleuswith6protonsand8neutronsis 14 6 C8 orcompletelyequivalently, 14 C.(Theolderliteratureusedtheform N Z ChemicalSymbolA ,so 14 CwasdesignatedasC14 .Thisnomenclature isgenerallyextinct.)Notethatsometimestheatomicchargeoftheentity containingthenuclideisdenotedasanupperright-handsuperscript.Thusa doublyionizedatomcontainingaLinucleuswith3protonsand4neutrons andonlyoneelectronisdesignatedas 7 Li2+ .

SampleProblem1.1:Labels

Considerthefollowingnuclei: 60m Co, 14 C, 14 N, 12 C, 13 N.Whichareisotopes?isotones?isobars?isomers?

Solution

60m Coistheisomer, 14 Cand 12 Careisotopesofcarbon, 13 Nand 14 Nare isotopesofnitrogen, 14 Cand 14 Nareisobars(A = 14),while 12 Cand 13 N areisotones(N = 6).

1.6PropertiesoftheNucleus

Wecannowmakeanestimateoftwoimportantquantities,thesizeandthe densityofatypicalnucleus.Wecansay

ifweassumethatthemassofeachnucleonisabout1uandthenucleuscanbe representedasasphere.Itturnsout(Chapter2)thataruletodescribetheradii ofstablenucleiisthatradius R is

Thuswehave

wherewehaveusedthevalueof1.66 × 10 24 gfor1u(AppendixA).Before evaluatingthedensity �� numerically,wenotethatthe A factorcancelsin theexpression,leadingustoconcludethatallnucleihaveapproximatelythe

samedensity.Thisissimilartothesituationwithdifferentsizeddropsofa pureliquid.Allofthemoleculesinadropinteractwitheachotherwiththe sameshort-rangedforces,andtheoveralldropsizegrowswiththenumber ofmolecules.Evaluatingthisexpressionandconvertingtoconvenientunits, wehave

≈ 200, 000metrictons/mm3

Acubeofnuclearmatterthatis1mmonasidecontainsamassof200,000 tonnes.WOW!Nowwecanrealizewhatalltheexcitementaboutthenuclear phenomenaisabout.Thinkofthetremendousforcesthatareneededtohold mattertogetherwiththisdensity.Relativelysmallchangesinnuclei(viadecay orreactions)canreleaselargeamountsofenergy.(Fromthepointofviewofthe studentdoingcalculationswithnuclearproblems,amoreusefulexpressionof thenucleardensityis0.17nucleons/fm3 .)

1.7SurveyofNuclearDecayTypes

Nucleicanemitradiationspontaneously.Thegeneralprocessiscalled radioactivedecay.WhilethissubjectwillbediscussedindetailinChapters3,7,8,and 9,weneedtoknowafewgeneralideasabouttheseprocessesrightaway(which wecansummarizeinthefollowing).

Radioactivedecayusuallyinvolvesoneofthreebasictypesofdecay, �� -decay, �� -decay,or �� -decayinwhichanunstablenuclidespontaneouslychangesinto amorestableformandemitssomeradiation.InTable1.1,wesummarizethe basicfeaturesofthesedecaytypes.

Thefactthattherewerethreebasicdecayprocesses(andtheirnames)was discoveredbyRutherford.Heshowedthatallthreeprocessesoccurinasampleofdecayingnaturaluranium(anditsdaughters).Theemittedradiations weredesignated �� , �� ,and �� todenotethepenetratingpowerofthedifferent radiationtypes.Furtherresearchhasshownthatin �� -decay,aheavynucleus spontaneouslyemitsan 4 Henucleus(an �� -particle).Theemitted �� -particles aremonoenergetic,andasaresultofthedecay,theparentnucleuslosestwo protonsandtwoneutronsandistransformedintoanewnuclide.Allnuclei with Z > 83areunstablewithrespecttothisdecaymode.

Nuclear �� decayoccursinthreeways, �� , �� + ,andEC.Inthesedecays,a nuclearneutron(proton)changesintoanuclearproton(neutron)withtheejectionofneutrinos(smallneutralparticles)andelectrons(orpositrons).(InEC, anorbitalelectroniscapturedbythenucleus,changingaprotonintoaneutronwiththeemissionofaneutrino.)Thetotalnumberofnucleonsinthe nucleus, A,doesnotchangeinthesedecays,onlytherelativenumberofneutronsandprotons.Inasense,thisprocesscan“correct”or“adjust”animbalance betweenthenumberofneutrons,andprotonsinanucleus.In �� + and �� decays,

CharacteristicsofRadioactiveDecay.

thedecayenergyissharedbetweentheemittedelectrons,theneutrinos,and therecoilingdaughternucleus.Thus,theenergyspectrumoftheemittedelectronsandneutrinosiscontinuousrangingfromzerotothedecayenergy.InEC decay,essentiallyallthedecayenergyiscarriedawaybytheemittedneutrino. Neutron-richnucleidecayby �� decaywhileproton-richnucleidecayby �� + or ECdecay. �� + decayisfavoredinthelightnucleiandrequiresthedecayenergy tobe > 1.02MeV(forreasonstobediscussedlater),whileECdecayisfound mostlyintheheaviernuclei.

Nuclearelectromagneticdecayoccursintwoways, �� -decayandIC.In �� -ray decayanucleusinanexcitedstatedecaysbytheemissionofaphoton.InICthe sameexcitednucleustransfersitsenergyradiationlesslytoanorbitalelectron thatisejectedfromtheatom.Inbothtypesofdecay,onlytheexcitationenergy ofthenucleusisreducedwithnochangeinthenumberofanyofthenucleons.

SampleProblem1.2:Balancingequations

Theconservationofthenumberofnucleonsinthenucleusandconservationofchargeduringradioactivedecay(Table1.1)makesitrelatively easytowriteandbalancenucleardecayequations.Forexample,consider

• The �� decayof 90 Sr

• The �� decayof 232 Th

• The �� + decayof 62 Cu

• TheECdecayof 256 Md

Solution

Thesedecayequationscanbewritten,usingTable1.1,as

• 90 38 Sr → 90 39 Y+ + �� + �� e

• 232 90 Th → 228 88 Ra +4 2 He

• 62 29 Cu → 62 28 Ni + �� + + ��e

Besidesitsqualitativedescription,radioactivedecayhasanimportantquantitativedescription.Radioactivedecaycanbedescribedasafirst-orderreaction,thatis,thenumberofdecaysisproportionaltothenumberofdecaying nucleipresent.Itisdescribedbytheintegratedratelaw N = N0 e ��t (1.12) where N isthenumberofnucleipresentattime t while N0 isthenumber ofnucleipresentattime t = 0.Thedecayconstant ��,acharacteristicofeach nucleus,isrelatedtothehalf-life

The half-life isthetimerequiredforthenumberofnucleipresenttodecreaseby afactorof2.Thenumberofdecaysthatoccurinaradioactivesampleinagiven amountoftimeiscalledthe activityA ofthesample.Theactivityisequaltothe numberofnucleipresent, N ,multipliedbytheprobabilityofdecaypernucleus, ��,thatis, A = �� N .Therefore,theactivitywillalsodecreaseexponentiallywith time,thatis,

= A0 e ��t

where A isthenumberofdisintegrationsperunittimeattime t and A0 isthe activityattime t = 0.Thehalf-livesofnucleiwithrespecttoeachdecaymode areoftenusedtoidentifythenuclei.

SampleProblem1.3

14 Cdecaysto 14 Nby �� decaywithahalf-lifeof5730years.Ifa1gsampleofcarboncontains15.0dis/min,whatwillbeitsactivityafter10,000 years?

Solution

• A = A0 e ��t

• �� = ln2 5730years = 1.210 × 10 4 ∕year

• A = (15dis/min) e−(1.210 × 10 4 )(10,000) = 4.5dis/min

Alllivingthingsmaintainaconstantlevelof 14 Cpergramofcarbon throughexchangewiththeirsurroundings.Whentheydie,thisexchange stops,andtheamountof 14 Cpresentdecreasesexponentiallywith time.Ameasurementofthe 14 Ccontentofadeadobjectcanbeused todeterminetheageoftheobject.Thisprocessandothergeologically importantdecayprocessesarediscussedinChapter3.

1.8ModernPhysicalConceptsNeededin NuclearChemistry

Whileweshallstrivetodescribenuclearchemistrywithoutusingextensive mathematicsandphysics,thereareseveralimportantconceptsfrommodern physicsthatweneedtoreviewbecausewewillusetheseconceptsinourdiscussions.

1.8.1ElementaryMechanics

Letusrecallafewelementaryrelationshipsfromclassicalphysicsthatweshall use.Forcecanberepresentedasavector, F,whichdescribestherateofchange ofthemomentumwithtime: F = d p dt (1.15) wherethemomentum p = m�� andwhere m isthemassand �� isthevelocity oftheparticle.Neglectingrelativisticeffects(Section1.8.2)thatareimportant forparticleswhosevelocityapproachesthespeedoflight,wecansaythatthe kineticenergyofamovingbody T isgivenas

= 1 2 m��2 (1.16)

ForthesituationdepictedinFigure1.3forthemotionofaparticlepastafixed point,wecansaythattheorbitalangularmomentumoftheparticle, �� ,with mass m withrespecttothepoint Q is l = r × p (1.17)

Thequantity �� isavectorwhosemagnitudeis m��r forcircularmotion.For motionpastastationarypoint,themagnitudeis m��b where b isthedistanceof closestapproachcalledthe impactparameter.

Letusalsorecalltherelationshipbetweenthemagnitudeofaforce F (r ) that dependsonthedistancebetweentwoobjects, r ,andthepotentialenergy, V (r ), thatis,

(1.18)

Figure1.3 Aparticleof mass, m,movingwitha velocity, ��,hasalinear momentum p = m��. Relativetopoint O,the particlehasanangular momentumof �� = r × p, where r isavector connectingpoint O andthe particle.Atthepointof closestapproach, r isequal toimpactparameter b. O

= r × p

y

Thus,iftheCoulombpotentialenergybetweentwochargedobjectsisgivenas

where r12 isthedistanceseparatingcharges q1 and q2 (andwhere k isaconstant),wecansay t themagnitudeoftheCoulombforce, FC ,is

Sinceforcesareusuallyrepresentedasvectors,itismoreconvenientwhendiscussingnuclearinteractionstorefertothescalar,potentialenergy.Fromthe previousdiscussion,weshouldalwaysrememberthatadiscussionofpotential energy V (r ) isalsoadiscussionofforce F (r ).

1.8.2RelativisticMechanics

AsEinsteindemonstrated,whenaparticlemoveswithavelocityapproachingthatoflight,theclassicalrelations(Section1.8.1)describingitsmotionina stationarysystemarenolongervalid.Nuclearprocessesfrequentlyinvolveparticleswithsuchhighvelocities.Thusweneedtounderstandthebasicelements ofrelativisticmechanics.Accordingtothespecialtheoryofrelativity,themass ofamovingparticlechangeswithspeedaccordingtotheequation

where m∗ and m0 arethemassofaparticleinmotionandatrest,respectively. TheLorentzfactor, �� ,isgivenas

where �� isthespeedoftheparticle, ��,relativetothespeedoflight, c,thatis, �� = ��∕c.Thus,asthespeedoftheparticleincreases,themassalsoincreases, makingfurtherincreasesinspeedmoredifficult.Sincethemass m∗ cannotbe imaginary,noparticlecangofasterthanthespeedoflight.Thetotalenergyof aparticle, Etot ,isgivenas

Sincethetotalenergyequalsthekineticenergyplustherestmassenergy,we canwrite

(1.24) where T istheparticle’skineticenergy.Thus

Aseriesofrelationshipshavebeenderivedbetweenthestationarycoordinate system(thescientistinhisorherlaboratory)andamoving(intrinsic,invariant)

Table1.2 ComparisonofRelativisticandClassicalExpressionsforaFree Particle.

ClassicalExpression RelativisticExpression

t = t2 t1

Totalenergy Etot = Ek (freeparticle)

coordinatesystemthatcanbecomparedtoclassicalcalculationsofdynamic variables(Table1.2).

Notethatforaparticleatrest

Etot = m0 c2 (1.26)

where m0 istherestmassand c thespeedoflight.Foramasslessparticle,such asaphoton,wehave

Etot = pc (1.27) where p isthemomentumofthephoton.Theseequationsmakeitclearwhythe unitsofMeV/c2 formassandMeV/c formomentumareuseful.Animportant questioniswhendoweuseclassicalexpressionsandwhendoweuserelativistic expressions?Aconvenientbutarbitrarycriterionformakingthisdecisionisto usetherelativisticexpressionwhen �� ≥ 1.1.Thiscorrespondsroughlytoa13% errorintheclassicalexpression.Whatdoesthiscriterionmean,inpractice? InTable1.3,weindicatethevaluesofthekineticenergyatwhich �� = 1.1for differentparticles.Thus,oneshouldalwaysusetherelativisticexpressionsfor photons,neutrinos,andelectrons(when Te > 50keV)orfornucleonswhen thekineticenergy/nucleonexceeds100MeV.

SampleProblem1.4:RelativisticMechanics

Considera 20 Neionwithakineticenergyof1GeV/nucleon.Calculateits velocity,momentum,andtotalenergy.

Solution

Thekineticenergy=20 × 1GeV/nucleon=20GeV=20,000MeV.But weknowthekineticenergyis T =(�� 1)m0 c2 ,andtherestmassis ∼ 20uor(20)(931.5)MeV/c or18,630MeV.Sowecanwrite

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The Project Gutenberg eBook of Rockabye, Grady

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Title: Rockabye, Grady

Author: David Mason

Illustrator: Temple

Release date: September 7, 2023 [eBook #71584]

Language: English

Original publication: New York, NY: Royal Publications, Inc, 1957

Credits: Greg Weeks, Mary Meehan and the Online Distributed Proofreading Team at http://www.pgdp.net

*** START OF THE PROJECT GUTENBERG EBOOK ROCKABYE, GRADY ***

Rockabye, Grady

Illustrated by TEMPLE

When on Pru'ut, you must do as the natives do—and that includes dying as they do!

[Transcriber's Note: This etext was produced from Infinity July 1957.

Extensive research did not uncover any evidence that the U.S. copyright on this publication was renewed.]

On the charts, it's P-1345-AZ, and a thin blue line marked with cryptic letters indicates that a Mallor Lines cargo ship stops three times in each local year. The Guide will tell you a little more; that it's a small hot planet, covered with fern forests and swamps, and inhabited by one of the innumerable primate-human species of the universe. It was also inhabited, for a while, by one Terran, James Grady.

The natives call it Pru'ut, which, freely translated, means "the world." They refer to themselves as Kya, which means "people." James Grady, being a realist, called it the Mudhole, and added a descriptive adjective or two; but he did not find it nearly as unpleasant a place as a few others in which he had been in the course of forty years of wandering.

Pru'ut has no inclination, and only one season, which is rather like a rainy August on Earth. When Grady arrived, he stepped from the landing stage of the Mallor Lines' Berenice into six inches of gluey mud; the sun was seldom out long enough to harden the surface of Pru'ut.

"It's not an easy place," the departing agent, Jansen, told Grady. "Rain, and heat, and getting along with the locals."

"Anything the matter with 'em?" Grady asked. He was watching the tall, yellow-pale shapes of natives loading bales into the Berenice's cargo slings.

"Nothing much," Jansen said. "Sane as any primitives. All kinds of complicated rules and taboos, and naturally they'll get as mad as hell at you if you scratch a single rule. Most of the data on that is in the agent's notebooks. You add anything to the record that seems to be worth putting down, the way the rest of us have."

"And if they get mad at you, they stop packing plants," the Berenice's mate put in. "Which will make the Mallor Company mad at you, too. This place is a regular bargain basement for drug materials. At least

eight different drug plants, all of them worth as much as uranium. More, in some ways."

"Mm." The ex-agent picked up a handful of brown leaves from a table. "This, for instance. It's a distant relation of coca. The natives chew it for fun, but it's the source of a first class anesthetic. And this. If your kidneys ever break down, the doctors use this stuff to keep you alive. Kerosin, it's called. Anyway, you'll find price lists and descriptive material in the files. You've worked for Mallor before, haven't you?"

"Yes," Grady said. "I put in three years on Tengo, in Port City Then I quit for a while. Had something else to do."

"Oh? What?"

Grady's face cracked into a slight grin. "Little bit of an argument. The Mutiny I joined the local army, if you could call it that. I had my own gun, so they made me a major on the spot."

"The Mutiny?" The Berenice's mate had heard of that brief and savage war, in which a handful of settlers and local militia had beaten off the troops of a powerful state, and had actually won. The mate hastily readjusted his opinion of Grady upward. A trader's agent was one thing; a man who had fought through the Mutiny was something more than that. The mate opened his mouth to ask more of the story; but the Berenice's air-horn cut him off with a long wail.

"Take-off in twenty minutes," the mate said, as the noise subsided. "You ready, Jansen?"

The ex-agent nodded, and shook hands with Grady "Good luck," he said, and started for the ship, the mate following.

"Yeah," Grady said, closing the door of the agency. He had completely put the Berenice out of his mind by the time the roar of her departure split the wet air of Pru'ut. He was, in fact, well on his way to settling down as a permanent resident by that time.

A year later, the Berenice had called twice, and her captain and mate were calling Grady by his first name. He had also acquired a native woman, who, in accordance with one of the innumerable customs, could not call him by name at all. She referred to him as Kotasa, which is a sort of title. He, also in accordance with customs, called her Shallra, which was not her name, but that of her mother. Grady was also extremely careful not to speak to her mother at all, because of another custom.

Grady—Kotasa to his wife, and Shassa to the rest of the village— fitted in well, better than any Terran had until his coming. Grady had spent most of his life living in odd places and with strange people; and had come to the conclusion that it was always a good idea to be a conservative by local standards. He could recall, quite clearly, the day he had found what was left of Steynert, who had tried to change the dietary habits of the inhabitants of Kree.

By comparison with the Kree, the Kya were an easy people to get along with. Their lives were not hard, since Pru'ut was a fertile world, and full of food sources. The Kya farmed their garden patches, fished, and hunted, and spent the remaining time gathering plants for Grady and reciting endless and complex genealogies. Grady paid for the plants with goods from the trade warehouse, and listened gravely to the genealogies, making mental notes whenever anything was mentioned that might be of practical use. He did not consider himself as a collector of scientific information; he was a practical man, and he selected information for practical ends.

Shallra was the best wife he had ever had, and Grady had lived on several worlds. She spoke little, and when she did, it was direct and to the point. She was affectionate, but, like most Kya, undemonstrative. She had been brought up to consider that males were equals, but that certain male privileges, such as the lodge magics and the use of horn pipes, were inviolable. Grady had lived on one world where men were considered very much superior to women, and had found that the attitudes which result are not as pleasant as they might seem. And lastly, Shallra was probably the best cook on Pru'ut, if not the best on several worlds.

The Kya generally liked and trusted Grady, and, after two years, he was almost one of them. Standing on the agency porch, in the weak sunlight, he seemed to have acquired the same yellowish skin and lean face, and he was dressed in the same loose kilt. Shallra came out to stand beside him, and they looked like any other Kya.

"The sun," she said gravely. "There will be a dance tonight."

Grady nodded. "Like to see it," he said. "The dance, I mean."

"It is for men," Shallra said. "Koor," she pointed at the sun, "is a god belonging to men. The women dance when the sky clears in the night."

"Men's dance, eh?" Grady said, sucking on his pipe. "You're probably right about it being all right for me to go. But I'd better check with the Chief anyway."

He started down the log-paved walk, toward the Chief's house on the other side of the village. He could see it clearly at the far end of the long, muddy street, but it was necessary to walk along a twisting detour, rather than directly toward it. There was an acre of ground in the center of the village, filled with crumbling, empty huts, and no Kya walked through this ground. It belonged to Sa'ahah, whose ghost walked in a wide circle around the hut where a jealous rival had speared him in his sleep.

The house was the usual Kya affair, on tall stilts, with painted signs on its facade, but much more elaborate as befitted the Chief's position. He was Anla-Who-Speaks-for-the-Ancestors. There were several other kinds of chief, but it was Anla whom Grady consulted before trying anything in the least unusual. Anla sat on his porch now, regarding the sun through slitted eyes.

Grady greeted him in proper form, and Anla returned the greeting, rising and bowing.

"Is there any reason why this person may not attend the dance of Koor with his brothers on this night?" Grady asked.

Anla thoughtfully pulled his lower lip; then, nodding, he said, "No, there is no reason not to."

Then Grady made the mistake. He made it in full view of Anla's mother-in-law, who sat peering balefully out from her special room in the corner of the Chief's house; and of Anla's wife, and of his wife's innumerable relations, who were clustered on the porch. When Grady saw their silent staring, he looked down at his feet, and he saw what it was that he had done. Anla saw it too, and the two men looked up again, and at each other, very gravely.

Grady did not say he was sorry It would have been of no use whatever. Nor did he point out that the sun came out so infrequently that his mistake was one which could be excused. Among the Kya there are very few mistakes which can be excused, and stepping on the shadow of a chief is not one of them.

Neither did Anla make any reference to the long friendship between them, because there would have been no point in doing so. Anla's eyes grew darker, and the wrinkles at their corners deepened, but his words were calm, the correct words for such a time.

"Your name was Shassa," Anla said. "You have broken the ghostcloak of the Chief, and your name cannot be Shassa. From this place and this time I take back your name, Shassa, and you have no name."

Grady did not say anything, because a Kya cannot hear the words of a man without a name; besides, there was nothing to say, though a great deal to think about. The Berenice was due in four days. Four days during which a man without a name would have to avoid the custom which decreed that such a man must be killed. Killed as soon as possible, because each day he continued to live was a day which must be removed from the calendar, a day on which no man's birth date might be celebrated, or any animal killed for food, or any root taken from a garden.

Grady turned, and walked slowly, with a stiff back, down the path away from the Chief's house. To run, or to show fear, would be fatal; the Kya were themselves in a state of shock at the thing which had

happened, and it would be an hour or more before they began to prepare for what they had to do. Therefore, Grady held his spine straight, feeling a cold spot between his shoulderblades where the first iron-headed arrow might strike in.

Ahead of him, through the village, the silent children ran on light feet, darting into the houses and out again—the children, who were the bearers of news. He saw three of them dash toward the agency, and enter it; and in a moment, as he came up the path, Shallra came out on the porch, carrying a clay pot in her hands.

"You who were Kotasa," she said, "take this, and drink it to free me of your name."

It was the standard form of divorce among the Kya, and if the eyes of Shallra had not been bright with tears, Grady might have slipped. He took the clay pot, but he did not drink, because he could smell the faint and bitter odor about it, which was not the odor of the fruit wine that it should have held.

"Why?" he asked her, quietly.

"Because it is an easier death than the knife and the arrow," she said, and added, "When you were Kotasa, you were—a good man for me. Drink the wine." She said it pleadingly. He shook his head.

"I am sorry," Shallra said, and there is nothing harder for a Kya to say. But she added something even harder for a Kya woman to say; his name, his proper name, which she had always known but could never use. Then she walked away, and out of Grady's life, because he was now a man without a name.

He set the pot down carefully on the agency's steps and went inside. As he closed the door, there was a high, whistling noise, and a sharp thud against the door planks. He did not need to look to know that an arrow stood in its wooden panels.

Grady closed the heavy wooden shutters carefully, not even jumping when a second arrow whickered through the last shutter as it swung. He lit a table lamp and took the heavy, seldom-used rifle from the wall. He did not need to check it; he had oiled and cleaned it once a week for two years. Instead, he laid it on the table and took a book down from a shelf.

"General Code of the Federation Authority," Grady read the words on the spine, and opened it. "Extent of responsibilities of individuals on mandated planets...."

Under the circumstances, Grady discovered, he could kill any number of Kya if he were so inclined. The Authority would require a full report, in quadruplicate, of the circumstances—and as another arrow struck the door, Grady wondered wryly who would make out that report.

Also, Grady was not in the least inclined to kill any Kya. If doing so would have saved his life, he would have shot any number of them without any particular qualms. But there were no reasons at all to think that killing any of them would do Grady any good. And Grady thoroughly understood why it was that they had to kill him. He was no more angry with the Kya than he had been with the Imperial Guards, five years before, when they had come up Kanno Hill with their band playing and their bayonets gleaming. He could remember how military and colorful they had looked, in comparison to the overalled, grimy rabble who stood beside him; and how they had come up that hill again and again, fewer of them each time, and the band losing a bit of verve on the last. Grady's anger then had been at the damned fool, whoever he was, who ordered those useless charges; and his anger now was with himself, because it had been his own mistake.

There was a growing murmur outside the agency. The villagers were gathering in the street, and in the yards behind the building. There was no way out now, and nowhere to go if there had been a way out. Grady got up, and walked to the door. He opened the sliding panel a crack and peered out.

The rain had begun again, and through its thin gray curtain he could see the ranks of villagers, silent, standing around the house, along the railings, and watching. The men stood in front, each holding his weapons, his bow bent in his hands. There was Lahrsha, who had been brother in the Lodge to Grady, and whose blood had been mixed with his to seal the tribal bond. There was Ahl, whose small son Grady had nursed through a bad week. There were Grady's friends and neighbors and brothers, each with an arrow on the nock for Grady.

"It's a queer thing to happen," Grady said to himself, aloud. The sound of his own voice startled him; he had become so much a Kya that to him a man without a name should not have a voice.

The arrows struck oftener now. Grady saw a small group of men move away, and then return, carrying a short log.

The door, Grady thought. They'll break it down, and come in, with their grave faces and their polite ways, and they'll cut my throat. And it won't matter if I kill one or two or ten of them; they'll do it anyway. They won't hear an argument, because they can't hear me at all, without a name; they won't even hear any noise I make when they finish me off.

The log had begun to beat against the door, with a steady thunder. Grady opened a cabinet, and took out a jar of brown liquid. Quickly he drank it and sat down, his face graying. His head fell forward on his arms, and the book of regulations fell to the floor, atop the unfired rifle.

The Berenice swung outward, riding home to port with an empty hold. The Mallor Company would not be pleased, but there were other jobs. And the mate, sitting across the messroom table from James Grady, put the matter in its simplest terms.

"Just one of those things," the mate said. "You can't be blamed. They'll take another agent without any fuss, I imagine."

"No doubt of it," Grady said. "Can't say I'm glad to leave, though. It was a good place."

"I still don't get it," the mate said. "We came in and found you in the agency, out cold with coca. The door was down, and arrows all over

the place. Why didn't they come in and dig a knife into you?"

"Customs and taboos," Grady said. "I took a chance on it, but I was pretty sure I was right. Common sense—by their standards. Man's asleep—his ghost is walking around. If you kill him in his sleep, you free his ghost, which is very bad, very strong magic. So you have to wake him up to kill him. And they couldn't wake me up; I was full of that coca leaf, enough for a week."

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