Chapter4

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SolutionstoChapter4EndofChapterProblemsGammaVersion
Section4.1.
PeriodicityandthePeriodicTable
4.1.

ThemodernPeriodicTableisbasedonthestructureofatoms.Thiswasnottheevidence
thatMendeleevusedwhenheproposedtheperiodicarrangementofelementsin1869.
(a) WhydidntMendeleevbasehistableonstructureofatoms?
(b) WhatwasthebasisforMendeleevsperiodictable?
(c) WhyweretheremissingelementsinMendeleev'speriodictable?
Answerto4.1:
(a)Thiswouldhavebeenimpossible,becausethestructureofatomswasnotunderstood
untilconsiderablyafterthetimeofMendeleev.Thebasisforunderstandingthepresent
periodicarrangementofatoms,thenumberofprotonsinthenucleus,wasnot
experimentalevidenceavailabletoMendeleevin1969.
(b)Mendeleevsperiodictablewasbasedonempiricalcorrelations.Theevidence
gatheredshowedthatthepropertiesofthe60elementsknownatthattimeshowed
repeatedpatternsbasedonrelativeatomicmass.
(c)ForMendeleevtoalignknownelementswithsimilarchemicalpropertiesinfamilies,
hehadtoleavegapsinthefirstperiodictable.Mendeleevconcludedthatthegapswould
befilledbyelementsthathadnotyetbeendiscovered.

4.2.

Considerthesedatafortheatomicradiioftheelementsinthefirstthreeperiods.
AtomicRadii(pm)
Element

Radius

Element

Radius

Element

Radius

H
He
Li
Be
B
C

37
32
134
90
82
77

N
O
F
Ne
Na
Mg

75
73
71
69
154
130

Al
Si
P
S
Cl
Ar

118
111
105
102
99
97

(a) Usethesedatatofindaperiodicpatternintheatomicradiiofthefirsttheeperiodsof
maingroupelements.
(b) Displaythedatagraphically.

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(c) Whichdisplay,thetabulatedvaluesoryourgraph,bestfacilitatesunderstandingof
therelationshipsamongthedata?Explainyourreasoning.
(d) Whatdoyoupredictthattheatomicradiuswillbeforpotassium?forcalcium?What
isthebasisforyourprediction?
(e) Useaprintorwebbasedreferencetocheckthepredictionsmadeinpart(d).Were
yourpredictionsaccurate?Whyorwhynot?
Answerto4.2:

A
Perio
21050Atomic
1050
0E
lem
ntsA
rangedbyIncreasingA
tom
icN
um
ber

(a)Ineachcase,theatomicradiidecreasesastheatomicnumberincreasesfromleftto
rightacrosstheperiodictable.

(b)MoststudentswillchoosetomakeagraphsimilartoFigure4.1inthetext.Hereisan
example.

However,somestudentswillprepareagraphicaldisplayinwhichtherelativeradiusis

displayedusingcirclesofrelativesizearrayedonaperiodictable.Thissampleisbased
onFigure1.7inthetext.

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2
3

I
hydrogen
H

II

III

IV

lithium
Li

beryllium
Be

boron
B

carbon
C

sodium
Na

magnesium
Mg

aluminum
Al

silicon
Si

potassium
K

calcium
Ca

10pm

StructureofAtoms

VI

VII

VIII
helium
He

nitrogen
N

oxygen
O

fluorine
F

neon
Ne

phosphorus
P

sulfur
S

chlorine
Cl

argon
Ar

Scale

(c)Formoststudents,itwillbeeasiertovisualizethetrendsfromawellmadegraphical
representationthantryingtopickoutthetrendsfromtheTable.Exactnumericalvalues
aremoreeasilyfoundfromtheTable.ItcouldalsobearguedthattheTablecouldhelp
facilitaterecognizingperiodicpatternsifthedatahadbeenseparatedorshadedby
period.
(d)Theatomicradiusforpotassiumwillbelargerthanthatofsodium,soapredictionof
approximately220pmisreasonable.Kryptonwillbelargerthanargon,butconsiderable
smallerthanpotassium.Apredictionofapproximately110pmisreasonable.These
predictionsmaybemadeeitherfromagraphorfromtheTableofData.
(e)TheactualradiusforKis227pm,andforKris112pm.Thepredictionsshould
matchthetruevaluesratherclosely,againshowingtheusefulnessofperiodictrends.

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4.3.

StructureofAtoms

Figure4.4showsthevaluesforthefirstionizationenergiesforelementswithatomic
numbers1through20.
(a) Howdoyoupredictthevalueforthesecondionizationenergyforhelium(lossofan
electronfromHe+(g))wouldcomparewithitsfirstionizationenergy?Writeequations
representingthefirstandsecondionizationstohelpexplainyourreasoning.Hint:Use
equation(4.1)asamodel.
(b) Howdoyoupredictthatthevaluesofthefirst,second,andthirdionizationenergies
forberylliumwouldcompare?Writeequationsrepresentingthefirst,secondandthird
ionizationstohelpexplainyourreasoning.
Answerto4.3:
(a)Theenergyrequiredtoremoveasecondelectronfromheliumshouldbe
considerablygreaterthanthatrequiredtoremovethefirstelectron.Heliumonly
hastwoelectronsperatom,soremovingthesecondelectronrequiresadding
enoughenergytopullthenegativelychargedelectronawayfromthetwo
positivelychargedprotonsinthenucleus.
Firstionizationenergy:
He(g)He+(g)+e
2372kJ.mol1
Secondionizationenergy:
He+(g)He2+(g)+e 7300kJ.mol1
(b)Thesecondionizationenergyforberylliumshouldbegreaterthanthefirst
becausetheelectronisbeingremovedfromthepositivelychargedion.Thethird
ionizationenergyshouldbemuchgreater,becausethiselectroniscomingfrom
theelectroncore,nottheoutervalenceelectrons.
Firstionizationenergy:
Secondionizationenergy:

Be(g)Be+(g)+e
Be+(g)Be2+(g)+e

900kJmol1
1760kJmol1

Thirdionizationenergy:Be2+(g)Be3+(g)+e 14850kJmol1
4.4.

Figure4.4showsthetrendinfirstionizationenergiesforthefirst20elements.Hereisan
alternaterepresentationoffirstionizationenergydata.

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Compareanddiscussthetwodifferentrepresentations,payingparticularattentionto:
(i) howwellthepatternsacrossperiodsarerepresented.
(ii) howwellthepatternswithinafamily(group)arerepresented.
(iii) howeasyitistodiscernashellstructureforatoms.
Answerto4.4:Figure4.4maybeamorefamiliarrepresentation,butthethree
dimensionalrepresentationhassomeaddedadvantages.Thisrepresentationshowsmain
groupelementsforsixperiods,notjustthefirstthree.Bothrepresentationsshowthe
changeinionizationenergywithineachperiodandgroup.Itmaybeeasiertoobservethe
apparentirregularitiesinthepatternwiththethreedimensionalgraph.Forexample,why
isthevaluefornitrogensomuchhigherthanexpectedwithinthesecondperiodand
withinthe5Agroup?Whydobothhydrogenandheliumhavesuchrelativelyhighvalues
offirstionizationenergiesrelativetothoseinGroup8A?Theserelationshipsarenotas
immediatelyobviousinthemorefamiliartwodimensionalrepresentation.

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4.5.

StructureofAtoms

Valuesforthesecondionizationenergiesofthefirsttwentyelementsarerepeatedhere
fromTable4.2.ThesearetheenergiesforreactionssuchasNa+(g)Na2+(g)+e(g).
SecondIonizationEnergy(IE2),kJmol1
Element
H
He
Li
Be
B
C
N

IE2

Element

IE2

Element

IE2

5248
7300
1757
2430
2350
2860

O
F
Ne
Na
Mg
Al
Si

3390
3370
3950
4560
1450
1820
1580

P
S
Cl
Ar
K
Ca

1904
2250
2297
2666
3052
1145

(a) Whyisnovaluegivenforthesecondionizationenergyofthehydrogenatom?
(b) Plotthesesecondionizationenergiesasafunctionofatomicnumber,aswasdone
forfirstionizationenergiesinFigure4.4.HowdoesyourplotcomparetoFigure4.4?
Howdoyouexplainthesimilarities?thedifferences?
Answer4.5:
(a)Thehydrogenatomhasonlyoneelectron,sothereisnotasecondonetolose.
(b)Theplotofthedatagivethisgraph:
8000
7000
6000
5000
4000
3000
2000
1000
0

10

atomicnumber

15

20

ComparisonofthisplotwithFigure4.4showsthattheshapeofthetwocurvesis
essentiallyidentical,exceptthatthisplotismovedoveroneatomicnumberhigherand
theenergiesonthisplotareagooddealhigher.Itlooksliketheionizationenergiesofthe

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mononegativeionsfromHe+throughCa+,followexactlythesamepatternasthefirst
ionizationenergiesforHthroughK.Eachioninthisseriesofionshasthesamenumber
electronsasthecorrespondingatomintheotherseries.Thatis,He+hasoneelectronand
HhasoneelectronandsoontoCa+andK,eachofwhichhas19electrons.Theshell
structureappliestoionsaswellasatomsanddependsonthenumberofelectrons
surroundingthenucleus.Thesecondionizationenergiesforanelementalatomareall
higherthanthefirst,becausetheelectronisbeingremovedfromapositiveionandis
heldmoretightly.(ComparewiththesolutiontoProblem4.3.)
4.6.

WEBChap4.ClickonthecircledPinthelefthandmenutoaccesstheinteractive
WEB
periodictable.Onthetabsatthetopofthewindow,clickonPlotData.
(a) Ontheplotofmolarmass(relativeatomicmass)asafunctionofatomicnumber,
canyoufindpairsofrelativeatomicmassesthatareoutoforder,thatis,decreaseas
theatomicnumberincreases?Checktheseoutontheperiodictableontheinsidefront
coverofthetexttoconfirmthattherelativeatomicmassesoftheseelementalpairsare
outoforder.
(b) Couldtheelementalpairsyoufoundinpart(a)havecausedproblemsforMendeleev
whenheconstructedhisperiodictable?Explaintheproblemshemighthaveencountered.
Isthereanyevidenceinhistable(showninthechapteropeningillustration)tosuggest
thathehadsuchproblems?
Answerto4.6:
(a)Threepairsthatareoutoforderandonepairthatareidenticalareshownonthis
screencapturefromtheWebResource.Themodernrelativeatomicmassesareshownfor
eachelement.(Otherpairsathigheratomicnumberarealsooutoforder,butinthese
cases,oneorbothoftheelementsdoesnotexistnaturally,soonlytheisotopesthathave
beenpreparedsyntheticallyareavailableandwedonotknowwhatanatural
distributionofisotopeswouldbe.)

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(b)SinceMendeleevorderedtheelementsbyrelativeatomicmass(ormolarmass),he
wouldhaveproblemswiththethreepairsthatareoutoforder,becausetheirchemical
propertieswouldnotfitinthefamilyinwhichtheirmasswouldhaveputthem.This
wasnotaproblemfortheArKpair,sinceAr(andtheothernoblegases)hadnotbeen
discoveredwhenMendeleevcreatedhisfirsttable.FortheCoNipair,notethat
Mendeleevassignedthemboththesamerelativeatomicmass,whichwasprobablythe
bestdataavailablein1869.FortheTeIpair,Mendeleevgivesthecorrectrelativeatomic
masses(heusesJ,theGermansymbolforiodine,sincehepublishedinaGerman
journal),butreversestheordergivenbytheatomicmass,inordertoputtheelementsin
thecorrectchemicalfamilies(iodinewiththeotherhalogens).Heindicateshisconcern
aboutthisbyplacingaquestionmarkafterthevalueofTe,presumablytoindicatethat
thisvaluemightbesuspect.

Section4.2.
AtomicEmissionandAbsorptionSpectra
4.7.

WhyisitnecessarytoheatthesodiumvaporsamplerepresentedinFigure4.6(b)?Hint:
Useareferencehandbooktofindthepropertiesofsodium.
Answerto4.7:
Sodiummetalisasolidatroomtemperature.Themetalmeltsat97.8Candboilsat
882.9C.Itisnotnecessarytoheatthesampletoitsboilingpointtodotheexperiment
representedinFigure4.6(b);avaporpressurelessthanoneatmosphereprovides
sufficientgaseousatomstoobservetheabsorptionspectrumshowninthefigure,sothe
sampleonlyneedstobeheatedtoafewhundreddegrees.

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4.8.

StructureofAtoms

Explainwhyatomsatthesurfaceofthesunemitlight,whereasatomsinalayerfurther
awayabsorblight.RelateyourexplanationtotheexperimentsrepresentedinFigure4.6.
Answerto4.8:
Atomsstronglyheatedatthesunssurface,liketheatomsinanelectricaldischargetube
inFigure4.6(a),aregivenagreatdealofenergythattheylosebyemittinglight.Atoms
furtherfromthesunarenotheatedstronglyenoughtomakethememit,buttheycan
absorblightenergyfromthesun,justasthesampleofatomsinFigure4.6(b)does.

Section4.3.
LightasaWave
4.9.

Sketchawaveandlabelordefine:
(a) wavelength
(b) amplitude
(c) node
(d) cycle
Answerto4.9:SeeFigure4.5.

4.10.

(a) AtitsclosestapproachtoEarth,Marsis56millionkmfromEarth.Howlongdoesit
takearadiomessagefromaspaceprobeonMarstoreachtheEarthwhenthetwoplanets
arethisdistanceapart?
(b) Doesyouranswerinpart(a)suggestproblemscontrollersonEarthmighthavein
maneuveringaremotecontrolledvehicle,Figure1.39,ontheMartiansurface?Explain.
Answerto4.10:(a)

time =

56

(b)Yes,buttherewouldbeadelayof187seconds.
4.11.

Calculatethewavelengthandidentifythetypeofradiationthathasafrequencyof:
(a) 101MHz
(b) 251015Hz
(c) 200GHz[1gigahertz(GHz)=109Hz]
Answerto4.11:
Foreachofthesequestionsyoucancalculatethewavelength()byusingtherelationship
betweenthefrequency(),andthespeedoflight(c)whichisc=.

(a) 3.00 (FMradio;VHFTV)

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(b) 1.2 10 m (ultraviolet)

3
(c) 1.5 10 m (microwave)
8

4.12.

Calculatethefrequencyandidentifythetypeofradiationthathasawavelengthof:
(a) 400nm
(b) 25km
(c) 4.5104m
Answerto4.12:
14
(a) 7.5 10 Hz(visiblelight)
(b) 1.2 10 4 Hz (radiowaves)
11
(c) 6.6 10 Hz(infrared)

4.13.

Awavehasawavelengthof0.34mandafrequencyof0.75s1.
(a) Whatisthespeedofthewave?
(b) Isthewaveelectromagneticradiation?Explain.
Answerto4.13:
(a)speed=0.255m/s(b)No,thespeediswaytoolowforelectromagneticradiation.

4.14.

Whatisthewavelengthofmicrowaveradiationwithafrequencyof1.1451010s1?
Note:Microwaveradiationhasfrequenciesintherange109to1012s1.
3.00 10 8 m/s
= 2.62 10 2 m
Answerto4.14:
1.145 1010 s 1

4.15.

Ultravioletvisible(UVVis)spectroscopyistypicallyusedtodetermineconcentrations
ofproteinsamples.Ifaproteinabsorbslightat280nm,whatfrequencydoesthis
correspondto?
15 1
Answerto4.15: 1.07 10 s

4.16.

Radioandtelevisionantennasaredesignedsothatthelengthofacrossbaris
approximatelyequaltothewavelengthofthesignalreceived.Ifyouknowthatan
antennareceivesasignalwithfrequencyof3102MHz,calculatethelengthofa
crossbarintheantenna.
Answerto4.16:Thelengthofthecrossbaris1m.Sincethelengthofacrossbaris
approximatelyequaltothewavelengthofthereceivingsignal,itisconsistentwiththe
observation.

4.17.

WEB
WEBChap4,Sect4.2.4.

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(a) Howisthecorrectsetofoscillatingarrowsrelatedtotherepresentationofthe
electromagneticwave?Beasspecificaspossibleinyourdescription.
(b) Howisthecorrectsetofoscillatingarrowsrelatedtothedescriptionof
electromagneticradiationgiveninthischapter?Explainclearly.
Answerto4.17:
Section4.4.
LightasaParticle:ThePhotoelectricEffect
4.18.

Explainhowthepredictionsofthewavetheoryoflightdifferedfromtheobserved
distributionofwavelengthsofemissionfromglowingbodies.
Answerto4.18:
Figure4.14showsthatthewavetheory(whichassociateswaveamplitudewithenergy)
predictsemissionthatismoreintensethanisobservedanddoesnotdropoffatshorter
wavelengths.

4.19.

(a) Explainhowthephotoelectriceffectwasevidencefortheparticulatenatureoflight.
(b) Explainwhythewavetheoryfailedtoexplainthephotoelectriceffect.
Answerto4.19:
(a)Theintensityoflightdidnotaffecttheelectronbeingejectedonlythewavelengthof
light.Thisindicatesthatthelightenergyisquantizedandnotcontinuous.
(b)Thewavetheorypredictedthat,ifthelightbeam,whichshinesonametalsurface,
wasbrightenough(hadalargeenoughamplitudeorintensity),anyfrequency
(wavelength)oflightcouldknockanelectronoutfromametalsurface.Theexperimental
resultshoweverdidnotsupportthisprediction,becauseelectronswereknockedoutof
themetalonlybyhighfrequencylight.

4.20.

ExplaintheroleEinstein'sexplanationofthephotoelectriceffectplayedinthe
developmentofourunderstandingofthedualnatureoflight.
Answerto4.20:
WhenEinsteinanalyzedtheexperimentaldataquantitatively,hefoundthatlightis
quantizedandcomesindiscreteenergypackets,E=h.Heusedthetermphotonto
describetheenergypacketsoflight.Photonsofhigherfrequencyradiationhavehigher
energies,andphotonsoflowerfrequencyradiationhavelowerenergy.Ifthephotonsof
theradiationhavelessenergythantheenergywhichisrequiredfortheelectronto
overcometheattractiveforces,thatholdelectronwithinmetal,theelectroncannotescape
fromthemetal.

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Chapter4
4.21.

StructureofAtoms

Classicalphysicsassumedthatatomsandmoleculescouldemitorabsorbanyarbitrary
amountofradiantenergy.However,Planckstatedthatatomsandmoleculescouldemit
orabsorbenergyonlyinquanta.Giveafewexamplesfromeverydaylifethatillustrate
theconceptofquantization.
Answerto4.21:
Someexamplesofquantizedmattermightbe:
(a) waterdelivereddropbydroptoaglass(adropinthisexamplerepresentsaquant).
(b) moneysystemwhichisbasedonaquantumofvaluecalledapenny.

(c)thepitchofapianocanbevariedonlyinsteps,thenotesonthepianoarequantized
4.22.

Whatistheenergyofaphotonwithafrequencyof1.255106s1?
Answerto4.22:
E = 6.626

4.23.

Theenergyofonephotonassociatedwithatypicalmicrowaveovenisapproximately
1.641024J.
(a) Whatisthefrequencyoftheradiationassociatedwithonephotonofthismicrowave
radiation?
(b) Howdoesthisfrequencycomparewiththefrequencyofgreenlightwitha
wavelengthof515nm?
(c) Whichhasmoreenergyaphotonofgreenlightoraphotonofmicrowave
energy?
Answerto4.23:
(a)Giventheenergyofthephoton,thisrelationshipcanbeusedtofindthe
frequency.

1.6

v

Tomakethecomparison,itisnecessarytocalculatethefrequencyofgreenlight.This
canbedoneusingtherelationship c .
c

3.00

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Thisfrequencyisapproximately105or100,000timeshigherthanthefrequency
ofamicrowave.Note:Thefrequencycouldalsobefoundfromtheenergyof
greenlightalreadycalculatedin3B.24CheckThisusingtherelationship E .
(c)Frequencyisdirectlyproportionaltoenergy,sothephotonsofgreenlighthaveabout
105or100,000timesmoreenergythanphotonsofmicrowaves.
4.24.

A500MHznuclearmagneticresonance(NMR)spectrometerisroutinelyusedtohelp
determinethestructuresofbiomolecules.
(a) Calculatethewavelength(inmeters)ofthisinstrument.
(b) UsingFigure4.13,determinetheregionoftheelectromagneticspectruminwhich
thisinstrumentoperates.
(c) Tohowmuchenergy,inkJmol1,does500MHzcorrespond?
Answerto4.24:
(a)=0.600m;
(b)Betweenradar,UHFTV,cellphonesandFMradio,VHFTV.

E = h

(c)

4.25.

Calculatetheenergyofonephotonandonemoleofphotonswith:
(a) afrequencyof101MHz.
(b) awavelengthof400nm.
Answerto4.25:

(a) E = h

6.692

(b)E=4.971019J/photon;E=2.99105Jmol1
4.26.

Astudentcalculatedthatthesmallestincrementofenergy(quantumofenergy)thatcan
beemittedfromayellowlightwithwavelengthof589nmis4.21019J.Verifythe
studentsanswer.
Answerto4.26:

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E=3.371019J.Thestudentdidnotcalculatethecorrectanswer.Accordingto
Planck'stheory,anobjectemittingradiationwithawavelengthof589nmcannotlose
energyexceptinmultiplesof3.371019J.Thestudent'sanswerisnotamultipleof3.37
1019J.
4.27.

InInvestigateThis4.29,youexploredtheeffectoflightonsilverchloride.Howcanthis
sameeffectbeusedtoproducethelensesforeyeglassesthatchangewiththelightlevel?
Hint:Thinkaboutreaction(4.7)inConsiderThis4.30.Youmaywanttoresearchyour
predictioninprintorwebbasedreferencestoconfirmorrefuteyoursuggestion.
Answerto4.27:
Thelensesincontinuousphotograyorphotosuneyeglassescontainsilver
chloridecrystalsevenspacedinaglassorhighlycrystallineplasticmatrix.As
lighthitsthecrystal,theelectronistransferredfromsilveriontochlorideion,
formingtinyspecksofsilvermetalthatcausethelenstodarken.Thechlorine
atomisnotfreetojoinotherchlorineatomsandescapeasgaseouschlorine
becauseitisstilllockedwithinthecrystallinematrix.Thisreactionisreversible,
sointheabsenceoflight,silvermetalandchlorineatomsrejointoformsilver
chloridecrystals,whichdonotblocklight.Thelensregainsitsformertransparent
appearance.

Ag

4.28.

Cl

lightenergy
(s)

Ag (s)
silvermetal

Cl

(aq)
chlorineatom

BasedontheresultsofInvestigateThis4.29,whydoesaphotographicdarkroomusea
redsafelight?
Answerto4.28:AredsafelightwillnotcauseAg+toreact,formingAgmetal.Blue,
greenandvisiblelightswillasdemonstratedinInvestigateThis4.20.

4.29.

InaSciencearticle,scientistsreportedvariationsintheconcentrationsofthoriumand
potassiumonthemoonssurface.Theyusedgammarayspectrometrythatrecordedthe
gammarayemissionfrompotassiumatapproximately1.4MeVandfromthoriumat
approximately2.6MeV.Calculatethefrequenciesofthesetwogammarayemissions.
Calculatethewavelengthsofthesetwogammarayemissions.Note:1MeV=1106eV
(electronvolt)and1eV=1.6021019J.

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Answerto4.29:
Forpotassium,1.4 MeV

E 2.243 10 13 J
20 1
=
34 = 3.385 10 s
h 6.626 10

c 3.00 108 m/s

13
=
m
20 1 = 8.86 10
3.385 10 s

Forthorium, 6.286 10 s and = 4.77 10 m

20 1

13

Section4.5.
TheQuantumModelofAtoms
4.30.

(a) Explainwhathappenstoelectronswhenanatomicemissionspectrumisproduced.
(b) Explainwhathappenstoelectronswhenanatomicabsorptionspectrumisproduced.
(c) Howarethesetwotypesofspectrarelated?
Answerto4.30:
(a) Thespectrumoftheradiationemittedbyasubstanceiscalledanemissionspectrum.
Whenthisemittedlightisdispersedbyaprism,onlycertainwavelengthsarefound
tobepresent.Thesewavelengthscorrespondtothedifferenceinenergybetweenthe
energylevels.
(b) Theemissionspectrumconsistsofseveralsharplines.Whencontinuous
electromagneticradiation,suchasthatfromalightbulb,passesthroughasubstance,
certainwavelengthsmaybeabsorbed.Thespectrumoftheradiationthatpasses
throughiscalledanabsorptionspectrum.Theabsorptionspectrumconsistsofwhat
lookslikeacontinuousspectruminterruptedbyblacklines.
(c) Forthesameatom,absorptionspectrumiscomplementarytoitsemissionspectrum
(missinglinesinanabsorptionspectrumshowintheemissionspectrum),becausein
theemissionandabsorptionprocesses,lightofexactlythesamewavelengthis
emittedorabsorbed.

4.31.

Choosethebestphrasetocompletethissentence.
Theintensityofaspectrallineinanatomicemissionspectrumcanbedirectlyrelatedto:
(i) thenumberofenergylevelsinvolvedinthetransitionthatgivesrisetotheline.

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(ii) thespeedwithwhichanelectronundergoesatransitionfromoneenergylevelto
another.
(iii) thenumberofelectronsundergoingthetransitionthatgivesrisetotheline.
Answerto4.31:Thecorrectansweris(i).Themoreelectronsthatundergothe
transition,themoreintensethelineis.
4.32.

Choosethebestphrasetocompletethissentence.
Whenelectronsareexcitedfromagroundstatetoanexcitedstate,
(i) lightisemitted.
(ii) heatisreleased.
(iii) energyisabsorbed.
(iv) anemissionspectrumresults.
Answerto4.32:Thecorrectansweris(iii).Theexcitedstateisastatewithhigher
energy.Itneedstoabsorbelectronsinordertoreachthisstate.

4.33.

Neonlightsglowbecauseanelectricaldischargeispassedthroughalowpressureofneon
intheglasstubing.Inanexperiment,emissionfromaneonlightwasdispersedbya
prismtoformaspectrum.Thespectrumthatwasformedwasnotcontinuousbut
consistedofseveralsharplines.Explainwhyalinespectrumwasproduced.
Answerto4.33:Thelightemittedbyneongasisthefamiliarredorangeglowofmany
neonlights.Thelampemitslightwhenhighenergyelectronsreturntolowerenergy
levels.Theelectronsinneonatomsareexcitedinanelectricaldischarge.Whenthis
emittedlightisdispersedbyaprism,onlycertainwavelengtharefoundtobepresent,
whichcorrespondtothedifferenceinenergybetweentheenergylevels.Theseenergy
changesarequantized.Thismeansthatonlycertainfrequenciesoflightareemitted,
thereforethespectrumisnotcontinuousbutconsistsofseveralsharplines.

4.34.

Whenenergyisaddedtoanelectronitmaybecomeexcitedandmovefartherfromthe
nucleus.Thatenergyisreleasedwhentheelectronreturnstoitsoriginalenergy.What
happenswhenyouaddsomuchenergythattheelectroncompletelyleavestheatom?
Answerto4.34:Itbecomesanionsincetheelectroniscompletelyremovedfromthe
atom.

4.35.

Todistinguishbetweenasolutionofsodiumionsandasolutionofpotassiumions,a
simpleflameemissiontestcanbeused.Adropofthesolutiontobetestedisheldin
burnerflameandthecoloroftheflameisobserved.(SeeProblem3.4attheendof

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Chapter3.)Asolutionofsodiumionsgivesabrightyellowflame,whileasolutionof
potassiumionsgivesavioletflame.
(a) Towhatapproximatewavelengthsintheelectromagneticspectrumdothese
emissionscorrespond?
(b) How,ifatall,arethesedatarelatedtoFigure4.6?Explain.
(c) Whichionsemissionhasthehigherenergy?Explainyouranswer.
Answerto4.35:
(a)TheyellowflameofNa+correspondsto610nm(6.17X107m)whilethe
violetflameofpotassiumcorrespondsto380nm(3.80X107m).
(c)Potassiumhasthehigherenergy.Sincewavelengthisinverselyproportionalto
energy,alowerwavelengthcorrespondstoahigherenergy.
4.36.

Theemissionspectrumofmercurycontainssixwavelengthsinthevisiblerange:405,
408,436,546,577,and579nm.
(a) Towhatcolordoeseachofthesewavelengthscorrespond?
(b) Whichwavelengthcorrespondstothelargestdifferenceinenergybetweenthe
atomicstatesresponsiblefortheemission?
(c) Whichwavelengthcorrespondstothesmallestdifference?
Answerto4.36:(a)Blueviolettoblue:405nm,406nm,436nm;Green:546
nm;Yellowgreen:577nm,579nm.
(b)405nm
(c)579nm

4.37.

Howdothelinespectraofhydrogen,helium,mercury,andneonsupporttheideathatthe
energyofelectronsisquantized?
Answerto4.37:Therewereonlyafewlinesobserved.Therefore,onlycertainenergies
musthavebeenavailablefortheexcitedelectrons.

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4.38.

StructureofAtoms

Forthefollowingelectrontransitions(betweentheenergylevelson
thisenergyleveldiagram)saywhetherthetransitionwouldresultin
absorptionoremissionofaphoton,andranktherelative
wavelengthsofthephotonsabsorbedoremittedfromshortestto
longest.
(a) E1E2
(b) E2E1
(c) E4E3
(d) E4E5
(e) E6E2
(f) E6E1
Answerto4.38:E1E2absorption;E2E1emission;E4E3emission;E4E5
absorption;E6E2emission.

Section4.6.
IfaWaveCanBeaParticle,CanaParticleBeaWave?
4.39.

SincedeBroglie'shypothesisappliestoallmatter,doesanyobjectofagivenmassand
velocitygiverisetoawave?Isitpossibletomeasurethewavelengthsofanymoving
object?
Answerto4.39:Intheory,anymovingobjectgivesrisetoacharacteristicmatterwave
anddeBrogliesequationcanbeappliedtobothmacroscopicandforsubmicroscopic
objects.However,thewavepropertiesbecomeobservableonlyforsubmicroscopic
objects.Thewavelengthsoflargemovingobjects,(likevehiclesorballs),aresosmall
thattheycannotbedetectedbyanyexistingmeasuringdevice.

4.40.

Calculatethewavelengthofabaseballofmass0.5kgtravelingat30ms1.Whydoesthe
wavelengthofmacroscopicobjectsnotaffectthebehavioroftheobject?
Answerto4.40:UsethedeBrogliewavelengthequationtocalculatethewavelength.
=4.42X1035m.Thewavelengthissoshortthatitdoesnotaffectthebehaviorofthe
baseball.

4.41.

Calculatethewavelengthofanelectronofmass9.11031kgtravelingat1.5106ms1.
Isthiswavelengthsignificantrelativetothesizeofanatom?
Answerto4.41:UsethedeBrogliewavelengthequationtocalculatethewavelength.
=4.40X1010m.Thiswavelengthisaboutthesizeofanatomsoitissignificant.

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4.42.

StructureofAtoms

Explainwhythedistinctionbetweenawaveandaparticleismeaningfulinthe
macroscopicworldandwhythedistinctionbecomesblurredattheatomiclevel.Hint:
Considerthewavelengthsofmacroscopicandatomiclevelparticles.
Answerto4.42:Inthemacroscopicworld,particleshaveenoughmasssothattheirwave
characteristics,althoughalwayspresent,arenotsignificantandcannotbeeasily
observed.Attheatomiclevel,bothcharacteristicsofparticleswithverysmallmassescan
beobservedandareimportantinunderstandingtheinteractionswithmatter.

4.43.

(a)WhatisthedeBrogliewavelengthofanalphaparticlethatistravelingatavelocityof
1.5107ms1?Themassofanalphaparticleis6.61024g.
(b) Inwhatregionoftheelectromagneticspectrumdoesthewavelengthofthisalpha
particlefall?
Answerto4.43:
(a)ThedeBrogliewavelengthcanbefoundbyusingtherelationship

h
.
m u

6.626 1034 J s
1kg
(6.6 1024 g 3 )(1.5 107 m s 1 )
10 g

6.69 10 15 m

(b)Thisisanextremelyshortwavelength,evenbeyondwavelengthsassociatedwith
highlyenergeticgammarays.
Section4.7.
TheWaveModelofElectronsinAtoms
4.44.

Thesoundsyouhearwhenmusicalinstrumentsareplayedarecreatedbystandingwaves
intheinstruments.Theairmoleculesincontactwiththeinstrumentaresetinmotionby
thestandingwavesandformtravelingwaves.Thetravelingwavesreachus,setour
eardrumsvibrating,andourbrainsinterpretthemotionasmusic.Wehaveseenthat
standingwavesonaguitarstringareresponsibleforthesoundproducedbytheguitar.
Whatstandingwavesareresponsibleforthesoundproducedbytheseothermusical
instruments?Explainyouranswers.
(a) drums
(b) flutes
(c) tuningforks
Answerto4.44:

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(a)Thedrumheadondrumsissetinmotionbythedrumstick(s)andtwodimensional
standingwavesaresetuponthehead.
(b)Asairisblownacrossthemouthpiecebytheflutist,standingwavesaresetupinside
thetube.Thewavelengthofthesewavesiscontrolledbythelengthofthetubethatis
closed,whichtheplayercontrolsbyopeningandclosingthevalvesontheinstrument.
Youcangetthesameeffectbyblowingacrossthetopofabottlewithanarrowopening,
suchasasoftdrinkbottle.Thefrequencyofthesoundyouproducecanbechangedby
changingtheamountofliquidinthebottle(thuschangingthesizeoftheaircolumnyou
aresettinginmotion.
(c)Whenatuningforkisstruck,itslegsbegintovibrate.Thestandingwavesaresetup
inthelegs,verymuchlikewavesonastring,butabitmorecomplicatedbecausethefork
legsarethickerandonlyoneendisfixed.Thepitchoftheforkdependsuponitsvarious
dimensions(length,crosssectionofthelegs,etc.)
4.45.

Whatcontributionsdidthesescientistsmaketoourunderstandingofatomicand
electronicstructure?
(a) Bohr
(b) Heisenberg
(c) Einstein
(d) deBroglie
Answerto4.45:
Answerto4.1: (a)Bohr:developedthetheoryofquantizedelectronenergy
levels.
(b)Heisenberg:developedtheUncertaintyTheorywhichstatesthatasyouto
verysmall(atomic)scaleyoucannotaccuratelyprovideboththeenergyand
positionoftheelectron.
(c)Eistein:usedquantizationofelectromagneticradiationtounderstandthe
photelectriceffect.
(d)DeBroglie:developedtheorytoexplainwave/particlenatureofmatter.

4.46.

WhatdoestheHeisenberguncertaintyprinciplestateaboutwhatwecanandcannotknow
aboutanelectronsbehavior?
Answerto4.46:

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Themoreyouknowaboutthelocationofanelectron,thelessyouknowaboutits
momentumandvisaversa.
4.47.

WhydidthedeBrogliewavemodelandHeisenberg'suncertaintyprinciplegiverisetoa
newapproachinwhichitwasnotappropriatetoimagineelectronsmovinginwell
definedorbitsaboutthenucleus?
Answerto4.47:
Bohrthoughtthattheelectronsorbitthenucleusinawelldefinedpath,andinthis
approachitwouldbepossibletodeterminepreciselyboththepositionoftheelectron
(fromtheradiusoftheorbit)anditsmomentum(fromitskineticenergy)atthesame
time.However,accordingtodeBrogliewavemodelelectronexhibitspropertiesofa
waveaswellasofaparticle.Sinceawaveextendsinspaceitisnotpossibletodetermine
exactlywheretheelectronislocatedataspecifictimewhichisconsistentwith
Heisenberguncertaintyprinciple.

4.48.

Whyisitthatwecancalculateexactlythepositionandthemomentumofarollingball
butwecannotcalculatethesameforanelectronthatexhibitswaveproperties?
Answerto4.48:
Thewavelikepropertyoftherollingball,forexample,isnotobservablesowecaneasily
measurethepositionandmomentum(i.e.velocityandamass)ofthisball.Wecannot
measurethepositionandmomentumofverysmallparticleslikeelectronsthatshow
wavelikeproperties.

Section4.8.
EnergiesofElectronsinAtoms:WhyAtomsDontCollapse
4.49.

Discussthefactorsthataffectthesizeofahydrogenatomwithregardtothekineticand
potentialenergyoftheelectronwaveandthenucleus.
Answerto4.49:
Astheradiusoftheelectroncloudincreasesthekineticenergyoftheelectronincreases,
raisingtheenergyofthesystem.Atthesametime,thepotentialenergyofthesystem
decreasesasthedistancebetweenthenucleusandtheelectronclouddecreases,lowering
theenergyofthesystem.Theminumumenergyofthesystemisaround0.08nm,the
radiusofthehydrogenatom.

4.50.

IfparticleAhasamassof1.561025kgandparticleBhasamassof4.251024kg,
whichparticlehasthegreaterkineticenergyiftheyarebothtravelingatavelocityof
3.15105ms1?Explainyourreasoning.

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Answerto4.50:
ParticleB.Sincetheparticlesaretravelingatthesamevelocity,ParticleBwillhavea
greaterkineticenergybecauseithasmoremass.
4.51.

Howisthepotentialenergyofanelectronwaverelatedtoitsdistancefromthenucleus?
Answerto4.51:
Thegreaterthedistance,thelowerthepotentialenergy.

4.52.

InFigure4.27,whyisthepotentialenergynegativeandthekineticenergypositive?
Answerto4.52:Thepotentialenergyisnegativebecauseyoumultiplethe1chargeby
the+1chargeandgetanegativenumber.Thekineticenergyispositivebecauseallthe
variablesthatneededtocalculatekineticenergyarepositive.

4.53.

WEBChap4,Sect4.7.1.Whatisthesignificanceoftheredcircleonthisinteractive
WEB
page?Explainhowitisrelatedtotheenergiesthatarerepresentedonthegraph.
Answerto4.53:

Section4.9.
MultielectronAtoms:ElectronSpin
4.54.

Explainwhichpropertyofanelectronisresponsibleforitsinteractionwithamagnetic
field.
Answerto4.54:Theelectronspinisthepropertyoftheelectronthatmakesitbehaveas
thoughitwasatinymagnet.Theelectronspinisresponsibleforelectronsinteracting
withmagneticfields.

4.55.

ExamineFigure4.28.Explainwhythemagnetdoesnotseemtoaffectheliumatomsbut
doesaffectlithiumatoms.
Answerto4.55:Thespinsofthetwoelectronsinheliumareoppositesotheycancel
eachotherout.Thespinoftheextraandunpairedelectroninlithiumisdrawntowardthe
magnet.

4.56.

Whatexperimentmightyouperformtotellwhetheratomsofanelementhaveodd
numbersofelectrons?
Answerto4.56:Passastreamofatomsoftheelementthroughamagneticfield.Those
elementswithunpairedelectronswillsplitintotwobeamsasthespinupandspindown
electronsareaffectedbythemagneticfield,asshowninFigure4.29.

4.57.

Experimentsonnitrogenatomsshowthatthegroundstateatomhasthreeelectronswith
unpairedspins.

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(a) Howmanyofthenitrogenatomselectronsarespinpaired?Explainhowyouget
youranswer.
(b) Whatdoestheelectronspindatatellyouabouttheorbitaldescriptionsofthethree
electronswithunpairedspins?Explain.
Answerto4.57:
Section4.10.PeriodicityandElectronShells
4.58.

DefinethePauliexclusionprincipleandhowitcanbeusedtoexplaintheverylow
ionizationenergyofthelithiumatom.
Answerto4.58:Pauliexclusionprinciplestatesthatonlytwoelectronsofoppositespin
canoccupyexactlythesameregionofspace(orbital)nearatomicnucleus.Forlithium,
thetwolowestenergyelectronswithpairedspinsoccupytheorbitalnexttonucleus.The
thirdelectron,(whichhasthesamespinasoneortheotherofthetwoelectrons),cannot
sharethesamespacewiththefirsttwoelectrons.Ithastobeatalargerorbitalfromthe
nucleus,andthereforehaslowerionizationenergythantwofirstelectrons.

4.59.

Whyisthesecondionizationenergyalwaysgreaterthanthefirstionizationenergyforan
atom?
Answerto4.59:Afterthefirstelectronisremoved,therearemoreprotonsthan
electrons.Thus,thereisagreatereffectivenuclearattractionfortheremainingelectrons.

4.60.

(a)Whatisthesameforeachoftheseionsandatom:Na+,Ne,F,andO2?
(b) Whichofthespeciesinpart(a)hasthehighestionizationenergy?Explainyour
answer.
Answerto4.60:Na+hasthemostprotonssoithasthehighesteffectivenuclearcharge.
SincealltheionsinthisexamplehavethesamenumberofelectronsasNe,Na+willhave
thehighestionizationenergy.

4.61.

Discussthefollowingpropertiesandtheirtrendsinrelationshiptotheperiodictable.
(a) ionizationenergy
(b) atomicradius
(c) electronegativity
Answerto4.61:
Answerto4.2: Allthesepropertiesdependontheeffectivenuclearcharge
whichincreasesasyougoacrossarowoftheperiodictable.Thus,electronsare
morestronglyattractedtothenucleus.(a)Theionizationenergywillincrease

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makingithardertoremoveelectronsthataremorestronglyattractedtothe
nucleus.(b)Theatomicradiiwilldecreaseasyougoacrossarowofthe
periodictable.Electronsaremorestronglyattractedtothenucleus,movingin
closertothenucleus.(c)Theelectronegativitywillincreaseasyougoacrossa
rowbecausetheeffectivenuclearchargeishigher,causingelementstoattract
electrons.
4.62.

Whatisthetrendinionizationenergyasyougofromlefttorightinarowontheperiodic
table?Howistheshellmodelforatomsrelatedtothistrend?
Answerto4.62:increases

4.63.

Whatisthetrendinionizationenergyasyougofromtoptobottominagrouponthe
periodictable?Howistheshellmodelforatomsrelatedtothistrend?
Answerto4.63:decreases

4.64.

Howmanyvalenceelectronsdoeseachoftheseelementshave?
(a) oxygen
(b) sodium
(c) chlorine
(d) argon
Answerto4.64:(a)6(b)1(c)7(d)8

4.65.

Theempiricalformulasofthesimplesthydrides(binarycompoundswithhydrogen)of
thesecondperiodelementsaregiveninthistable:
element

Li

Be

Ne

hydride

LiH

BeH2

BH3

CH4

NH3

OH2

FH

none

(a) Describeanypatternyouseeinthesedata.
(b) Doesthehydrideofhydrogen,H2,fitthepattern(s)youdescribedinpart(a).
(c) Whatdoyoupredictfortheempiricalformulasofthehydridesofaluminum,silicon,
andphosphorus?Explainthebasisofyourpredictionand,ifpossible,relateitto
periodicityandtheshellmodeloftheatom.
Answerto4.65:
4.66.

WEBChap4.ClickonthecircledPinthelefthandmenutoaccesstheinteractive
WEB
periodictable.Onthetabsatthetopofthewindow,clickonPlotData.

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(a) ClickonthePropertiesbuttonandthenon1stIonizationEnergytoselectthis
propertytobeplotted.ComparetheplotwithFigures4.4and4.30tobesureyouidentify
thesametrendsinallofthem.Whataresomeofthese?
(b) ClickonthePropertiesbuttonandthenon2ndIonizationEnergytoselectthis
propertytobeplotted.ComparetheplotwiththeoneyoumadeinProblem4.5.Arethe
conclusionsyoudrewfromthefirst20elementsinProblem4.5validfortherestofthe
elementsaswell?Explainwhyorwhynot.
(c) Selectthe3rdIonizationEnergytobeplotted.Howdoesthisplotcompareto
thoseforthefirstandsecondionizationenergies?Howdoyouexplainthesimilarities?
thedifferences?
4.67.

WEBChap4.ClickonthecircledPinthelefthandmenutoaccesstheinteractive
WEB
periodictable.Onthetabsatthetopofthewindow,clickonPlotData.Writea
problemaboutperiodicitythatisbasedonanalysisofoneormoreofthedataplots
accessiblefromthiswindow.Haveaclassmatesolveyourproblem.

4.68.

Onekindofperiodictableisathreedimensionalmodel
ofeightstacked,roundwoodendiscswiththesymbols
fortheelementsonthediscs.Shownherearethe
symbolsonthesecondtierofdiscs.Howdoesthis
periodictablerepresenttheelectronshellmodel?Do
youseeanyproblemswiththisrepresentation
comparedtoFigure4.31?Explainyourresponses.
Answerto4.68:Eachstackrepresentsaperiodorrowintheelectronshellmodel.Yes,
thereisaprobleminthatitdoesnotshowthefamilieslikeFigure4.32.
Note:The"PeriodicRoundtable"isan"invention"ofGaryKatz(PhDbiochemist),P.O.
Box156,Cabot,VT05647.Hesellsitinahardwoodversionforabout$50.Ithasbeen
reviewedintheJournalofChemicalEducation,2000,77(2),164,byGlenRogers,from
AlleghenyCollege.

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4.69.

StructureofAtoms

Twoviewsofathreedimensionalversionoftheperiodictableareshownhere(andwith
otherviewsinthechapteropening
illustration).
(a) Whatpartsofthistable
correspondtoaconventionaltable,
asontheinsidefrontcoverofthis
book?Explainthecorrespondences.

(b) Whatpartsofthistable

correspondtothespiraltable,Figure4.34?Explainthecorrespondences.
Answerto4.69:
Section4.11.WaveEquationsandAtomicOrbitals
4.70.

AnswereachofthefollowingwithTRUEorFALSE.Ifastatementisfalsecorrectit.
(a) TheSchrdingerwaveequationrelatesthewavepropertiesoftheelectrontoits
kineticenergy.
(b) Thewavefunction()isamathematicaldescriptionofanallowedenergystate
(orbital)foranelectron.
(c) Thewavefunction()isproportionaltotheprobabilityoffindingtheelectronina
givenlocationnearthenucleus.
(d) Orbitalswiththesameenergyarecalleddegenerate.
(e) Orbitalscanbethoughtofasaboxesintowhichelectronscanbeplaced.
(f) Eachcalculatedenergylevelcorrespondstoaspatialprobabilitydistributionforthe
electron.
Answerto4.70:
(a)False.Schrdingerwaveequationrelatesthewavepropertiesofelectronto
itstotalenergy,whichisasumofkineticandpotentialenergy.
(b)True.
(c)False.Thesquareofwavefunction(2)isproportionaltoprobabilityof
findingtheelectroningivenlocationaroundthenucleus.
(d)True.

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(e)False.Orbitalsdescribecalculatedenergystatesofanelectronsand
correspondingspatialdistribution.Orbitalsdonotdescribethedefinedspace
aroundthenucleuswhereelectronscanbefound.
(f)True.
4.71.

Verifythegroundstateelectronconfigurationsfortheelementslistedbelow.Forthe
configurationswhichareincorrect,explainwhatmistakeshavebeenmadeandwritethe
correctelectronconfigurations.
(a) Al 1s22s22p43s23p3
(b) P

1s22s22p63s23p2

(c) B 1s22s02p3
Answerto4.71:(a)2porbitalisnotfullyfilled.Thegroundstateconfiguration
forAlis1s22s22p63s23p1.
(b)ThisconfigurationisnotcorrectforPsinceitshowsithasonly14electrons.
Phosphorushas15electronsanditsgroundstateconfigurationis1s22s22p63s23p3.
(c)ThisisnotagroundstateconfigurationforBbecauseorbitalwithlowerenergy2sis
empty.Thecorrectconfigurationis1s22s22p1.
4.72.

Howmanyvalenceelectronsarelocatedinansorbitalineachofthefollowingelements?
(a) potassium
(b) fluorine
(c) magnesium
(d) boron
Answerto4.72:(a)1(b)2(c)2(d)2

4.73.

Howmanyvalenceelectronsarelocatedinaporbitalineachofthefollowingelements?
(a) phosphorus
(b) aluminum
(c) lithium
(d) bromine
(e) sulfur
Answerto4.73:(a)3(b)1

4.74.

(c)0 (d)5 (e)4

AtomsA,B,andChavetheelectronconfigurationsgivenbelow.Whichatomhasthe
largestthirdionizationenergy?Explainyouranswer.

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A=1s22s22p63s2

B=1s22s22p63s23p4

C=1s22s22p63s23p6

Answerto4.74:Awillhavethelargestthirdionizationenergy.Toremoveathird
electron,youwillneedtoremoveanelectronfromacompleteoctet,requiringthemost
energyofthethreeelectronconfigurations.
4.75.

UsingFigure4.37asatemplateandWorkedExample4.60asaguide,drawelectron
energydiagramsforthesulfuratomandthesulfideion.
Answerto4.75:

energy

ElectronenergydiagramfortheSulfurAtom

energy

ElectronenergydiagramfortheSulfideIon

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4.76.

StructureofAtoms

UsingFigure4.37asatemplateandWorkedExample4.60asaguide,drawelectron
energydiagramsforLiandNaatoms.
Answerto4.76:

energy

ElectronenergydiagramfortheLithiumAtom

energy

ElectronenergydiagramfortheSodiumAtom
4.77.

(a) WhatdoestheseriesofatomsfromHthroughArhaveincommonwiththeseriesof
monocationsHe+throughK+andtheseriesofdicationsLi2+throughCa2+?Explain.
(b) Howdoesyouranswerinpart(a)relatetoyourresultsandanswerstoProblems4.5
and4.66?Explain.
Answerto4.77:

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4.78.

StructureofAtoms

WEBChap4.ClickonthecircledPinthelefthandmenutoaccesstheinteractive
WEB
periodictable.Onthetabsatthetopofthewindow,clickonElectronConfiguration.
(a) HowdoesthegraphicintheelectronconfigurationwindowcomparetoFigure4.37?
Whatdoestheverticaldirectiononthegraphicrepresent?Explain.
(b) Movethecursorovertheblankperiodictableuntilthepointerisonlithium.Clickto
selectlithiumanddescribewhathappens.Howdoestheresultcomparetothegraphicsin
WorkedExample4.60?Explain.
(c) UsetheelectronconfigurationwindowtocomparewithyourresultsfromConsider
This4.62(a).Howdotheycompare?

4.79.

WEBChap4.ClickonthecircledPinthelefthandmenutoaccesstheinteractive
WEB
periodictable.Onthetabsatthetopofthewindow,clickonElectronConfiguration.
Theenergylevelsrepresentedintheelectronconfigurationwindow(asrowsofboxes)
areenoughtodescribethegroundstateelectronconfigurationsofalltheknownelements.
(a) Examinetheelectronconfigurationsofthefirstseriesoftransitionmetals,Sc
throughZn.Whatconclusion(s)canyoudrawabouttherelativeenergiesof4sand3d
electrons?Explainhowyoureachyourconclusion(s).
(b) Howaretheelectronconfigurationsandthespinsoftheelectronsforthefirstseries
oftransitionmetalsrelatedtotheruleyoufoundinConsiderThis4.62?Explainyour
reasoningand,ifnecessary,suggesthowtomodifyyourruletomakeitmoregeneral,
nowthatyouhavemoredata.
(c) Doelementsinthesecondtransitionmetalseries,YthroughCd,followthesame
electronconfigurationandelectronspinpatternasthefirstseries?Ifso,isthiswhatyou
expected?Explain.Ifnot,explainwhatfactor(s)mightcausedifferences.

Section4.13.EXTENSIONEnergiesofaSphericalElectronWave
4.80.

(a) AtwhatvalueofRdoesthetotalenergycurveinFigure4.27reachaminimum?
(b) Attheminimuminthetotalenergy,whatistherelationshipofthekineticenergyto
thepotentialenergyoftheprotonelectronwavesystem?Showyourwork.Hint:Usethe
valueofRyougotinpart(a)inequations(4.29)and(4.30).Assumethatthe
proportionalityisthesameinbothcasesandlettheproportionalityconstantbeH.

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(c) Expressthevalueofthetotalenergyatitsminimumfortheprotonelectronwave
systemasafunctionofHfrompart(b).Usetheionizationenergyforthehydrogenatom
todeterminethevalueofHinkJmol1.
Answerto4.80:
4.81.

(a) ForoneelectronionssuchasHe+andLi2+,youcanusethesameanalysisofthe
energiesasweusedforthehydrogenatom,withtheexceptionthatyoumustaccountfor
thehighernuclearcharge.Thepotentialenergy,equation(4.16),dependsonthenuclear
charge.Writeequation(4.16)foraoneelectronionwhichhasanuclearcharge+Z.
(b) Whatisthepotentialenergyofasphericalelectronwaveattractedtothenucleusin
part(a)?WritethispotentialenergyasafunctionofR,theradiusofthewave,H,the
proportionalityconstantfromProblem4.80(b),andZ.
(c) Whatisthetotalenergyofaoneelectronionwithanuclearcharge+Z?Writethe
energyasafunctionofR,H,andZ.Hint:Thekineticenergyoftheelectronwavedoes
notdependonthenuclearcharge.
(d) FindthevalueofRthatmakesthetotalenergyinpart(c)aminimum.Hint:There
areatleastthreewaystodothisproblem.(i)Ifyouarefamiliarwithcalculus,youcan
takethederivativeofEwithrespecttoR,dE/dR,setthederivativeequaltozero,and
solveforR.(ii)Useagraphingcalculatororcomputergraphingprogramtographthe
totalenergyfunctionandfindtheminimumbytracingthecurve.(iii)Assume(correctly)
thattherelationshipbetweenthekineticandpotentialenergiesattheenergyminimum,
whichyoufoundinProblem4.80,isthesameforalloneelectronatomsandions.Use
thisrelationshipwithRasanunknownandsolveforR.
(e) Usingyourresultfrompart(b),writetheminimumforthetotalenergyofaone
electronionasafunctionofHandZ.Useyourequationtopredicttheionizationenergies
forHe+,Li2+,andB4+.Howdoyourpredictionscomparewiththeexperimentalvaluesin
Table4.2?Canyoupredictothervaluesinthetable?Explain.
Answerto4.81:

GeneralProblems
4.82.

Thisimageofawhitebloodcellwasmadebyascanningelectron
microscope(SEM).Consultprintorwebbasedresourcestofind
outhowanelectronmicroscopediffersfromthetraditionallight
basedmicroscopeyouhaveprobablyusedinabiologyclass.

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4.83.

StructureofAtoms

Einsteinsrelativitytheoryshowsthattheeffectivemassofamovingparticle,mmoving,is
relatedtoitsrestmass,mrest,itsvelocity,u,andthespeedoflight,c,bythisequation:
m rest

mmoving=
1 u c
(a) Whatistheeffectivemassofa145gbaseballthrownat44ms1?Willabatterhave
tobeconcernedaboutrelativisticeffectsinthepitchedball?Explain.
(b) WhatistheeffectivemassofthemovingalphaparticleinProblem4.43(a)?How
doesthisresultaffectyouranswertoProblem4.43(b)?Explain.Hint:Usetheeffective
massinthedeBroglieequation.
(c) Whataretheeffectivemassandthewavelengthofanelectronmovingat50%the
speedoflight?
Answerto4.83:

4.84.

Particleacceleratorscanaccelerateprotons,electrons,andotherchargedparticlesto
extremelyhighenergies.Thesehighenergyparticlesaresometimesfusedwithlighter
elements,producingsyntheticheavierelements.
(a) Calculatethewavelength(inmeters)ofaprotonthathasbeenacceleratedto50%
thespeedoflight.Hint:SeeProblem4.83.
(b) Amoleofelectronsisacceleratedto90%thespeedoflight.Whatkineticenergy(in
kJmol1)dotheseelectronshave?Whatisthekineticenergyofasingleaccelerated
electron?Hint:SeeProblem4.83.
Answerto4.84:

4.85.

WEBChap4.ClickonthecircledPinthelefthandmenutoaccesstheinteractive
WEB
periodictable.Onthetabsatthetopofthewindow,clickonElectronConfiguration.
Examinetherepresentationoftheperiodictableatthebottomoftheelectron
configurationwindow.
(a) Explaintherelationshipofthisperiodictabletotheoneontheinsidefrontcoverof
thisbook.
(b) ExplaintherelationshipofthisperiodictabletothespiraltableshowninFigure
4.34.Howarecorrespondingpartsoftheatomicshellstructurerepresentedinthetwo
tables?
(c) Explaintherelationshipofthisperiodictabletothethreedimensionaltableshownin
Problem4.69andthechapteropeningillustration.Howarecorrespondingpartsofthe
atomicshellstructurerepresentedinthetwotables?

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