Chemistry101

Chapter8

ELECTRONCONFIGURATIONANDTHEPERIODICTABLE
Theelectronsinanatomfillfromthelowesttothehighestorbitals. Theknowledgeofthelocationoftheorbitalsontheperiodictablecangreatlyhelpthewritingofelectronconfigurationsfor largeatoms.

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Chemistry101

Chapter8

ForAGroups(RepresentativeElements): (sandp blocks) n=periodnumber

ForBGroups(TransitionElements) dblocks: n=periodnumber 1 fblocks: n=periodnumber 2

TheelectronicconfigurationofanelementcannowbegivenifthepositioninthePeriodic Tableisknown:

2 2 6 2 6 2 10 6 2 1s 2s 2p 3s 3p 4s 3d 4p 5s 2 or[Kr]5s (2outermostshellelectrons) 2 2 6 2 6 2 6 1s 2s 2p 3s 3p 4s 3d 2 6 or [Ar]4s 3d (2outermostshellelectrons)

2 2 6 2 3 1s 2s 2p 3s 3p 2 3 or[Ne]3s 3p (5outermostshell electrons)

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Chemistry101

Chapter8

GroupVIIIAelements(NobleGases)haveastableoutermostshellelectronconfiguration:

Element

OrbitalNotation

ElectronConfiguration
2 1s

#ofOutermost ShellElectrons

He Ne Ar Kr Xe Rn

-
1s

2 8 8 8 8 8

- - - -
2s 2p

2 6 2s 2p

- - - -
3s 3p

2 6 3s 3p

- - - -
4s 4p

2 6 4s 4p

- - - -
5s 52p

2 6 5s 5p

- - - -
6s 6p

2 6 6s 6p

2 6 2 Theelectronconfigurationof ns np (orns )isreferredtoasa noblegascore

ChemicalPropertiesofelementsaredeterminedbytheoutermostshellelectrons(electronsin highestenergylevel)theseelectronsareinvolvedinbonding. VALENCEELECTRONS: Valenceelectronsarethose outsidethenoblegascore Fortransitionelements, thesandpelectronsoftheoutermostshell(highestenergylevel) (delectronsarenotvalenceelectrons) NOTE: Mosttransitionelementshave2valenceelectrons Reason:Theyfilldorforbitalswhicharenotpartoftheoutermostshell Exceptions:Transitionelementswithirregularelectronicconfigurations:Cr,Cu,etc.

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Chemistry101

Chapter8

MAGNETICPROPERTIESOFATOMS
Everyelectronactslikeasmallmagnet Magneticattractionsfrom2electronswithoppositespincanceleachother Itfollows: Anatomwithpairedelectronshasnomagnetism. Anatomwithunpairedelectrons(excessofonespin)exhibitsmagnetism. Anelementwithatomsthatexhibitmagnetismisattractedtoastrongmagnet DIAMAGNETICELEMENTS Arenotattractedbyamagneticfield Sometimesevenrepelledbyamagneticfield Atomscontainpairedelectronsonly PARAMAGNETICELEMENTS Areweaklyattractedbyamagneticfield Atomscontainunpairedelectrons
1 Na [Ne]3s 2 2 C [He]2s 2p

Hg

2 14 10 [Xe]6s 4f 5d

FERROMAGNETICELEMENT Arestrongpermanentmagnetisminironduetothealignmentofmanyunpairedelectrons

Fe

[Ar]

4s3d Examples: 1. Writecompleteandcondensedelectronconfigurationforbromine(Z=35)anddeterminethenumber ofvalenceelectrons.

2. Writecompleteandcondensedelectronconfigurationforpalladium (Z=46)anddeterminethe numberofvalenceelectrons.

3. Writecompleteandcondensedelectron configurationforantimony (Z=51)anddeterminethe numberofvalenceelectrons.

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Chemistry101

Chapter8

PERIODICPROPERTIES
Periodicpropertiesarepropertiesoftheelementsthatarerepeatedaccordingtoaregular periodictrend. Threeimportantperiodicpropertieswillbediscussed: 1.AtomicRadius (sizeoftheatoms) 2.IonizationEnergy(I.E.) energyneededtoremovetheoutermostelectronfroma neutralatominthegaseousstatetoformapositiveion. 3.ElectronAffinity(E.A.) energy(absorbedor released)duringtheprocessofaddingan electrontoaneutral atominthegaseousstatetoforma negativeion Thevariationofthese3PeriodicPropertieswillbediscussed: withinagroup(verticaltrend) alongaperiod(horizontaltrend) Twoimportantfactorsdeterminethesetrends:

EffectiveNuclearChargeincreases

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Chemistry101

Chapter8

EffectiveNuclearCharge
Effectivenuclearcharge(Zeff)isthepositivechargethatanelectronexperiencesfromthe nucleus. ConsidertheelectronconfigurationoftheNaatom(Z=11)
2 2 6 1 1s 2s 2p 3s

3energylevels:
st 2electronson1 energylevel nd 8electronson2 energylevel rd 1electronon3 energylevel

8e 2e +11
Whatisthepositivechargethatthe outermostelectronfeels?

st nd 1. Itisnot+11,sinceitselectronsofthe1 and2 energylevel (10electronscarryachargeequal to10)=canceloutsomeofthe+11chargeofthenucleus(shieldingeffect)

2. Itisnot+1, sincethe10coreelectrons(charge=10)cannotcompletelycancelout10positive chargesofthenucleus. Reason:The10coreelectronsareinthenucleus,butsomedistanceaway Note:Theclosertothenucleusthecoreelectronsare,themoreeffectivetheyareincanceling outsomeofthepositivechargeofthenucleus(shieldingeffect) shieldingeffect st ofa1 shellelectron shieldingeffect nd ofa2 shellelectron

3. Theoutermostelectronisattractedtothenucleusbyapositivechargewhichislessthantheactual nuclearcharge(Z=+11)becauseoftheshieldingeffectofthecoreelectrons,butmorethan+1 EffectiveNuclearCharge=Zeff =+2.8(inthisparticularcase) TheNuclearChargeanoutermostelectronexperiencesisreducedbytheshieldingeffectof otherelectrons(Zeff=Z ShieldingEffect)

Zeff

Shieldingeffect

EffectiveNuclear Charge

ActualNuclear Charge

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Chemistry101

Chapter8

Alongaperiod,movingfromlefttoright:

Protonsareaddedtothenucleus Electronsareaddedto theoutermostshell

Zincreasesconsiderably Minimalincreasein shieldingeffect

Zeff

Shieldingeffect

Effective Nuclear Charge

Actual Nuclear Charge

Increases considerably

Minimal increase

MovingacrossaperiodZeffincreases(Zincreasesalot,ShieldingEffectincreaseslittle) Alongagroup,movingfromuptodown: Protonsareaddedtothenucleus Electronsareaddedto thenewshell Zincreasesconsiderably Considerableincreases shieldingeffect

Zeff

Shieldingeffect

Effective Nuclear Charge

Actual Nuclear Charge

Increases considerably

Increases considerably

MovingdownagroupZeff doesNOTincrease(Zincreasesalot,ShieldingEffectincreasesalot)

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Chemistry101

Chapter8

ATOMICRADIUS
ValuesofAtomicradiiareobtainedfrommeasurementsofdistancesbetweenthenucleiofatoms inthechemicalbondsofmolecularsubstances. Example:experimentalDeterminationoftheradiusofHatom:

AtomicRadius=distancebetweennuclei

distancebetweennucleiisdeterminedexperimentally (byXraycrystallography) AtomicRadiusdeterminedinthismannerarereferredtoasCovalentRadii. Atomsareverysmallconsequently,atomicradiihaveverysmallvalues ValuesofAtomicRadiiarelistedonthePeriodicTable(backside)andarecommonly expressedin: Angstroms(1A=10-10 m) or Nanometers(1nm=10-9 m) or Picometers(1pm=10-12 m) Histhesmallestatom: CovalentradiusofHatom=0.32A

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Chemistry101

Chapter8

ATOMICRADII

AtomicSizeIncreases

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Chemistry101

Chapter8

ATOMICRADII

Note:ThereislittlevariationinatomicSizethroughoutarowofTransitionElements: Reason:Considertheelementscompletingthe3dsubshell: FromSc..to.Zn 2 1 2 10 [Ar]4s 3d . ...to[Ar]4s 3d Movingalongperiod4fromlefttoright: 1protonisaddedwhenmovingfromonetransitionelementtothenext ACTUALNUCLEARCHARGE(Z)INCREASESCONSIDERABLY

Sc..Zn
rd 1electronisaddedtothe3dsubshellofthe3 shell(aninnershell) SHIELDINGEFFECTCAUSEDBYADDEDELECTRONINCREASESCONSIDERABLY

Recall:

Zeff =

Z ShieldingEffect increases increases considerably considerably

Result:

Zeffdoesnotchange

InsignificantvariationinAtomicSizefor3dblockelements Thistrendholdstrueforalltransitionelements(dblockelements)

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Chemistry101

Chapter8

IONIZATIONENERGY
IonizationEnergy(IE)istheenergyneededtoremovetheoutermostelectronfroma neutralatominthegaseousstatetoformapositiveion. IonizationEnergy: iscommonlymeasuredinkJ/mol isalsoreferredtoasIonizationPotential(electricalenergy)andcan alsobe measuredinVolts islistedonthePeriodicTable(backside) Considertheremovaloftheoutermostshellelectronfromsodium:

Na(g)
2 2 6 1 1s 2s 2p 3s 1 [Ne]3s (11p,11e)

IE1 FirstIonization Energy

+ Na (g) 2 2 6 1s 2s 2p [Ne] (11p,10e)

+ 1e -

Considertheremovalofasecondelectron:
+ Na (g) 2 2 6 1s 2s 2p [Ne] (11p,10e)

IE2 SecondIonization Energy

2+ Na (g ) + 1e - 2 2 5 1s 2s 2p 2 5 [He]2s 2p (11p,9e)

NOTES: 1.Removalofanelectronisanendothermicprocess(itrequiresenergytoremoveanelectron) AtomsdonotloseelectronsEnergyisrequiredtoremovetheelectrons 2.Alltheelectronscanberemovedsuccessively formanatom. Theenergiesrequiredateachstepareknownas: FirstIonizationEnergy(IE1),SecondIonizationEnergy(IE2),ThirdIonizationEnergy(IE3) . 3.Ingeneral: TheIonizationEnergiesforagivenelementincreaseasmoreelectronsareremoved: IE1 < IE2 < IE3 <IE4 <IE5 <IE6 < IE7 < IE8 andsoon. Reason:Theelectronisbeingremovedfromionswithincreasinglylargerpositivecharges (Thelargerthepositivechargeoftheion,thestrongertheelectronisattracted)

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Chemistry101

Chapter8

IONIZATIONENERGY

DownagroupIEdecreases,duetoincreasedatomicsize(thelargertheatom,thelessstronglyit holdsitselectronsintheoutershell) Acrossaperiod,IEgenerallyincreases,duetoincreasedeffectivenuclearcharge(thegreaterthe nuclearcharge,thestrongertheatomholditselectronsintheoutershell) SomeanomaliesinIEtrendoccurineachperiod(e.g.inperiod2,BislowerthanBeandOislower thanNsimilarlyinperiod3,Alislowerthan MgandSislowerthanP). Theseanomaliesareduetotheincreasedstabilitiesoftheelectronshellarrangementsforeachatom.

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Chemistry101 TheincreaseinthevaluesofsuccessiveIonizationEnergiesisnotgradual: Element IE1 H He Li Be B C N O F 1312 2372 520 899 801 1086 1402 1314 1681 5250 7298 1757 2427 2353 2857 3388 3374 11,815 14,848 3660 4620 4578 5300 6020 21,006 25,025 6222 7475 7469 8407 32,826 37,829 9445 10,989 11,022 47,276 53,265 13,326 15,164 SuccessiveIonizationEnergies(kJ/mol) IE2 IE3 IE4 IE5 IE6 IE7

Chapter8

71,333 17,867

NOTE:AverylargejumpintheIEvalueoccursafterall thevalenceelectronshavebeen removed Element IE1 H He Li Be B C N O F 1312 2372 520 899 801 1086 1402 1314 1681 5250 7298 1757 2427 2353 2857 3388 3374 11,815 14,848 3660 4620 4578 5300 6020 21,006 25,025 6222 7475 7469 8407 32,826 37,829 9445 10,989 11,022 47,276 53,265 13,326 15,164 71,333 17,867 SuccessiveIonizationEnergies(kJ/mol) IE2 IE3 IE4 IE5 IE6 IE7

Oncethevalenceelectronsareremoved,astablenoblegasconfigurationisobtained.Further removalofelectronswillinvolveelectronsfromacompleteinnershell. Forpurposesofcomparingthechemicalbehaviorofdifferentelements,usuallyonlytheFirst IonizationEnergy(IE1)iscompared.

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Chemistry101

Chapter8

SUMMARYOFATOMICRADIUS&IONIZATIONENERGY

NONMETALS HIGHIONIZATIONENERGY RELATIVELYSMALLATOMS

METALS LOWIONIZATIONENERGY RELATIVELYLARGEATOMS

Zeffdecreases IonizationEnergyDecreases

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Chemistry101

Chapter8

ELECTRONAFFINITY (EA)
ConsidertheelectronconfigurationoftheClatom(Z=17)
2 2 6 2 5 1s 2s 2p 3s 3p

3energylevels: st 2electronsonthe1 energylevel nd 8electrononthe2 energylevel rd 7electronsonthe3 energylevel

+17

Whatistheeffect(ifany)oftheClatomonan outsideelectron? Hypothetically,thereare3possibilities: 1.Theatomisneutral(+17nuclearchargeiscanceledoutbythe17negativeelectrons) Assuch,theoutsideelectronshouldbeunaffectedbytheneighboringClatom 2.The17electronsoftheClatom(charge=17) shouldrepeltheoutsideelectron 3.The17electronsoftheClatomcanceloutthepositivenuclearchargeof+17only partially(shieldingeffect).Thepositivelychargednucleuscreatesanelectricfieldwhich shouldattracttheoutsideelectron

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Chemistry101

Chapter8

TheoutsideelectronisattractedtotheClatom,andisacceptedbytheClatom. TheadditionoftheelectrontotheClatom doesnotrequireenergy(notendothermic) Theelectronisnaturallyattractedandreleasesenergy(exothermicprocess)

+17

Cl
2 2 6 2 5 1s 2s 2p 3s 3p 2 5 [Ne]3s 3p

e-

Cl-

349kJ/mole

2 2 6 2 6 1s 2s 2p 3s 3p 2 6 [Ne]3s 3p [Ar]

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Chemistry101 Recallthattheheattermisalwayswrittenonthereactantside(Thermochemistry)

Chapter8

Cl Cl

+ +

e- e-

349kJ/mole Cl-

Cl-

DH=349 kJ/mole (exothermic)

ELECTRONAFFINITY
ELECTRONAFFINITY(EA)istheenergychange(commonlyreleased)fortheprocessof addinganelectrontoaneutralatominthegaseousstatetoformanegativeion. (itisameasureofhoweasilyanatomacceptsanelectron) NOTE: 1. Themajorityofatomshaveahightendencytogainelectrons(ex:Cl) TheatomshaveHIGHEAs HIGHEA means LARGENEGATIVEEA LargeAmountofEnergygivenoff whenanelectronisgainedwillingly bytheneutralatom(stableionformed) (additionofelectronisexothermic) 2. Relativelyfewatomsresisttheadditionofanelectron(ex:NobleGasesandsomemetals) Theyhave LOWEAs LOWEA means ZeroorPositiveEA Energyisrequiredwhenanelectronisforced intheneutralatom (unstableionformed) (additionoftheelectronisendothermic)

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Chemistry101

Chapter8

ELECTRONAFFINITY TRENDS

Zeffincreases NONMETALS HIGHELECTRONAFFINITY (Atomsgainelectronseasily)

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Chemistry101

Chapter8

VARIATIONSINELECTRONAFFINITIES
I.EffectcausedbyInterelectronrepulsionsbetweenoutershellelectrons

IVA Period2 Period3 C Si

VA N P

VIA O S

VIIA F Cl

ExpectedTrendofEA EA Should increase

IVA Period2 EA (kJ/mol) Period3 EA (kJ/mol) C 122 Si 134

VA N 0 P 72

VIA O 141 S 200

VIIA F 328 Cl 349

ActualTrendofEA EA increases

Reason: AtomsofPeriod2elementsaremuch,muchsmallerthantheatomsofPeriod3elements(large nd rd energygapbetweenthe2 andthe3 energylevelsthisenergygapdiminishesasonemovesto th th th th 4 ,5 ,6 ,7 energylevels) Insmallatomsthereisverystronginterelectronelectronrepulsion(electronsarecrowded).The nd mutualrepulsionsbetween2 shell electronsactagainstaddinganadditionalelectrontotheatom. Crowded electrons inoutershell nd (2 shell) Stronginterelectron Repulsions between nd 2 shellelectrons

Period2 Elements

Smaller Atoms

Period3 Elements

Larger Atoms

Lesscrowding ofelectrons inoutershell nd (3 shell)

Weakerinterelectron Repulsions between nd 3 shellelectrons

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Chemistry101 II.Effectcausedbythestabilityofhalffilledsubshells

Chapter8

IIIA Period2 Period3 ExpectedtrendofEA IIIA Period2 E.A. (kJ/mol) Period3 E.A. (kJ/mol) B 27 Al 44 B Al

IVA C Si

VA N P

VIA O S

VIIA F Cl

EAshouldincrease

IVA C 122 Si 134

VA N 0 P 72

VIA O 141 S 200

VIIA F 328 Cl 349

E.A.increases

E.A.increases

Breakintrend! E.Aislessthanexpected!
Reason: ThemorestablehalffilledshellofgroupVAelementsrejectselectrons,leadingtoalowerEA.

Period2

[He]

IVA C - - 2s 2p Si - - 3s3p

[He]

VA N - 2s2p P - - 3s3p

- .

Period3

[He]

[He]

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Chemistry101

Chapter8

SUMMARYOFTRENDSINPERIODICPROPERTIES

NONMETALS(SMALLATOMS) HIGHIONIZATIONENERGY (difficulttoremoveelectrons) HIGHELECTRONAFFINITY (hightendencytogainelectrons)

METALS(LARGEATOMS) LOWIONIZATIONENERGY (easytoremoveelectrons) LOWELECTRONAFFINITY (difficulttogainelectrons)

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Chemistry101

Chapter8

METALLICCHARACTER
Thephysicalandchemicalpropertiesofthemaingroupelementsclearlydisplayperiodic character. Theclassificationofelementsintheperiodictableintometals,nonmetalsandmetalloidsis basedonfundamentalperiodictrends. Themoreanelementexhibitsthephysicalandchemicalpropertiesofmetals,thegreaterits metalliccharacter. Metalliccharacterincreases

Thebasicacidicbehavioroftheoxidesofelementsisagoodindicatoroftheirmetallic character. Oxidesareclassifiedasbasicoracidicbasedontheirreactionswithacidsandbases. Abasicoxideisanoxidethatreactswith acids.Mostmetaloxidesarebasic. Anacidicoxideisanoxidethatreactswithbases.Mostnonmetaloxidesareacidicoxides. Anamphotericoxideisanoxidethathasbothbasicandacidicproperties.

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