Chem102Lecturenotes

Thenotecomprisesoflecturetopicsofweek9andweek11
ThislecturehastostartwithsomequickreminderofsometerminologiestaughtinCHM101undertheperi
odictableandperiodicitylecturetopic.Thetermsincludes;Nuclearcharge,effectivenuclearcharge,shie
ldingeffect,ionizationenergy,atomicandionicsize,electropositiveandelectronegativecharacter,oxid
ationstateandvalenceelectrons.
Chemistryofselectedmetals
AlkaliMetals(grouponeelements)
Alkalielementsaregroup1/
IAelementsintheperiodictable.Theyareclassifiedasgrouponeelementsduetotheirmonovalentnature,
i.etheyhaveonlyoneelectronintheirvalenceshell.Theyarealsoconsideredass-
blockelementsbecausetheirvalanceelectronishousedbythesorbitalatdifferentenergylevels.Thealkal
imetalsareLithium,Sodium,Potassium,Rubidium,CaesiumandFrancium.Theyhaveageneralground
stateelectronicconfigurationofns1.

Symbo Names Electronicconfiguration

l
Li Lithium 1S22S1
Na Sodium 1S22S22P63S1
K Potassium 1S22S22P63S23P64S1
Rb Rubidium 1S22S22P63S23P63d104S24P65S1
Cs Caesium 1S22S22P63S23P63d104S24P65S25P66S1
Fr Francium [Rn]7S1

A. OccurrenceandAbundance
Grouponeelementsoccurasmetaloresinnatureduetotheirhighlyelectropositive(abilitytolosee
lectrons)propertiesandlowionizationenergy.Hencetheyarehighlyreactiveandhavetocoexisti
nnatureasmetalores.
 Lithiumisthe35thmostabundantelementbyweightontheearthcrustandoccursincombinedstate
withsiliconminerals:Spodumene(LiAl(SiO3)2andLepidolite(Li2Al2(SiO3)3(FOH)2).
 Sodiumisthe7thmostabundantelementbyweightintheearthcrustanditslargestsourceisthenatur
alsaltrockorseasalt(NaCl),naturalbrinesandChilesaltpetre.
 Potassiumisthe8thmostabundantelementbyweightintheearthcrust.Itcanbeseeninmineralslik
eSylvite,KCl;Carnallite,KCl.MgCl2.6H2Owhichisadoublesaltorfromsolublepotassiumsalts
calledPotash;Sylvinite,KCl/NaCl.
 RubidiumandCaesiumcanbeobtainedasbyproductsfromLithiumprocessingwhileFranciumi
sradioactiveandhasahalflifeof21minutes.

B. ExtractionofGrouponeelements
TheAlkalimetalsarecharacterizedbythethermalstabilityduetohighcohesiveforcesholdingthe
iratomstogetherwhichmakestheirseparationviathermaldecompositionnotpracticable.Also,t
heyareontopintheelectrochemicalseries(theyevendisplacehydrogenfromwater)soseparatio
 nviadisplacementreactionisimpossible.However,themostpracticablewaytopurifygroupone
elementsfromtheirorearethroughelectrolysisoftheirfusedsalts,usually,thefusedhalideswithi
mpuritiesaddedtoreducethemeltingpoint.
SodiumiseconomicallythemostimportantalkalimetalanditismanufacturedbyDownsprocessi
nwhichmoltenNaCliselectrolysed.
TheDowncellcomprisesofacylindricalsteelvessellinedwithfirebrickmeasuringabout2.5minheighta
nd1.5mindiameter.Theanodeisagraphiterodinthemiddle,andissurroundedbyacaststeelcathode.Ame
talgaugescreenseparatesthetwoelectrodesandpreventsthesodiumformedatthecathodefromrecombi
ningwithchlorineproducedattheanode,themoltensodiumrisesasitislessdensethantheelectrolyteandit
iscollectedinaninvertedtroughandremovedandpackedintosteeldrums.CaCl2isaddedtoreducetheope
ratingtemperaturetoabout870K,sincepureNaClmeltsat1073K.Themoltenmixtureisabout40%NaCl
and60%CaCl2inaDowncell.Thesmallamountofcalciumformedduringtheelectrolysisisinsolubleinth
eliquidsodiumanddissolvesintheeutecticmixtureandcanbeseparated.Thecellisdesignedtopreventth
erecombinationofNaandCl.

Figure:DiagramofaDowncell.
Cathode:Na+discharged
2Na++2e-→2Na
Anode:Cl-discharged
2Cl-→2Cl+2e-
2Cl→Cl2
Overallreactionis2Na++2Cl-→2Na+Cl2.

C. GeneralPhysicalPropertiesofgrouponeelements
i.Theyareallmetalsi.etheyaremalleable(Canbehammeredintovariousshapes),theyareductile(Canbe
drawnintotinysheetsofwire),theyaregoodconductorsofheatandelectricity
ii.Theyformmostlyionicandcolourlesscompounds
iii.Theyarethelargestelements(intermsofatomicsizes)intheirvariousperiods
iv.Theiroxidesandhydroxidesarestrongbases
v.Theyarestrongreducingagents(theyreadilydonateelectronforbondingthusreducingtheelementthat
willaccepttheelectron)
v.Theygivecharacteristicflameswhenignited,e.g.Li+-Scarlet;Na+-Golden-yellow,K+-Lilac.
vi.Theyarehighlyelectropositiveelements
vii.Theyaresoftunivalentmetals,
lllviiiTheyhavelowestionizationenergiesintheirrespectiveperiods.
ix.ThechemistryorchemicalpropertiesofLithiumaresimilartoMg(diagonalrelationship).
Carbonates,sulphates,hydrides,oxidesandhydroxidesofgrouponemetalsareallsolubleinwater.
D. Electronicpropertiesofgrouponeelements

i. AtomicandIonicSizes
Asearlydiscussedunderperiodictrendsintheperiodictable,atomicandionicsizesincreasedownthe
groupandreducefromlefttorightacrosstheperiod.Basedonthis,thegrouponeelementsarethelarges
telementsintheirrespectiveperiods.Thelithiumionoratomisthesmallestelementofthegroupwhile
franciumisthelargestofthem.Theincreaseinsizeasyoudescendfromlithiumtofranciumisasaresult
ofincreaseinthenumberofshellscontainedintheelements.

Compounds Valenceorbital Atomicradius/mm Ionicradius/nm

Li 2S1 0.133 0.060
Na 3S1 0.157 0.095
K 4S1 0.203 0.133
Rb 5S1 0.216 0.148
Cs 6S1 0.235 0.169
F 7S1 - -

Lithiumhasa2Sorbitalasitsvalenceorbital(whichisanorbitalatthe2ndenergylevelwithaprincipalq
uantumnumberof2),Nahasitsvalenceorbitalas3Sorbitalofthe3rdenergylevelwhileFranciumhasa
7Sorbitalasitsvalenceorbital(anorbitalatenergylevelof7,thatisprincipalquantumnumberof7).
Also,theincreaseinshieldingeffectofthevalenceelectronfromthenuclearchargeofthenucleusbyel
ectronsintheinnerenergylevelsoftheelementasyougofromlithiumtofranciumisanotherfactorresp
onsiblefortheincreaseinatomicsizedownthegroup.
Note:
1.Itisimportanttorememberthatcationsaresmallerinsizecomparedtoneutralatoms.Thereasonbei
ngthatgrouponeelementsformionsbylosingtheirvalenceelectron,theirbylosingtheirvalenceshell
toalowerenergylevel.Also,thereisanincreaseineffectivenuclearchargehencecausingashrinkinio
nicsize.ExampleLi+1issmallerinsize(0.060A)comparedtoLi(0.133A).
2.Thehighertheoxidationstatethesmallerthesizeofthecation.Thisisduetoincreaseineffectivenucl
earchargebecauseoflossofelectron(imbalancebwthenumberofprotonandelectron)thatshrinksthe
ionicsizeoftheelement.
ii. IonizationEnergy
Asearlydiscussed,ionizationenergyistheamountofenergyrequiredtoremovetheoutermostelectro
nfromthevalenceatomicorbitalofanatom.Itsmagnitudedependsonhowstronglytheoutermostelec
tronisheldbytheattractiveforceofthenucleus(effectivenuclearcharge)andthisreliesmuchontheat
omicorionicradiioftheelementandtheeffectivenessoftheshieldingofvalenceelectronbyinnerelec
tronsfromnuclearcharge.Hence,ionizationenergyincreasesacrosstheperiodfromlefttorightandd
ecreasedownthegroup.Grouponeelementshavethelowestionizationenergiesoftheirrespectivepe
riodsduetotheirlargeatomicsizes.Amongthealkalimetals,lithiumhasthehighestionizationenergy
duethefactthatitistheelementwiththesmallestatomicradii,thusitsoutermostelectronisheldmorest
ronglycomparetothatofCs.Thevaluesforthe2ndionizationenergiesforalkalimetalsaresohighthatt
heformationofm+2ionsunderchemicallyreasonableconditionsisnotviable.

Compounds 1stionizationenergy
KJ/mol-1
Li 520
Na 496
K 418
Rb 403
Cs 374

iii. Cohesiveforceandhardness
Cohesiveforceorenergyistheforceorenergyholdingatomsorionstogetherinthesolidform.Thisisth
esamemagnitudebutoppositeinsigntoenthalpyofatomization(thatenergyrequiredtochangeatomf
romasolidstatetoagaseousstate).Theenergyisdependentonavailabilityofvalenceelectronsforbon
ding,strengthofthebondandatomicsize.Increaseinthevalenceelectronincreasesthecohesiveenerg
y(increaseinnuclearcharge)whileincreaseinatomicsizedecreasesthem(decreaseinionizationener
gy).Thismeansthatcohesiveforceincreaseacrosstheperiodanddecreasesdownthegroup.Groupon
eelementshaveonlyonevalenceelectroninitsoutermostshellhencetheyhavelowcohesiveenergya
ndarethesoftestoftheirrespectiveperiods.Thecohesiveenergyforgrouponeelementsdecreasesfro
mLitoCsduetoincreaseinatomicsizeasyougodownthegroup.Grouponemetalsaregenerallysoftm
etalsduetotheiratomicsizeandpresenceofunivalentelectron.

Compounds Cohesiveenergy,KJ/Mol
Li 161
Na 108
K 90
Rb 82
Cs 78
iv. Meltingandboilingpoints
Meltingandboilingpointisafunctionofcohesiveforceinanatom.Thehigherthecohesiveenergyina
natom,thehigheritsmeltingandboilingpoint.Themeltingandboilingpointofgrouponeelementsde
creaseasyougofromLitoCsduetodecreaseincohesiveforce.Lithiummeltsat181 oCwhileCsmeltsat
28.5oC.
v. Electropositivecharacter(thetendencyoftheelementtoloseelectron).
Duetotheirlowionizationenergies,thesemetalshavegreattendenciestolosethens 1electrontoformp
ositiveions.Thusalkalimetalsarestronglyelectropositive.Furthermore,sinceionizationenergydec
reasesfromLitoCs,theelectropositivecharacterincreasesingoingdownfromLitoCs.Alsoduetothe
irhighelectropositivenatureCsandKareabletoreleaseelectrononexposuretolight(photoelectricef
fect).Lihavingthehigestionizationenergycannotbeusedforthispurpose.
Vi.Oxidationstate
Thealkalimetalatomshowonly+1oxidationstate.Becauseoftheirlowionizationenergies,theyeasil
ylosetheoutermostselectrontoformthemonopositivecation.Thecationsofgrouponeelementsarev
erystablebecausetheyhaveanoblegaselectronicconfiguration(ns2orns2p6).Therefore,moreenerg
yisrequiredtoremoveasecondelectronfromthestablecation.Theyarediamagneticandcolourlessd
uetoabsenceofunpairedelectron.Theyformcompoundsthataremostlycolourlessunlesstheanionc
ontainedinthemprovidesthecolouration.
Vii.Flamecolouration
Thealkalimetalsandtheirsaltswhenintroducetoflamegivescharacteristiccolourationtoflame.Thi
spropertyofthealkalimetalsoffersaverysignificantapplicationintheidentificationofalkalimetals
whicharedifficulttobeidentifiedusingchemicalmethods.Forexample,Li-Scarlet;Na-Golden-
yellow,K-Lilac.
Viii.Conductanceofheatandelectricity
Duetothepresenceoflooselyheldvalenceelectronswhicharefreetomovethroughoutthemetalstruc
ture,thealkalimetalsaregoodconductorsofheatandelectricity.
F.Chemicalpropertiesofgrouponeelements
Purealkalimetalsareveryreactiveasearlyelaborated.Li,Na,andKarestoredunderahydrocarbonat
mospheretopreventreactionwithatmosphericoxygenandwater.Buttheycanbehandledinanatmos
pherewithoutmoistandatmosphericoxygen.RbandCsareveryreactiveandcannotexistaspureelem
entsinordinaryatmospherebutrathermustbehandledinaninertatmosphere.
1. Reactionwithwater
Grouponeelementsreactswithwatertoformmetalhydroxidesandliberatehydrogen.
2M+2H2O→2MOH+H2
Thenatureofalkalimetal’sreactionwithwatervaries.Lithiummeltsoncontactwithwaterandreleasever
yhighenergyduetoitshighhydrationenergy.Sodiummeltsonthesurfaceofwaterandthemoltenmetalsk
atesaboutvigorouslyandmaycatchfire.Potassium,rubidiumandcesiumreactviolentlywithwaterandc
atchfireoncontactwithwater.Thehydroxidesarethestrongestbasesknown.Theyaresolubleinwaterexc
eptforthatoflithiumthatisslightlysoluble.
2. Actionofoxygentoformmetaloxides
Grouponeelementswhenheatedwithoxygenformsvariousoxides,thenatureoftheoxidedependsonthe
natureofthealkalimetal.AlltheoxidesofalkalimetalsarestrongbasesandtheirbasicityincreasesfromLi
2OtoCs2O.

a. Allgrouponemetalsformmonoxidesonreactingwithlimitedsupplyofoxygen
2M+1/2O2→M2O(Li2O;Na2O;K2O,Rb2OandCs2Oetc).
b. Allgrouponeelementsexceptlithiumformsperoxidesonreactingwithexcessair
2M+O2→M2O2(Na2O2,K2O2,Rb2O2andCs2O2)
c. K,RbandCsformssuperoxideonreactingwithexcessair
M+O2→MO2(KO2)
Themetaloxidesaresolubleinwaterforminghydroxides(Causticalkalis)intheprocess
M2O(s)+H2O→2MOH(s)
3. Reactionwithnitrogentoformlithiumnitride
Lithiumistheonlygrouponeelementthatreactswithnitrogentoformnitridesatroomtemperature.Theco
mpoundisionicinnature.
3Li+N→Li3N
4. Reactionwithalcoholtoformmetalalkaloids
Grouponeelementsreactswithalcoholtoformmetalalkaloids
M+ROH→ROM+1/2H2(Na+CH3OH→CH3ONa+1/2H2)
5. Reactionwithhalogenstoformmetalhalides
Grouponeelementsreactwithhalogenstoformmetalhalidesalts
2M+Cl2→2MCl
HowevertheeaseofthisformationdecreaseasyougodownfromLitoCssinceelectro-
positivityincreasesfromLitoCs.
Lithiumformshydratedsaltswhileothersformanhydroussalts.Allalkalihalidesaltsaresolubleinwatera
ndsubsequentlyelectrolytes.Howeverlithiumchlorideistheonlyonewhichisdeliquescent.Thesolubili
tyofthemetalhalidescanbeattributedtohighenergyofhydrationoftheionswhichovercomesthelatticee
nergy.
 6. Reactionwithhydrogentoformmetalhydrides
Theyreactwithhydrogenformingionichydrides.Howevertheeaseofthisformationdecreaseasyougod
ownfromLitoCssinceelectro-positivityincreasesfromLitoCs.
M+1/2H2→MH
Allthehydridesofthegroupareionic,withthemetalbeingpositivelychargedandthehydrogenbeingnega
tivelychargedinsolutions.Thehydrideionsarehighlyreactive.Themetalhydridereactswithwatertofor
mhydroxideandgivesoffhydrogen.
MH+H2O→MOH+H2
7. Reducingproperty:
Oxidationisaprocessinwhichelectronsarelostwhilereductionisaprocessinwhichelectronsaregained.
Henceoxidizingagentisasubstancewhichcanacceptelectronswhilereducingagentisasubstancewhich
canloseelectrons.Evidently,areducingagentmusthavelowionizationenergywhileanoxidizingagent
musthavehighionizationenergy(highelectronaffinity).Nowsinceionizationenergydecreasesonmovi
ngdownfromLitoCs,thereducingpropertyshouldincreaseinthesameorderfromLitoCs.Howeverlithi
umisanexception.Althoughithasthehighestionizationenergy,yetitisthestrongestreducingagentamon
gthegroup.Thiscanbeexplainedonthebasisthattheprocessofoxidationinvolveshydrationofgaseousio
ninitslaststage.Lithiumhaslargeheatofhydrationduetoitssmallsize(andextentofhydration)andhencet
hestrongestreducingagent.
8. ReactionwithAirtoformoxides,hydroxidesandcarbonates
Alkalimetalsaresoreactivethattheytarnishrapidlywhenexposedtoairbecauseoftheformationofoxide
s,hydroxidesandultimatelycarbonatesatthesurface.Hencetheyarekeptunderaninertliquidlikekerose
neoilwhichpreventsthemtocomeincontactwithairandmoisture.
4Na(s)+O2(g)→2Na2O(s)
Na2O(s)+H2O(l)→2NaOH(s)
2NaOH(s)+CO2(g)→Na2CO3(s)+H2O(l)
Metaloxides,hydroxidesandcarbonatesofgrouponeareverysolubleinwaterformingalkalinesolutions
.
E. Anomalous(differences)betweenLithiumandothergrouponeelements
Althoughlithiumexhibitsmostofthecharacteristicpropertiesofthegroup1elements,itdiffersinma
nyrespects.Theanomalousbehaviouroflithiumisduetoextremelysmallsizeoflithiumatomanditsi
on.ThesmallsizeofLi+ionleadstoitshighchargedensity.Lithiumionthereforepossessesthegreatest
polarizationpower(ioniccharge/
ionicradii)outofallthealkalimetalions.Henceitexertsagreatdistortingeffectonthenegativeion.Co
nsequentlytheLi+ionhasgreattendencytowardssalvationandcovalentbondformation(thepolarizi
ngpowerisresponsibleforitscovalentbondformationtendencies).Furthermore,thepolarizingpow
er(abilitytodrawelectrontoitselfwhenfoundinacompound)ofLi+hasbeenfoundtobesimilartothat
 ofMg2+ioningrouptwo.Thetwoelementswhichareplaceddiagonallyintheperiodictableresemblev
erymuchintheirproperties.
i. Lithiumisthehardestandlightestmetalinthegrouponethisisduetoitshighcohesiveforceandsm
allradius.
ii. Lithiumhasthehighestmeltingandboilingpointduetoitshighionizationenergy.
iii. Duetoitshighionizationenergy,itistheleastreactiveofallalkalimetalstowardsvariousreagents
exceptnitrogen.Lithiumunlikeotheralkalimetalsisnotaffectedbydryair.
iv. Lithiumistheonlygrouponeelementthatreactswithnitrogentoformlithiumnitrideandsiliconto
givelithiumsilicide.
v. Lithiumdoesnotformperoxidesliketherestofthegroups.Itformsmonoxidelikemagnesiumwh
enburntinoxygen.
vi. Lithiumunlikeotheralkalimetals,decomposeswaterslowlytolibratehydrogenduetoitshighme
ltingpoints
vii. Grouponemetalsarestrongreducingagentswithexceptionoflithiumbecauseofsmallatomicsiz
eandhighionizationenergy.
viii. Lithiumionsshowtendencytoformcomplexeswithammoniaandwaterandalsoformsalargenu
mberoforganometalliccompounds
ix. Lithiummonoxidedissolveinwaterquietlywhiletheotheroxidesdissolveinwatermoreenergeti
cally.
x. Carbonates,phosphates,fluorideandoxalatesoflithiumaresparinglysolubleinwaterwhilethec
orrespondingsodiumandpotassiumsaltsareverysolubleinwater.
xi. Lithiumcompoundsparticularlylithiumhalidesarepartlycovalentinnatureandthussolubleinor
ganicsolventswhileotheralkalimetalhalidesarepurelyionicandhencesolubleinwater.
xii. Lithiumcarbonatesarenotstabletoheatbuttheotheralkalimetalcarbonatesareverystabletoheat
.

D.Usesofcompoundsofgrouponeelements
i.Liqiudnitrogenisusedascoolantsinnuclearreactors
ii.95%ofpotassiumcompoundsareusedinfertilizerplantsforfertilizerproduction
iii.NaOH(Causticsoda),KOH(CausticPotash)andNa2CO3(sodiumcarbonate)areusedinmakingsoap
sanddetergents.
iv.NaHCO3(bakingpowder)isusedinthebakery
iv.Li2CO3isusedtotoughenglassinglassindustriesanditisalsoaddedasanadditiveduringthepurificatio
nprocessofbauxiteforaluminumproduction
v.K2CO3isusedintheproductionofceramics,colouredTVandfluorescentlighttubes
Vi.KO2(potassiumsuperoxide)isusedinthesubmarineforbreathingapparatus.
 AlkalineEarthMetal(Group2/IIA)
AlkalineearthmetalsareelementsofgrouptwointhelongperiodictableandgroupIIAintheshortperi
odictable.Theyareclassifiedass-
blockelementsintheperiodictable.TheyhavetwoelectronsinthevalenceSorbitalwithageneralelec
tronicconfigurationofelectronicconfigurationofnS2.

ElementName Symbo Electronicconfiguration

l
Beryllium Be 1S22S2
Magnesium Mg 1S22S22P63S2
Calcium Ca 1S22S22P63S23P64S2
Strontium Sr 1S22S22P63S23P63d104S24P65S2
Barium Ba 1S22S22P63S23P63d104S24P65S25P66S2

Radium Ra [Rn]7S2

A. OccurrenceandAbundance
Likethealkalimetals,Alkalineearthmetalsareveryreactiveandarenotfoundfreely(inafreestate)in
naturebutinformofmineralores.Beforetheirdiscovery,thereoxideswerefirstknownandfoundinth
eearthcrust.Theyarealkalineinnatureandbehavedlikeearth(stabletohightemperature).That’swhy
theparentelementswhendiscoveredwherecalledalkalineearthmetals.

 BerylliumisfoundinsmallquantitiesinnatureenclosedinsilicatemineraloreBeryl,Be3Al2Si6O1
8andPhenacite,Be2SiO4.Itisnotveryabundantinnature.
 Magnesiumisthesixthmostabundantelementintheearthcrust.Itoccursassaltsandfoundinseaw
ater(about0.13%),mountainsinformofmineraloresdolomite(MgCO3.CaCO3),orasmineralsil
icates;Olivine(Mg.Fe)2SiO4,ChrysotileMg3(OH)4Si2O5etc.
 Calciumisthe5thmostabundantelementintheearth’scrustanditoccursallovertheworldinformo
fmineralslikelimestone(CaCO3)inmountainranges.
 StrontiumandBariumarelessabundantandoccursasconcentrateoreswhichareeasytoextract.S
trontiumisminedasCelestite(SrSO4)andStrontianite(SrCO3).BariumisminedasBarytes.
 Radiumisextremelyscareandradioactive.ItwasfirstprocessedbyPierreandMarieCuriebyproc
essingmanytonesoftheUraniumorepitchblonde.

B. ExtractionofAlkalinemetals
 Likethealkalimetalstheyareextractedviaelectrolysisoftheirfusedchlorideduetothestrongionizati
onenergyandhighmeltingpoints.Allthealkalinemetalscanbeobtainedbyelectrolysisofthefusedch
loride,withsodiumchlorideaddedtolowerthemeltingpoint.Forexample,magnesiumisextractedth
roughelectrolysisonfusedMgCl2oronpartiallyhydratedMgCl2.TheMgCl2isproducedthroughDows
eawaterprocessandlaterelectrolyzed.
Dowseawaterprocess:
Thismethodsimplyinvolvestheadditionofslakedlimetoseawatercontainingmagnesiumchloridet
oprecipitatemagnesiumhydroxide.Seawatercontainsabout0.13%Mg2+ionsofdifferentsaltswitht
heirchloridebeingpredominant,butinthepresenceofslakedlime,Ca(OH)2itprecipitatesMg(OH)2.
Therefore,slakedlime,Ca(OH)2isaddedtoseawater,MgCl2toprecipitateMg(OH)2.ThesolidMg(O
H)2isfilteredoff,treatedwithHCltoproducemagnesiumchloridewhichisfurtherelectrolyzed.Thee
quationofreactionispresentedbelow.
Ca(OH)2+MgCl2→Mg(OH)2+CaCl2
SlakedLimeSeawaterPrecipitate

Mg(OH)2(s)+HCl(aq)→MgCl2(s)

MgCl2(S)→(electrolysis)Mg(s)andCl(s)

C. Electronicpropertiesofgrouptwoelements

i. Atomicorionicsizes
AtomicandionicsizeincreasesfromBerylliumtoRadiumduetoincreaseinthenumberofshellinthea
tomicorbital.Thegrouptwoelementsarelargebutsmallerthangrouponeelements.Theirionsarealso
largecomparedtotheotherelementsbutsmallerthangrouponeelements.Thisisduetohighernuclear
chargeoftheseatomswhichtendtotheseatomswhichtendtodrawtheorbitalelectronstowardsthenu
cleus.

Names Symbol Atomicradii

Beryllium Be 1.12
Magnesium Mg 1.60
Calcium Ca 1.97
Strontium Sr 2.15
Barium Ba 2.22
Radium Ra -

Berylliumusuallyformscovalentcompoundswhiletherestofthegroupformsioniccompounds.Thi
sisbecauseitssizeperchargeratio(polarizingpower)issosmallthatitobeysFajan’srulewhichstatest
hatsmallhighlychargedionstendtoformcovalentcompounds.Thisisnotsowiththerestofthegroups
becauseofincreaseinatomicsize.
ii. Ionizationenergy
IonizationenergydecreasesdownthegroupasyougofromBetoRa.Berylliumhasthesmallestatomi
csizeinthegroupandthereforehasthehighestionizationenergy.Sincetheyaresmallerthangroupone
element,theiroutermostelectronareheldmoretightlymakingitrequiringmoreenergytoknockanele
ctronforcationformation.Hencegrouptwoelementshavehigherionizationenergycomparedtogro
uponeduetogreaternuclearchargeandsmalleratomicsize.The2ndionizationenergyisgreaterthanth
efirstionizationenergyduetoincreaseineffectivenuclearcharge.

Symbo Name 1stIonizationenergy 2ndionizationenerg

l y
Be Beryllium 9.32 18.2
Mg Magnesium 7.64 15.0
Ca Calcium 6.11 11.8
Sr Strontium 5.70 11.0
Ba Barium 5.21 10.1
Ra Radium - -

iii. MeltingPoint
Asdiscussedwithgrouponeelements,Meltingandboilingpointofgrouptwoelementsdecreasedow
nthegroupanditisafunctionofthecohesiveforcesoftheirmetalatoms.Thehigherthecohesiveenerg
yinanatom,thehigheritsmeltingandboilingpoint.Themeltingandboilingpointofgrouptwoelemen
tsdecreaseasyougofromBetoRaduetodecreaseincohesiveforcecausebyincreaseinatomicsize.
iv. OxidationState
Duetothefactthatthedivalentionofthealkalineearthmetalhasnoblegaselectronicconfiguration,th
emetalsareusuallyina+2oxidationstate.Thedivalentionhasnounpairedelectronsotheyarediamag
neticandcolourless.
v. Natureofbonds
Alkalineearthmetals(exceptBe)formpredominatelyioniccompounds.Mostoftheseioniccompou
ndsaresolubleinwater.Berylliumformscovalentcompoundsduetotheirsmalleratomicandionicra
diiandhencesolubleinorganicsolvents.

vi. Electropositiveandelectronegativecharacter
Alkalineearthmetalsarestronglyelectropositiveelements.However,theyarenotasstronglyelectro
positiveasthealkalimetalsbecausetheyhavesmallersize,highernuclearchargeandhigherionizatio
 nenergythanthealkalimetals.Hencetheydonotemitelectronsonexposuretolightlikethealkalimeta
lsdo.Onmovingdownthegroup,electropositivecharacterincreasesduetoincreaseinatomicsizeand
decreaseinionizationenergy.Ontheotherhand,theyhavelowelectronegativecharacter(tendencyto
acceptorgainelectron).Theelectronegativecharacterdecreasesdownthegroup.Berylliumhasthehi
ghestelectronegativecharacterduetoitssizetochargeratioandtendstoformcovalentbonds.
vii. Flamecolouration
ChloridesofalkalineearthmetalsexceptforthatBeandMgproducecharacteristiccolourtoflamedue
toeasyexcitationofelectronstohigherenergylevels.BeandMgduetotheirsmallsizebindtheirelectr
onsmorestrongly.
viii. Density
Theyaredenserthanthealkalimetalsbecausetheyarepackedmoretightlyduetotheirgreaterchargea
ndsmallerradii.However,theirdensitiesdonotshowaregulartrendwithincreasingatomicnumberd
uetodifferenceincrystalstructureandvariationsintherateofexchangeofatomicweightascompared
toatomicradii.
ix. Reducingproperty(oxidationpotentials)
Alkalineearthmetalshavetwoelectronsoutsidethenoblegasconfiguration.Duetotheirlargesizean
dlowionizationenergy,theycaneasilyloseoutermosttwoelectronsandhenceundergooxidation(los
sofelectron)easily.
M→M2++2e-
Theyarestrongreducingagents.FurthermoresincetheirionizationenergydecreasefromBetoRa,th
ereducingcharacterofthealkalineearthmetalsincreasesfromBetoRa.Thealkalineearthmetalsarel
esselectropositiveandweakerreducingagentscomparedtothealkalimetals.

Chemicalpropertiesofgrouptwoelements
i. Reactionwithwatertoformhydroxides
Alkalineearthmetalsreactslowlywithwaterliberatinghydrogenandformingmetalhydroxidesexce
ptberyllium.Berylliumdoesnotreactwithwaterbecauseitismuchlesselectropositivethanotherme
mbersofitsgroup.Magnesiumdoesnotreactwithcoldwaterbutwithhotwaterforminghydroxidesan
dliberateshydrogen.Othermembersofthegrouptwoelementsreactwithcoldwatertoformhydroxid
esandliberatehydrogen.Thereactionisnotasvigorousasalkalimetaldoes.
Ca+2H2O→Ca(OH)2+H2
Mg+2H2O→Mg(OH)2+H2

ii. ReactionwithAcidtoliberatehydrogen
Allthegrouptwoelementsreactwithacidtoliberatehydrogen.
 M+2HCl→MCl+H2
iii. Reactionwithair
Allmembersofthisgroupreactwithairtoformmonoxidesveryslowlyunlikethatofalkalimetals.Ber
ylliumisnotreactiveunlessexposuretoairatatemperatureabove600oC.MgandCaformmonoxides
whileSrtoRaformsperoxides.
M+O2→MO
Ca+O2→CaO(quicklime)
iv. Reactionwithhalogentoformmetalhalides
Group2metalsreactwithhalogenstoformmetalhalidesatelevatedtemperature.
M+Cl2→MCl2
Berylliumhalidesarecovalentwhiletherestofthegroupisionicandthusdissolveinwaterandconduct
electricityinaqueousmedium.
v. Reactionwithhydrogentoformmetalhydrides
Group2metalsexceptberylliumandmagnesiumreactwithhydrogentoformionicmetalhydrides.
M+H2→MH2
BeH2andMgH2arecovalentinnature
Vi.Formationofsulphatesandcarbonates
Theyformsulphatesandcarbonates.Thesolubilityofthesulphatesdecreasesfromtoptobottomofthegro
up.BeSO4andMgSO4aresolubleinwaterduetohighenthalpyofsalvationofsmallerBeandMgions.CaS
O4issparinglysolublewhilesulphatesoftherestgrouptwoelementsareinsolubleinwater.
Vii.Complexformation
Group2elementsformcomplexesmorereadilythangrouponeelements,duetoreductioninsizeandincre
aseincharge.Complexformationfavoursahighsizetochargeratio.Berylliumisappreciablysmallerthan
therestofthegroupsoformscomplexesmorereadily.Forexample[BeF3]-,
[Be(H2O)4]2+etcCalciumandtherestofthegroupformcomplexeswithstrongcomplexingagentswithox
ygendonoratoms.

D. UsesofcompoundsofGrouptwoelements
i. CaO(quicklime)isusedinmakingglass
ii. quicklimeisusedforwatersoftening
iii. slakedlime(calciumhydroxide)isaddedchlorinetomakebleachingpowder
iv. CalciumsulphateisusedinmakingplasterofParisformedicalorhousingpurposes.CaSO4.1/2H2
O+H2O→CaSO4.2H2O(Gypsum)
POPinliqiudform Solidform
v. Calciumisgoodforbuildingstrongbonesandteeth.
vi. Mg(OH)2(milkofmagnesium)isusedtotreatstomachacidity
vii. MgSO4(empsomsalt)
viii. MgispresentinChlorophyll
ix. Ca(OH)2(slakelime)isusedinConcreteformation.

AnomalousbehaviorofBeryllium
Theanomalousbehaviuorofberylliumismainlyduetoitssmallsizeandpartlyduetoitshighelectronegati
vity.Thesetwofactorsincreasethepolarizingpower(ioniccharge/
ionicradii)ofBe2+ionstosuchextentthatitbecomessignificantlyequaltothepolarizingpowerofAl 3+ions.
Hencethetwoelementsresembleverymuch.
1. Berylliumhasthehighestelectronegativeandlowestelectropositivecharacteringrouptwo.
2. Duetosmallsize,berylliumhasahighchargedensityandexhibitsstrongtendencytoformcovalen
tcompounds.ThussaltsofBehavelowmeltingpointandaresolubleinorganicsolvents.Magnesi
umalsoshowstendencytoformcovalentcompoundsbutotheralkalineearthsdonotformcovalen
tcompounds.
3. Berylliumdoesnotdecomposewaterevenonboilingbecauseoftheirweekelectropositivechara
cter.Otheralkalineearthsdecomposeevencoldwaterevolvinghydrogen.
4. Unlikeotheralkalineearths,Beisnoteasilyaffectedbydryair.
5. Berylliumchloridesarecovalent
BeO+C+Cl2→BeCl2+CO
6. Berylliumhydroxideisamphotericwhileoxidesandhydroxidesofothergroup2membersarebas
icincharacter.
7. Amongotheroxidesofalkalineearthmetals,onlyberylliumoxideisextremelyhard,nonvolatile,
hashighmeltingpointandisamphoteric(dissolvesinacidsaswellasinalkalies).
BeO+2HCl→BeCl2+H2O
BeO+NaOH→Na2BeO2+H2O
8. Amongthealkalineearthmetals,onlyberylliumformsmanychelatetypecomplexesespecially
withoxygendonors.

Chemistryofselectednonmetals
GroupVIIBelements(halogens)

Element Symbol Electronicconfiguratio OxidationState

n
Fluorine F 1S ,2S2,2P5
2
-1
Chlorine Cl Is ,2S2,2P6,3S2,3P5
2
-1,+1,+III,+IV,+V,+VI,VII
 Bromine Br [Ar]3d10,4S2,4P5 -1,+1,+III,+IV,+V,+VI
Iodine I [Kr]4d10,5S2.5P2 -1,+1,+III,+V,VII
Astatine At [Xe]4F14,5d10,6S2,6P5 -

Thegroup17/
VIIBelementsareknownashalogens.Theyarenonmetalswithsevenelectronsintheirvalenceshellanda
generalelectronicconfigurationofn2p5.Theyhaveoneelectronlessthananoblegaselectronicconfigura
tion.Hence,theyprefertogointobondingbyacceptinganelectrontoattainstability.
OccurrenceandAbundance
Fluorineandchlorinearethe13thand12thmostabundantelementbyweightintheearthcrustrespectively.
Themajorsourceoffluorinearemineralslike;fluorspar(fluorite,CaF2),cryolite(Na3[AlF6])andfluorap
atite,
(Ca5F(PO4)3).ChlorinesourceislinkedtothoseofNaandK;rocksalt(NaCl),Sylite(KCl)andCarnallite(
KCL.MgCl2.6H2O.SeawaterisonesourceofBr2butsignificantlyhigherconcentrationsofBr-
arepresentinsaltlakesandnaturalbrines.Thenaturalabundanceofiodineisseawateranditisusuallytake
nupbyseeweedsfromwhereitisextracted.ImpureChilesaltpetra(caliche)containsupto1%sodiumioda
tewhichisanimportantsourceofiodine.Astatineisaradioactiveisotopewithashorthalflife.
Extraction
Group17elementsarehighlyelectronegativeandhenceveryreactive.Theirreactivityvariesasyougodo
wnthegroup;hencetheirextractionmethodologyisalsodifferent.
FlourineisobtainedbytreatingCaF2withconcentratedH2SO4togiveanaqueousmixtureofHF.Thisisthe
ndistilled,yieldingliquidHFwhichisaddedtoacoolsolutionofKHF2andelectrolyisedgivingF2andH2.
CaF2+H2SO4→CaSO4+2HF
KF+HF→K[HF2]
HF+K[HF2]electrolyse→H2+F2
Chlorineisproducedcommerciallyonavestscalebytwomethods;1.ElectrolysisofaqueousNaClsoluti
onduringtheproductionofNaOH.
2NaCl+2H2Oelectrolysis→2NaOH+Cl2+2H2
2.ElectrolysisoffusedNaClinthemanufactureofsodium
2NaClelectrolysis→2Na+Cl2
Bromineisextractedfromseawaterandbrinelakes.FirstthepHisadjustedto3.5bytheadditionofH2SO4.
Cl2gasispassedthroughthesolutiontooxidizetheBr-
toBr2.Thisisanexampleofdisplacementofoneelementbyanotherhigherintheelectrochemicalseries.Io
dineisobtainedfromChilesaltpetraornaturalbrine.ChilesaltpetraismainlyNaNO 3butitcontainstraces
ofsodiumiodateNaIO3andsodiumperiodatesNaIO4.PureNaNO3isobtainedbydissolvingsaltpetrainw
aterandcrystallizingNaNO3.Theiodateresiduesthusaccumulateandconcentrateinthemotherliquor.Iti
sreducedwithNaHSO4togiveI-.Astatinedoesnotoccurinnaturebutisasyntheticradioactiveelementwit
hover20isotopes.

PhysicalProperties
1. Allhalogensexistinfreestateasdiatomicmolecules
2. Theyareallcolouredgases;Fgasislightyellow,Clgasisyellowgreen,Brgasandliquidaredarkre
dbrownandIgasisviolet.Thecoloursarisefromtheabsorptionoflightonpromotinganelectronfr
omthegroundstatetoahigherstate.
3. Theyexhibitseveraloxidationstatesexceptfluorine(withonly-1oxidationstate)butthe-
1oxidationstateisthemostcommon.Halogenscanexhibita+1or-
1oxidationstatedependingonwhetherhalogenisthemostelectronegative.Thelackoflowlyinge
mptydorbitalinthe2ndenergylevelforfluorineisthereasonitcanexistonlyin-1oxidationstate.
4. Theyarestrongoxidizingagents
5. Theiratomicsizesincreasedownthegroup.Fluorineisthesmallestofthegroup.

Exceptionalreactivityoffluorine
Fluorineisthemostreactiveofalltheelementsintheperiodictable.Itreactswithalltheotherelementsexce
ptthelighternoblegaseslikeHe,NeandAr.Itsreactionwithmanyelementsisvigorousandoftenexplosiv
e.Thegreatreactivityoffluorineisattributedtotwofactors:
1. ThelowdissociationenergyoftheF-
Fbond(whichresultsinalowactivationenergyforthereaction)
2. Theverystrongbondsitformsduetoitshighpolarizingpower.
3. Theyhaveverysmallatomicsizeandthushighionizationenergy
4. Veryoxidizingpower

Chemicalproperties
1. Reactionwithwater
Thehalogensareallsolubleinwaterbuttheextenttowhichtheyreactwithwaterandreactionmechanismv
aries.
Fluorineisastrongoxidizingagentthatitoxidizeswatertooxygen.Thereactionisspontaneousandstrong
lyexothermic.oxidationislossofelectronsthatmeansoxidizingagentsgainelectrons.
F2+3H2O→2H3O++2F+1/2O2
Chlorinereactswithwatertoproduceanacidandhypochloride.
Cl2+H2O→HCl+HOCl
ThesametypeofdisproportionationreactionoccurstoaverylimitedextemtwithBr 2andI2.
 2. Reactionwithhydrogentoformhydrogenhalides
Halogensallreactwithhydrogenandformanhydroushydrogenhalides.Theirreactivitytowardshydrog
endecreasesdownthegroup.Hydrogenandfluorinereactviolently.Thereactionwithchlorineisslowint
hedark,fasterindaylightandexplosiveinsunlight.Iodinereactswithhydrogenveryslowlyinroomtempe
rature
M2+H2→2HM
ExampleH2+F2→2HF
3. Reactionswithmetals
Halogensreactwithmetalstoformmetalhalides.Themetalhalidesaremostlyionicinnature.
M+X2→MX2
Ca+Cl2→CaCl2
4. Reactionwithnonmetals
Halogensreactwithnonmetalstocovalentcompounds.
2M+X2→2MX
2C+3F2→2CF3

Usesofhalogens
1. Tracesofflorideionsindrinkingwaterortoothpaste(informofNaF)helptogreatlyreducetoothd
ecay.
2. Fluorideionsmaketheenamelonteethmuchharderbyconvertinghydroxyapatite[3Ca3PO4)2.C
a(OH)2]
(theenamelonthesurfaceofteeth)intothemuchharderfluoroapatite[3(Ca 3PO4)2.CaF2].
3. Chlorinegasisusedinplasticindustriesas1,2dichloroethaneandvinylchloridemonomer.
4. Chlorineisusedtoproduceawidevarietyofinorganicchemicalslikebleachingpowders,sodium
hypochloriteNaOCl,ChlorinedioxideClO2andSodiumchlorateNaClO3.
5. Chlorineisusedinpurifyingdrinkingwaterbecauseitkillbacteria
6. Chlorineisusedinmakinginsecticides
7. Bromineisusedasnematocides(killearthworm)informofMeBr
8. Bromineisusedinmakingfireretardants.Itiscommonlyusedasfireprooffabricsandcarpetsbytr
eatingthemwithtris(dibromopropyl)phosphate.
9. Bromineisusedinthemanufactureofphotographicemulsions.AgBrislightsensitive.
10. KBrisusedasasedativeandasananticonvulsantintreatingepilepsy.
11. KIisaddedtoanimalandpoultryfeeds.Thisistopreventthediseasegoiter.
12. Iodineisusedasantiseptic.