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TheCommonIonEffect
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Thesolubilityofinsolublesubstancescanbedecreasedbythepresenceofacommonion.AgClwillbeour
example.
AgClisanionicsubstanceand,whenatinybitofitdissolvesinsolution,itdissociates100%,intosilverions
(Ag+ )andchlorideions(Cl).
Now,considersilvernitrate(AgNO3).Whenitdissolves,itdissociatesintosilverionandnitrateion.Inthe
chemistryworld,wesaythatsilvernitratehassilverionincommonwithsilverchloride.Now,considersodium
chloride.ItproducessodiumionandchlorideioninsolutionandwesayNaClhaschlorideionincommonwith
silverchloride.
WhatwedoistrytodissolveatinybitofAgClinasolutionwhichALREADYhassomesilverionorsome
chlorideion(neverbothatthesametime)dissolvedinit.WhatwillhappenisthatthesolubilityoftheAgClis
loweredwhencomparedtohowmuchAgCldissolvesinpurewater.
Wecallthisthecommonioneffect.
Example#1:AgClwillbedissolvedintoasolutionwhichisALREADY0.0100Minchlorideion.Whatisthe
solubilityofAgCl?
Bytheway,thesourceofthechlorideisunimportant(atthislevel).Letusassumethechloridecamefromsome
dissolvedsodiumchloride,sufficienttomakethesolution0.0100M.
Solution:
1)ThedissociationequationforAgClis:
AgCl(s)Ag+ (aq)+Cl(aq)
2)TheKspexpressionis:
Ksp=[Ag+ ][Cl]
3)Theaboveistheequationwemustsolve.FirstweputintheKspvalue:
1.77x1010=[Ag+ ][Cl]
4)Now,wehavetoreasonoutthevaluesofthetwoguysontheright.Theproblemspecifiesthat[Cl]is
already0.0100.Igetanother'x'amountfromthedissolvingAgCl.Bythe1:1stochiometrybetweensilverion
andchlorideion,the[Ag+ ]is'x.'Substituting,weget:
1.77x1010=(x)(0.0100+x)
5)Thiswillwinduptobeaquadraticequationwhichissolvableviathequadraticformula.However,thereisa
simplifiedwaytosolvethisproblem.Wereasonthat'x'isasmallnumber,suchthat'0.0100+x'isalmost
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2/15/2017 TheCommonIonEffect
exactlyequalto0.0100.Ifweweretouse0.0100ratherthan'0.0100+x,'wewouldgetessentiallythesame
answeranddosomuchfaster.Sotheproblembecomes:
1.77x1010=(x)(0.0100)
and
x=1.77x108M
Thereisanotherreasonwhyneglectingthe'x'in'0.0100+x'isOK.ItturnsoutthatmeasuringKspvaluesare
fairlydifficulttodoand,hence,haveafairamountoferroralreadybuiltintothevalue.Sotheveryslight
differencebetween'x'and'0.0100+x'reallyhasnobearingontheaccuracyofthefinalanswer.Whynot?
BecausetheKspalreadyhassignificanterrorinittobeginwith.Our"adding"abitmoreerrorisinsignificant
comparedtotheerroralreadythere.
Example#2:WhatisthesolubilityofAgIina0.274molarsolutionofNaI.(KspofAgI=8.52x1017)
Solution:
1)Dissociationequation:
AgI(s)Ag+ (aq)+I(aq)
2)Kspexpression:
Ksp=[Ag+ ][I]
3)LetussubstitueintotheKspexpression:
8.52x1017=(x)(0.274+x)
4)Theanswer(afterneglectingthe+xin0.274+x:
[Ag+ ]=3.11x1016M
Bythe1:1stoichiometrybetweensilverionandAgI,thesolubilityofAgIinthesolutionis3.11x
1016M
5)Bytheway,thesolubilityofAgIinpurewateristhis:
8.52x1017=(x)(x)
x=9.23x109M
ThesolubilityoftheAgIhasbeendepressedbyafactorofabitlessthan30milliontimes.
Example#3:Themolarsolubilityofagenericsubstance,M(OH)2in0.10MKOHsolutionis1.0x105mol/L.
WhatistheKspforM(OH)2?
Solution:
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Inthiscase,wearebeingaskedfortheKsp,sothatiswhereour'x'willbe.Thatmeanstherighthandsideofthe
Kspexpression(wheretheconcentrationsare)cannothaveanunknown.
1)Dissociationequation:
M(OH)2(s)M2+ (aq)+2OH(aq)
2)Kspexpression:
Ksp=[M2+ ][OH]2
3)LetussubstitueintotheKspexpression:
x=(1.0x105)(0.10)2
The1.0x105comesfromthemolarsolubilityinformation,coupledwiththefactthatforeveryoneM(OH)2,
oneM2+ isproduced.
Also,wecouldhaveused(0.10+2.0x105)Mforthe[OH].However,the2.0x105M,beingmuchsmaller
than0.10,isgenerallyignored.
4)Theanswer:
Ksp=1.0x107
Example#4:Whatisthesolubility,inmolesperliter,ofAgCl(Ksp=1.77x1010)in0.0300MCaCl2
solution?
Solution:
1)Concentrationofchlorideionfromcalciumchloride:
0.0300Mx2=0.0600M
fromhere:
CaCl2(s)>Ca2+ (aq)+2Cl(aq)
2)CalculatesolubilityofAg+ :
Ksp=[Ag+ ][Cl]
1.77x1010=(x)(0.0600)
x=2.95x109M
Sincethereisa1:1ratiobetweenthemolesofaqueoussilverionandthemolesofsilverchloridethatdissolved,
2.95x109MisthemolarsolubilityofAgClin0.0300MCaCl2solution.
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Example#5:WhatisthesolubilityofCa(OH)2in0.0860MBa(OH)2?
Solution:
1)Dissociationequation:
Ca(OH)2(s)Ca2+ (aq)+2OH(aq)
2)Kspexpression:
Ksp=[Ca2+ ][OH]2
3)TheKspforCa(OH)2isknowntobe4.68x106.Weset[Ca2+ ]=xand[OH]=(0.172+2x).Substituting
intotheKspexpression:
4.68x106=(x)(0.172+2x)2
Bytheway,Ba(OH)2isastrongbaseso[OH]=2times0.0860=0.172M
Ignoringthe"2x,"wefindx=1.58x104M
Sincethereisa1:1molarratiobetweencalciumionandcalciumhydroxide,1.58x104Misthe
concentrationofthecalciumhydroxide.
Comment:ThereareseveraldifferentvaluesfloatingabouttheInternetfortheKspofCa(OH)2.Igotminefrom
theCRCHandbook,73rdEdition,pg.843.
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