2/15/2017 TheCommonIonEffect

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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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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2/15/2017 TheCommonIonEffect

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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2/15/2017 TheCommonIonEffect

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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