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~-- Analytical Chemistry
SOLUBILITY EQT!ILIBRIA
Solubility product ksp

The solubility product is the equilibrium constant for the reaction in which a solid salt dissolves , to give
its constituent ions in solution
Solid is an ionic compound
It is a strong electrolyte---------- completely ionized
++ 2· .
Example; BaS04cs)+-+Ba (aq) + S04 (aq)

•
Example; BaS04(S)+-+Ba+ (aq) + S04 2• (aq)
t
pure solid
When we write the eq. cons. For heterogeneous equilibrium we ignore the cone. Of pure solids and liquid
.therefore,
The _eq. cons.exp. For dissolving of a slightly soluble ionic solid depends only on the molar cone. Of the
species in solution
Ksp=[Ba2+][SO/°]

Dissolving silver sulfate, Ag2S04, in water

When silver sulfate dissolves it dissociates info ions. When the solution is saturated, the following
equilibrium exists:

Since this is an equilibrium, we can write an equilibrium expression for the reaction:

Notice that the Ag2S04 is left out of the expression! Why?

-~ Since K is always calculated by just multiplving concentrations, it is called a "solubility

product" constant - Ksp.
Calculating the K.P from the Molar Solubility

• The molar solubility of a substance is the number of moles that dissolve per liter of solution .

• For very soluble substances (like sodium nitrate, NaN03), this value can be quite high, exceeding
10.0 moles per liter of solution in some cases .

• For insoluble substances like silver bromide (AgBr), the molar solubility canoe quite small. In the
case of AgBr, the value is 5.71x10-7 moles per liter. . -··-------···-----

1
 calculating the KsP of the substance
1) Write the chemical equation for the substance dissolving and dissociating.
2) Write the Ksp expression.
3) Insert the concentration of each ion and multiply out.

• AB

AgCl (s) +-Ag" (aq) +er (aq)

x x

Ksp=[Ag+][Cr ] =X2
Sor X = ..JK;

S is molar solubility.
The molar solubility of a substance is the number of moles that dissolve per liter of solution _
Determine the K,;p of silver bromide, given that its molar solubility is 5.71x10- 7 nioles per liter.

When AgBr dissolves, it dissociates like this:

1-AgBr(s) <=>Ag+ (aq) +Br" (aq)
The Ksp expression is:
2-KsP =[Ag+] [Br-]
There is a 1:1 ratio between AgBr and Ag+ and there is a 1:1 ratio between AgBr and Br". This means
that, when 5. 71 x 10--7 mole per liter of AgBr dissolves, it produces 5. 71 x 10-7 moles per liter of Ag+ and
5.71x10- 7 moles per liter of Br- in solution.
Putting the values into the Ksp expression, we obtain:
. 3-Ksp = (5.71x10--7) (5.71x10-'7) = 3.26 x 10-13

2+
CaF2 (S) ~ Ca (aq) + 2F- (aq)
x 2X

x., = (X) (2X)2

x., = 4X3

x~jK:
Determine the Ksp of calcium fluoride (C~2), given that its molar solubility is 2.14 x 10-4 moles per liter.
l-CaF2 (s) <=> Ca2+ (aq) + 2 F- (aq)______ _ .
------- 2
 2+, - 2
2-Ksp = [Ca J [F ] .
3-Ksp = (2.14 x 10-4) ( 2x2.14 X 10-4)2 = 3.92 X 10-11
(4.28 x 1 o-4)2

3)A2B ------------Ag2Cr04
Ag2S04 (s) ~ 2Ag+ (aq) + S042-(aq)
2X x
Ksp =(2X)2 (X)
Ksp= 4 X3

x= 3!ffe
4)AB3
Fe(OH)3 (s) !:; Fe3+ (aq) +30ff (aq)
X 3X
Ksp =(X) (3X)3

Ksp=27 X4
x = 4{KsP
...}27

5)A2B3 or A3B2 , Pb3(po4)2

BhS3 (s) !:; 2Bi3+ (aq) +3s2- (aq)
2X 3X

x., =(2X)2 (3X) 3

~Ksp
X = 4x27

~ Calculate the x., for Ce(I03)4, given that its molar solubility is 1.80 x 10-4 mol/L
The Ksp expression is:
x., =- [Ce4j [103-)4
We know the following:·~ ---- . -·· - - - - -- - -- -~-
These is a 1:4 ratio between the concentrations of the cerium(IV) ion and the iodate ion .There is a 1:1
ratio between the molar solubility and the cerium(IV) ion's concentration.
Therefore:
Ksp = (1.80 x 10-4)(7.20 x 10-4)4
Ksp = 4.84 x 10-17

3
 )- Calculate the Ksp for Mg3(P04)2, given that its molar solubility is 3 .57 x 1 o-6 mol/L
The Ksp expression is:
Ksp = [Ivig2+]3 [P043-]2
We know the following:
These is a 3:1 ratio between the concentration of the magnesium ion and the molar solubility of the
magnesium phosphate .There is a 2:1 ratio between the concentration of the phosphate ion and the
molar solubility of the magnesium phosphate. · ·
Therefore:
Kso = (1.071X10-5)3 (7.14 X 10-6)2
Ks~= 6.26 x 10-26 .

example, what is the concentration ofHg22• in equilibrium with 0.1 O M er in a solution of KCI
containing excess, un dissolved Hg2Cl2(s)?

Writing solubility product expressions ...

• For each salt below, write a balanced equation showing its dissociation in water.

• Then write the Ksp expression for the salt.

Mn (II) hydroxide, Mn(OH)2

Nickel sulfide, NiS
Silver chromate, Ag2Cr04
Zinc carbonate, ZnC03
Calcium fluoride, CaF2
Solubility Products, Ksp1 and Ion Products Q~P
formations of precipitates are chemical
equilibria phenomena" and we usually write
these heterogeneous equilibrium in the
following manner, and call the equilibrium
constants solubility products, Ksr,:

. . .
Equilibrium . Expressbnfor K,p and C2,p

Agt.l(s) =Ag+(aq)+Cr(aq) (Ag"][Cl1

[Ca2'][C0:.1-.

[Li"]2[C031

ion product, Qsp.

If the solution is not saturated, no precipitate will form. In this case, the product is called the ion product,
Qsp· . - ~- ---- --~----
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 The role of the ion product Qsp in solubility calculation
THE ION PRODUCT
Is the product of the concentrations of the ions at any moment in time.
When the ion product is equal to the solubility product for the salt ,the system .is~ .. at equilibrium.

• Qsp < Ksp Unsaturated solution Qsp = Ksp Saturate solution Qsp > Ksp Oversaturate solution

Predicting Precipitation (Ksp vs Q)

Will a precipitate form when 0.10 L of 8.0 x 10·3 M Pb(N03)2 is
x =
added to 0,40 L of 5.0 Ht3 M tia2SQ4? (K1P 6.3 x 10·7)

REMEMBE.Rr TAKE INTO ACCOUNT OF CONCENTRATION OF IONS IN

MIXTURE (DllUTION UPON MIXING)

PbS04{S)~ Pb2•(aq)+SOl'(aq)

[Pb2+] 0.1 x8.0x10 .3 0.0016 M

0.1+0.4

[SOl·] = 0.4 xS.OxlO-3 0.004 M

0.1+0.4

Q = [Pb2+] [SO/·]= (0.0016) (0.004)

= 6.4X10 ·G> Ksp = 6.3x10 -7
Q>Ksp -ti. ppt will form

Step 1: Is a sparingly soluble salt formed?

We can see that a double replacement reaction can occur and produce PbCr04. Since this salt has a
very small Ksp, it may precipitate from the mixture. The solubility equilibrium is:

PbCr04 (s) ~ Pb2+ (aq) + CrO,/- (aq)

Ksp = 2 x 10·16 = [Pb2l[Cr0l]

If a precipitate forms, it means the solubility equilibrium has shifted BACKWARDS.

This will happen only if Qsp > Ksp in our mixture.

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 Step 2: find the concentrations of the ions that form the
sparingly soluble salt.
Since we are mixing twosolutlons in this example, the
concentrations of the Pb1+ and Crol'-will be diluted. We
have to do a dilution calculation!

{Pb2·•]= C,V1 = (Oc024M)(15 ml) =O~OOBOM Pb2+

V2 (45mL}

CjV1 (0.030M)(20 ml) 2

[CrO.e.2°]= y2 (4Sml) 0.020M Cr04 -

Step 3: Calculate Qsp for the mixture.

Qsp .; [Pb2j[CrO/] = (0.0080 M)(0.020 M)

Qsp = 1.6 x 104

Step 4: Compare Qsp to Ksp.

Since Qsp >> Ksp, a precipitate will form when the two solutions are mixed!

Note: If Qsp = Ksp, the mixture is saturated

If Qsp < Ksp, the solution is unsaturated

Either way, no ppte will form!

Chemical analysis gave

[Pb2+] = 0.012 M, and [Br"] = 0.024 M in a solution. From a table, you find Ksp for PbBr2 has a
value of 4x10·5 • Is the solution saturated, oversaturated or unsaturated?

[0.012] [0.024]2 = 6.9x10"6 < 4x10"5 (Ksp)•

This question deals with the concept of ion product, Qsp·

H Qsp = [Pb2+] [Br"]2 < Ksp the solution is unsaturated.

Factors affecting solubility

1. Common Ion Effect

2. pH of solution
3. Formation of Complexes

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As a result the solubility eq. of CaF2 is shifted to right.
CaF2 (s) ~ Ca2+ (aq) + 2F- {aq)
1
addition of H30+
F-+ H+ HF
Over all Ca F2 (s) +2H+ (aq) ~ Ca2+ (aq} + 2HF (aq)

In generalrule;the solubtlltv ofsllghtlv sqluble salts

containing basic anions increases as [H I increases (as
PH is lowered)

S 2·=.Kssp c·1+ [H3.0+]) ·

General rule Ka
Salt B)(A, Of poly basic add HaA

o.·.+ ]2 + - - - -)·
S::;
{X+YJ
xxKspyY ( 1 + [H30Ka +] + [H.3.
K
a Ka-:
-

2. pH of Solution
Mg(OH)2 (s) ~ Mg2+ (aq) + 20ff (aq)

Ksp = 1.8 x 10·11 (25 °C)Calculate the molar solubility of Mg(OH)2 in pure water.
What is the pH of the resulting solution?

Ksp = [Mg2l[Off]2 = (x)(2x)2

x=Solubility = 1.651 x 10·4 mol/L = 1. 7 xl 0-4 M
[Off]= 2x = 3.302x10-4 M
pOH = ~ log(3.302x 10-4) = 3.48
pH = 10.5 pH of Solution

2.
What is the solubility ofMg(OH)2 in a less alkaline solution buffered at pH 9?pOH =5
Mg(OH)2 (s) ~ Mg2+ (aq) + 20ff (aq)
[Off] = 1.0 x 10·5 M
Ksp = [Mg2+] [Off]2
Ksp = 1.8 X 10"11 (25 °C) = [Mg2+](1.0 X 10"5)2

S=[Mg2+] = 0.18 M COMPARE WITH 1. __.,J. x=Solubillty=L'Z xl T' M

Which of the following substances will be more soluble in acidic solution than in basic solution: (a)
8
 Ni(OH)z(s) (b) CaC03(s) (c) BaS04 (s) (d) AgCI (s)?
SOLUTION
(a) We can conclude that Ni(OH)2(s) will be more soluble in acidic solution because of the basicity of
011; the It ion reacts with the OH~ ion, forming water:
(b) Similarly, CaC03(s) dissolves in acid solutions because co,': is a basic anion:

Ni(Oli}i($)-- . . .•. •Ni:t-+·cllq) + 20H-(aq)

20H-·(aq) + 2H +(aq) ~ 2HP(l)
Overall~ Ni(OH)2(s) + 21-I"'(aq) ~Nl.,.(itq) + 21{.z(Xl)

CO}~{aq)+ 2H'"(aq} · · lli~(!Uf)

H~~(aq} ~C°'i{g) + HP(/)
Overall: CaCO:)(s) + 2IP(aq) _,. ci"'(aq)' + COi{g) + HP(l)

(c) The solubility of BaS04 is largely unaffected by changes in pH because so,': is a rather weak base
and thus has little tendency to combine with a proton. However, BaS04 is slightly more soluble in
strongly acidic solutions.
(d) The solubility of AgCl is unaffected by changes in pH because er is the anion of a strong acid and
therefore has negligible basicity.

3-Formation of Complex Ions

A characteristic property of metal ions is their ability to act as Lewis acids,or electron-pair
acceptors, toward water molecules, which act as Lewis bases, or electron-pair donors.

Lewis bases other than water can also interact with metal ions, particularly with transition-metal
ions. Such interactions can have a strong effect on the solubility of a metal salt.

Lei.visatld + Lewis base ::-""" adduct ·

Electron pair Electron pair
acceptor donor

For example, AgCl, whose Ksp = 1.8 10-10, will dissolve in the presence of aqueous ammonia
because of the interaction between Ag+ and the Lewis base NH3,

This process can be viewed as the sum of two reactions, the solubility equilibrium of AgCl

and the Lewis acid-base interaction between Ag+ and NH3:

9
 AgC~($) ~Ag+ {aq) + er (aq)
Ag i:(aq) + 2Nll:J(aq) .· · ·. . Ag(Nli,.t)i +(aq)

Qv:erall: AgCl{s) + 2NH3(ttq) ......,.._-:-"' Ag(NH:J1+ (aq) + Cl" (aq

The presence of NH3 drives the top reaction, the

solubHity equilibrium of AgCt, to the right as Ag+(aq) ls
removed to form Ag{NH3)i.+.
a metal ion and the Lewis bases bonded to it, such as
Ag(NH3)i+, is called a complex ion

The stability of a complex ion in aqueous

solution can be measured by Kr
For example, the equilibrium constant for
formation of Ag{NH3)/ is L7 x107
. t~)i+] .....
1" = [Ag+j[Nitji = 1.1 x 101

Such an equilibrium constant is called a

formation constant, K1

• For a Lewis base such as N H3 to increase the

solubility of a metal salt, it must be able to
interact more strongly with the metal ion than
water does.
• The N H3 must displace solvating H20
molecules in order to form Ag(NH3)/:

. Ag. +c·"'I
· · )· f· . '»...TU~(
'·"" ~ aq·~1 ---...:
~
A~TU_\...tt ·\
at>\' u. "JIZ \aq1 ·

10
 EXAMPLE;
If Pb2+ and 1- only reacted toform solid Pb 12:, then the solubility of Pb hwould
alwaysbeveryiow
· ..

Pbl2(s) ~- Pb2+ + 2r
inthe·presenceofexcessl-highconcentrationso.fl-ca.usesolidPbl2.todissclve.We
explain this by the formation of esertesot comptex ions
. + 1--~~
Pb~+. Pbl+ Kt""' [Pbl+:VIPbHJ[rJ =LO x lo':?
. + '>I-
PbH - ,• ~
...---- 'Phl. z._,..,,_. 1q·1· ~1=lPhlz(aq}lt[Pb~+HrJz==1.4 x u}t
.Pn~+ + sr ~ PM; ~J = -[Pbl;JtIPQ?:+ ni,- J1 = sJ x J(il
2+
.P. .b- +_- ...·"l"" ~ Pbl.t2- ~-.f =-· I Pblj'"" Jtf Pb2 +-JI I"" J4 "" 3,:Q X IO~

Jn generaITheoverall,orcumulative,formation constants are denoted ~i:

M. + nX: JJ.. . MX~ ~11- - [MX"JllMHXl~

Fin9 the wnccnlratior\$ of Pbl "~ Pbl2(aq), Phl i ;iud Pbl}- in a solution saturated "ith
1<

Pblz(.S) and conlai.nfog diwl\·ed r with a (.1JOCCrtltillk1n of (a) 0.001 0 M: and (b) L-0 M.
(a) Front K~p for Reaction

FROM
stepwise formatlon constants
tPt1+1"" K,[Pn2+n-1 ... ,1,<lx rn2>f7•9x 10~3x1.ox 10~3,
• 7.9 X 10-it M
l Phb(aq}J "" ~2l Ph2+ nr J1 .. i.J X 10-~ M
[J>b1;1- ~.,f Ph2~1rr1s = 6.6 x 10-s M
[Pbll"' J "" ~J[ Pb2+ ]( .r y'· eo 2.4 X 10-10 M
b) If, instead. we; take. [I" J = LQ M, lhcn analogous compuutions sl1qw tha!
. - - -------(Pb2.,, J • 7.9 x 1Ct9. M--- lPbI_;J • 6.6 X IO-~ M
I Pbl+ l * 1l) X 10'"1 M t.Pbii ... ,I st 2.4 x 10-4 M
lPbh(aq}j"'" 1.1.X10-5 M

11
The solubility of slightly soluble salt which form
a complex calculated

S= ~ksp (l+k1[L]+K1K2[L] 2+------)

Or

s -kSQ (1 +k1[L]+K1K2[LJ 2+--)

Where k is formation or stability constants.

• EXERCISE
• Calculate the concentration of Ag+ present in
solution at equil.ibrium when concentrated
ammonia is added to a 0.010 M solution of
AgN03 to give an equilibrium concentration of
[NH3] = 0.20 M, Neglect the small volume
change that occurs on addition of NH3.'

Because~ is quite Iarge, we begin with the

assumption that essentially all of the Ag+ is
converted to Ag(NH3)2+,
in accordance with Equarton
Ag+ (aq) + l:NH3(aq) • =- Ag(Nl~:J)2-r (4q)
Thus, [Ag+] will be small at equilibrium. tf:[Ag+] is
n.010 M initiaU~ then [Ag(NH3J2 +] wiU be 0.010 M
. Let the concentration ofAg+ at. equilibrium hex.
Then, at equilibrium ·

12

·~---·---
~ ·-

The stability of a complex ion in aqueous

solution can be measured by Kr
For example, the equilibrium constant for
formation of Ag{NH3)i+ is 1.7 x107

.,x. ;:: .-I~

~· _, -~ ;:;: ;' 1~··-"·1x:
n7
(Ag L - . \T
Such an equilibrium constant is called a
formation constant, K1

Calculate the molar solubility of CdC03 in 1.5 M NHa. Note that Cd2+ forms the Cd(NHal/+ complex ion for
which Kt is 1.3 x 107• Ksp for CdCO:i is 5.2x10-12•
CdC03(s) ¢:::== -G&!+-fa:EI1 + CQ32-(aq) Ksp=S.2x10-12
td~faf.tl+ 4NH3(aq) ¢:::== Cd(NH3)42+(aq) Ke1.3 x 107
CdC03(sJ + 4NH3 (aq) ¢:::== Cd(NH3)42+(aq)+ C032-(aq) K= Kspx Kr
=(5.2x10-12)(1.3x107)
=6.76x10-5

K=[Cd(NH3}42+J[C03U= x2 = 6.76x10-s
[NH3]4 (1.S-4*}4

x= 11.H x 10-2 Mi

~ Calculate the molar solubility of AgC! i.n 12 M NH3•

KspAgCl = 1.8x10~10 ·Kt Ag(NHa)i = 1.7x107
Ag Cl (s) <= Ag+{aij + Cl-(aq). vl\sp a:1·. · a·· x 10-10
I . . ..

Arfa<tl+ 2NH3(aq) -~ Ag(NH~l(aq) Ke1.7x 107

AgCl(s) + 2NH3{aq) ¢:;:;; Ag(NH3)i+ + Cl-(aq) K= KspX Kr
=3.06 x10·3

13
K=[Ag(NH3}i+] [Cl]= x2 = 3.06x10-3
[NH3]2 -. (12-~

x= !6.6x10-1 Mi

4)Temperature
The sofubility of slightly soluble salt increased as
the result of increasing the temperature of the
solution.
increasing the temperature, increase the cone.
Of ions in the soln. and Ksp increase.

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