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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/°]
Since this is an equilibrium, we can write an equilibrium expression for the reaction:
• 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. . -··-------···-----
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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
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.
2+
CaF2 (S) ~ Ca (aq) + 2F- (aq)
x 2X
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
~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)?
• For each salt below, write a balanced equation showing its dissociation in water.
. . .
Equilibrium . Expressbnfor K,p and C2,p
[Li"]2[C031
• Qsp < Ksp Unsaturated solution Qsp = Ksp Saturate solution Qsp > Ksp Oversaturate solution
PbS04{S)~ Pb2•(aq)+SOl'(aq)
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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!
Since Qsp >> Ksp, a precipitate will form when the two solutions are mixed!
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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)
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?
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
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:
(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.
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.
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
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AgC~($) ~Ag+ {aq) + er (aq)
Ag i:(aq) + 2Nll:J(aq) .· · ·. . Ag(Nli,.t)i +(aq)
. Ag. +c·"'I
· · )· f· . '»...TU~(
'·"" ~ aq·~1 ---...:
~
A~TU_\...tt ·\
at>\' u. "JIZ \aq1 ·
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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~
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
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The solubility of slightly soluble salt which form
a complex calculated
• 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.'
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·~---·---
~ ·-
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
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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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