SOLUBILITY EQUILIBRIA AND

PRECIPITATION TITRATIONS
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Copyright 2013

2013/3/6 © L. Lapitan 2011 1

SOLUBILITY EQUILIBRIA AND
PRECIPITATION TITRATIONS
Required Reading: Ch 3 and 11
(Fundamentals of Analytical Chemistry : An Introduction
By Skoog, West, Holler ,Crouch, and Chen – 8th ed.)`

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Solubility Equilibria
• MmXx (s)  m Mn+ (aq) + x Xy- (aq)

• The equilibrium is established

when we have a saturated
solution of ions forming the
solid and solid is dissociating
to form the ions in solution.
The rates of these processes
must be equal.

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Solubility Equilibria
• For a dissolution process, we give the
equilibrium constant expression the name
solubility product (constant) Ksp. For
• MmXx (s)  m Mn+ (aq) + x Xy- (aq)
• Ksp = [Mn+]m [Xy-]x
• refer to a specific balanced equation
(by definition this balanced equation is one
mole of solid becoming aqueous ions)
• at a specific temperature.
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Problem
• Write the expressions of Ksp of:
a) AgCl K sp = [Ag ][Cl ]
+ −

b) PbI2 K sp = [Pb ][I ]

2+ − 2

c) Ca3(PO4)2 K sp = [Ca ] [PO 4 ]

2+ 3 3− 2

d) Cr(OH)3 K = [Cr ][OH ]

3+ − 3
sp

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Problem
1. If a saturated solution of BaSO4 is prepared by
dissolving solid BaSO4 in water, and [Ba2+] = 1.05 x 10-5
mol⋅L-1, what is the Ksp for BaSO4?

→ 2−
BaSO 4 (s) ← Ba 2+ (aq) + SO 4 (aq)

[ ][
K sp = Ba 2+ SO 4
2−
]
[ ] [ ] = 1.05 x 10 M
K sp = x 2 if x = Ba 2+ = SO 4
2. Calculate the Ksp for Ca3(PO4)2 (FW = 310.2) if the
2− -5

K = (1.05 x 10 ) [Ans. 1.3x10-26]

-5 2
solubility is 8.1x10-4 g/L
sp

K sp = 1.1 x 10 -10

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Molar solubility
• If we know the Ksp value for a solid, we can
calculate the molar solubility, which is the
number of moles of the solid that can dissolve
in a given amount of solvent before the
solution becomes saturated.
• The molar solubility leads to the solubility (by
using the molar mass) which is the mass of the
solid that can dissolve in a given amount of
solvent before the solution becomes saturated.

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Problem
1. Lead iodide, PbI2 is a dense, golden yellow “insoluble”
solid used in bronzing and in organometal work, requiring
golden color. Calculate the molar solubility of lead iodide
in pure water at 25oC given its Ksp = 7.1 x 10-9

2. A handbook lists the aqueous solubility of lithium

phosphate (Li3PO4) as 0.034 g per 100 mL at 18 °C.
What is the Ksp of lithium phosphate at 18 °C? The
molar mass of Li3PO4 is 115.794 g⋅mol-1. [Answer: Ksp =
2.0
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x 10-9]
© L. Lapitan 2011 8
 Solubility Product Constant
• Ksp indicates how soluble an ionic compound
is in water at a certain temperature
Equilibrium Reaction Ksp @ 25oC
AgBr(s) = Ag+(aq) + Br-(aq) 7.7 x 10-13
AgCl(s) = Ag+(aq) + Cl-(aq) 1.6 x 10-10
AgI(s) = Ag+(aq) + I-(aq) 8.3 x 10-17

• The higher the Ksp, the more soluble the compound is.

AgCl > AgBr > AgI

Note: the solutes are above are f the same type (MX or MX2 or M2X…)
therefore their molar solubilities can be related in the same way as their Ksp
values)
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Solubility Product Constant
• If solutes are not of the same type, you’ll have
to calculate the each molar solubility and
compare the results.
Ex. AgCl and Ag2CrO4
Which has the greater molar solubility:
AgCl with Ksp = 1.8 x 10-10 or
Ag2CrO4 with Ksp = 1.1 x 10-12?
Answer: The molar solubility of AgCl is 1.3 x 10-5 M while the
molar solubility of Ag2CrO4 is 6.5 x 10-5 M. Silver chromate has a
higher molar solubility.
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The Common-ion Effect
• MmXx (s)  m Mn+ (aq) + x Xy- (aq)

• If we have dissolved a solid in pure water and we

add to this solution another solution containing one
of the common ions, then Le Chatalier’s Principle
tells us what will happen:
• The presence of the common-ion in the
added solution will force the dissolution
reaction to the left, meaning more solid
will form!
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The Common-ion Effect

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The Common-ion Effect
MmXx (s)  m Mn+ (aq) + x Xy- (aq)
• If instead of dissolving a solid in pure water we try
and dissolve it into a solution that already contains
one of the common ions, then Le Chatalier’s
Principle tells us what will happen:
• The presence of the common-ion
already in solution will force the
dissolution reaction to the left, meaning
less solid will dissolve than would
dissolve in pure water!

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Problem
1. What is the molar solubility of PbI2 in 0.1 M KI
solution? Ksp = 7.1 x 10-9

2. Calculate the molar solubility of MgF2 (Ksp = 7.4 x

10-11) in pure water and in 0.10 mol⋅L-1 MgCl2 at 25
°C. [Answer: The molar solubility is 2.6 x 10-4 M in pure
water and 1.4 x 10-5 M in 0.10 M magnesium chloride.]
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Criteria for Precipitation and its
Completeness
• Can we predict if a solid will form if we mix
two solutions of different ions?
• Consider the mixing of two different
solutions, one with Ca2+ ions and one with F-
ions. A formation of solid is the dissolution
reaction in reverse, so we can express the
reaction using the dissolution equation
CaF2 (s)  Ca2+ (aq) + 2 F- (aq) Ksp = [Ca2+ ][F-]2

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Criteria for Precipitation and its
Completeness
• When we mix the solutions (BE CAREFUL –
mixing ALWAYS changes the concentrations of
both our ions!)
• the system is most likely not at equilibrium.
• Like in other equilibrum problems, we can use a
reaction quotient Qsp (often called the ion
product) to tell us in which direction the system
must go to reach equilibrium
Qsp = [Ca ][F ]
2+ - 2

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Criteria for Precipitation and its
Completeness
If Qsp > Ksp, the solution is supersaturated, so the
system is not at equilibrium. The concentration of
the ions is greater than it would be at equilibrium,
and so the reaction wants to shift from ions
towards the solid.
We expect precipitation to occur!

If Qsp = Ksp, the solution is saturated, and the

system is at equilibrium.

2013/3/6
No precipitation occurs!
© L. Lapitan 2011 17
Criteria for Precipitation and its
Completeness
•If Qsp < Ksp, the solution is unsaturated, so the
system is not at equilibrium. The concentration of
the ions is less than it would be at equilibrium, and
so the reaction wants to shift from solid towards
the ions.
No precipitation can occur!

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Problem
1. Three drops of 0.20 M KI solution is added to 100.0 mL
of 0.0101 M Pb(NO3)2. Will a precipitate of lead iodide
form? (Assume 1 drop = 0.05 mL)

2. Will a precipitate form when 0.150 L of 0.10 mol⋅L-1

Pb(NO3)2 and 0.100 L of 0.20 mol⋅L-1 NaCl are mixed?
Ksp of PbCl2 is 1.2 x 10-5 [Answer: Qsp = 3.8 x 10-4 > Ksp so
precipitation should occur]

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Complete Precipitation
• Generally we treat precipitation as complete if
99.9% of the original ion concentration has
been lost to the precipitate.
• For example, if our initial [Pb2+] is 0.10 M,
then precipitation by adding I- is complete
when our solution contains a [Pb2+] less than 1
x 10-4 M.

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Problem
1. The first step in a commercial process in which
magnesium is obtained from sea water involves
precipitating Mg2+ as Mg(OH)2. the magnesium ion
concentration in sea water is about 0.059 M. If sea
water sample is treated so its [OH-] is maintained at
0.20 x 10-3 M.
(a) what will be the [Mg2+ ]remaining in the solution
when precipitation stops Ksp = 1.8 x 10-11

(b) can we say that precipitation of Mg(OH)2 is

complete under these conditions?

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Problem
2. A typical Ca2+ concentration in seawater is 0.010 M.
Will the precipitation of Ca(OH)2 be complete from a
seawater sample in which [OH-] is maintained at
0.040 M? Ksp of Ca(OH)2 is 5.5 x 10-6
[Answer: Since the final [Ca2+] is 3.4 x 10-3 M, which is 34 % of
0.010 M, the precipitation is not complete.]

3. What [OH-] should be maintained in a solution if, after

precipitation of Mg2+ as solid magnesium hydroxide,
the remaining [Mg2+] is to be at a level of 1µg⋅L-1?
Molar mass Mg is 24.305 g⋅mol-1 ,Ksp of Mg(OH)2 is 1.8
x 10-11 [Answer: [OH-] needed is 1.6 x 10-2 M]
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Separation of Ions by Fractional
Precipitation
• The process by which two or more aqueous
substances in a solution are separated
through the addition of a common ion, taking
advantage of their different concentration
needs in order to form a precipitate.

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 Separation of Ions by Fractional
Precipitation
• If we have a solution with both CrO42-
ions and Br- ions
• and add a large amount of Ag+ ions at
once,
• then both Ag2CrO4 and AgBr will
precipitate
• in our container at the same time.

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Separation of Ions by Fractional
Precipitation
• If we slowly add the Ag+ solution instead the
solid with the significantly lower molar
solubility (AgBr in this case – do the
calculations to check this for yourself)
• will precipitate first
• and consume the added Ag+
preferentially.
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Separation of Ions by Fractional
Precipitation
• In other words,
• the concentration of Ag+
• CAN NOT become large enough
• to precipitate Ag2CrO4
• until the AgBr
• precipitation is complete.
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Fractional precipitation

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Problem
• Sodium Iodide (NaI) crystals are slowly added
to a solution that is 0.100 M Pb(NO3)2 and
0.100 M AgNO3. Which will precipitate first?
Ksp AgI = 8.31 x 10-17 Ksp PbI2 = 7.1 x10-9

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Problem
Which Will Precipitate First?
1. CaCO3
(Ksp: 8.7x10-9)
2. CaF2
(Ksp: 4.0 x 10-11)
3. Ca3(PO4)2
(Ksp: 1.2 x 10-26)

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Problem
1. Solid NaI is slowly added to a solution that is 0.010 M
in Cu+ and 0.010 M Ag+.
(a) Which compound will begin to precipitate first?
(b) Calculate [Ag+] when CuI just begins to precipitate.
(c) What % of Ag+ remains in solution at this point?
• AgI Ksp = 8.3 x10-17
• CuI Ksp = 1.00 x 10-12

[Answer a) AgI; b) 1.6 x 10-17 M; 1.6 x 10-3%]

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Problem
1. AgNO3 is slowly added to a solution with [Cl-]
= 0.115 M and [Br-] = 0.264 M. What percent
of the Br- remains unprecipitated at the point
at which AgCl (s) begins to precipitate?
Ksp values AgCl = 1.8 x 10-10
AgBr = 5.0 x 10-13

Answer: 0.12 % of Br- remains.

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Precipitation Titrations
• Titrations with silver nitrate are sometimes
called argentometric titrations.

Example
Calculate the pAg of the solution during the
titration of 50.00 mL of 0.0500 M NaCl with
0.1000 M AgNO₃ after the addition of the
following volumes of reagent:
(a) 0.00 mL, (b) 24.50 mL,
(c) 25.00 mL, (d) 25.50 mL.
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 (a) Because no AgNO₃ has been added, [Ag⁺] 0 and
pAg is indeterminate.
(b) At 24.5 mL, [Ag⁺] is very small and cannot be
computed from stoichiometric considerations, but
[Cl¯] can be obtained readily.

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 (c) This volume corresponds to the
equivalence point where [Ag⁺]=[Cl¯] and

(d) At this volume of the titrant, there is excess

of the Ag+ ions

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The Shapes of Titration Curves
•Effect of titrant
concentration on
precipitation titration
curves. Note the
increased sharpness of the
break for the more
concentrated solution, A.

Curve A shows 50.00 mL of 0.0500 M NaCl with 0.1000 M AgNO3,

Curve B shows 50.00 mL of 0.00500 M NaCl with 0.01000 M AgNO3 .
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 The Shapes of Titration Curves
•Effect of reaction
completeness on
precipitation
titration curves.
Note that smaller values of
Ksp give much sharper
breaks at the end point.

For each curve, 50.00 mL of a 0.0500 M solution 10-36

2013/3/6 of the anion was2011

© L. Lapitan titrated with 0.1000 M AgNO3 36
Precipitation Titrations: Indicators
• Three types of end points are encountered in
titrations with silver nitrate:(1) chemical, (2)
potentiometric, and (3) amperometric.
• The Mohr Method: Formation of a Colored
Precipitate.

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Precipitation Titrations: Indicators
The Mohr Method: Formation of a Colored
Precipitate
• the high chromate ion concentration imparts
such an intense yellow color to the solution.
• lower concentrations of chromate ion are
generally used, and, as a consequence, excess
silver nitrate is required before precipitation
begins. An additional excess of the reagent
must also be added to produce enough silver
chromate to be seen.
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Precipitation Titrations: Indicators
The Mohr Method: Formation of a Colored
Precipitate
• The Mohr titration must be carried out at a pH of 7
to 10 because chromate ion is the conjugate base
of the weak chromic acid. Consequently, in acidic
solutions, where the pH is less than 7, the
chromate ion concentration is too low to produce
the precipitate.
• Titration at pH < 7 : Formation of HCrO4-
• Titration at pH > 10 : Formation of Ag hydroxide ppt
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Precipitation Titrations: Indicators
The Fajans Method: Adsorption Indicators
• Fluorescein is a typical adsorption indicator
• In the early stages of the titration of chloride
ion with silver nitrate, the colloidal silver
chloride particles are negatively charged
because of adsorption of excess chloride ions.
The dye anions are repelled from this surface
by electrostatic repulsion.

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Precipitation Titrations: Indicators
The Fajans Method: Adsorption Indicators
• Beyond the equivalence point, the silver
chloride particles strongly adsorb silver ions
and thereby acquire a positive charge.
Fluoresceinate anions are now attracted into
the counter-ion layer.
• The net result is the appearance of the red
color of silver fluoresceinate in the surface
layer of the solution surrounding the solid.

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Precipitation Titrations: Indicators
The Volhard Method: Forming a Colored
Complex
• Silver ions are titrated with standard solution
of thiocyante ion:

• Iron (III) serves as the indicator

• The titration must be carried out in acidic

solution to prevent precipitation of iron(III) as
the hydrated oxide.
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Precipitation Titrations: Indicators
The Volhard Method: Forming a Colored
Complex
• The most important application of the Volhard
method is for the indirect determination of
halide ions.
• A measured excess of standard silver nitrate
solution is added to the sample, and the
excess silver ion is determined by back-
titration with a standard thiocyanate solution.

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Precipitation Titrations: Indicators
The Volhard Method: Forming a Colored
Complex
• a distinct advantage over other titrimetric
methods of halide analysis because such ions
as carbonate, oxalate, and arsenate (which
form slightly soluble silver salts in neutral
media but not in acidic media) do not
interfere.
• Silver chloride is more soluble than silver
thiocyanate.
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Precipitation Titrations: Indicators
The Volhard Method: Forming a Colored
Complex
• This reaction causes the end point to fade
• This error can be circumvented by filtering the
silver chloride before undertaking the back-
titration.

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Indicators for Precipitation Titrations: Summary
1. Volhard Method: Indicator -> Ferric Alum
Endpoint : bloody red color
Rxn: Ag+ + SCN- = AgSCN(s)

2. Mohr Method: Indicator -> Chromate (CrO42-)

Endpoint: brick red color
Rxn:2Ag+ + CrO42- = Ag2CrO4 (s)

3. Fajans Method: Indicator -> Fluorocein

Endpoint: AgX:Ag+::Fl- (adsorbed pink color)
(Fl- symbolizes the anion of a weak acid)
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Blank Titration
• In Blank determinations, all steps for the
analysis are performed in the absence of the
sample.
• Blank determinations reveal errors due to
interfering contaminants from vessels or
reagents employed in analysis
• Blanks also allow the analyst to correct titration
data for the volume of reagent needed to cause
an indicator to change color at an endpoint

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Applications of Precipitation Titrations
1) To an aqueous solution containing solution of a
1.6000 g sample consisting of a mixture of CaBr2⋅H2O
(FW = 308.0) and inert matter is added 52.00 mL of
0.200 M AgNO3. The excess Ag+ requires 4.0 mL of
0.1000 M KCNS for the precipitation of AgCNS. What
is the percentages of Br and of inert matter in the
sample?

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Applications of Precipitation Titrations
2) A 0.5131-g sample containing KBr is dissolved in 50
mL of distilled water. Titrating with 0.04614 M AgNO3
requires 25.13 mL to reach the Mohr end point. A
blank titration requires 0.65 mL to reach the same
end point. Report the %w/w KBr in the sample.

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Applications of Precipitation Titrations
3) A mixture containing only KCl and NaBr is analyzed by
the Mohr method. A 0.3172-g sample is dissolved in
50 mL of water and titrated to the Ag2CrO4 end
point, requiring 36.85 mL of 0.1120 M AgNO3. A blank
titration requires 0.71 mL of titrant to reach the
same end point. Report the %w/w KCl and NaBr in
the sample.

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Applications of Precipitation Titrations

4) The phosphorus in a 4.258-g sample of a

plant food was converted to PO43- and
precipitated as Ag3PO4 through the addition of
50.00 mL of 0.0820 M AgNO3. The excess
silver nitrate was then back titrated with 4.06
mL of 0.0625 M KSCN. Express the results of
this analysis in terms of % P2O5.

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Applications of Precipitation Titrations
A 2.414 g sample containing KCl, K2SO4, and inert materials
was dissolved in sufficient water to give 250.00 mL of
solution. A Mohr Titration of the 50.00 mL aliquot required
41.36 mL of 0.05818 M AgNO3. A second 50.00 mL aliquot
was treated with 40.00 mL of 0.1083 mL M NaB(C6H5)4. The
reaction is:
NaB(C6H5)4 + K+ →KB(C6H5)4 (s) + Na+
The solid was filtered, redissolved in acetone and titrated
with 49.98 mL of the AgNO3 solution according to the
reaction:
KB(C6H5)4 + Ag+ → AgB(C6H5)4(s) + K+
Calculate the percentage of KCl and K2SO4 in the sample.

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