CAPE Module 2: 5.2-5.

5
More Equilibria In Aqueous Solutions:
Slightly Soluble Salts
Objectives:
1. Learning about precipitation reactions
2. Learning about the solubility constant
expression Ksp and how to use it
3.Learning about the solubilities of various
classes of ionic solids and how to use that
knowledge to analyze for the presence of
unknown ions in solution
Lets review a bit and make sure we see the big picture

MODULE 2

2:1 Kinetics
2:2 Chemical equilibria
2:3-4 Acid-Base equilibria
2:5: Precipitation equilibria
2:6: Equilibria and Thermodynamics
 The Solubility Product Constant, Ksp
Many important ionic compounds are only slightly
soluble in water and equations are written to
represent the equilibrium between the compound
and the ions present in a saturated aqueous
solution.
The solubility product constant, Ksp, is the
product of the concentrations of the ions involved
in a solubility equilibrium, each raised to a power
equal to the stoichiometric coefficient of that ion
in the chemical equation for the equilibrium.
The Solubility Equilibrium Equation And Ksp

CaF2 (s) Ca2+ (aq) + 2 F- (aq)

Ksp = [Ca2+][F-]2 Ksp = 5.3x10-9

As2S3 (s) 2 As3+ (aq) + 3 S2- (aq)

Ksp = [As3+]2[S2-]3
Some Values For Solubility Product
Constants (Ksp) At 25 oC
 Ksp And Molar Solubility
The solubility product constant is related to the
solubility of an ionic solute, but Ksp and molar
solubility - the molarity of a solute in a saturated
aqueous solution - are not the same thing.
Calculating solubility equilibria fall into two
categories:
determining a value of Ksp from experimental data
calculating equilibrium concentrations when Ksp is
known.
 Calculating Ksp From Molar Solubility

It is found that 1.2x10-3 mol of lead (II) iodide, PbI2,

dissolves in 1.0 L of aqueous solution at 25 oC.
What is the Ksp at this temperature?
 Calculating Molar Solubility From Ksp

Calculate the molar solubility of silver chromate,

Ag2CrO4, in water from Ksp = 1.1x10-12 for Ag2CrO4.
The Common Ion Effect In Solubility Equilibria
The common ion effect also affects solubility
equilibria.
Le Chteliers principle is followed for the shift in
concentration of products and reactants upon
addition of either more products or more reactants
to a solution.
The solubility of a slightly soluble ionic compound
is lowered when a second solute that furnishes a
common ion is added to the solution.
The common ion effect is frequently used in
analytical chemistry to determine such things as
the percent of an element present in an unknown
sample.
 Solubility Equilibrium Calculation
-The Common Ion Effect
What is the solubility of Ag2CrO4 in 0.10 M K2CrO4?
Ksp = 1.1x10-12 for Ag2CrO4.

Comparison of solubility of Ag2CrO4

In pure water: 6.6 x 10-5 M
In 0.10 M K2CrO4: 1.7 x 10-6 M
The common ion effect!!
 Determining Whether Precipitation Occurs

Qip is the ion product reaction quotient and is

based on initial conditions of the reaction.
Qip can then be compared to Ksp.
To predict if a precipitation occurs:
- Precipitation should occur if Qip > Ksp.
- Precipitation cannot occur if Qip < Ksp.
- A solution is just saturated if Qip = Ksp.
 Determining Whether Precipitation Occurs
An Example
The concentration of calcium ion in blood plasma
is 0.0025 M. If the concentration of oxalate ion is
1.0x10-7 M, do you expect calcium oxalate to
precipitate? Ksp = 2.3x10-9.

Three steps:
(1) Determine the initial concentrations of ions.
(2) Evaluate the reaction quotient Qip.
(3) Campare Qip with Ksp.
 Determining Whether Precipitation Occurs
An Example
In applying the precipitation criteria, the effect of
dilution when solutions are mixed must be
considered.

Example:
A 250.0 mL sample of 0.0012 M Pb(NO3)2 (aq) is
mixed with 150.0 mL of 0.0640 M NaI (aq).
Should precipitation of PbI2 (s), Ksp = 7.1x10-9,
occur?
Determining Whether Precipitation Occurs
Another Example

How many grams of KI should be dissolved in

10.5 L of 0.00200 M Pb(NO3)2 solution so that
precipitation of PbI2 (s) will just begin?
Ksp = 7.1x10-9
 Determining Whether Precipitation Is
Complete
A slightly soluble solid never totally precipitates
from solution, but we generally consider
precipitation to be essentially complete if about
99.9% of the target ion is precipitated and only
0.1% or less is left in solution.
Three conditions that generally favor completeness
of precipitation are:
A very small value of Ksp.
A high initial concentration of the target ion.
A concentration of common ion that greatly
exceeds that of the target ion.
 Determining Whether Precipitation Is
Complete - An Example

A 0.50 L solution of 0.0010 M BaCl2 is added to

0.50 L solution of 0.00010 M Na2SO4. Will the
precipitation of SO42- as BaSO4 (s) be complete?
Ksp = 1.1x10-10.
Selective Precipitation

a) The first precipitate to

form when AgNO3(aq)
is added to an aqueous
solution containing Cl-
and I- is yellow AgI(s).
b) Essentially all the I- has
precipitated before the
precipitation of white
AgCl(s) begins.
 Selective Precipitation An Example
Example 16.10
An aqueous solution that is 2.00 M in AgNO3 is slowly
added from a buret to an aqueous solution that is 0.0100 M
in Cl- and also 0.0100 M in I-
AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.8x10-10
AgI (s) Ag+ (aq) + I- (aq) Ksp = 8.5x10-17
a. Which ion. Cl- or I-, is the first to precipitate from solution?
b. When the second ion begins to precipitate, what is the
remaining concentration of the first ion?
c. Is separation of the two ions by selective precipitation
feasible?
 Effect of pH on Solubility
The solubility of an ionic solute may be greatly
affected by pH if an acid-base reaction also occurs
as the solute dissolves.
If the anion of the precipitate is that of a weak
acid, the precipitate will dissolve somewhat when
the pH is lowered; if, however, the anion of the
precipitate is that of a strong acid, lowering the pH
will have no effect on the precipitate.
Since CO2 is lost from the reaction of an insoluble
carbonate with acid, this concept does not apply.
Effect of pH on Solubility - An Example
Determine the molar solubility of Fe(OH)3 in
pH = 2.70 buffer. Ksp = 4.0x10-38 for Fe(OH)3.
 Qualitative Inorganic Analysis
Acid-base chemistry, precipitation reactions,
oxidation-reduction, and complex-ion formation all
come into sharp focus in an area of analytical
chemistry called classical qualitative inorganic
analysis.
Qualitative signifies that the interest is in
determining what is present, not how much is
present.
Although classical qualitative analysis is not as
widely used today as instrumental methods, it is
still a good vehicle for applying all the basic
concepts of equilibria in aqueous solutions.
 Cations of Group 1
If aqueous HCl is added to an unknown solution of
cations, and a precipitate forms, then the unknown
contains one or more of these cations: Pb 2+, Hg22+, or
Ag+.
These are the only ions to form insoluble chlorides.
If there is no precipitate, then these ions must be
absent from the mixture.
If there is a precipitate, it is filtered off and saved for
further analysis.
The supernatant liquid is also saved for further
analysis.
 Cation Group 1 (continued)
Analyzing For Pb2+
Of the three possible ions in solution, PbCl2 is the
most soluble in water.
The precipitate is washed with hot water and the
washings then treated with aqueous K2CrO4.
If Pb2+ is present, chromate ion combines with lead
ion to form a precipitate of yellow lead chromate,
which is less soluble than PbCl2.
If Pb2+ is absent, then the washings just become
tinged yellow but no precipitate is in evidence.
 Cation Group 1 (continued)
Analyzing For Ag+
Next, the undissolved precipitate is treated with
aqueous ammonia.
If AgCl is present, it will dissolve in this solution.
If there is any remaining precipitate, it is separated
from the supernatant liquid and saved for further
analysis.
The supernatant liquid (which contains the Ag+, if
present) is then treated with aqueous nitric acid.
If a precipitate reforms, then Ag+ was present in the
solution, if no precipitate forms, then Ag+ was not
present in the solution.
 Cation Group 1 (continued)
Analyzing For Hg22+
When precipitate was treated with aqueous
ammonia in the previous step, any Hg22+
underwent an oxidation-reduction reaction to form
a dark gray mixture of elemental mercury and
HgNH2Cl that precipitates from the solution.
If this dark gray precipitate was observed, then
mercury was present in the original unknown
sample.
If this dark gray precipitate was not observed,
then mercury must have been absent from the
original unknown sample.
Group 1 Cation Precipitates

left: cation goup 1 ppt: PbCl2,

PbCl2, AgCl (all white)
middle: product from test for
Hg22+: mix of Hg (black) and
HgNH2Cl (white)
right: product from test for Pb2+:
PbCrO4 (yellow) when
K2CrO4(aq) is reacted with
saturated PbCl2
Prentice-Hall 2002 Chapter Sixteen Slide 29 of 32
 Hydrogen Sulfide In The
Qualitative Analysis Scheme
H2S is a weak diprotic acid; there is very little ionization of the
HS- ion and it is the precipitating agent.
H2S (aq) + H2O H3O+ (aq) + HS- (aq) Ka1 = 1.0x10-7
HS- (aq) + H2O H3O+ (aq) + S2- (aq) Ka2 = 1.0x10-19

H2S (aq) + H2O H3O+ (aq) + HS- (aq)

M2+ (aq) + HS- (aq) + H2O (l) MS (s) + H3O+ (aq)
Overall: M2+ (aq) + H2S (aq) + 2 H2O (l) MS (s) + 3 H3O+ (aq)
 Cation Groups 2, 3, 4 And 5
The concentration of HS- is so low in a strongly
acidic solution, that only the most insoluble
sulfides precipitate.
These include the eight metal sulfides of Group 2.
Of the eight cations in Group 3, five form sulfides
that are soluble in acidic solution but insoluble in
an alkaline ammonia/ammonium chloride buffer
solution. The other three group 3 cation form
hydroxide precipitates in the alkaline solution.
The cations of groups 4 and 5 form soluble
sulfides, even in basic solution.
 Cation Groups 2, 3, 4 And 5
The hydroxides of Groups 4 and 5, with the
exception of Mg2+, are also moderately or highly
soluble.
The group 4 cations are precipitated as carbonates
from a buffered alkaline solution.
The cations of group 5 remain soluble in the
presence of all common reagents.
Within each of the qualitative analysis groups,
additional reactions to dissolve group precipitates
and to separate and selectively precipitate
individual cations for identification and confirmation
are used.
 Summary
The solubility product constant, Ksp, represents
equilibrium between a slightly soluble ionic
compound and its ions in a saturated aqueous
solution.
The common ion effect is responsible for the
reduction in solubility of a slightly soluble ionic
compound.
Precipitation is assumed to be complete if no more
than 0.1% of the target ion remains in solution.
The solubilities of some slightly soluble
compounds depends strongly on pH.
 Summary

Precipitation, acid-base, and oxidation-reduction

reactions, together with complex-ion formation, are
all used extensively in the classical scheme for the
qualitative analysis of common cations.