Chem 2

Module 4
Solubility Product Constant
and Gravimetric Analysis
 Objectives
1. Identify the type of equilibria involving
solubility product constant
2. Apply the concept of solubility product
constant and mathematical concept to solve
problems in Ksp
3. Apply the concept of Le Chatelier’s Principle
and mathematical concept to solve problems
that involves factors affecting solubility
4. Solve problems involving gravimetric analysis
 Solubility
• Equilibria involved in the dissolution or precipitation of
ionic compounds
• These reactions are heterogeneous.
• The dissolving and precipitating of compounds are
phenomena that occur both within us and around us.
– The fact that substances such as sugar and table salt dissolve in water
allows us to flavour foods easily.
– The fact that calcium sulphate is less soluble in hot water than in cold
water causes it to coat tubes in boilers, reducing thermal efficiency.
– Tooth decay involves solubility. When food lodges between the
teeth, acids form that dissolve tooth enamel causing tooth decay.
– The precipitation of certain salts in our kidneys produces kidney
stones.
– Precipitation of calcium carbonate from ground water is
responsible for the formation of stalactites and stalagmites
within limestone caves.
Solubility
Exercise #1: Classify the following ionic
compounds as soluble or insoluble in water.

1. Na2CO3 soluble
2. PbSO4 insoluble

3. Co(OH)2 insoluble

4. Ba(NO3)2 soluble

5. (NH4)3PO4 soluble
 Exercise #2: Predict what will happen when the following pairs of
solutions are mixed. Will there be a precipitate?

1. KNO3(aq) and BaCl2(aq) – KCl + Ba(NO3)2, no ppt

2. Na2SO4(aq) and Pb(NO3)2(aq) – NaNO3 + PbSO4 will ppt
3. KOH(aq) and Fe(NO3)3(aq) – KNO3 + Fe(OH)3 will ppt
4. FeSO4(aq) and KCl(aq) – FeCl2 + K2SO4, no ppt
5. Al(NO3)3(aq) and Ba(OH)2(aq)
- Al (OH)3 will ppt + Ba(NO3)2
 Using Solubility-Product Constants
• Most sparingly soluble salts are completely dissociated in saturated
aqueous solution, which means that the very small amount that does go
into solution dissociates completely.
• When an excess of barium iodate is equilibrated with water, the
dissociation process is adequately described as

Ba ( IO3 ) 2 ( s )  Ba 2 (aq )  2 IO3 (aq )

• “An excess of barium iodate is equilibrated with water” means that more
solid barium iodate is added to a portion of water than would dissolve at
the temperature of the experiment.
• Some solid BaIO3 is in contact with the solution.

•
K
Ba IO 
2  2
3
Ba ( IO3 ) 2 ( s)
 Using Solubility-Product Constants

The denominator is the molar concentration of Ba(IO3)2 is in the

solid.
The concentration of a compound in its solid state is constant,
therefore, the equation can be rewritten as:
K [ Ba ( IO3 ) 2 ( s )]  K sp  Ba  2
IO 
 2
3

where the new constant is called the solubility-product constant

or the solubility product.

The equation shows that the position of this

equilibrium is independent of the amount of Ba(IO3)2
as long as some solid is present.
Using Solubility-Product Constants

• The constant Ksp is called the

solubility product constant or simply
solubility product for the equilibrium
expression. It is the equilibrium
constant for the equilibrium that
exists between a solid ionic solute
and its ions in a saturated aqueous
solution.
©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Exercise #3: What are the dissociation
products and write the expression for the
solubility product constant for:
1. CaF2(s) ↔ Ca + 2F Ksp = [Ca][F]^2
2. BaCO3(s) ↔ Ba + CO3 Ksp = [Ba] [CO3]
3. Ag2SO4(s) ↔ 2 Ag + SO4 Ksp = [Ag]^2 [SO4]
4. Ni(OH)2(s) ↔ Ni + 2OH Ksp = [Ni][OH]^2
5. Ag3PO4(s) ↔ 3 Ag + PO4
Ksp = [Ag]^3 [PO4]
The Solubility of a Precipitate in Pure
Water Sample Problem
The Solubility of a Precipitate in Pure
Water Sample Problem
The Solubility of a Precipitate in
Pure Water
 Problem Set
1. Copper (I) bromide has a measured solubility of
2.0 x 10-4 mol/L at 25oC. Calculate its Ksp value.
2. Calculate the Ksp value for bismuth sulphide
which has a solubility of 1.0 x 10-15 mol/L at 25oC.
3. The Ksp value for copper (II) iodate is 1.4 x 10-7 at
25oC. Calculate its solubility at 25oC.
4. What mass (in grams) of barium iodate, Ba(IO3)2,
can be dissolved in 500 mL of water at 25oC? Ksp
Ba(IO3)2 is 1.57 x 10-9. Atomic wts: Ba = 137 I =
127 O = 16
 The Effect of a Common Ion on the
Solubility of a Precipitate
What happens when the water contains
an ion in common with the dissolving
salt?
The common-ion effect is a mass-action
effect predicted from Le Chatelier’s
principle.
𝐴𝑔𝑁 𝑂 3 + 𝑁𝑎𝐶𝑙 ↔ 𝐴𝑔𝐶𝑙(𝑠) + 𝑁𝑎𝑁 𝑂3
−

𝐴𝑔𝐶𝑙( 𝑠 ) ↔ 𝐴𝑔+¿ + 𝐶𝑙 ¿

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

• The solubility of an ionic precipitate decreases when a
soluble compound containing one of the ions of the
precipitate is added to the solution. This behavior is
called the common-ion effect.

• Solubility depends on stoichiometry

– Check Sample Problem 10.9
 The
Themolar
molarsolubility
solubilitydepends
dependsononthe
thestoichiometry
stoichiometryof
ofthe
thesalt.
salt.
AA1:1
1:1salt
saltisisless
lesssoluble
solublethan
thanaanonsymmetric
nonsymmetricsalt
saltwith
withthe
thesame
sameKKsp. .
sp

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
• Check Sample Problem 10.10 and compare molar
solubility of PbSO4 and PbI2

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Relative Solubilities
• A salt’s Ksp value gives us information
about its solubility. However, we must be
careful in using Ksp values to predict the
relative solubilities of a group of salts.
There are two possible cases:
1. The salts being compared produce the
same number of ions.
• Example: AgI(s) Ksp = 1.5 x 10-16
• CuI(s) Ksp = 5.0 x 10-12
• CaSO4(s) Ksp = 6.1 x 10-5
 Relative Solubilities
• Each of these solids dissolves to produce two ions:
Salt ↔ cation + anion
Ksp = [cation] [anion]
• If x is the solubility in mol/L, then at equilibrium
[cation] = x [anion] = x
Ksp = [cation][anion] = x2
X=
• Therefore, in this case we can compare the solubilities for
these solids by comparing the Ksp values:
CaSO4(s) > CuI(s) > AgI(s)
Most soluble Least soluble Largest
Ksp smallest Ksp
 Relative Solubilities
2. The salt being compared produce different numbers of
ions.
• Example: CuS(s) Ksp = 8.5 x 10-45
Ag2S(s) Ksp = 1.6 x 10-49
Bi2S3(s) Ksp = 1.1 x 10-73
• Because these salts produce different numbers of ions
when they dissolve, the Ksp values cannot be compared
directly to determine relative solubilities. In fact, if we
calculate the solubilities, we obtain the results
summarized below:
Salt Ksp Calculated
solubility (mol/L)
CuS(s) 8.5 x 10-45 9.2 x 10-23
Ag2S(s) 1.6 x 10-49 3.4 x 10-17
Bi2S3(s) 1.1 x 10-73 1.0 x 10-15
 Relative Solubilities
• The order of solubilities is
Bi2S3(s) > Ag2S(s) > CuS(s)
Most soluble Least soluble
• which is opposite to the order of the Ksp
values.

• Note: Relative solubilities can be predicted by

comparing Ksp values only for salts that
produce the same total number of ions.
 Problem Set
1. Calculate the solubility of solid CaF2 (Ksp
= 4.0 x 10-11) in a 0.025 M NaF solution.
2. Calculate the molar solubility of Ba(IO3)2
in a solution that is 0.0200 M in
Ba(NO3)2.
3. Calculate the solubility of Ba(IO3)2 in a
solution prepared by mixing 200 mL of
0.0100 M Ba(NO3)2 with 100 mL of 0.100
M NaIO3.
 GRAVIMETRIC ANALYSIS
• Gravimetric analysis, or determining the
amount of a substance via mass measurements,
is a technique often used to analyze substances
in our daily lives even if we are unaware of it.

Think about:
Gravimetric Analysis As Part of Daily Life
 Some examples of daily usage

 nutritional
information tables on
foods as many of the
components listed are
analyzed in a lab and
% composition
measured by mass.
 determining the
mineral content of
your drinking water,
minerals such as lead,
fluoride, mercury,
calcium, etc..
 Some examples of daily usage

 Determining total
suspended solids in water
is another gravimetric
application.
 Another is making sure
the gold content in your
jewelry is what it says it
is.
 Determining the amount
of fat in milk can be done
by gravimetric analysis.
 Some examples of daily usage

 Even being weighed at the doctor's office is a form of gravimetric

analysis as quantified weight changes could be a sign of illness.
 Diagnostic lab results
 GRAVIMETRIC ANALYSIS
• Gravimetric analysis is one of the most
accurate and precise methods of macro-
quantitative analysis. The analyte is
selectively converted to an insoluble
form (precipitate). The separated
precipitate is dried or ignited, possibly
to another form, and is accurately
weighed. From the weight of the
precipitate and a knowledge of its
chemical composition, the weight of
analyte in the desired form is calculated.
GRAVIMETRIC ANALYSIS
Several analytical methods based on mass ELECTROGRAVIMETRY
measurement.
1. In _________ the analyte is separated from Atomic mass
a solution of the sample as a precipitate and spectrometry
is converted to a compound of known
composition that can be weighed. PRECIPITATION
2. In_______ , the analyte is separated from
other constituents of a sample by GRAVIMETRIC
conversion to a gas of known chemical TITRIMETRY
composition. The weight of this gas then
serves as a measure of the analyte
concentration.
VOLATILIZATION
3. In ________, the analyte is separated by
deposition on an electrode by an electrical
current. The mass of this product then
provides a measure of the analyte
concentration.
GRAVIMETRIC ANALYSIS
Several analytical methods based on mass ELECTROGRAVIMETRY
measurement.
4. In ______ the mass of the reagent, of Atomic mass
known concentration, required to react spectrometry
completely with the analyte provides the
information needed to determine the analyte PRECIPITATION
concentration.
GRAVIMETRIC
5. In ______ uses a mass spectrometer to TITRIMETRY
separate gaseous ions formed from the
elements making up a sample of matter. The VOLATILIZATION
concentration of the resulting ions is then
determined by measuring the electrical
current produced when they fall on the
surface of an ion detector.
https://slideplayer.com/slide/14373511/
 GRAVIMETRIC ANALYSIS
Experimental variables that affect the
particle size of precipitates:
1. Solubility
2. Temperature
3. Reactant concentrations
4. Rate at which reactants are mixed
Steps of a Gravimetric Analysis
• The steps required in a gravimetric analysis,
after the sample has been dissolved, can be
summarized as follows:
1. Preparation of the solution
2. Precipitation
3. Digestion
4. Filtration
5. Washing
6. Drying or igniting
7. Weighing
8. Calculation
Steps of a Gravimetric Analysis

https://www.slideshare.net/rajendra00/gravimetry-24895229
 Some common terms in gravimetry:

_______________ solution is an unstable solution

that contains a higher solute concentration than a
saturated solution. With time, this solution is
relieved by precipitation of the excess solute.

DETPUSSREARUAT

SUPERSATURATED
 Some common terms in gravimetry:

__________is a process in which a minimum

number of atoms, ions or molecules join
together to give a stable solid.

ITONCLEAUN
NUCLEATION
 Some common terms in gravimetry:

____________is a process in which a

substance (gas, solid or liquid) is held on the
surface of a solid.

IONASDORTP

ADSORPTION
 Some common terms in gravimetry:

_ _ S_ ___I__
involves retention of a substance within the
pores of a solid. ABSORPTION

C____I_A_ __S__N___N
are tiny particles invisible to the naked eye and
show no tendency to settle from solution, nor
are they easily filtered. COLLOIDAL SUSPENSION
 Some common terms in gravimetry:

Crystalline suspension – temporary

dispersion of particles in a liquid phase;
particles tend to settle sponstaneously and
are readily filtered.
Curdy precipitate – made up of fine particles
that have not grown together to form an
extensive lattice structure.
Gelatinous precipitate – much larger in
number and of much smaller dimension
than those of crystalline precipitate where
a large quantity of water is adsorbed.
 Some common terms in gravimetry:
• Peptization is a process by which a
coagulated colloid returns to its dispersed
state.
• Digestion is a process in which a precipitate
is heated for an hour or more in the solution
from which it was formed (the mother
liquor).
• Mother liquor is the solution from which
precipitate was formed.
• Coprecipitation is a process in which
normally soluble compounds are carried out
of solution by a precipitate.
 Calculation of Results From
Gravimetric Data
• The results of a gravimetric analysis
are generally computed from two
experimental measurements:
1. the mass of sample; and
2. the mass of a product of known
composition.
©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Practice: Write an equation showing how the mass of
the substance sought (analyte) can be converted from
the mass of the weighed substance
Sought Weighed
1. SO2 BaSO4
2. Pb3O4 PbO2

1.

2.
 1)
174.18 g/mol 2)
514.15 g/mol 3) 233.40 g/mol

1)

2) 0.42
3) 0.734

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

• Refer to your book/ e-book for more examples.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Gravimetry Sample Problem
2. An iron ore (known to contain a mixture of Fe2O3 and
Fe3O4) was analyzed by dissolving a 1.1324 g sample in
concentrated HCl. The resulting solution was diluted with
water, and the iron (III) was precipitated as the hydrous
oxide Fe2O3.xH2O by the addition of NH3. After filtration
and washing, the residue was ignited at a high
temperature to give 0.5394 g of pure Fe2O3. Calculate (a)
%Fe and (b) %Fe3O4 in the sample.
(atomic mass: Fe=55.85 O=16)
A) GF = 2*Fe/Fe2O3 = 2*55.85/159.7 = 0.69943
B) %Fe = (0.5394 g * GF/1.1324 g) *100 = 33.32%
GF for %Fe3O4 = 2Fe3O4/3Fe2O3 = 0.96660
C) %Fe3O4 = (0.5394 * GF/1.1324 g) * 100 = 46.04 %
Gravimetry
Gravimetryisislimited
limitedin
inuse,
use,but
butcan
canprovide
providevery
veryaccurate
accurateresults
results
when
whenapplicable.
applicable.
 Organic
Organicprecipitating
precipitatingagents
agentsare
arechelating
chelatingagents.
agents.
They
Theyform
forminsoluble
insolublemetal
metalchelates.
chelates.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)