Solubility Product Constant Experiment Eight

Determination of the Solubility Product Constant of PbI2;

Application of the Debye-Hückel Limiting Law
In this experiment you will determine the solubility product constant of lead(II) iodide,
PbI2. Lead(II) iodide is relatively insoluble, having a solubility of less than 0.002 mole
per liter at 20oC. The equation for the solution of PbI2 is:

PbI2(s) ⇌ Pb2+(aq) + 2I-(aq) (1)

The solubility product expression associated with this reaction is

Ksp = [Pb2+] [I-]2 (2)

Equation 2 implies that in any system containing solid PbI2 in equilibrium with its ions,
the product of [Pb2+] times [I-]2 will at a given temperature have a fixed magnitude,
independent of how the equilibrium system was initially made up.

In the first part of the experiment, known volumes of standard solutions of Pb(NO3)2 and
KI will be mixed in several different proportions. The yellow precipitate of PbI2 formed
will be allowed to come to equilibrium with the solution. The value of [I-] in the solution
will be measured experimentally. The [Pb2+] will be calculated from the initial
composition of the system, the measured value of [I-], and the stoichiometric relation
between Pb2+ and I- in Equation 1.

By mixing the solutions as we have described, we approach equilibrium by precipitating

PbI2 and measuring the concentrations of I- and Pb2+ remaining in the solution. We will
also carry out the reaction in the other direction, by first precipitating PbI2, washing it
free of excess ions, and then dissolving the solid in the inert salt solution. Under such
conditions, the concentrations of Pb2+ and I- in the saturated solution will be related in a
1:2 ratio by Equation 1, since both ions come from pure PbI2. From the measured value
of [I-] in the saturated solution, we can calculate [Pb2+] immediately.

The concentration of I- ion will be found spectrophotometrically as in Experiments 6 & 7.

Although the iodide ion is not colored, it is relatively easily oxidized to I2, which is
brown in water solution. Our procedure will be to separate the solid PbI2 from the
solution and then to oxidize the I- in solution with potassium nitrite, KNO2, under slightly
acidic conditions, where the conversion to I2 is quantitative. Although the concentration
of I2 will be rather low in the solutions you will prepare, the absorption of light by I2 in
the vicinity of 525 nm is sufficiently intense to make accurate analyses possible.

In all of the solutions prepared, 0.2 M potassium nitrate KNO3 (note this distinction
between KNO2 and KNO3!) will be present as an inert salt. This salt serves to keep the
ionic strength of the solution essentially constant at 0.2 M and promotes the formation of
well-defined crystalline precipitates of PbI2.

Chemistry M01B Laboratory Manual pp. 41

 Solubility Product Constant Experiment Eight

Debye-Hückel Limiting Law

In addition to using molarities, the equilibrium constant for the following generalized
chemical reaction aA + bB ⇌ cC + dD can also be expressed in terms of activities:

d c
a D aC
Kc = a b
(3)
a A aB

The dimensionless quantity a is the activity of a given chemical species involved in the
equilibrium. The activity of a species in a mixture is related to the molar concentration
of that species through the following equation:

a = fM (4)

where f is the activity coefficient (0 < f < 1) and M is the molarity of that species. A
fairly good approximation is to let f = 1 and thus let the values of the activities be the
same as the values of the molar concentrations, which leads to the more familiar:

[ D] d [C ]c
Kc = (5)
[ A] a [ B]b

Once again, consider the heterogeneous aqueous equilibrium of the insoluble salt lead(II)
iodide: PbI2(s) ⇌ Pb2+(aq) + 2I-(aq). The equilibrium constant for this process, known
as the solubility product constant Ksp, can be expressed in the following way:

K sp = (a Pb 2 + )(a I − ) = [ Pb 2+ ][ I − ] 2
2
(6)

If the concentrations of the ions are sufficiently low, then the activities of each species
are approximately the same value as their respective molar concentrations as shown in
Equation 6 above. However, because any aqueous heterogeneous equilibrium involving
salts results in a mixture of electrically charged particles, there are Coulombic forces of
interaction between the ions. Depending on the concentrations of the ions, this can result
in the formation of small ion clusters that effectively reduce the number of free ionic
particles in solution. Consequently, the activities of each ion are actually less than the
molar concentrations of the ions (this is analogous to the effect of intermolecular forces
on pressure that is observed for real gases in the van der Waals equation). It is often
necessary to determine the activities of the ions in solution in order to experimentally
determine Ksp. Thus, one needs a way to determine the activity coefficient f.

Chemistry M01B Laboratory Manual pp. 42

 Solubility Product Constant Experiment Eight

The Debye-Hückel limiting law provides a method for calculating the activity coefficient
of an ion in solution. This relationship takes into account the ionic charges and ionic
radii of all ions in solution. We will use a simplified version which only considers the
ionic charges. The activity coefficient is thus given by the equation:

log f = -0.51 Z2 (µ)½ (7)

where f = the activity coefficient of an ion; Z = the charge of that ion; and µ = ionic
strength, a measure of the concentration of all ions in solution.

The ionic strength µ is calculated by:

µ = 0.5 (M1Z12 + M2Z22 + M3Z32 + …) (8)

where M1 is the molarity of the first ion with charge Z1, etc. An example of calculating
Ksp for a salt in solution using activities is presented below.

PROBLEM SET: In a particular experiment, it is found spectrophotometrically that the

equilibrium concentration of SO4-2 equals 0.014 M when [Ca+2] = 0.014 M at
equilibrium. What is the calculated Ksp for CaSO4? Now calculate the Ksp for the
dissociation of calcium sulfate in water taking activities into account. How does this
value compare to using molarities only? Is it better to calculate Ksp with activities or
uncorrected molarities (Ksp for CaSO4 = 2.4 x 10-5)? Briefly explain, and show your
work below.

Chemistry M01B Laboratory Manual pp. 43

 Solubility Product Constant Experiment Eight

Procedure

In this experiment, it is essential that the volumes of reagents used to make up the
mixtures in the test tubes be measured accurately.

Label five regular test tubes 1 to 5. Use the burets to add the required amounts of each
reagent into each test tube. The composition of the final mixture in each tube is
summarized in Table One.

Table One - Volumes of Reagents Used In Precipitating PbI2 (mL)

Test Tube 0.012 M Pb(NO3)2 0.030 M KI 0.20 M KNO3

(in 0.20 M KNO3) (in 0.20 M KNO3)

1 5.00 2.00 3.00

2 5.00 3.00 2.00
3 5.00 4.00 1.00
4 5.00 5.00 0
5 10.00 10.00 0

Note: The 5 test tubes can be prepared a week in advance and stored in your locker to
insure equilibrium is reached; this saves time the day of the experiment.

Stopper each test tube and shake thoroughly at intervals of several minutes while you are
proceeding with the next part of the experiment.

In the fifth test tube, shake the mixture vigorously for a minute or so. Let the solid settle
for a few minutes, and then decant and discard most of the supernatant solution. Transfer
the solid PbI2 and the rest of the solution to a small test tube and centrifuge. Discard the
liquid, retaining the solid precipitate. Add 3 mL 0.20 M KNO3 and shake to wash the
solid free of excess Pb2+ or I-. Centrifuge again, and discard the liquid. Repeat this
washing and centrifuging procedure a second time and again discard the liquid. By this
procedure you should now have prepared a small sample of essentially pure PbI2 in a
little KNO3 solution. Add 0.20 M KNO3 to the solid in the small test tube until the tube
is about three-fourths full. Shake well at several one minute intervals to saturate the
solution with PbI2.

It is essential that all five mixtures be shaken thoroughly so that equilibrium can be
established. Insufficient shaking of the test tubes will result in not enough PbI2
precipitating to reach true equilibrium; if the small test tube is not shaken sufficiently, not
enough PbI2 will dissolve to attain equilibrium. Preparing the test tubes a week in
advance avoids this problem and eliminates the need for shaking time.

Chemistry M01B Laboratory Manual pp. 44

 Solubility Product Constant Experiment Eight

When each of the mixtures has been shaken for at least 15 minutes, let the tubes stand for
three to four minutes to let the solid settle. Pour the supernatant liquid from test tube 1
into a small dry test tube until it is three-fourths full and centrifuge for about three
minutes to settle the solid PbI2. BE SURE YOU ARE NOT USING A CUVETTE IN THE
CENTRIFUGE! Pour the liquid into another small dry test tube; if there are any solid
particles or yellow color remaining in the liquid, centrifuge again. When you have a
clear liquid, dip a small piece of clean, dry paper towel into the liquid to remove floating
PbI2 particles from the surface. Add 3.0 mL of 0.020M KNO2, potassium NITRITE
(not KNO3, potassium nitrate), 2 drops of 6 M HCl, and 3.0 mL of the clear, centrifuged
solution together. Gently stir the solution with a clean, dry stirring rod to mix the
reagents. Measure the absorbance of the solution.

ALL BUBBLES MUST BE REMOVED FROM THE CUVETTE BEFORE PLACING IT

INTO THE SPECTROPHOTOMETER.

Set the wavelength to 525 nm and calibrate. Use the equation A = k M, with k = 70.0 to
determine the concentration of I- ion in equilibrium with PbI2. Use the same cuvette
(clean and dry between samples) to measure the absorbance of all the solutions.

Data and Calculations

From the experimental data, we obtain the equilibrium [I-] directly. To obtain Ksp for
PbI2, we must calculate [Pb2+] in each equilibrium system. This is most easily done by
constructing an equilibrium table as shown on the next page. We first find the new,
diluted initial concentrations of Pb2+ and I- ions in each system from the way the mixtures
were made up. Knowing the equilibrium [I-] and the formula of lead(II) iodide allows us
to calculate the equilibrium [Pb2+]. Ksp then follows directly. Finally, use the Debye-
Hückel limiting law (outlined above via Equations 4, 6, 7, and 8) to correct the
equilibrium concentrations of Pb+2 and I- and determine the Ksp once more. Compare
your two calculated Ksp values that you determined using molarities and activities with
the literature (known) value. Notice there are 4 ions to include while solving for µ: Pb+2,
I-1, K+1, and NO3-1.

QUESTION: Determine if it is better to calculate Ksp with activities or uncorrected

molarities and comment below:

Chemistry M01B Laboratory Manual pp. 45

Data: Determination of the Solubility Product Constant of PbI2; Application of the Debye-Hückel Limiting Law

Vol. of 0.012 M Vol. of 0.030 M Vol. of 0.20 M

Mixture Pb(NO3)2 (in mL) KI (in mL) KNO3 (in mL) Absorbance [I-]
____________________________________________________________________________________________________________

1 5.00 2.00 3.00 _________ _________

2 5.00 3.00 2.00 _________ _________

3 5.00 4.00 1.00 _________ _________

4 5.00 5.00 0.00 _________ _________

5 10.00 10.00 0.00 _________ _________

____________________________________________________________________________________________________________
Mixture Initial Concentrations Equilibrium Concentrations
AFTER MIXING Ksp Ksp
+2 - +2 -
[Pb ]o [I ]o [Pb ] [I ] (molarities) (activities)

1 ____________ ____________ ____________ ____________ ____________ ____________

2 ____________ ____________ ____________ ____________ ____________ ____________

3 ____________ ____________ ____________ ____________ ____________ ____________

4 ____________ ____________ ____________ ____________ ____________ ____________

5 ____________ ____________ ____________ ____________ ____________ ____________

Literature Ksp: ____________ Avg. Ksp: ____________ ____________

 Solubility Product Constant Experiment Eight

Advance Study Assignment: Solubility Product Constant

1. When 5.00 mL of 0.012 M Pb(NO3)2 are mixed with 5.00 mL of 0.030 M KI, a
yellow precipitate of PbI2(s) forms. Calculate the new, diluted concentrations of
the Pb2+ and I- ions.

[Pb2+]o____________ M; [I-]o____________ M.

2. In a spectrophotometer the equilibrium solution is analyzed for I-, and its

concentration is found to be 8.0 x 10-3 mole/liter. Use the initial concentrations of
the Pb2+ and I- ions along with the equilibrium concentration of the I- ion and the
reaction stoichiometry to determine the equilibrium concentration of the Pb2+ ion.

PbI2(s) ⇌ Pb2+(aq) + 2I-(aq)

initial _________ _________

∆(change) _________ _________

equilibrium _________ _________

[Pb2+] = ____________M; [I-] = ____________M.

3. What is the value of Ksp for the reaction? (Use Equation 2 and the results of
Problem #2)

4. Convert the molarities from Problem #2 to activities as described in this lab

and recalculate Ksp using activities. (Refer to Equations 4, 6, 7, and 8)

Chemistry M01B Laboratory Manual pp. 47