Chemistry 1C Name
Solubility Product Constant Partner
Determination of a Solubility Product Constant and the Common
Ion Effect1
Objectives
• To understand the solubility product constant, ksp.
• To find the solubility product constant for a simple salt.
• To understand the common ion effect.
• To experimentally compare solubility in the absence and presence of a common ion.
• To experimentally determine the effect a common ion has on a Ksp value.
Discussion – Solubility Product Constant
In this experiment we will determine the solubility product constant, Ksp, of the slightly soluble salt potassium
hydrogen tartrate, KHC4H4O6. To demonstrate the effect of a common ion on solubility, an example of Le
Chatelier’s Principle, we will measure the solubility of this salt in pure water and in a solution containing KCl.
We will also determine the effect a common ion has on a Ksp value.
A sparingly soluble salt is in equilibrium with its constituent ions in solution. In general for a salt having a
formula XaYb, the solubility equilibrium may be expressed as:
XaYb(s) <—> aXn+(aq) + bYm– (aq) (1)
The equilibrium constant for this process is called the solubility product constant, Ksp
Ksp = [Xn+]a [Ym–]b (2)
For example, the equilibrium expression for barium sulfate dissolving in water is represented by the equation
BaSO4(s) <—> Ba2+(aq) + SO42–(aq) (3)
And the solubility product constant, Ksp is expressed by the following equation
Ksp = [Ba2+][SO42–] (4)
The value of the solubility constant depends only on temperature for a given salt and is completely
independent of the quantity of the solid, undissolved salt that remains. The solubility product constant for
BaSO4 in pure water at 25.0°C is 1.1x10-10. If solid BaSO4 is dissolved in pure water to form a saturated
solution, then:
Ksp = [Ba2+][SO42–] = 1.1x10-10 (5)
Mathematically we can write Ksp expressions using molar solubility, S, in place of individual ion concentrations.
If we define S as the molar solubility of BaSO4, then S moles of this salt dissolve in one liter of solution. In a
saturated solution of pure BaSO4, [Ba2+] = [SO42–] = S and equation (5) can be rewritten as
Ksp = SxS = 1.1x10-10 therefore (6)
"10
S= 1.1x10 = 1.0x10–5 M (7)
-5
This means that, at 25.0°C, 1.1x10 moles of BaSO4 will dissolve in one-liter solution to produce a saturated
solution. In the discussion above, we considered the case in which the salt BaSO4 was dissolved in pure water.
If we dissolved BaSO4 in a dilute solution containing either Ba2+ or SO42- ions (from another source), we have
to consider the effect of the already present ions on the solubility of BaSO4. Suppose we dissolve BaSO4 in a
0.10 M solution of sodium sulfate. On a molecular level, there is no distinction among SO42- ions in solution,
whether they were produced from the solid BaSO4 dissolving or from another salt. The solubility product
constant must be satisfied for BaSO4 regardless of what else is present in the solution. However, the
concentration of SO42-(aq) in the solution is already 0.10 M before BaSO4 was added to the solution. When
substituting into the expression for Ksp in equation (5) we must consider the already present 0.10 M sulfate
ions.
1
Adapted from an experiment by N. Rezaie.
1
Chemistry 1C Name
Solubility Product Constant Partner
Ksp = [S][S + 0.10] = 1.1x10-10 M (8)
2+
In this case, S is the molar solubility of BaSO4 in the presence of 0.10 M Na2SO4. The concentration of Ba in
this solution is S, but [SO42–] = [S] + [0.10]. Since Ksp is very small, we can make the approximation [S +
0.10] ≈ 0.10 and easily solve for [Ba2+]:
[Ba2+] = 1.1x10-9 M, [SO42–] ≈ 0.10 M
Since the only source of Ba2+ ion is from the dissolving of BaSO4(s), then 1.1x10-9 mol/L of BaSO4(s) must be
dissolved to reach saturation in the presence of the common ion, SO4–2(aq). This is approximately 10,000
times less BaSO4(s) than dissolved in one liter of pure water. The presence of the common ion already in the
solvent has decreased the solubility of BaSO4(s) by five orders of magnitude.
Application to the Slightly Soluble Salt Potassium Hydrogen Tartrate
In this experiment, we will first determine Ksp for the salt potassium hydrogen tartrate, KHC4H4O6(s), in pure
water. Potassium hydrogen tartrate is a slightly soluble salt and dissolves in water with the following
equilibrium:
KHC4H4O6(s) <—> K+(aq) + HC4H4O6–(aq) (9)
Ksp = [K+][HC4H4O6–] or Ksp = [K+][HT–] where HT– represents HC4H4O6– (10)
We will dissolve enough potassium hydrogen tartrate, KHT, in deionized water to make a saturated
solution. In this solution the concentration of potassium ion is equal to the concentration of hydrogen tartrate
ion. Since the hydrogen tartrate ion, HT–, behaves as a weak acid its concentration can be determined by
acid-base titration using NaOH as the titrant. Thus, the molar solubility of KHT and the value of Ksp can be
determined. By defining S as the molar solubility of KHT then, in a saturated solution of pure KHT,
[K+] = [HT–] = S and equation (10) can be rewritten as:
Ksp = [K+][HT–] = SxS = S2 (11)
In the second part of this experiment, we will dissolve enough potassium hydrogen tartrate in a dilute solution
of KCl(aq) to also make a saturated solution of KHT. In this case a common ion is present from the
KCl(aq). Again, the concentration of HT– can be determined by titration. However, in this case the
concentration of K+ is not equal to the concentration of HT– as before since a significant amount of K+ is
present from the KCl. The concentration of HT– is still S, but [K+] = [S] + [KCl] and equation (10) becomes:
Ksp = [K+][HT–] = ([S] + [KCl])xS (12)
In this case, S is the molar solubility of KHT in the presence of the KCl. If the concentration of KCl(aq) is
known, then Ksp can be determined in the presence of the common ion.
Materials
Day 1 Day 2
(2) 250-mL Erlenmeyer flasks with stoppers 50-mL buret
100-mL volumetric flask (1) 50 mL beaker
Pure KHT 6 M NaOH
Pure KCl (1) 25-mL pipet and pipet pump
(1) magnetic stirrer (1) 500-mL round bottom flask
(1) magnetic stir bar Phenolphthalein solution
(2) 250-mL Erlenmeyer flasks
(1) 10-mL graduated cylinder
Medium grade filter paper
Short stem funnel
Digital Thermometer
Safety
Wear safety glasses at all times.
The 6M NaOH is corrosive. Avoid contact with skin and clothes. If contacted, wash immediately with tap water.
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Chemistry 1C Name
Solubility Product Constant Partner
Procedure Day 1
Pure KHT solution.
Weight about 0.70 g of KHT on a weighing paper. (No need to record the actual mass in your notebook; why
not?) Place this powder into a 250-mL Erlenmeyer flask and add 100-ml of deionized water. Label this flask
“Pure KHT”. Add a magnetic bar to this solution and stir for 25 minutes using, a magnetic stirrer and stir bar.
When done, stopper this flask and store in your locker until the next lab period. Rinse and dry the magnetic
stir bar.
KHT in KCl solution.
Weigh accurately about 0.08 grams of KCl into a small clean and dry 50-ml beaker. Record the mass of KCl to
the nearest milligram. Add about 30 ml of DI water to the beaker to dissolve the potassium chloride and
transfer quantitatively into your 100 ml volumetric flask. Bring the volume of the solution to the mark with
DI water. Invert several times to mix and transfer the contents to a clean and dry 250-ml Erlenmeyer flask.
Calculate the concentration of KCl in this solution and label the flask with the concentration and contents. To
this flask add about 0.70 g of KHT (Again, no need to record the actual mass in your notebook; why not?) and
stir the solution by magnetic stirrer for at least 25 minutes as before. Stopper the flask and store it in your
locker until the next lab period.
Procedure Day 2
Standardization of NaOH
Dilute 1.6-1.8 ml of 6 M desk reagent NaOH solution to a total volume of about 400 mL using a clean 500-mL
round bottom flask. Stopper the flask and mix thoroughly by repeatedly inverting the solution. Clean
thoroughly a 50-ml buret using a little soap solution, then rinse the buret first with tap water, then with DI
water and finally with three small portions (about 5 mL each) of your NaOH solution. Now fill the buret with
your NaOH solution, making sure there is no air bubbles trapped in the tip of the buret. Accurately weigh, by
difference, 0.12- 0.15 grams of potassium hydrogen tartrate into a 250-ml Erlenmeyer flask. Dissolve the
acid sample in about 50-ml fresh distilled water. Add three drops of phenolphthalein indicator and titrate the
sample with the NaOH solution from the buret until the first permanent appearance of light pink-color Record
the initial and final buret readings to the nearest 0.05 ml for each titration. Repeat the titration two more
times. Calculate the precise molarity of NaOH solution from your three trials.
Titration of KHT solutions in pure water
Measure and record the temperature of the KHT solution prepared last period. Obtain a clean, dry 250-mL
Erlenmeyer flask and filter the solution using a dry funnel and medium grade filter paper (do not wet!) into
the flask. Label the flask and stopper it. Using a 25-ml volumetric pipet remove a small portion of this solution
to rinse the pipet. Transfer 25-ml of filtered KHT solution into a clean 250-mL Erlenmeyer flask Add 2 drops of
phenolphthalein indicator to the flask. Record the initial volume of NaOH solution in the buret to the nearest
0.05 ml. Titrate the sample of KHT solution in pure water to the light pink phenolphthalein end point. Record
the final volume of NaOH solution from the buret to the nearest 0.05 ml. Repeat this titration two more
times.
Titration of KHT solutions in KCl
Measure and record the temperature of the KHT in KCl solution prepared last period. Obtain a clean, dry 250-
mL Erlenmeyer flask and filter the solution using a dry funnel and medium grade filter paper (do not wet!)
into the flask. Label the flask and stopper it. Using a dry 25-ml volumetric pipet remove a small portion of this
solution to rinse the pipet. Transfer 25-ml of filtered KHT solution in KCl into a clean 250-mL Erlenmeyer flask
Add 2 drops of phenolphthalein indicator to the flask. Record the initial volume of NaOH solution in the buret
to the nearest 0.05 ml. Titrate the sample of KHT solution in KCl to the light pink phenolphthalein end point.
Record the final volume of NaOH solution from the buret to the nearest 0.05 ml. Remember if the common ion
effect is present the volume of base used should be less than in the titration of pure KHT in water. Repeat
this titration two more times.
Clean-up
Thoroughly rinse your buret before returning it to the stockroom. Dispose of the filter paper, the titrated
solutions, any unused NaOH and any left over solutions of KHT or KHT/KCl in the waste container that is
provided for this experiment. (All wastes can be added to the same container.)
3
Chemistry 1C Name
Solubility Product Constant Partner
Data
Day 1 – Solution preparation
Mass of KCl dissolved into the 100 mL volumetric flask
Day 2 – Titrations
1. NaOH Standardization
Trial Volume NaOH used Grams KHT titrated
1
2
3
2. Titration of KHT in water:
Temperature of Solution:
Trial Volume NaOH used
1
2
3
3. Titration of KHT in KCl solution:
Temperature of Solution:
Trial Volume NaOH used
1
2
3
Calculations
1. Using the standardization of the NaOH data for trial 1 show how the precise molarity of the NaOH can be
determined.
a) Calculated results for trial 2 and trial 3
b) Average NaOH molarity
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Chemistry 1C Name
Solubility Product Constant Partner
2. Using the data from the titration of pure KHT in water, show how the molar solubility, S, of the KHT can
be determined for trial 1.
a) Calculated results for trial 2 and trial 3
b) Average molar solubility
3. Using the data from the titration of KHT in KCl show how the molar solubility, S, of the KHT can be
determined for trial 1 in the presence of a common ion, K+.
a) Calculated results for trial 2 and trial 3
b) Average molar solubility in the presence of K +
5
Chemistry 1C Name
Solubility Product Constant Partner
4. Using the average molar solubility found for pure KHT in water calculate Ksp for KHT.
5. Look up the literature value of Ksp for KHT. The literature value can be found on the internet with a little
searching. Compare your results to the literature value by calculating a percent error. Don’t be surprised
if your value is significantly in error.
a) Can you think of a reason, related to experimental conditions, that can cause your value to disagree
with the literature value? (Hint: What does the value of an equilibrium constant for a given process
depend upon?)
6. Compare the molar solubility of KHT in pure water to that of KHT in KCl. Calculate the percent change.
Percent change = [(SKCl – Spure)/Spure] x 100%
a) Are these results what you would expect? Why?
7. Using the molar solubility found for KHT in KCl and the calculated concentration of the KCl, calculate a Ksp
for KHT in the KHT/KCL solution.
a) How does this value compare to your answer in 4? Do you expect them to be the same or different?
Explain.
6
Chemistry 1C Name
Solubility Product Constant Partner
Follow-up Questions
1. The molar solubility of Ag2CrO4 in water at 25 °C is 7.8x10-5 M.
a) Calculate Ksp
b) What is the solubility expressed as g Ag2CrO4 per 100 mL of solution?
2. 25 mL of 0.10 M Pb(NO3)2 is mixed with 50-mL of 0.090 M Na2SO4.
a) Write an equation for a possible precipitation reaction.
b) Under the conditions specified will a precipitate from? Show your work!
