University of Oregon Thailand Distance Learning Program Green Chemistry

2010

Connecting Solubility, Equilibrium, and Periodicity

Chemical Concepts
Equilibrium; solubility; solubility product; periodic properties; acid/base titration.
Green Concepts
Preventing waste; safer chemicals. (Consider Green Principles 1, 3, 11, and 12.)
Introduction
Chemical equilibrium is one of the core concepts in chemistry, and a firm understanding of
the concept is essential if one is to understand reaction chemistry, acid/base chemistry,
biochemistry, or any of myriad other facets of chemistry. Beginning students, however,
frequently have difficulty with the concept of equilibrium and regularly misunderstand both
its meaning and its implications. Crystallization the separation of a solid compound from a
solution of the compound is a relatively simple phenomenon that may be used to highlight
some of the essential features of equilibrium in an intuitive and understandable way. Most
students have observed, for example, that sugar dissolves slowly in cold water (or coffee or
tea), but more rapidly and in larger amounts in hot water. Many have seen that cooling of a
hot solution of sugar can lead to the formation of crystalline sugar, illustrating that there is an
equilibrium between sugar molecules in solution and those in the solid state.
In this experiment, we will examine the solubility in water of three group II hydroxides,
Mg(OH)2, Ca(OH)2, and Sr(OH)2, using titrations to determine the amount present in a
saturated solution. From the resulting titration data, we will determine the solubility products
for each of the three hydroxides, gaining familiarity with the concept of Ksp and thereby with
consideration of simple solubility equilibria. Based on the trends in solubility products
determined for the three hydroxides, we will then form a hypothesis regarding the solubility
of the two group II hydroxides not examined experimentally, Be(OH)2 and Ba(OH)2.
While the determination of solubility products is a common laboratory procedure, reported
experiments often rely on the precipitation of sparingly soluble compounds such as PbI2 or
BaSO4, thereby risking student exposure to hazardous heavy metals and generating wastes
that are hazardous and costly to dispose of. In contrast, this experiment uses group II
hydroxides that, while requiring the usual amount of care appropriate for work with basic
substances, are neutralized and present no disposal hazards. The more toxic group II elements,
beryllium and barium, are avoided, but students are able nonetheless to explore their
chemistry indirectly, by recognizing the trend in solubility displayed by the three compounds
and extrapolating to predict the solubilities of the remaining two.
Laboratory
Note: For this workshop, each group will titrate only a single group 2 hydroxide, then share
their results with the other groups.

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Materials needed
Saturated solution of Mg(OH)2
Saturated solution of Ca(OH)2
Saturated solution of Sr(OH)2
0.002 M HCl
Phenolphthalein solution (0.1% in ethanol)

2010

50 mL burette with clamp and stand

250 mL Erlenmeyer flask
Magnetic stir bar
Magnetic stir plate

Titrate each Group II metal hydroxide saturated solution with 0.002 M HCl using
phenolphthalein as the indicator, using the following procedure.
1. Fill buret with 0.002 M HCl solution. Record the starting volume of the titrant.
2. Obtain a sample of one of the analytes either 50.0 mL of Mg(OH)2, 1.00 mL of
Ca(OH)2, or 0.500 mL of Sr(OH)2.
3. If you are using Ca(OH)2 or Sr(OH)2, add approximately 50 mL of distilled water.
4. Add 3 drops of phenolphthalein solution.
5. While stirring magnetically, add titrant until the indicator undergoes a color change.
Record the final volume of the titrant.
Questions
1. Calculate the Ksp value for your sample, then share your data with other groups so that
you all have experimental results for the three hydroxides.
2. What periodic trend in Ksp values do your experimental findings show? Did you find
the same periodic trend in Ksp values as the trend given in the lab report?
3. Based on your results, which of the following values of Ksp do you think is most likely
for beryllium hydroxide, Be(OH)2? Explain your choice.
3.0 10-8
7.0 10-22
2.0 10-3
4. Based on your results, which of the following values of Ksp do you think is most likely
for barium hydroxide, Ba(OH)2? Explain your choice.
3.0 10-8
7.0 10-22
2.0 10-3
5.
a) How do beryllium hydroxide and barium hydroxide each compare to the Group
II metal hydroxides you did titrate in the lab in terms of ionic size and effective
nuclear charge (Zeff) on the ions?
b) Based on the comparison of size and Zeff, which of the three values of Ksp listed
in question 3 would Coulombs Law predict for beryllium hydroxides Ksp?
c) Based on the comparison of size and Zeff, which of the three values of Ksp listed
in question 4 would Coulombs Law predict for barium hydroxides Ksp?
6. Of the five Group II metal hydroxides, Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, and
Ba(OH)2, beryllium hydroxide and barium hydroxide are definitely the most toxic.
The goal of this experiment was to determine the periodic trend in the solubility of
Group II hydroxide compounds. Explain how this experiment is more aligned with the

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2010

concepts of green chemistry than an experiment calling for titrations of all five Group
II metal hydroxides.
Research Questions
1. Why is beryllium so toxic, when all the surrounding elements (e.g., Li, Na, Mg) are so
benign?
2. What are some uses of beryllium or its compounds?
References
This is an adaptation of Connecting Solubility, Equilibrium, and Periodicity in a Green,
Inquiry Experiment for the General Chemistry Laboratory, Kristen L. Cacciatore, Jose
Amado, Jason J. Evans, and Hannah Sevian*, J. Chem. Ed. 2008, 85(2), 251-253. The
following pages provide a reproduction of this original article. A nice packet of supporting
information is available on-line at the Journal of Chemical Education web site see the
reference to this information at the end of the following article.

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University of Oregon Thailand Distance Learning Program Green Chemistry

Copyright Kenneth M. Doxsee, University of Oregon

2010

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University of Oregon Thailand Distance Learning Program Green Chemistry

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2010

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University of Oregon Thailand Distance Learning Program Green Chemistry

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2010

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University of Oregon Thailand Distance Learning Program Green Chemistry

2010

Determination of Acetylsalicylic Acid in an Aspirin Tablet

Chemical Concepts
Acid-base chemistry; titration.
Green Concepts
Safer reagents; prevent waste. (Consider Green Principles 1, 2, 3, 4, 8, and 11.)
Introduction
This is a simple and inexpensive microscale experiment with aspirin (acetylsalicylic acid,
ASA) that can be successfully used in an introductory experimental chemistry course. It
introduces the concepts of acid/base chemistry and titration. Using a commercial aspirin
tablet, the experiment makes connections between the laboratory and real life, and can be
used to raise issues related to drug purity and analysis, as well as more complex related
matters, such as the manufacture of drug tablets, which contain various excipients, fillers, etc.
in order to provide them with desired shelf life, appearance, and solubility properties.
Acid/base titration is routinely taught in the high school and general chemistry laboratory.
Conceptually, such a titration should not generate hazardous waste, regardless of the scale at
which it is performed, since the titration leads to neutral, easily disposable solutions. In
practice, however, one would be hesitant to introduce the final solutions to the environment,
for fear that titrations were carried out incorrectly and had not properly neutralized the
solutions. Thus, a student titration experiment can lead to a large amount of waste that must
be treated as hazardous. In this experiment, we introduce a simple and effective means of
dramatically reducing the volumes required for titration experiments while maintaining an
appropriate level of accuracy and precision.
Laboratory
Materials needed
Porcelain mortar and pestle
1 commercial aspirin tablet
50-mL beaker
Precision balance
Ethanol, 20 mL
Distilled or deionized water

Standard 0.05 mol L-1 NaOH

Phenolphthalein indicator
Two 1-mL syringes (insulin type)
One three-way plastic stopcock
One automatic delivery pipette tip
Silicone hot glue

Sample preparation and dissolution

1. Weigh a commercial aspirin tablet.
2. Grind the tablet to a powder in a porcelain mortar.
3. Transfer the powder to a 50-mL beaker, weighing before and after to determine the
amount transferred.

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University of Oregon Thailand Distance Learning Program Green Chemistry

2010

4. Add 20 mL of ethanol and 20 mL of distilled water, gently swirling to effect

dissolution.
Sample filtration and titration
(When an aspirin tablet is dissolved in an ethanol/water mixture, the filler/binder from the
commercial aspirin tablet remains in suspension. It does not interfere with the final result, but
the endpoint of the titration is better detected if the solution is filtered.)
1. Allow the mixture to reach room temperature, then filter it quantitatively into a 100mL volumetric flask containing 20 mL of distilled water.
2. Add additional distilled water to the 100-mL mark.
3. After thorough mixing, aliquots of 1 mL are titrated with standard 0.05 mol L-1 NaOH
contained in a 1 mL syringe (the exact concentration, previously determined by a
technician, is given to the students). The Figure illustrates the microtitration apparatus.
Insert the tip of the syringe into a plastic 3-way stopcock valve or an automatic pipette
tip. No needles are needed, and they should be avoided to prevent accidental pricks.
Phenolphthalein is used as the indicator.

1 mL syringe
(for titration)

T hree- way stopcock

1 mL syringe
(for refilling)

Automatic delivery pipet tip

TH E MEXICAN MICRO SCALE

TITRAT ION SYSTEM

Data reporting and results

During the experiment, a data sheet must be completed by the students (Table 1). A sheet with
typical data obtained by a group of students using aliquots of 20 mL (and titrating with
normal size glassware) appears in Table 2 for comparison.

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University of Oregon Thailand Distance Learning Program Green Chemistry

2010

Table 1. Data Sheet with Actual Experimental Data and Results (using aliquots of 1 mL)
DETERMINATION OF ASA IN COMMERCIAL ASPIRIN
Aspirin tablet
mass
Analyzed mass

g
g

.1

ASA molar mass

180 g mol

NaOH concentration

mol L

Titration with NaOH

Results
sample
volume
1

mL

mL

3
average volume
used

mL
mL

ASA amount per sample

ASA amount in analyzed
mass
%ASA in tablet
% error, assuming 99.3%
purity

.1

(in moles
and grams)
g
%
%

Table 2. Data Sheet with Typical Experimental Data and Results (using aliquots of 20 mL)
DETERMINATION OF ASA IN COMMERCIAL ASPIRIN
Aspirin tablet
mass
Analyzed mass

0.5819 g
0.5716 g

Titration with NaOH

sample
volume
1

11.20 mL

11.15 mL

3
average volume
used

11.25 mL
11.20 mL

.1

ASA molar mass

180 g mol

NaOH concentration

0.0462 mol L

.1

Results
-4

ASA amount per sample

ASA amount in analyzed
mass
%ASA in tablet
% error, assuming 99.3%
purity

5.17 10 mol
or 0.0931 g
0.466 g
81.5 %
4.4 %

The calculations for Table 2 are as follows:

For equal equivalents, V1M1 = V2M2
11.20 mL (0.0462 mol/L) / 20 mL = M2 = 0.0258 M
The amount of ASA per 20-mL sample is then:
0.0258 (mol/L)(180 g/mol)(0.020 L) = 0.093 g or 5.17 x 10-4 mol of ASA.
In 100 mL, this is equivalent to:
0.093 g (100 mL/20 mL) = 0.466 g of ASA dissolved from the tablet. Since 0.5716 g was the
total amount used, this means that the ASA content is
(0.466 g/0.5716 g) x 100 = 81.5%

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2010

Since the US official standard regulates that each tablet must contain 500 50 mg ASA, we
will assume the ASA content to be 0.5000 g. Then, knowing that only 0.5716 g out of 0.5819
g was transferred, the total ASA dissolved is:
(0.5716 g /0.5819 g) x 0.5000 g = 0.9823 x 0.5000 g = 0.4911 g
The titration gave 0.466 g of ASA, which then gives an error of:
(0.4911 g - 0.466 g) / (0.4911 g) x 100 = 5.1% error
Since the ASA purity is not 100% but 99.3% (see below), the average error decreases to:
{[(0.4911 g x 0.993) - 0.466 g] / (0.4911 g x 0.993)} x 100 = 4.4% error
Results obtained by students (using aliquots of 20 mL) are typically 5% lower than the mean
value calculated from the manufacturers data. Tests with pure acetylsalicylic acid, performed
by a technician using the same method, showed an average value of 98.5% for the pure acid
after 24 repetitions. This result validates the method because in this particular case, the purity
of the acetylsalicylic acid employed was tested to be 99.3%. Lower ASA percentage values
determined by the students are probably due to losses arising from poor quantitative transfer
to the volumetric flask. (Typical aspirin tablets contain 75% to 90% ASA by weight.) There is
also the possibility that the ASA content in aspirin tablets is lower than 500 mg, as has been
reported in the literature.
Questions
1. Provide the data requested in Table 1.
2. How do your results compare with the sample data provided in Table 2?
3. If your results differ, is the difference significant? If so, discuss possible reasons for
the difference.
Research Questions
1. Drug tablets usually contain many things in addition to the active drug compound.
What is an excipient? What is a filler? What is a binding agent?
2. What other types of materials are used in preparing drug tablets? Why are they added?
3. Compare drug administration in tablet form vs. injected drugs. What are the
advantages of tablet dosage? What are some of the difficulties that must be overcome
in order to administer a drug as a tablet?
References
This procedure was adapted by Jorge Ibaez (Universidad Iberoamericana, Mexico) from the
original paper, Katia B. Gusmo, Emilse M. A. Martini, and Suzana T. Amaral.
Determination of Acetylsalicylic Acid (ASA) in Aspirin: A General Chemistry Experiment.
Chem. Educator 2005, 10, 444-446.

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