University of Oregon Thailand Distance Learning Program Green Chemistry

2010

The One-Penny Solar Cell

Chemical Concepts
Properties of metals; metal oxides; redox; electrochemistry; graphing.
Green Concepts
Alternative energy; safer materials. (Consider Green Principles 2, 3, 5, 8, and 9.)
Introduction
The ongoing search for alternative energy sources has resulted in the development of many
new technologies, including the solar cell, through which light from solar radiation is
converted into electricity. Most solar cells are made of silicon due to the availability of this
element (especially as SiO2) and the reasonably good energy match between solar radiation
and the semiconductor energy bands. However, the requirements of high temperature and
high purity for their fabrication greatly diminish their technical and economic feasibility.
Alternatively, cuprous oxide (Cu2O) has also been studied for this purpose due to the wide
availability, low toxicity and low cost of its elements. In addition, it can be fabricated by a
variety of methods. As a result of oxygen excess from stoichiometry (or copper vacancies) it
is a p-type semiconductor, symbolized as p-SC with a band gap of 2.0 eV that makes it a good
candidate for photovoltaic cells since it absorbs an important portion of the solar spectrum.
Challenges that remain to be solved for the commercial utilization of cuprous oxide solar cells
include the fact that this oxide is prone to reduction to metallic Cu and to oxidation to CuO. In
addition, the corresponding Cu-Pourbaix diagram shows that Cu2O is stable only in a small EpH region, which makes its preparation from aqueous solutions somewhat difficult.
In the present experiment, students will fabricate a photoresponsive copper (I) oxide layer on
a copper surface by simple thermal, chemical and electrochemical procedures. An easily
measurable photovoltage is obtained in each case under visible light illumination.
The likely reactions occurring at the Cu surface to produce Cu2O are:
(a) Thermal method
2Cu(s) + 1/2O2(g)

Cu2O(s)

(1)

Oxide films formed between 1040oC and 1050oC consist entirely of Cu2O and show p-type
semiconductivity while those grown between 200oC and 970oC consist of a mixture of cupric
oxide (CuO) and Cu2O. Since both oxides are semiconductors, the qualitative results and
conclusions of the present experiment are not affected by the presence or absence of CuO.

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2010

(b) Chemical method

Cu(s) + Cu2+(aq) + 1/2O2(g)

Cu2O(s)

(2)

(c) Electrochemical method

Cu(s) + 2H2O(l)

Cu(OH)2-(aq) + 2H+(aq) + e-

(3)

2Cu(OH)2-(aq)

Cu2O(s) + H2O(l) + 2OH-(aq)

(4)

Laboratory
Materials Needed
The following procedures use pre-1982 US one-cent coins (i.e., copper pennies). Note that
pennies produced after this year are mainly composed of Zn, covered with Cu. Alternatively,
other coins (e.g., 2 Eurocents and 50 Mexican cents) or copper strips also give measurable
results.
Electrode preparation
1. Use fine sand paper to smooth both sides of several pennies until they shine.
2. Place them in 3 M HNO3 for 1 minute. Caution: You may wish to carry out this
treatment for your students to avoid exposure to nitric acid or to the fumes generated
during nitric acid treatment. Use eye protection and rubber gloves. Carry out this
treatment in a fume hood, as the reaction of nitric acid with Cu metal produces the
toxic gases NO and NO2.
3. Rinse the pennies three times with deionized water, then follow the procedures below
to fabricate a (reddish) semiconducting layer on the Cu surface.
a) Thermal method
1. Grasp one of the clean pennies with tweezers and heat it for 30 seconds at the interface
between the cold (i.e., gas feed) and hot (i.e., combustion) zones in the flame of a
Bunsen burner. The penny should acquire a brown-reddish color, indicative of the
formation of the semiconductor Cu2O.
2. Set the hot penny (red side up) on a clean and dry surface and allow it to cool to room
temperature.
3. If black CuO is also formed, it can be carefully peeled off from the surface or else
removed by rinsing with dilute HCl (e.g., 0.01 M).
b) Chemical method
1. Place 5 mL of a 0.1 M CuSO4 solution in a 20 mL beaker.
2. Immerse a clean penny in the solution and heat at 45-50 C for 2 h.

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2010

3. Then, extract the penny with the aid of forceps, rinse it twice with deionized water and
allow it to dry in air. Note the color on the surface of the penny exposed to the
solution (it should be reddish). (The bottom surface of the penny, less exposed to the
solution, may or may not develop a red color. The photovoltaic cell works equally
well, regardless.)
c) Electrochemical method
1. Place a water bath on a heating plate.
2. Place 10 mL of a 0.1 M Na2SO4 solution in a small beaker and immerse it in the water
bath. (Note: a small amount of NaCl may be added to the electrolyte to speed up the
oxidation of Cu.)
3. Grasp one of the pennies with an alligator clip and connect it to the anode of a variable
DC power source. The counter electrode (cathode) can also be another penny or a
copper plate or foil (other materials may be tested as well, since the function of the
cathode is primarily to close the circuit).
4. Place both electrodes in the Na2SO4 solution (do not allow them to touch each other).
A fixed and steady separation of 0.5 mm is recommended. Heat the solution to 4550C with constant stirring. (The experiment can be speeded by heating to higher
temperatures, i.e., 85C.)
5. Turn the power source on and adjust the applied voltage to 1 V. Allow the experiment
to proceed for 1 h. (Some Cu metal deposition may be noted at the cathode, but this
obviously does not interfere with the experiment.)
6. Extract the anodic penny with the aid of forceps, rinse it with water and allow it to dry
in air. Note the color of its surface (it should be reddish due to formation of Cu2O
from the oxidation of metallic Cu). If black CuO is also formed at the anode it can be
carefully removed by rinsing with dilute HCl (e.g., 0.01 M).
Cell preparation
Since the reddish layer on each penny treated by the above procedures
contains a photoactive surface, we will need to convey the
photocharges generated upon exposure to light into an external circuit.
For this, we will form a sandwich with two copper strips (3 cm long,
1 cm wide) made from sanded copper foil or thin copper sheet. The
penny will be like the ham in the sandwich. See Figure 1.

Figure 1. The one-penny photovoltaic cell

Then, place approximately 15 mL of a 0.1 M NaCl solution in a 20 mL beaker. Insert into the
solution the Cu2O electrode so that only a portion of the protruding penny is submerged, not

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2010

the copper strips holding it, and a counter electrode to close the circuit for measurement (e.g.,
a clean penny or a small Cu plate). Do not allow the two electrodes to touch each other.
Photovoltage measurement
1. Connect both electrodes to a multimeter (set the scale to a maximum of 200 mV).
Record the initial measurement.
2. Place a 100 W incandescent light bulb about 10 cm from the electrochemical cell, in
front of the semiconducting layer. (If one desires to remove any infrared light before it
reaches the cell in order to prevent undesired heating effects, a 100 mL beaker full of
water can be placed between the light bulb and the cell).
3. The set up is now ready. Measure and monitor for a few minutes the baseline voltage
produced by the cell in the dark (or until it becomes more or less stable, varying less
than 1 mV per min), taking measurements every 30-60 s.
4. Then turn the light on and similarly monitor for another few minutes the photovoltage
produced.
5. Repeat this cycle several times until you reach a total of 30 min. If more consistent
results are desired, the entire set up can be enclosed inside a cardboard box during
measurements.
6. Plot your results.
Questions
1. Report the results of your study, as illustrated by your graph prepared above.
Research Questions
1. Discuss the relative advantages and disadvantages of silicon-based and copper oxide
based solar cells.
2. Which type of solar cell seems more promising?
3. What are some other materials under exploration for solar energy capture?
4. Are there technologies for solar energy capture that do not require the use of toxic
metals? What are their prospects for future development?

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University of Oregon Thailand Distance Learning Program Green Chemistry

2010

Metal Ion Recovery by Cementation

Chemical Concepts
Metallic properties; displacement reactions; comparison of reactivities of metals;
stoichiometry; redox; electrochemistry; equilibrium; thermodynamics.
Green Concepts
Waste prevention. (Consider Green principles 1, 2, 3, 8, 10, 11, and 12.)
Introduction
The uncontrolled release of metal ions poses a threat to the environment. An alternative
removal scheme is cementation, whereby redox activity takes place between a metal substrate,
M1 and the ions of a more noble metal, M2 (i.e., a metal with a more positive standard
potential that needs to be removed from the solution), due to a thermodynamically
spontaneous reaction.
In general, a cementation process can be described by equation 1 (for simplicity, two divalent
metals are considered here).
M2+(aq) + N0(s) = M0(s) + N2+(aq)

(1)

In this way, N is the sacrificial metal, and M is the cemented metal (that is, the one to be
removed). Besides the spontaneous nature of the process, other advantages include its relative
simplicity, ease of control, and the possible recovery of valuable metals. Challenges to this
process involve the presence of chelating agents, mass transfer limitations, and the
introduction of new species into the medium. Some examples of applications of cementation
processes include:
removal of polluting metal ions from aqueous effluents
purification steps in metallurgical operations
recovery of spent metals from different chemical operations
The present experiment is an example of this last application. It comprises the cementation of
Cu2+ (E0Cu2+/Cu = 0.34 V) by Zn (E0Zn2+/Zn = -0.76 V) in a small-volume spectrophotometer
cuvette. The concentration of Cu2+ may be easily monitored using a simple
spectrophotometer, but in the absence of such an instrument, the concentration may be
estimated and monitored in situ by comparing it visually to that of pre-prepared solutions of
known concentrations. The resulting concentration versus time data points are plotted and a
first rate plot of removal kinetic data can be analyzed.
While waste treatment does not represent a primary principle of green chemistry, it represents
a necessary topic for study for the foreseeable future, as we continue to deal with the
environmental aftermath of centuries of mining and other activities that have brought us into

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2010

contact with heavy metals. In addition, a firm grasp on the many key chemical concepts
presented in this experiment will provide students with the intellectual tools needed to address
the green principles more directly as they continue their studies.
Laboratory
Materials needed
0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 and 0.1 M CuSO4
1 Zn pellet
Eleven 3-mL spectrophotometer cuvettes (path length = 1 cm)

1. Fill each of ten of the cuvettes with the ten different concentrations of CuSO4 solution.
These will serve as standards, allowing visual comparison of the test solution and
estimation of its approximate concentration.
2. Using forceps, find a Zn pellet of appropriate dimensions such that it cannot fall to the
bottom of the spectrophotometer cuvette (see Figure).
3. Rinse the pellet with acetone or ethanol to remove any grease or other foreign
substances from its surface, allow it to dry, and place it in the final cuvette as shown in
the Figure.
4. Next, with a Pasteur or a Beral pipet, fill the cuvette with 0.1 M CuSO4 solution as to
completely cover the Zn pellet.
5. Compare the concentration of Cu2+ inside the test cell every 5 minutes to that of the 10
pre-prepared solutions of known concentrations. Select the concentration that best
resembles that in the test cell. Record the time and the estimated concentration.
6. Continue making observations until the concentration of Cu2+ has decreased by at least
50% from the original concentration.
7. Plot the results on a concentration vs. time curve.
8. Literature reports typically show first order kinetics for the removal of ions by
cementation. If desired, test for this hypothesis as applied to your system by
calculating the corresponding first rate equation.

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2010

At the end of the experiment separate the Cu-covered Zn pellet, observe its color and place it
in a labeled container. The instructor may choose to recycle it for future experiments. Collect
all the solutions containing Cu(II). The instructor may choose to recover the Cu from these
solutions by electrolysis or other means.
Questions
1. Predict whether the following reactions are spontaneous or not, assuming T = 25oC
and that all concentrations are 1 M. Find the necessary data in any table of standard
potentials.
a) 2Ag(s) + Ni2+(aq) 2Ag+(aq) + Ni(s)
b) Ca(s) + Cd2+(aq) Ca2+(aq) + Cd(s)
c) 2Br- + Sn2+(aq) Br2(l) + Sn(s)
2. Write a general equation for the removal of a metal ion, Mx+(aq) from an aqueous
solution by cementation on a solid metal, N0(s) that becomes Ny+(aq).
3. During the removal of Cu2+ ions by cementation on elemental Fe, the following
reactions occur:
Cu2+(aq) + 2e- = Cu(s)

(1)

Fe(s) = Fe2+(aq) + 2e-

(2)

a) If the system is allowed to reach thermodynamic equilibrium, then the

concentration of Cu2+ ions will be greatly reduced, whereas the concentration of
Fe2+ will increase.
b) What will be the ratio of the concentrations at equilibrium, Q = [Fe2+]/[Cu2+]?
(Note: Assume that the concentrations of the ions are approximately the same as their
activities).
Research Questions
1. Give three examples of real cases where the cementation technique is utilized for the
removal and/or recovery of metal ions.
2. If a metal ion (M1) is to be cemented and it has a standard potential of + 0.50 V (vs.
the standard hydrogen electrode, SHE), which of the following metals (M2) could be
used to achieve that operation? Select the standard potential of the metal half reaction
that would be useful. a) 0 V, b) + 0.50 V, d) + 1.00 V vs. SHE. Explain.

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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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