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Edwardo A.

Gonzalez
Analysis of Copper in a Penny by Atomic Absorption Spectroscopy and Ultraviolet-Visible
Spectroscopy
Abstract
Thought the years the United States has changed the composition or amount of copper
that is in the penny (United States Mint, 2014). The biggest change in penny Cu composition
happed in 1982, decreasing the amount of Cu drastically (United States Mint, 2014). This
experiment will test the validity that each penny has the % mass Cu that the U.S. Mint states.
This was testes using two calibration curves that were made using two different methods, Atomic
Absorbance Spectroscopy (AA), and Ultraviolet-Visible Spectroscopy (UV-Vis). The UV-Vis
rendered mass % of Cu for the pre and post 1982 pennies of 94 .7% and 3.12 The AA
rendered mass % of Cu for pre and post 1982 pennies of 11111% and 2.96.23%. Both the
UV-Vis and the AA mass % of Cu for each penny did not meet the expected U.S. standards. All of
the results gathered were statistically different from each other, meaning that they do not agree
with each other within the experimental error.
Introduction
Copper is a solid, malleable, transition medal with atomic number 29 and atomic weigh
of 63.546 amu (Bentor, 2014). It has many uses in modern society. Some of the most prominent
uses of copper are for making strong alloys, for plumbing material, making fine jewelry, and
used as an electrical conductor (Bentor, 2014). But the most common and wide spread use of
copper in the United States is in the penny, having a value of one cent.
The composition of a penny has been changed many times since it first was introduced in
the United States in 1793 (United States Mint, 2014). This has come about because of the
increasing value of copper and economic inflation. When the penny mint first came out it was
composed of pure copper, this lasted until 1837 (United States Mint, 2014). Since those years the
Unites States government has used both zinc and tin to dilute the amount of copper actually used
in the United States penny. After 1837 and before 1982, with some exceptions the U.S. penny
was 95% copper and 5% tin and zinc.1982 was the last change that the United States made to the
penny mint and is now composed of 97.5% zinc and 2.5% copper (United States Mint, 2014).
In this experiment two copper pennies will be analyzed, one before 1982 and one
after 1982, to determine the actual amount of copper concentrations. Finding these
concentrations of copper will then help to compare that of government stated standards as well as
other students. Two different methods will be used to analyze the mass percentage of copper in
the penny, by using Atomic Absorption (AA) and UV-Vis spectroscopy (UV-Vis). The first step
in analyzing both pennies is to dissolve the pennies with concentrated Nitric Acid. Then two
different dilutions will be made of this sample since AA needs less analyte to work.
Both methods involve making a standard calibration curve of five different dilutions
using 1 M copper nitrate. The absorbances that are found form the know concentrations are then
plotted, which should give a linear line. This linear line is then the calibration curve which will
be used to calculate and find unknown conversation of the copper in penny solution prepared.
AA and UV-Vis both use Beers Law to determine the concentration of a certain analyte.
Beers Law: A = bc
Beers Law states that absorbance A, which is dimensionless, equals (molar absorptivity)
multiplied by the c (concentration) and b (path length) (Harris, 2007).
The first method involves using AA in which a flame is used to evaporate and atomized
the analyte (Harris, 2007). Once the analyte, in this case copper, is atomized, a hollow-cathode
lamp then emits light specifically chosen to emit the same frequencies absorbed by the copper
(Harris, 2007). The light then passes thought to the monochromator then to the detector where
the amount of light that is passing though is measured (Harris, 2007). AA will then report the
amount of light absorbed at that certain wavelength.
UV-Vis is similar to AA, both measure light absorbed by the analytic. The notable
difference with UV-Vis is that a higher concentrations are needed because it has a higher limit of
detection. UV-Vis does not use a flame instead it has a tungsten lamp (Harris, 2007). The lamp
shines straight at the monochromoeter, where a specific wavelength of light is chosen according
to the analyte, then hits the sample and finally reaches the detector, where the light absorption is
measured (Harris, 2007). The UV-Vis repots light absorbed at specific wavelengths.

Measurement of Copper in AA and UV-Vis
In this experiment two different pennies, one from 2013 and one from 1979, were
analyzed to calculate their percent mass of copper. This mass percent of copper in each where
analyzed using two different machines. The first machine was an Atomic Absorption machine
and the second was a UV-Vis machine. Both machines are located in DBH 166 in Cal State
Fullerton.
In order to calculate the percent mass using the AA or UV-Vis machines, a calibration
curve had to be set up for both by making several dilutions. Starting with 1.001 M Copper
Nitrate two different dilutions were used for each machine. Four dilutions were made for the AA
machine of copper nitrate: 5*e-6M, 1*e-5M, 5*e-5M, and 1*e-4M (lab). For the UV-Vis
machine five dilutions of copper nitrate were made: 5*e-4M, 1*e-3M, 5*e-3M, .01M, and .1M
(Haan, 2014). These curves were then graphed and used to calculate the percent mass of copper
in the pennies.
The pennies were also prepared to be analyzed in each machine. The weights of the
pennies were first recorded: 1979: 3.0761g and 2013: 2.4928g. They were then simultaneously
dropped in a beaker with deionized water and concentrated nitric acid. The 1979 penny was
dissolved in 5 mL of water and 15mL of acid and the 2013 penny was dissolved in 10 mL of
water and 10 mL of acid (Hanns, 2014). After the reaction was complete then the two pennies
were diluted twice, rendering four different samples. The 1979 penny was diluted 20 fold for the
UV-Vis machine and again to a 20,000 dilution factor for the AA machine (Hanns, 2014). The
2013 penny was diluted into a 50mL volumetric flask for the UV-Vis machine and then diluted
to a 200 dilution factor for the AA machine.
UV-Vis Resutls
A Hewlett Packard Laserjet 6L UV-Vis machine was used to analyze the absorption of
copper in samples. Each of the samples rendered similar looking graphs but had different peak
heights depending on copper concentration. The machines monochromator was configured to
shine light at wavelengths from 600 nm to 800 nm, knowing that copper absorbs light around
800nm (Haan, 2014). Figure 1 shows a sample reading of the UV-Vis spectra of one of the
dilutions for the calibration curve. When creating the calibration curve, absorbencies at 800nm
were taken from each concentration and then plotted (Figure 2).

Figure 1. UV-Vis spectroscopy of copper sample dilution .1M using a Hewlett Packard Laserjet
6L machine.

0
0.2
0.4
0.6
0.8
1
1.2
1.4
590 640 690 740 790 840
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)

Wavelenght (nm)
UV-Vis Spectra
y = 11.686x - 0.0028
R = 1
0.00E+00
2.00E-01
4.00E-01
6.00E-01
8.00E-01
1.00E+00
1.20E+00
1.40E+00
0.0000 0.0200 0.0400 0.0600 0.0800 0.1000 0.1200
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)

[Cu
2+
] (M)
Calibration Curve prepred using UV-Vis
Figure 2. Calibration curve derived using a Hewlett Packard Laserjet 6L UV-Vis machine from
5 diluted sampled of 1.001 M Copper Nitrate. Dilutions used were .1, 1*E-2, 5*E-3, 1*E-3, 5*E-
4M.

After graphing the calibration curve using the absorption at 800 nm from each diluted
concentration, a known check standard B was used to determine the validity of the calibration
curve (Hanns, 2014). This known concentration was also measured by the UV-Vis machine.
Using equation (1), derived from the calibration curve, the concentration of the measured check
standard A was calculated, and then equation 2 was used to calculate the Check Standard
Recovery (Table 1). Acceptable results ranged from 85-115% (Hanns, 2014). In equation (1) x is
the concentration, y is the absorbance, b is the y-intercept, and m is the slope of the line (Harris,
2007).

(1)

(


) (2)


Table 1. Check Standards for UV-Vis method. Known concentrations were given while
measured concentration of Check Standards were calculated using calibration curve.
After the check standard recovery was calculated, the concentration of each of the
pennies was calculated. To get the absorption of each penny, three different trials of the same
sample for each penny where ran though the UV-Vis machine. The average of these three runs
was used as the absorption. Once the average was calculated then they were entered into
equation (1) from the calibration curve to solve for the concentration of each. The concentrations
of each penny were calculated to the 95% confidence interval using equation (3) where x is the
concentration, t is the Students t for n-2 degrees of freedom, and

is the sample standard


deviation or standard error (Harris, 2007). These concentrations were then converted to grams of
copper by multiplying by their dilution factor along with the molar mass of Cu and volume. Then
Cu concentration was divided by the pennys actual mass to give mass % of Cu in each penny
(Table 2).

(3)
Check Standrad for Calibration Curve
Known Concentraion Measure Concentraion Check Recovery
UV-Vis 3.03E-03 3.32E-03 110.00%


Table 2. Mass % of copper for pennies measured from UV-Vis machine and calculated using
calibration curve at 95% confidence interval.

The limit of detection (LOD) and limit of quatification (LOQ) was calculated for the
Hewlett Packard Lasterjet 6L UV-Vis machine (Table 3). To determine standard deviation used
to calculate the LOD and the LOQ, the smallest concentration used for the calibration curve was
measured 7 different times and then calculated. This resulted in a standard deviation of 0, which
when calculating the LOD and LOQ would be 0 as well. So a simulated standard deviation of
.0005 was used. The LOD and LOQ were calculated using equation (4) and (5), where s is the
standard deviation of the seven measured absorptions, and m the slope of the calibration curve
(Harris, 2007).

LOD =

(4)

LOQ =

(5)


Table 3. Limit of Detection and Limit of Quantification from Hewlett Packard Laserjet 6L UV-
Vis machine. Standard Deviation used for UV-Vis was .0005 since using actual standard
deviation would equal zero.
AA Results
A Buck Scientific 210 VGP Atomic Absorption Spectrophotometer was also used,
making measurements for the AA diluted samples, pennies, and check standard B. To collect
data a team of two people was needed. One person would read off absorption given off by the
machine every second, while the other wrote down a total of ten readings. For each different
dilution concentration, penny, and check standard this process was repeated three times. Each
UV-Vis Mass % Reuslts
Penny Year Mass % Cu
1979 94.0 + .7
2013 3.12 + .03
Limit of Detection and Quantification for UV-Vis
LOD LOQ
UV-Vis 1.28E-04 4.27E-04
data se was averaged, and then the three data sets were averaged together, giving the absorption
of each dilution, penny, and check standard.
The averages of all the samples were revised to take away error due to the AA drifting
when reading while reading where being taken. To do this, starting with the first sample
measured, the difference between the first average and the third average was subtracted to the
final average. For the second sample the same difference used from the first plus the difference
of second, was subtracted from the average to give the fixed absorption, and so on. With the
recalculated absorptions of the dilutions the calibration curve was made (Figure 3).


Figure 3. Calibration Curve derived from an AA machine using four dilutions prepared from
1.001 M Copper Nitrate solution. Dilutions are 1*E-4, 5*E-5, 1*E-5, and 5*E-6.

Again the check standard B concentration was calculated using equation (1). Using this
measured concentration and the known concentration that was given, the check standard
recovery was calculated using equation (2) (Table 4). This helps validate the accuracy of the
calibration curve (Hanns, 2014).

Table 4. Check Standards for AA machine. Known concentrations were given while measured
concentration of Check Standards were calculated using calibration curves derived using
calibration curve.
y = 5792x + 0.0056
R = 0.9991
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.00E+00 2.00E-05 4.00E-05 6.00E-05 8.00E-05 1.00E-04 1.20E-04
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)

[Cu
2+
] (M)
Calibration Curve prepred using AA
Check Standrad for Calibration Curve
Known Concentraion Measure Concentraion Check Recovery
AA 3.02E-05 5.03E-05 167%
The concentrations of the pennies were also determined using equation (1). These mass
% Cu for both the 1979 and the 2013 penny were calculated at the 95% confidence interval using
equation (3). These concentrations were then converted to grams of copper by multiplying by
their dilution factor along with the molar mass of Cu and volume. Then each Cu mass was
divided by the pennys actual mass to give mass % of Cu in each penny (Table 5).

Table 5. Mass % of copper from pennies measured form AA machine and calculated using
calibration curve at 95% confidence interval.
The LOD and the LOQ for the Buck Scientific 210 VGP Atomic Absorption
Spectrophotometer was also calculated. The standard deviation of the three averaged results from
the lowest concentration, in this case

M, was used in the LOD and LOQ calculations.


Equation (3) and (4) were used to solve for the LOQ and the LOD (Table 6).

Table 6. Limit of Detection and Limit of Quantification from a Buck Scientific 210 VGP Atomic
Absorption Spectrophotometer machine.
Comparing AA to UV-Vis
Statistical analysis was used to compare the results of the UV-Vis absorption readings to
those of the AA. Using equation (6) the F-test was applied to compare the 1979 UV-Vis results
to those of the 1979 AA results (Table 7). This was also done to the 2013 penny. In equation (6),
s is the standard deviation (Harris, 2007). For the UV-Vis the standard deviations was gathered
from the three different readings taken form the machine. The AA standard deviation used was
taken from the three averaged averages for each penny. These F-calculated were then compared
to F-table with degrees of freedom n-1 for each sample.


F-cal =

(6)

AA Data Results
Penny Year Mass % Cu
1979 111.4 + 11.5
2013 2.96 + .23
Limit of Detection and Quantification for AA and UV-Vis
LOD LOQ
AA 1.87E-06 6.24E-06

Table 5. F-test statistical results comparing both AA and UV-Vis of each penny.
Since both the F-calculated were smaller than the F-table, equation (8) was used to run a
T-test (Harris, 2007). Before calculating for the T-test, the spooled or equation (7) had to be
calculated. In both equations s is the standard deviation, n is the number of trials, and x is the
mass percent (Harris, 2007). These results for each comparison where then compared to a T-table
with 4 degrees of freedom at the 95% confidence interval (Table 6).

Spooled =

(7)

T-cal =
[

(8)


Table 6. T-Test statistical results comparing both AA and UV-Vis of each penny.
Discussion
The mass percent of copper calculated using the UV-Vis machine form the 1979 penny is
94 + .7% and the mass percent of the 2013 penny is 3.12 + .03%. For the AA machine the 1979
penny had a mass of 111 + 12% copper and the 2013 pennys mass percent copper is 2.96 +
.23%. The United States Mint states that pennies in 1979 are 95% copper and pennies form 2013
are 2.5% copper (United States Mint, 2014). Only the 1979 penny sample measured with the
UV-Vis machine was very close to the U.S. Mint standards, being off only by .3%. Both the
2013 pennies measured with the AA and UV-Vis were higher than the expected U.S. Mint
standards. The 1979 penny measured with the AA was also much larger than the U.S. standards.

The UV-Vis method for analyzing the mass percent of copper was more accurate than the
AA method. The 1979 penny from the UV-Vis almost met with the U.S. Mint standards and the
2013 was just a bit higher (table 3, 4). The AA on the other hand had both the 1979 and 2013
F Test
F-Calc F-table F-cal Comparison
1979 penny 0.09874 19 F-cal < F-table
2013 penny 0.0382 19 F-cal < F-table
T Test
T-calc T-table T-cal Comparison
1979 penny 81 2.776 T-cal >T-table
2013 penny 147 2.776 T-cal >T-table
pennies percent mass of copper to be much higher than the known U.S. Mint standards. The
check standards form the UV-Vis is also much better, being 110% while the AA has it at 167%,
showing once again that the UV-Vis is more accurate than the AA method. Both the UV-Vis and
the AA method had good precision, the UV-V being slightly better. The precision of both
methods are shown with the coefficient of determination. The UV-Vis coefficient of
determination is exactly 1 and the AA is .9991.
Statistically the two methods do not agree with each other. When calculating the F-test
for the two methods for each penny you see that F-calculated is greater than the F-table showing
that the standard deviations are significantly different from each other in the 95% confidence
level for both pennies. The t-calculated is also much greater than the t-table, again showing that
they are significantly different in the 95% level. This would mean that the two methods do not
agree with each other within the experimental error.
All the standard dilutions for the UV-Vis are greater than the LOD and LOQ. The LOD
and LOQ for the UV-Vis are 1.24*E-4 and 4.27*E-4 and the smallest dilution used in the UV-
Vis was 5*E-4 which is just a bit higher than the LOQ, the smallest amount the machine can read
that can be used to make an accurate measurement. For the AA all the dilutions are greater than
the LOD but the LOQ is greater than the smallest dilution which is 5*E-6 and the LOQ is 6.24E-
6. This would mean that the last dilution would not be an accurately measured by the AA
machine. Since the AA machine needs less sample than the UV-Vis machine and has a smaller
LOD and LOQ, then the AA machine must be more sensitive than the UV-Vis machine.
Both the AA and the UV-Vis machine are selective to measure copper in the diluted
samples. The AA is selective for copper because it has a hollowed cathode tube that is filled with
copper. This helps then shine specific light that would be absorbed by copper, which then the
detector would only read the copper absorption and nothing ells dissolved in the samples. The
UV-Vis is selective to copper because zinc and nitric acid are colorless samples, and copper is a
blue color when in sample. So when the UV-Vis tungsten lamp is turned on it is only absorbed
by the blue copper color and not by any other component in the sample.
All experiments contain a certain amount of error, both indeterminate and determinate.
This experiment had a lot of opportunity for determinate error. When making the dilutions for
the AA and the UV-Vis calibration curve along with the penny dilutions, each dilution could
have been read incorrectly or had parallax error, and since there were many dilutions made this
could have greatly been responsible for many of the experimental error. The AA machine also
created some determinate error because as measurements were being made the machine drifted,
increasing the absorption with the passing of time. The check standards could have been known
to be contaminated and would also create determinate error. Indeterminate error was also present
when running the experiment. The students inexperience with the experiment along with noise
created by the machines when running the experiment make most of the indeterminate error.
For future analysis of copper I would recommend the use of the UV-Vis machine. Unlike
the AA machine, this machine does not drift when making measurements and does not require
another person in order to get data. The Check standards solutions should be well managed and
periodically revised for contamination. Having more volumetric flasks would help increase the
speed in which the dilutions are made because there would be no need to condition as many
times after every dilution.
Conclusion
The mass % of copper in pennies were analyzed using two different methods, AA
and UV-Vis. Both these two methods were chosen because they are both selective to analyze Cu
absorption in samples. Pennies form post and pre 1982 were chosen to be analyzed because of
their known quality of possessing different mass % of Cu (United States Mint, 2014). Mass % of
Cu form the pennies given form the UV-Vis were: 1979 penny was 94.0 and 3.12
for the 2013 penny. Both the 1979 and 2013 pennies were not in range of the U.S. Mint
standards, but the 1979 penny came very close. For the AA the penny mass % were: 1979 was
and for the 2013 penny. Again both pennies did not meet with the
U.S. Mint standards, but this time the 2013 penny was closer to the known mass % than the 1979
penny. Statistically comparing the UV-Vis and the AA results show that they are significantly
different from each other, meaning that they do not agree with each other within the
experimental error.

















References
Bentor, Yinon. Chemical Element.com - Copper. Feb. 23, 2014
<http://www.chemicalelements.com/elements/cu.html>.
Haan, J., Experiments for Quantitative Analysis Laboratory. Spring 2014. pg. 16-17
Harris, D. C. (2007). Quantitative Chemical Analysis (7
th
Ed.). New York, NY: W. H. Freeman
and Company.
United States Mint. (2014).
http://www.usmint.gov/about_the_mint/fun_facts/?action=fun_facts2 viewed on
February 23, 2014