S.

Andrzejewski - Le - Pretzer

Introduction

Aspirin is an important pharmaceutical, however, not many people understand the

processes behind synthesizing the drug. The purpose of this experiment was to synthesize aspirin

and determine the percent yield and purity of the sample. The research gathered in this

experiment can be used in the real world to bring attention toward the process behind the

synthesis of aspirin, and to help to make the aspirin of a higher quality. This was accomplished

through the chemical reaction between acetic anhydride and salicylic acid in order to synthesize

the aspirin, as well as by using absorbance and melting point tests to calculate the purity and the

percent yield of each sample (“The Synthesis”).

Beer’s law states that the absorbance and the molarity of a solution have a direct, linear

relationship with each other. This means a linear model can be created to predict the molarity of

the solute in the solution after absorbance tests are performed on solutions with a known

molarity. The percent yield was then calculated from the molarity of the salicylic acid recorded

in each sample.

One characteristic of the melting point of pure crystalline solids, such as aspirin, is that

the substance has a relatively small melting range. A large melting range indicates impurities

within the sample. Impurities within the sample can shift the melting point more towards the

impurities (“Melting Point Determination”). The known melting point of aspirin is known to be

at 135 °C, so a higher or lower recorded melting point can also indicate impurities (“The

Synthesis”).

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Review of Literature

The purpose of this experiment way to synthesize and analyze acetylsalicylic acid on a

small scale and to bring light to some of the processes behind its production. Acetylsalicylic acid

(C​9​H​8​O​4​), better known as aspirin, is a common medication used in everyday life, but not many

people know the processes behind its production. Aspirin was synthesized by a chemical reaction

of salicylic acid and acetic anhydride. The purity of the sample was then tested by testing the

melting point and the ​spectrophotometric absorbance. The melting point and absorbance of

aspirin is always the same, regardless of the amount (​Experiment 8​). This experiment did not

differ from previous research, but instead further supported previous data.

The chemical reaction to produce aspirin is C​7​H​6​O​3​ + C​4​H​6​O​3​ → C​9​H​8​O​4​ + C​2​H​4​O​2​.

Salicylic acid and acetic anhydride reacts to produce acetylsalicylic acid and acetic acid, with the

addition of phosphoric acid, H​3​PO​4​, as a catalyst. The reaction occurred at around 75 °C

(Synthesis). A catalyst is a substance that reduces the activation energy of the reaction causing

the reaction to be more rapid​. The catalyst is not used in the reaction. The process is called

catalysis (​Catalyst​).

Figure 1. Reaction of Salicylic Acid and Acetic Anhydride

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Figure 1 shows the chemical reaction between salicylic acid and acetic anhydride in the

experiment to produce acetylsalicylic acid and acetic acid (Exp: Synthesis).

The aspirin was separated from the solution and purified after the synthesis. Purifying the

sample is to remove the salicylic acid and acetic anhydride that did not react, as well as the

phosphoric acid, and the acetic acid produced from the aspirin. To achieve this, the aspirin was

washed with cold, distilled water and recrystallized afterwards (aspirin is insoluble, allowing it to

be washed). The acetic anhydride was decomposed and the phosphoric acid and acetic acid was

ionized in the cold water. Ionization is the process in which an ionic compound, the solute, is

separated into ions in a solvent (“The Synthesis”).

Two tests were performed to determine the purity of the aspirin; absorbance and melting

point. Absorbance is a measure of the capacity of a substance to absorb radiation (​"Beer-Lambert

Law"​). In this experiment, green light was used, which has a specified wavelength of 565nm.

The absorbance was used to calculate the percent yield. The amount of light absorption was

calculated using a colorimeter. The concentration of a solution can be calculated using

absorbance if the absorbance value of a known concentration of the solution is recorded

beforehand according to Beer’s Law. Beer’s Law states that the absorbance value will increase

as the concentration of the solution increases (“Beer’s Law”). A linear model can be made with

the absorbance as the independent variable and the concentration as the dependent variable. The

concentration of a solution is the amount of moles over liters and the unit is in molarity or M. A

mole is 6.02 × 10​23​ molecules of a compound.

Melting point was also used to determine the purity of the aspirin samples. Melting point

is when the solid and liquid state of a substance exist in equilibrium (“​Melting Point, Freezing

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Point​”). The known melting point of aspirin was found to be 135°C. This was reached by heating

1000 mL of mineral oil and recorded using a Vernier Temperature Probe connected to a

LabQuest with LoggerPro software.​ If impurities were to be found in the sample, then the

melting point for the sample would shift towards the melting point of the impurities.

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Problem

Problem Statement​:

The purpose of this experiment was to synthesize acetylsalicylic acid, more commonly

known as aspirin, from salicylic acid and acetic anhydride, and to determine the percent yield

and analyze its purity by comparing melting point and light absorbance.

Hypothesis​:

It was believed that the synthesized aspirin will fall within 10 °C of the known melting

point of aspirin (135°C), within 0.100 of the recorded absorbance of aspirin, and that the percent

yield will be more than 70%.

Data Measured​:

The independent variable of the experiment was the synthesized aspirin, and the

dependent variables of the experiment were the percent yield and the purity. The purity was

checked by testing the melting point (°C) and light absorbance of the synthesized aspirin. Light

absorbance was measured using the molar concentration of the solution. The statistical analysis

used in this experiment is descriptive statistics. Descriptive statistics was used because there

were not enough trials done to conduct a t-test or variables to change for a design of experiment.

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Experimental Design

Materials​:

50 mL Erlenmeyer flask 15 g Salicylic Acid, C​4​H​6​O​3

filter flask 20 mL Acetic Anhydride, C​4​H​6​O​3
(2) 10 mL graduated cylinders 3 g ​Acetylsalicylic Acid, ​C​9​H​8​O​5
25 mL graduated cylinder 1 mL 85% Phosphoric Acid, H​3​PO​4
(4) 150 mL beaker 17.5 mL 95% Ethanol, ​C​2​H​6​O
(2) 300 mL beaker 232.5 mL 0.025 M Iron (III) Nitrate,
1000 mL beaker Fe(NO​3​)​3​•9H​2​O
250 mL volumetric flask 1000 mL mineral oil
B​ü​chner funnel 4 L distilled water
filter paper stir magnet
stopper ice bath
vacuum trap hot plate
rubber tube mortar and pestle
3 mL plastic pipette test tube clamps
spatula (2) clamp
scoopula ring stand
tongs (2) glass stir rod
(2) rubber band analytical scale (0.0001 g)
(2) 25 mL test tube (2) LabQuest with LoggerPro software
(3) safety goggles Vernier Temperature Probe (0.1 °C)
(4) glass capillary tubes Vernier Colorimeter
(2) plastic cuvette (12) weigh boats
(5) watch glass TI-Nspire Calculator

Procedure​:

Part I: Synthesizing Aspirin

1. Obtain and wear goggles

2. Measure out 2.0 grams of salicylic acid into a 50 mL Erlenmeyer flask.

3. Add 5.0 mL of acetic anhydride and 5 drops of 85% phosphoric acid. Swirl the mixture. If
necessary, use a sparingly small amount of distilled water to rinse down any bits of solid that
may be on the inner walls of the flask.

4. Synthesize the aspirin.

a. Plug in and turn on the hot plate to be used for the hot bath.

b. Place the 1000 mL beaker filled with water on the hot plate and wait until the water is

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between 70 and 80 degrees Celsius by checking the temperature with a thermometer.

c. Submerge the 50 mL Erlenmeyer flask for 15 minutes, or when the mixture ceases
releasing vapors in the hot bath. Use the tongs to keep the flask upright. Stir the mixture
occasionally during heating with a glass rod.

d. After about 10 minutes, add 2 mL of distilled water to the flask. Set up a Büchner funnel
and filter flask so that the reaction mixture is ready to filter after it has cooled.

5. Once the reaction is completed, carefully remove the flask from the hot plate and add 20 mL
of distilled water. Allow the mixture to cool to near room temperature. Transfer the flask to
an ice bath for about five minutes. As the mixture cools, crystals of aspirin should form in the
flask.

6. Transfer the contents of the cooled flask to a Büchner funnel assembly. Filter the mixture
with a vacuum suction. When most of the liquid has been drawn through the funnel, turn off
the suction and wash the crystals with 5 mL of cold, distilled water. After about 15 seconds,
turn the suction back on. Wash the crystals with 5 mL of cold, distilled water twice more in
this manner.

7. Separate the sample into 3 equal groups using a scale groups.

8. Store the aspirin crystals in a safe place and prepare to test their purity.

9. Repeat steps 2 through 8 to synthesize another batch of aspirin.

Part II: Testing the Melting Temperature of an Aspirin Sample

10. Use a mortar and pestle to pulverize 0.2 g of pure aspirin and place it in a small pile in the
mortar. Push the open end of a capillary tube into the pile of aspirin powder. Pack aspirin
into the capillary tube to a depth of 1 cm by tapping the tube lightly on the table top.

11. Connect the temperature probe to the LabQuest and connect the LabQuest to the outlet.

12. Use a rubber band to fasten the capillary tube to a test tube. The tip of the capillary tube
should be even with the tip of the test tube.

13. Prepare the hot bath.

a. Fill the 1000 mL beaker with mineral oil and place it on the hot plate.

b. Inset a stir magnet.

c. Plug in and turn on the hot plate on 10 and set the stir magnet on 4.

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14. In the trial, observe the melting process to estimate the melting temperature.

a. Put the test tube in the mineral oil.

b. Carefully observe the sample and record when the sample starts to melt and when the
sample has completely melted. This range is the estimated melting point and is
recorded.

c. Turn off the hot plate to let the mineral oil cool before use in the next trial.

15. Repeat step 14 with all of the samples.

16. Turn off the hot plate, recollect the mineral oil, dispose of the capillary tube, and put away
the materials.

Part III: Test the Colorimetric Absorbance of an Aspirin Sample

17. Quantitatively prepare the stock salicylic acid solution.

a. Measure out about 0.20 g of salicylic acid. Record the precise mass used.

b. Transfer the salicylic acid to a 250 mL beaker and add 10 mL of 95% ethanol. Swirl the
beaker to dissolve the solid.

c. Add 150 mL of distilled water to the beaker. Mix the solution.

d. Quantitatively transfer the solution from the beaker to a 250 mL volumetric flask.
Thoroughly rinse the beaker with several portions of distilled water, and transfer the
rinse water to the volumetric flask. Add distilled water, as needed, to fill the flask to the
250 mL mark. Mix the solution thoroughly. Calculate the precise molar concentration of
the stock solution and record it on a data table.

18. Prepare four standard solutions of varying concentrations of salicylic acid.

a. To prepare 100 mL of the standard solution , quantitatively transfer 10 mL of the stock

salicylic acid solution prepared in Step 17 to a 100 mL beaker.

b. Add 90 mL 0.025 M Fe(NO​3​)​3​ solution to the beaker.

c. Prepare the remaining three salicylic acid standard solutions according to the table
in Appendix A, diluting the standard solution in the 100 mL beaker with distilled water.
Mix each solution thoroughly.

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19. Prepare a blank by filling a cuvette 3/4 full with distilled water. To correctly use cuvettes,
remember:

a. Wipe the outside of each cuvette with a lint-free tissue.

b. Handle cuvettes only by the top edge of the ribbed sides.

c. Dislodge any bubbles by gently tapping the cuvette on a hard surface.

d. Always position the cuvette so the light passes through the clear sides.

20. Connect a Colorimeter to the LabQuest.

21. Calibrate the Colorimeter and prepare to test the standard solutions.

a. Prepare a blank by filling an empty cuvette 3/4 full with distilled water. Place the blank
in the cuvette slot of the Colorimeter and close the lid.

b. To calibrate the Colorimeter, press the < or > button on the Colorimeter to select the
wavelength of 565 nm (Green). Press the CAL button until the red LED begins to flash
and then release the CAL button. When the LED stops flashing, the calibration is
complete.

c. Remove the cuvette from your Colorimeter and pour out the water. Use the solution in
the first 100 mL beaker of salicylic acid to rinse the cuvette twice with ~1 mL
amounts and then fill it 3/4 full. Wipe the outside with a tissue and place it in the
Colorimeter.

22. The absorbance-concentration data for the four standard solutions is now ready to be
collected.

a. Leave the cuvette, containing the solution in the first 100 mL beaker of
salicylic acid, in the Colorimeter.

b. Wait for the absorbance value displayed on the monitor to stabilize, then record
the absorbance value and the molar concentration of the solution.

c. Discard the cuvette contents as directed by the instructor. Using the solution in the
second 100 mL beaker, rinse the cuvette twice with ~1 mL amounts, and then
fill it 3/4 full. Wipe the outside, place it in the device. (Close the lid of the
Colorimeter.) When the absorbance value stabilizes, record the absorbance value and
the
molar concentration of the solution.

d. Repeat the procedure for the remaining salicylic acid solutions that was prepared.

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e. When the preparation of the the last salicylic acid solution has been finished, click Stop.
Record the absorbance and concentration data pairs for the standard solutions in the data
table.

f. Make a graph of absorbance vs. concentration on the Ti Nspire calculator. To calculate

the best-fit line equation, click Menu, 4, 6, and 1. Record the linear regression equation.

23. Prepare the aspirin sample for testing. Complete this step quickly.

a. Measure out 0.02 grams of pure aspirin and transfer it to the 25 mL graduated cylinder.
Record the precise mass of aspirin that was used.

b. Add 0.5 mL of 95% ethanol to the beaker of aspirin sample.

c. Add distilled water, as needed, to fill the flask to the 12.5 mL mark. Mix the solution
thoroughly.

d. Transfer 0.5 mL of the aspirin solution from the 25 mL volumetric flask to a clean and
dry 10 mL graduated cylinder. Add 0.025 M Fe(NO​3​)​3​ solution to the flask to make
precisely 10 mL. Mix the solution thoroughly.

24. Measure and record the absorbance of the treated aspirin sample. This must be done within
5 minutes of completing Step 23.

a. Rinse and fill the cuvette 3/4 full with the sample. Place the cuvette in the
Colorimeter and close the Colorimeter.

b. If the absorbance value falls within the range of the salicylic acid standard solutions,
record it in the data table. If it does not, repeat Step 24. Prepare a more dilute, or more
concentrated sample, depending on the absorbance value from the first test.

c. Repeat Parts a–c of this step twice with new aliquots of the treated aspirin sample.

25. Repeat steps 23 and 24 with all of the samples.

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Diagrams​:

Figure 2. Büchner Funnel Assembly

Figure 2 shows the setup of the Büchner funnel assembly used to filter out the aspirin

crystals from the solution.

Figure 3. Hot Bath Assembly

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Figure 3 shows the hot bath setup used to test the melting point of the aspirin samples,

and to synthesize each aspirin sample.

Data and Observations

Many variables were taken into account when observing the collected data. Testing each

sample is considered very tedious and drawn out, and has to be performed with exact

measurements to achieve a pure sample. Accurate data is key when observing each test

performed on each sample of synthesized aspirin. To test the purity of each sample of aspirin, a

light absorbance test and a melting point test was executed. The data for these tests were

collected and shown below.

Table 1
Absorbance of Synthesized Aspirin Samples and Pure Aspirin Comparison Sample
Absorbance
Trial
Pure Aspirin Sample 1 Sample 2 Sample 3 Sample 4
1 0.038 0.825 0.797 0.512 0.129
2 0.039 0.876 0.775 0.489 0.129
3 0.040 0.855 0.797 0.514 0.130
4 0.044 0.637 0.801 0.777 0.049
5 0.033 0.662 0.761 0.780 0.055
6 0.028 0.651 0.757 0.780 0.055
7 0.000 0.595 0.535 0.765 0.115
8 0.000 0.583 0.546 0.732 0.118
9 0.023 0.592 0.547 0.791 0.117
Average 0.027 0.697 0.702 0.682 0.100

Table 1, above, shows the data collected for the absorbance of aspirin for each trial. The

tests were also done on pure aspirin in order to get a baseline to compare out results with using

the equipment we had available. From the table, it can be inferred that samples 1, 2, and 3 had a

high salicylic acid content because the level of absorbance is close to that of the salicylic acid

solution. Sample 4, however, is incredibly close to the absorbance values to that of pure aspirin,

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indicating that this sample is successful. Again, notice that the absorbances listed above does not

have a unit because there is no unit that correlates with absorbance. Trials 7, 8, and 9 of the pure

aspirin may have been so low due to a flaw during the creation of the solution being tested.

Table 2
Melting Point of Synthesized Aspirin Samples and Pure Aspirin Comparison Sample
Aspirin Sample Pure Aspirin Sample 1 Sample 2 Sample 3 Sample 4
Melting Point (°C) 135.7 150+ 144.8 150+ 133.6

Table 2, above, shows the average melting temperature for each synthesized sample of

aspirin, and the melting point of the pure aspirin. The tests were also done on pure aspirin in

order to get a baseline to compare out results with using the equipment we had available. Melting

point was tested once per sample because it took a great amount of time to conduct each trial,

and to the lack of time left to conduct the research.

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Table 3
Synthesis Observations
Date Observations
When preparing the salicylic acid solution, Fe(NO​3​)​3​ crystals started off pink, turned yellow
25-Apr
when added to distilled water, and turned a dark red-violet when the salicylic acid was added.
26-Apr The Fe(NO​3​)​3​ solution strangely smells like maple syrup after being left to sit.
While synthesizing the first sample of aspirin, the solution started off milky white, but in hot
bath it turned into a clear liquid. There were also a lot of particles left in the buchner funnel
27-Apr
after filtration.
(mass of salicylic acid: 2.0048 g; average hot bath temperature: 72.75​°C)
While synthesizing the second sample of aspirin, the solution started off as a clear liquid, but
28-Apr did not crystallize after 5 minutes in the ice bath.
(mass of salicylic acid: 2.0055 g; average hot bath temperature: 73.25​°C)
1-May The second sample of aspirin was completely crystallized by the end of the weekend.
While synthesizing the third sample of aspirin, the solution turned clear after being removed
1-May from the hot bath.
(mass of salicylic acid: 2.0018 g; average hot bath temperature: 71.65​°C)
While synthesizing the fourth sample of aspirin, the solution started off milky white, but in hot
1-May bath it turned into a clear liquid (similar to sample 1). There were also a lot of particles left in
the buchner funnel after filtration.
1-May Two filter sheets were used accidentally during the filtration of the second sample.
After being left to dry, the fourth sample smelled strongly of acetic anhydride and was still wet
3-May and clumpy. This sample was discarded and remade
While re-synthesizing the fourth sample of aspirin, the hot bath temp exceeded 80​°C.​ Solution
bubbled when water was added because of its high temperature. Leftovers in the buchner
3-May
funnel was refiltered through the system again.
(mass of salicylic acid: 2.0071 g; average hot bath temperature: 78.65​°C)

Table 3, above, shows the observations made during the synthesis process and setup for

each sample. Five samples were made in total, but one of the samples was discarded due to a

flaw in the preparation process.

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Table 4
Absorbance Observations
Date Observations
During the absorbance testing, the first sample turned a dark, red-violet color when mixed with
28-Apr iron (III) nitrate, similar to what happened when the salicylic acid was added to the iron (III)
nitrate solution.
During the absorbance testing, the first sample again turned a dark, red-violet color when
1-May mixed with a new solution of iron (III) nitrate. The absorbance was lower on trials 2 and 3 than
it was on trial 1.
During the absorbance testing, the second sample turned a dark, red-violet color when mixed
4-May
with iron (III) nitrate, like the first sample.
During the absorbance testing, the third sample turned a dark, red-violet color when mixed
4-May
with iron (III) nitrate, like the first and second samples.
During the absorbance testing, the fifth sample did not change color when mixed with iron
5-May
(III) nitrate, unlike the first, second, and third samples.

Table 4, above, shows the observations made during the absorbance tests. Sample 5 was

the most successful, having the lowest absorbance out of all samples. The fact that it didn’t

change color when introduced to the iron (III) nitrate solution shows it had a relatively low

quantity of salicylic acid in the final product.

Table 5
Melting Point Observations
Date Observations
During the testing for melting point of the first sample, the rubber band snapped and started to
4-May melt in the mineral oil. This mineral oil was later discarded.
During the second attempt for testing the melting point of the first sample, the glass beaker
5-May started to creak when reheated, so a new beaker was used.

Table 5, above, shows the observations made during the melting point tests. The beaker

that the rubber band melted into started to creak. It was unsure if it was safe, so a new beaker

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was used to test the melting point. Observations were not taken for samples 2, 3, and 4 because

the testing ran without notable observations.

Figure 4. Synthesized Aspirin Samples

Figure 4, above, shows the aspirin crystals synthesized in samples 1, 2, 3, and 4. The

crystals in sample 1 (far left) are long and thin. Like sample 1, The crystals in sample 2 (second

to the left) are thin, but are not as long. Notice that there is a small impurity that can be spotted in

sample 2, of which may have potentially led to any alterations in the data. The crystals in sample

3 (second to the right) appear to be very fluffy and compact in appearance. This characteristic

could have contributed to the melting temperature above 150​°C. ​Sample 4 (far right) was

considered to be the purest sample of the 4. This is because the absorbance was found to be very

close to the absorbance value of pure aspirin. The crystals are small and granular, similar to that

of sand or salt.

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Figure 5. Discarded Sample

Figure 5, above, shows the crystals synthesized in the discarded sample. This sample was

synthesized between the time it took to synthesize samples 3 and 4, and was the worst of the

samples, having not completed synthesizing. The dark stain on the filter paper (circled above)

can be attributed to the acetic anhydride having not reacted in solution. The crystals in this

sample were soft and clumped together.

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Data Analysis and Interpretation

The research performed explored the synthesis of aspirin and tested its purity through

light absorbance and melting point. The data for melting point were recorded using degrees

Celsius, the mass of aspirin synthesized was measured in grams, and the concentration of a

solution used in the data collection process was measured in Molarity. The absorbance of the

aspirin samples does not have a unit listed, this is because absorbance does not actually have a

unit. The appropriate approach for this research topic was a descriptive analysis because there

wasn’t enough data collected to conduct a proper t-test, and the process to synthesize the aspirin

was too time consuming to conduct a design of experiment. In order to maintain consistent

conditions and establish a control for the experiment, each sample was synthesized in the same

location and at the same room temperature, each absorbance trial was zeroed using the same

water-filled cuvette, and each melting point trial was conducted in the same bath of mineral oil.

Each researcher that conducted the trials was randomly selected by first being assigned a number

and then by using the TI-Nspire CX random number generator. A total of four samples of aspirin

was synthesized. Each sample was tested on absorbance nine times each. Melting point,

however, was decided to be left out of the analysis almost entirely, with only a brief description

being given. This is because only one melting point test was conducted for each synthesized

sample due to the great amount of time each melting point test took to conduct. To confirm that

the data collected in the absorbance test was normal, a box plot was made for each sample.

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Figure 6. Boxplot of the Absorbance of the Pure Aspirin Sample

Figure 6 shows the data collected for the absorbance of the pure aspirin comparison

sample. This box plot was mainly used as a baseline to compare the synthesized aspirin samples

to confirmed and reliable data gathered using the equipment available. The median absorbance

for the pure aspirin was found to have an absorbance value of 0.033, a very low value compared

to the medians of the other four samples shown in Figures 7, 8, 9 and 10. In comparison to the

synthesized samples, this box plot is incredibly condensed. Because of this characteristic, the

data was found to be reliable and pose as a valuable reference for the synthesized aspirin

samples.

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Figure 7. Boxplot of the Absorbance of Synthesized Aspirin Sample 1

Figure 7 shows the data collected for the absorbance of the first synthesized aspirin

sample. The box plot also appears to be heavily skewed to the right, meaning that the data is

more spread out in the upper half, indicating that the absorbance trials of this sample were

inconsistent. The cause of this could be from errors made during the testing process. However,

the data is considered normal due to not containing any outliers.

Figure 8. Boxplot of the Absorbance of Synthesized Aspirin Sample 2

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Figure 8 shows the data collected for the absorbance of the second synthesized aspirin

sample. Similar to Figure 7, this box plot has a wide range, indicating that the data collected was

inconsistent and plagued with a variety of errors. This result could be due to the researchers

being inexperienced with the use of the colorimeter. The box plot also appears to be heavily

skewed to the left instead of the right like in Figure 7. This indicates a larger spread in the lower

half of the collected data. Again, the box plot showed no outliers so the data is considered

normal.

Figure 9. Boxplot of the Absorbance of Synthesized Aspirin Sample 3

Figure 9 shows the data collected for the absorbance of the third synthesized aspirin

sample. The box plot for samples 2 and 3 appear very similar. This relation indicates that there

could be an important factor contributing to both of these results. The wider spread in the data,

again, implies that the data may be unreliable. The data also appears to be heavily skewed to the

left, similar to the data shows in Figure 8 above.

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Figure 10. Boxplot of the Absorbance of Synthesized Aspirin Sample 4

Figure 10 shows the data collected for the absorbance of the fourth synthesized aspirin

sample. Unlike the boxplots in Figure 7, 8, and 9, this box plot appears to be condensed to a

smaller range. This indicates that the data collected featured a small number of errors compared

to the other samples. However, the box plot also features no outliers similar to the previous

samples, again indicating that the data collected here is normal. The median absorbance of the

fourth sample is the closest of all four synthesized aspirin samples to the pure aspirin sample.

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Figure 11. Boxplots of the Absorbance Collected for All Aspirin Samples

Figure 11 shows the data collected for the absorbance of all of the aspirin samples that

were tested, including the pure aspirin comparison sample. The first, second, and third samples

appear to share a similar correlation with each other, as most of their graphed data overlaps. The

second and third samples also share similar median, with only a 0.004 difference in this

absorbance values. These factors indicate that these samples are very similar, and show a level of

consistency in the experiment. The fourth sample was the only sample that was vastly different

than the rest, and hosted the closest absorbance values to those of the pure aspirin comparison

sample. The pure aspirin’s box plot appeared to be small in appearance because the values of

absorbance are condensed, as should be expected when drawing from a pure aspirin sample.

However, due to inconsistencies and impurities in the synthesized samples, their box plots are

much more spread out. This is because when drawing aspirin from the same sample more than

once if it is not absolutely pure, the aspirin drawn may host impurities and different

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concentrations than that of a different drawn sample, altering the data collected from each

solution.

The absorbance trials in this experiment were the main determining factor of the purity

for each synthesized aspirin sample. Below are the base-lines that were established as a means of

comparison for the salicylic acid and aspirin content of each sample.

Table 6
Absorbance of Salicylic Acid Solutions
Salicylic Acid Solution Concentration (M) Absorbance
1 5.925​×​10​-4 0.965
2 4.443​×​10​-4 0.784
3 2.962​×​10​-4 0.550
4 1.481​×​10​-4 0.235

Table 6 shows the absorbances of the salicylic acid solutions that were tested first in the

colorimeter in order to establish another control to compare each sample to and get a visible

representation of each sample’s salicylic acid content. Notice that the absorbances listed above

do not have a unit because there is no unit that correlates with absorbance.​ ​Each solution was

tested at different levels of dilution in order to establish a linear regression model for the

concentration of salicylic acid in a 0.025 M iron (III) nitrate solution by absorbance, as seen in

Figure 12 below.

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Figure 12. Absorbance Regression Model

Figure 12 shows the regression equation used to model the absorbance of salicylic acid

solutions. The horizontal axis is the absorbance value, found in Table 6, and the vertical axis is

the molarity of the salicylic acid within the solution, also found in Table 6.

The salicylic acid solutions were used as a control to compare the aspirin samples and

get an accurate calculation of how much salicylic acid remained in solution, of which will also

play a role in determining the purity and percent yield of the samples. The Beer-Lambert law

states that the absorbance value and the concentration of the solution share a direct relationship

with each other. This allows the concentration of salicylic acid to be calculated from the

absorbance value of the iron (III) nitrate solution. The mass of the salicylic acid and aspirin was

calculated from that molarity and a percent of aspirin by mass was calculated from those two

numbers as shown in Table 7. With that percent by mass, the mass of aspirin synthesized in the

sample and the percent yield was calculated as shown in Table 8.

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Table 7
Percent Purity of Synthesized Aspirin Samples
Synthesized Aspirin Sample 1 2 3 4
Absorbance of Fe(NO​3)​3 Solution 0.697 0.702 0.682 0.100
Molarity of Salicylic Acid in Fe(NO​3​)​3​ Solution (M) 4.08×​10​-4 4.11×​10​-4 3.99×​10​ 4.92​×​10​-5
-4

Moles of Salicylic Acid in Aspirin Solution (mol) 3.06​×​10​-4 3.09​×​10​-4 3.00​×​10​-4 3.69​×​10​-5
Mass of Salicylic Acid in Aspirin Solution (g) 4.23​×​10​-2 4.26​×​10​-2 4.13​×​10​-2 5.09​×​10​-3
Mass of Sample Used to Test Absorbance (g) 0.0668 0.0695 0.0633 0.0608
Mass of Aspirin in Solution (g) 2.45​×​10​-2 2.69​×​10​-2 2.20​×​10​-2 5.57​×​10​-2
Percent of Aspirin in Solution by Mass (%) 36.7 38.7 34.7 91.6

Table 7 shows the purity percent of the synthesized aspirin samples based on mass. All of

the previous rows show the math conducted behind these calculations. See Appendix B for a

sample calculation.

Sample 4 had the highest total percent of aspirin by mass at 91.6%. The other three

samples, however, all had a percent of aspirin by mass below 40%. The low percentages of

samples 1, 2, and 3 can be attributed to human errors during the synthesis process of all of the

samples, and the high level of salicylic acid left in solution. All of the other rows show the math

conducted behind these calculations.

Table 8
Percent Yield of Synthesized Aspirin Samples
Synthesized Aspirin Sample 1 2 3 4
Initial Mass of Aspirin Sample (g) 1.3222 1.0445 1.4575 1.1473
Mass of Aspirin in Sample (g) 0.485 0.404 0.506 1.05
Moles of Aspirin in Sample (mol) 2.70​×​10​-3 2.25​×​10​-3 2.81​×​10​-3 5.84​×​10​-3
Mass of Salicylic Acid (g) 2.0048 2.0055 2.0018 2.0071
Moles of Salicylic Acid (mol) 1.4528​×​10​-2 1.4533​×​10​-2 1.4506​×​10​-2 1.4544​×​10​-2
Percent Yield (%) 18.6 15.5 19.4 40.2

Table 8 shows the percent yield of the synthesized aspirin samples. The initial mass of

the aspirin sample represents the mass yielded at the end of the each synthesis, while the mass of

the aspirin sample represents the mass of each sample that was actually aspirin, calculated by

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multiplying the initial mass by the percent of aspirin in Table 7. See Appendix B for the process

and a sample calculation behind these numbers.

Sample 4 had the highest percent yield, 40.2%, out of the four synthesized samples. The

other three samples, however, all had a percent yield below 20%. The table show that all of the

samples has an incredibly low percent yield. This can be attributed mostly to mistakes made

during the synthesis process. One such mistake can be found during the hot bath and ice bath

procedures used when synthesizing each sample. Time was accurately followed except during

the fourth sample. Because of this, in some situations, the aspirin may or may not have been

completely finished reacting before being removed from the hot bath, and may not have

completely finished crystallizing before being removed from the ice bath, resulting in a loss

through the filtration of the aspirin. Any solution that had not finished crystallizing would have

passed through the filter paper along side of the water being used.

There was not enough data collected during the melting point tests, so the data cannot be

considered valid. The melting point for the first and third samples were both above 150 degrees

celsius. The rest of results from this experiment, however, were biased from a plethora of

uncontrollable factors and mistakes. What ended up happening with the results was that the

synthesized aspirin samples contained a large amount of excess salicylic acid, and in some cases

had not finished reacting entirely. This led to the aspirin appearing clumpy and having a soft

texture, and one failed sample still smelling strongly of acetic anhydride. The excess salicylic

acid in the first, second, and third samples led to a very low percent yield as shown in Table 8

above. What should have happened, if there were less errors made in the synthesis process, is

that the synthesized samples would have a very similar salicylic acid and aspirin content to that

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of pure aspirin. With such results, the comparison would focus moreso on the percent yield of the

samples, and the comparison of the samples with the pure aspirin comparison sample would have

been much easier to conduct.

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Conclusion

The purpose of this experiment was to synthesize aspirin (acetylsalicylic acid) from

salicylic acid and acetic anhydride, and to determine the percent yield and analyze its purity by

comparing melting point and light absorbance to a standard. The light absorbance was used to

calculate the percent yield of the sample. It was believed that the synthesized aspirin will fall

within 10 °C of the known melting point of aspirin (135°C), within 0.100 of the recorded

average absorbance of aspirin, and that the percent yield will be more than 70%. This hypothesis

was rejected. This is due to the melting point of sample 1 and 3 being outside of the predicted

range, both exceeding 150.0 °C. Sample 2 was at the very edge of the range, having a melting

point of 144.8 °C. The only sample that came very close to the known melting point of aspirin

was sample 4, having a melting point of 133.6 °C. The second part of the hypothesis was

rejected due to three of the four samples, 1-3 having an average absorbance value 0.600 greater

than the average absorbance of the pure aspirin, at 0.027. The last part of the hypothesis was

rejected due to all four samples having a percent yield lower than 45%. The highest percent yield

recorded was in sample 4, calculated to be 40.2%.

The experimental design was modified from ​Advanced Chemistry with Vernier​ lab

number 22 ​The Synthesis and Analysis of Aspirin​ ("The Synthesis") and a previous research

paper, ​The Analysis of Synthesized Aspirin ​(Marougail). The downside of this experiment were

the restrictions on both time and materials available for use. Because each trial took a great

amount of time to conduct, redoing trials were not an option, and testing​ ​different amounts and

effects on the aspirin was not either. The research agrees with current research on the topic even

though the data gathered was that of bad samples. Even though there were many errors plaguing

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the experiment and its design, the methods used to determine the purity and percent yield match

that of data collected from a more accurately performed experimental design.

The percent yield for the synthesis of aspirin for samples 1, 2, 3, and 4 are 18.6%, 15.5%,

19.4%, and 40.2% respectively. These high percent errors show that the method used to

synthesize aspirin was not very effective. There are many reasons why the percent error is so

high. Many mistakes were experienced throughout the synthesizing process, as each step requires

maximum attention, accuracy, and becomes very tedious.

One such error was encountered during the synthesis process. During this process, a hot

bath was used to jump start the reaction between the acetic anhydride and salicylic acid. The

temperature was supposed to maintain a temperature between 70 °C and 80 °C, but fluctuations

were a common occurrence, even exceeding 80 °C at times, resulting in vast differences between

some of the samples. For example, sample 4, which was left in the hot bath at a temperature

exceeding 80 °C, turned out entirely different than every other sample that was synthesized,

having a granular texture and very close purity to that of actual aspirin.

A second error was encountered during the filtration process for each of the samples.

During this process, distilled water is pulled through the sample via a vacuum filter and B​ü​chner

funnel. Perhaps due to a shortage of time in the ice bath, the samples were not given enough time

to crystallize before being filtered, and the uncrystallized aspirin passed through the filter along

with the distilled water, resulting in an incredibly low percent yield. This factor can be seen in

sample 4, of which had almost twice as much aspirin. Because the sample was given more time

to crystallize in the ice bath (about 5 extra minutes) and the water that had collected in the flask

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after filtering the first time had been filtered back through the aspirin, it can be inferred that these

factors directly tied with the percent yield of each sample.

A third error was encountered during the melting point process. During this process,

small amounts of each of the samples are added to a capillary tube and put into a mineral oil hot

bath in order to test their melting point. The melting point is the point at which the chemical is in

equilibrium between solid and liquid states at one atmosphere (“Melting Point Determination”).

The known melting point of aspirin is 135 °C ("The Synthesis"). When testing samples 1 and 3,

the temperature exceeded the range and was incorrectly recorded as 150+ °C, indicating that the

sample is not pure aspirin, but rather a mixture. Because of the inconsistent data and low number

of trials, the melting point was considered to be unreliable source data in determining the purity

of each samples, and was not used.

A fourth error was encountered during the absorbance process. During this process, small

amounts of each samples were added to an iron (III) nitrate solution and placed in cuvettes to

have their absorbance tested through the use of a colorimeter. The absorbance of the solution was

used with Beer’s Law in order to calculate the concentration of the salicylic acid content in each

solution. Beer’s Law states that as concentration increases in a solution, the absorbance, or the

amount of light that makes does not pass through the solution, increases as well in a linear

pattern (“Beer’s Law”). Three solutions were made per sample, and each solution made was

tested a total of three times in the colorimeter. Because of this, trials from the same solution

varied. Perhaps this can be attributed to the fact that the solutions were not entirely mixed

through, and different quantities of aspirin were found in different parts of solution. This can

especially be seen when testing the absorbance of the pure aspirin. The trials of the third solution

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were all completely off, with trials 7 and 8 at an absorbance value of 0.000 and trial 9 at an

absorbance value of 0.023. Some of the other fluctuations may be attributed to any bubbles,

scratches, or even issues with the colorimeter itself. When an absorbance value seemed off, it

was retested. However, if it remained off, the data would still be used.

If this experiment were to be conducted in the future, then the method of collecting the

melting point should be more precise. The amounts of each chemical needed to synthesize the

aspirin and make the solutions should also be changed, as there was discovered to be a large

surplus of unneeded or unused solutions and chemicals. The temperature of the hot bath during

the synthesis process should also be increased because it was observed that a higher temperature

results in a higher percent yield. When synthesizing the aspirin, there was excess salicylic acid,

so, it can be inferred that the reaction did not complete. Some factor to solve this could be to

increase the temperature of the hot bath or the duration kept in the hot bath. The filtration process

could also be improved to catch more crystals by refiltering the excess solution. These factors

could further help to establish and expand on existing data, and also determine the best method

for synthesizing aspirin.

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