Chemistry 315

Experiment 5:
Determination of the Acetaminophen
Concentration in Tylenol
Using Cyclic Voltammetry
Zhuo Gao

School of Chemical Sciences, 505 S. Mathews Ave., Urbana, IL 61801

[email protected]

Lab partner: Haydan R, Aidan L, Jason R

Lab section: AC5, Tuesday AM

Major: Chemistry

Date of lab work: 09/24/2024

Due date of report: 10/01/2024

In this experiment, employing cyclic voltammetry, the standardized curve of

acetaminophen was determined with Randles-Sevcik equation. With this information, the
concentration of acetaminophen in Tylenol was confirmed. Comparing to provided lowest
concentration, the Tylenol was determined as qualified.

Keywords: ACETAMINOPHEN, CYCLIC VOLTAMMETRY, IRREVERSIBLE

OXIDATION REACTION, RANDLES-SEVCIK EQUATION, TYLENEOL.

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Experimental Details
The experiment commenced with the formulation of an acid buffer, utilizing KCl,
Na2HPO4, and C6H8O7•H2O, mixed in a 1 L flask filled with deionized water.
Subsequently, six distinct acetaminophen solutions were concocted in 25 mL volumetric
flasks. Each of these solutions had different concentrations of acetaminophen stock and
were diluted using the previously prepared acid buffer (concentrations were 0.0mM,
0.2mM, 0.4mM, 0.6mM, 0.8mM and 1.0mM). Following this, three Tylenol solutions
were crafted by measuring out roughly 1.2 g (1.2328g, 1.2052 g, and 1.2349g) of Tylenol
into a glass vial, which was then transferred to 100 mL flasks and diluted to the indicated
mark with the acid buffer. From these, 2.5 mL of each solution was pipetted into a 25 mL
volumetric flask and further diluted with the acid buffer. With the samples ready, the
working electrode underwent a polishing process. Once polished, the instrument's
parameters were configured as presented in Table 1.
Table 1 General parameters setting for CHI 600D [1].

Initial E 0.250 V
High E 1.000 V
Low E 0.250 V
Final E 0.250 V
Initial Scan Polarity Positive
Scan Rate 0.025 V/s
Sweep Segments 2
Sample Interval 0.001 V
Quiet Time 2 sec
Sensitivity 1×10-006 A/V
After configuring the parameters, a background scan was initiated with barely acid buffer
solution. Subsequent to this, voltammograms for each of the six standard solutions were
recorded. Upon completing the voltammogram for the final standard solution, the scan
rate was adjusted from 0.025 V/s to 0.010 V/s, and another voltammogram was captured.
This procedure was reiterated, capturing voltammograms at rates of 0.050, 0.100, and
0.200 V/s. Following these measurements, the scan rate was reverted to 0.025 V/s, and
voltammograms for the Tylenol samples were recorded. Within this experiment, a
platinum disk served as the working electrode, a platinum wire functioned as the counter
electrode, and Ag/AgCl was employed as the reference electrode. The experiment

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utilized the CHI600D Electrochemical Analyzer software. The make and model were CH
Instruments Electrochemical Analyzer 1.

Data and Results

The measured valued during the lab is shown in Table 2.
Table 2. The Theoretical Concentrations of Standard Solutions with The Measured Nodic
Peak Current (ipa) and Anodic Peak Potential (Epa):

Standard Concentration ipa Epa

of Acetaminophen (mM) (A) (V)

0 0 (Background) 0
0.2 1.334e-6 0.700
0.4 2.838e-6 0.684
0.6 4.232e-6 0.684
0.8 5.623e-6 0.686
1.0 7.027e-6 0.684

The data shows a positive correlation between concentration and current. As concentration
increased, current also increased. The potential remained relatively constant, with minor
fluctuations. The Epa for 0.2 mM is 0.700 V, but as soon as acetaminophen was gradually
introduced (0.4 mM), the potential drops to around 0.684 V and stays within that range.
This suggests that the redox reaction responsible for the current occurs at a consistent
potential, indicating electron transfer between acetaminophen (AAPH) and N-acetyl-p-
quinoneimine (NAPQ).

i𝑝𝑓 = 268,600𝑛3/2 𝐴𝐷1/2 𝑣 1/2 𝐶 ∗ (1)

In the Randles-Sevcik equation (shown in Equation 1), the anodic peak current (ipa) obeys
this relationship under room-temperature with the number of electrons transferred per
molecule electrolyzed (n, in this case is 2), the electrode area (A in this case is 0.02cm2),
the diffusion coefficient of the electroactive species (D in cm2s-1), scan rate (v in Vs-1), and
the concentration of the sample (C in mM). 268,600 is the constant with units of C·mol-
1
V-1/2 which is only reliable under room-temperature of 298K2. With consistence of testing

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electroactive species, which is ancetaminophen, ipf has linear relationship with C*. Then
plot the anodic peak current vs concentration plot shown in Fugure 1.

Anodic Peak Current vs. Concentration Plot

0.000008
0.000007
Anodic Peak Current (A)

0.000006
0.000005
0.000004 y = 7.057E-06x - 1.929E-08
R² = 0.9998
0.000003
0.000002
0.000001
0
0 0.2 0.4 0.6 0.8 1 1.2
-0.000001
Concentration of AAPH (mM)

Figure 1 Anodic Peak Current Vs Concentration Plot.

With 99.98% of the variability (R2) in the current being explained by changes in
concentration, the data points are consistent with this linear relationship, with no significant
outliers observed.

From this, the coefficient of C*, which is the slope (7.057𝑒 − 06 = 268,600𝑛3/2 𝐴𝐷1/2 𝑣1/2 ).
Similarly, the concentration of acetaminophen in Tylenol can also be determined through
the slope calculation with measured value of Tylenol samples (shown in Table 3).

Table 3. Tylenol Sample Data Table:

Mass of Tylenol
Dissolved (g) ipf (A) Epf (V)

1.1922 1.166e-6 0.690

1.2323 1.104e-6 0.687

1.3030 2.218e-6 0.689

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The data appears to show that as the concentration increased, the current also slightly
increased. However, an outlier with slightly increase of Tylenol but twice the current
showed up. Further calculation is presented to discrbe the exact concentration of Tylenol.

Calculation S1. Calculation of Concentration oof Tylenol Sample 1 from The Randles-
Sevcik Equation.
3 1 1
1.166e − 6A = 268,600𝑛2 𝐴𝐷2 𝑣 2 𝐶 ∗

1.166e − 6A = 7.057e − 6C · cm3 /s/mol × C∗

𝐶 ∗ = 0.165 𝑚𝑀 = 0.000165𝑀
25𝑚𝐿 1.1922𝑔
𝐶 = 0.000165𝑀 × ( ) × 100𝑚𝐿 × 1/( ) = 0.173𝑚𝑀
2.5𝑚𝐿 1.25𝑔/𝑚𝐿
Other calculations for Tylenol sample 2 and 3 will be included in Supplementary
Information: Calculation S3 and Calculation S4.

Table 4. Molar Concentration of Acetaminophen in Tylenol Table:

Mass of Tylenol Average and Standard

Molarity (mM)
Dissolved (g) Deviation (mM)
1.1922 0.173
1.2323 0.158 0.211±0.064
1.3030 0.301

Furthermore, the Randles-Sevcik equation can help determined diffusion coefficient with
varied scan rate as another controlled variable. The data recorded is shown in Table 5.

Table 2. The Varied Square Root of Scan Rate of 1.0mM of Standard Solutions with The
Measured Nodic Peak Current (ipa) and Anodic Peak Potential (Epa):

Square Root of Scan Rate Epa (V) ipa (A)

(√𝑽 · 𝒔−𝟏)
0.100 0.673 4.798e-6
0.158 0.684 7.027e-6

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 0.224 0.687 9.571e-6
0.316 0.693 1.198e-5
0.447 0.700 1.672e-5

And their relationship is shown in Figure 2.

Anodic Peak Current vs. Square Root of Scan Rate

Plot
1.80E-05
1.60E-05
Anodic Peak Current (A)

1.40E-05
1.20E-05
1.00E-05
8.00E-06
6.00E-06
4.00E-06 y = 3.368E-05x + 1.632E-06
R² = 0.9966
2.00E-06
0.00E+00
0 0.1 0.2 0.3 0.4 0.5
Square Root of Scan Rate (√(V/s )

Figure 2 Anodic Peak Current Vs Square Root of Scan Rate Plot

The table indicates that as the square root of the scan rate increases, the peak anodic current
also shows an increase proportionally, which is co with the equation implied.

The potential also displayed a slight increase as the square root of the scan rate increases.
This might suggest a slight potential shift due to the change in scan rate.

The R2 value provided is 0.9966. This value is extremely close to 1, which indicates that
the data fits the linear model exceptionally well. And the trend is consistent and reliable.

Calculation S2. Calculation of diffusion coefficient.

3 1
3.368𝑒 − 5 = 268,600𝑛2 𝐴𝐷2 𝐶
3
3.368𝑒 − 5 = 268,600 × 22 × 0.0201𝑐𝑚2 × 1.0e − 6mol/𝑐𝑚3 × 𝐷1/2

𝐷 = 4.864e − 6cm2 · 𝑠 −1

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Discussion
The results show a strong linear relationship between anodic peak current and both
concentration and the square root of scan rate, as indicated by the high R2 values of 0.9998
and 0.9966. While minor deviations, such as the small negative intercept lower than one
percent of the slope in the first plot, could arise from factors like instrumental calibration,
electrolyte impurities, or electrode surface conditions, the overall data closely follows
theoretical expectations. These strong correlations suggest reliable and accurate
experimental outcomes, with any discrepancies likely due to systematic influences rather
than fundamental errors in the procedure. As the concentration amplified, an alteration in
potential was documented. A myriad of factors could be attributed to this phenomenon.
One plausible explanation is that the solution's resistance with increasing concentration
was fluctuating while measuring3. To improve this, the concentration could be increased
by smaller interval.

The calculated concentration of acetaminophen in Tylenol is 0.211±0.064mM, which is

31.895±9.674g/L. It has reached the lowest limitation for the concentration of
acetaminophen in Tylenol which is 30g/L. The percentage of error is calculated as 6.317%.
By this token, the calculated concentration is very close to expected value. However, there
was an inconsistence with sample 3. With showing Epa was similar to other sample data,
the error was less possible from measurement. The loss of compound may be happened
with spill or uneven texture of the medicine.

The calculated diffusion coefficient from the experimental data is D=4.864e−6 cm2/s. This
value falls within the typical theoretical range for diffusion coefficients in similar systems,
which is between the 10-9 to 10-5 cm2/s. The fact that the experimental value is closer to the
upper end of this range suggests that the diffusion process in this case is relatively efficient,
and the experimental conditions are consistent with theoretical expectations for diffusion
rates in electrochemical reactions. Given the closeness to the higher end of the range, it
indicates that the analyte is diffusing at a relatively high rate, supporting the reliability of
the experiment's methodology.

In conclusion, the experiment demonstrated strong linear relationships between anodic

peak current and both concentration and scan rate, with reliable results and minimal

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discrepancies. The calculated concentration of acetaminophen in Tylenol and the diffusion
coefficient were consistent with theoretical expectations. However, small deviations, such
as those in sample 3, suggest that more precise control of experimental conditions, like
concentration intervals and sample preparation, could improve accuracy. For future
experiments, increasing the concentration in smaller increments and ensuring uniform
sample texture and preparation would help minimize potential errors and further enhance
the reliability of the findings.

References
1. Ansar, H.; Croslow, S.W.; Kim, D.O.; Martin, K.; Miller A.; Mirman B.; Shiau A.; Sur
S.; Wiegand K.; Experiment 5. CHEM 315 Laboratory Notes. [Online] 2024.
http://canvas.illinois.edu (accessed 09/10, 2023).

2. Team, P. Randles-Sevcik Equation: The Cyclic Voltammetry Peak Current (IP).

https://psiberg.com/randles-sevcik-equation

3. Lozeman, J. J.; Führer, P.; Olthuis, W.; Odijk, M. Spectroelectrochemistry, the Future
of Visualizing Electrode Processes by Hyphenating Electrochemistry with Spectroscopic
Techniques. The Analyst 2020, 145 (7), 2482–2509. DOI:10.1039/c9an02105a.

Supplementary Material
Calculation S3. Calculation of concentration of Tylenol sample 2 from the Randles-Sevcik
equation.
3 1 1
1.104e − 6A = 268600𝑛2 𝐴𝐷2 𝑣 2 𝐶 ∗

1.104e − 6A = 7.057e − 6C · cm3 /s/mol × C∗

𝐶 ∗ = 0.156𝑚𝑀 = 0.000156𝑀
25𝑚𝐿 1.2323𝑔
𝐶 = 0.000156𝑀 × ( ) × 100𝑚𝐿 × 1/( ) = 0.158𝑚𝑀
2.5𝑚𝐿 1.25𝑔/𝑚𝐿
Calculation S4. Calculation of concentration of Tylenol sample 3 from the Randles-Sevcik
equation.
3 1 1
2.218e − 6A = 268600𝑛2 𝐴𝐷2 𝑣 2 𝐶 ∗

2.218e − 6AA = 7.057e − 6 · cm3 /s/mol × C∗

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 𝐶 ∗ = 0.313 𝑚𝑀 = 0.000313𝑀
25𝑚𝐿 1.3030𝑔
𝐶 = 0.000313𝑀 × ( ) × 100𝑚𝐿 × 1/( ) = 0.301𝑚𝑀
2.5𝑚𝐿 1.25𝑔
𝑚𝐿
Calculation S5. Calculation of the concentration of acetamimophen in Tylenol.
𝑔
151.163 × (0.211 ± 0.064)M = 31.895 ± 9.674 g/L
𝑚𝑜𝑙
Calculation S5. Calculation of percent error of the concentration of acetamimophen in
Tylenol.
|31.895 − 30|
𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝑒𝑟𝑟𝑜𝑟 = × 100% = 6.317%
30
Calculation S6. Calculate the mean and SD of Tylenol sample

Figure S 1 Excel calculation

CV diagram for standard solution 6 at scan rate of 0.1 V/s

1.20E-05

1.00E-05

8.00E-06
Current (A)

6.00E-06

4.00E-06

2.00E-06

0.00E+00
0 0.2 0.4 0.6 0.8 1 1.2
-2.00E-06
Potential (V)

Figure S 2 CV diagram for standard solution 6 at scan rate of 0.1 V/s

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 CV diagram for Tylenol sample 2 at scan rate of 0.025 V/s
1.20E-06
1.00E-06
8.00E-07
6.00E-07
Current/A

4.00E-07
2.00E-07
0.00E+00
0 0.2 0.4 0.6 0.8 1 1.2
-2.00E-07
-4.00E-07
-6.00E-07
Potential/V

Figure S 2 CV diagram for Tylenol sample 2 at scan rate of 0.025 V/s

Figure S 3 Labnote

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