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Cyclic Voltammetry

An Example of Voltaic Methods


March/2007, Prof. S. Shippy and M-J Lu

Objective
This experiment is designed to acquaint the student with the techniques of cyclic
voltammetry for the study of redox systems. The "computer age" has provided us the
opportunity to control the experiment and process the results with very little effort. What
is meant by control? How does this apply to electrochemical analysis? How does this
apply to chemical analysis? Answers to some of the questions are provided by the BAS100 Electrochemical analyzer, a sophisticated instrument which provides both diverse
control and data reduction functions for the study of redox phenomena.

Theory
Cyclic Voltammetry (CV) is perhaps the most effective and versatile electroanalytical
technique available for the mechanistic study of redox systems. It enables the electrode
potential to be rapidly scanned in search of redox couples. Once located, a couple can
then be characterized from the potentials of peaks on the cyclic voltammogram and from
changes caused by variation of the scan rate. CV is often the first experiment performed
in an electrochemical study.

Figure 1. Typical excitation signal for cyclic voltammetry.

The repetitive triangular potential excitation signal for CV (Figure 1) causes the potential
of the working electrode to sweep back and forth between two designated values (the
switching potentials). To obtain a cyclic voltammogram, the current at the working
electrode is measured during the potential scan (Figure 2).

Figure 2. Cyclic voltammogram of Fe2+ in 1M H2SO4.


During the scan +250 to +750 mV, the applied potential becomes sufficiently positive at
400 mV to cause oxidation of Fe2+ to occur at the electrode surface. This oxidation is
accompanied by anodic current, which increases rapidly until the surface concentration of
Fe2+ approaches zero, as signaled by peaking of the current at point c in Figure 2.

The current then decays (after c) as the solution surrounding the electrode is depleted of
Fe2+ due to its oxidation to Fe3+. This depletion of Fe2+ and accumulation of Fe3+ near the
electrode is depicted by concentration-distance profiles a-e as shown in Figure 2. The
magnitude of the current is related to the slope of the c-x profile for Fe2+, as described by
the following equation:

where:

It
n
F
A
C
Do
t
X

=
=
=
=
=
=
=
=

Current at time t, (Amperes).


Number of electrons, eq/mole.
Faraday's constant, 96,485 e/eq.
Electrode area, cm2.
Concentration of oxidized species, mol/cm3. (not mol/L!)
Diffusion coefficient of oxidized species, cm2/s.
Time (s).
Distance from the electrode (cm).

The product Do (Co/X) at x = 0,t is the flux or the number of moles of oxidized species
diffusing per unit time to unit area of the electrode in units of mol/cm2s.
During the positive scan in which Fe2+ is oxidized to Fe3+, the depletion of Fe2+ in the
vicinity of the electrode is accompanied by an accumulation of Fe3+. This can be seen by
the concentration distance profiles at various potentials in the shown figure. After the
direction of the potential scan is switched at 750 mV to a negative scan, oxidation
continues (as is evident by the anodic current and the C-X profile, (e), as seen in Figure 2,
until the applied potential becomes sufficiently negative to cause reduction of the
accumulated Fe3+. Reduction of Fe3+ is signaled by the appearance of cathodic current.
Once again, the current increases as the potential becomes increasingly negative until all
of the Fe3+ near the electrode is reduced. When the concentration of Fe3+ is significantly
depleted, the current peaks, and then decreases. See f, g, and h in Figure 2. Thus the
physical phenomena that caused a current peak during an oxidation cycle also cause a
current peak during the reduction cycle. This can be seen by comparing the
concentration-distance profiles for the two scans.
Simply stated, in the forward scan Fe3+ is electrochemically generated, as indicated by
the anodic current. In the reverse scan, this Fe3+ is reduced back to Fe2+, as indicated by
the cathodic current. Thus, CV is capable of rapidly generating a new species during the
forward scan and then probingits fate on the reverse scan. The important parameters of
cyclic voltammetry are the magnitude of the peak currents, Ipa and Ipc, and the potentials
at which peaks occur, Epa and Epc. Difficulty inobtaining accurate peak currents is
perhaps the biggest liability of CV.
A redox couple in which both species rapidly exchange electrons with the working
electrode is termed an electrochemically reversible couple. The following equation
applies to a system that is both electrochemically and chemically reversible:
Ep = Epa - Epc ~ 0.059/n (at 25C)
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where n = number of electrons transferred. The values of Ipa and Ipc are similar in
magnitude for a reversible couple with no kinetic complications.
In most CV experiments there is little advantage to be gained by carrying on the potential
scan for more than two to three cycles (Note: The first voltammogram is not quite the
same as the reproducible curve obtained after several cycles.)
Apparatus
Instrument for CV such as BAS 100B
Electrochemical cell
Platinum auxiliary electrode (red wire)
Ag/AgCl reference electrode (white wire)
Carbon plaster working electrode (black wire)
Pt working electrode (black wire)
Au working electrode (black wire)
N2 tank with regulator
Rubber Gloves: For good results you must wear rubber gloves when handling the
electrodes. The electrodes are extremely sensitive to
contamination from any source and especially from your fingers.
Operation of the BAS 100B
I. Start-Up Procedure
1. Turn the Isobar surge suppressor located on top of the BAS 100B system unit.
2. Turn on the BAS 100B with the red power switch located on the back of the system
unit.
3. Turn on the cell stand power with black power switch on the back of it
4. Open the N2 gas tank located on the left hand side corner.
5. Turn on the Gateway computer with the power switch on the front panel.
6. Turn on the monitor.
7. If it is not already on, turn on the laser printer located by the balance with its power
switch located on the left side of the printer.
8. Log into Windows NT after the computer has finished booting: This is done by
entering CTRL+ALT+DEL when prompted to do so. The system will then display a
login box. The user name is chem 421 and there is no password so just press ENTER
or click OK
9. If this is your first time using this computer create a sub-directory to store your data
inside the directory for your section before you open the BAS 100B program.
10. To launch the BAS 100B program :double click on BAS 100 W icon, after BAS logo
is on screen, press any key or click on the graphic image to continue the work.
II. Establishing a directory
The first time you use the system you must create a directory to store all of your data.
1. Click on my computer and go to C drive. Find myfiles folder and click on.
2. Create your own folder under chem421 folder.
3. Close the windows.

After each scan be sure to save your data to your folder.


III. Setting the parameters
1. On the toolbar, located on the top of the BAS window, click on Method
2. Choose Select Mode
3. The next screen that should appear is the 'Mode of Operation.' On this screen, the
category highlighted should be Sweep Techniques and the techniq ue that should be
highlighted is Cyclic Voltammetry. Then click OK
4. The next screen should be 'CV General Parameters.' This is where you want to enter
the appropriate parameters for each run, then click OK
5. To change the parameters for each run, click on method, which is located on the
toolbar at the top.
6. Choose General Parameters, then the 'CV General Parameters' screen will appear and
you are able to make changes to the parameters for each scan.
IV. Running a scan:
1. Before a scan can be completed, the solution in the cell should be stirred and purged
before each run.
2. After the solution is stirred and purged, for about five minutes, then pull the nitrogen
gas line out of the solution, so that the nitrogen gas is blowing over the solution, but
not producing any bubbles on the surface of the solution. This prevents oxygen from
reentering the solution.
3. To run a scan, press the F2 key, or click on Control, which is on the toolbar at the
top, then choose, start run.
4. After the scan is complete, save the data to your file by clicking on the following in
this order:
File (which is on the toolbar)
Save Data
C Drive
MYFILE
chem421
click on your own folder
give the file a name
Click ok
5. After your data is saved, then print your data, by pressing F8
6. If you are prompted by a window that does not allow you to print, do the following:
Click on Print (which is on the toolbar)
Choose Print Setup
Reselect the same printer
Click Ok
Then your data should be sent to the printer
By pressing F8, you can print out additional copies
If you still encounter printer problems, notify the TA. The above procedure might
need to be done each time you want to print a new voltammogram.
7. Once your data is printed, then you are able to go onto the next scan.

V. Shut down procedure


1. Go to File and then exit from the BAS 100W software.
2. Click on Start, in the lower left hand corner, then click on Shut Down, make sure
that Shut down the computer is highlighted and then click OK.
3. Wait for the computer to tell you that it is ok to turn off the computer before
proceeding any further.
4. Once the computer screen reads that it is now safe to shut off the computer, press the
power button on the Gateway Tower
5. Turn off the monitor
6. Turn off the power to the BAS 100B electrochemical analyzer, by pressing the red
POWER button on the side of the BAS 100B.
7. Turn off the power to the surge suppressor, which is located on top of the BAS 100B
Electrochemical analyzer.
8. Turn off the printer, if and only if all the other groups are also done printing their
data.
VI. Hints:
Do not stir any of the solutions when running a cyclic voltammogram. But, always
stir the solution for at least 10 seconds before scanning.
Do not fill the cell any higher than 1 cm below the Teflon cover.
Make sure that the working electrode and the reference electrode are approximately at
the same height.
Be sure that the surface of the working electrode is clean. It may be polished briefly
after cleaning by rubbing on a clean sheet of unprinted paper.

Part I
Dissolved Oxygen, Potential Limits & Surface Effects
When investigating a chemical system for the first time with CV, there are several
experimental conditions that need to be established. You need to choose the appropriate
solvent, electrode, and supporting electrolyte, and determining whether O2 is an
interferent. This effort is justified because it demonstrates how to design an efficient CV
experiment for almost any chemical system of interest.
Reagents
25 ml of 1.0 M H2SO4
500 ml of 0.1 M Phosphate Buffer (pH = 7.0)
KH2PO4 and K2HPO4
Hint for buffer preparation:
Buffer preparation is based on Henderson-Hasselbalch equation:
HA
H+ + ApH = pka + log ([A-]/[HA])
where pKa for KH2PO4 is 6.86
Procedure
A three electrodes system is used in this section:
1. Au electrode/Pt electrode/Carbon electrode (black wire)
2. Pt auxiliary electrode (red wire)
3. Ag/AgCl reference electrode (white wire)
1. Start with using the gold working electrode, a cyclic voltammogram of 0.1 M
phosphate buffer with initial scan limits of 700 mV and -1000 mV is run. This is
initiated at 400 MV in the negative direction with a scan rate 50 mv/s.
2. Before running a cyclic voltammogram, be sure that there are not any bubbles on
the bottom of the electrodes. Also, never stir the solution when running a cyclic
voltammogram. Fill the cell with 12-13 ml of solution. Do not overfill the cell!
3. Run the cyclic voltammogram. After viewing the results adjust the scan limits so that
the current at the ends of the scan do not exceed 10 A.
4. Stir the solution for 10 seconds. Rescan the solution. When you obtain satisfactory
results. Print the graph and store your data in your sub-directory on disk.
5. After finishing gold working electrode, switch to platinum electrode, run a cyclic
voltammogram of the same solution and repeat step 2~4.
6. Switch to carbon electrode, run a cyclic voltammogram of the same solution and
repeat step 2~4.
7. After the first three cyclic voltammograms are acquired, deoxygenate the solution for
ten minutes by bubbling nitrogen gas through it. After approximately ten minutes,

raise the nitrogen tubes out of the solution so that the nitrogen gas is blowing over the
solution. This will prevent oxygen from reentering the solution.
8. Now, acquire a cyclic voltammogram of the deoxygenated solution using the carbon
electrode.
9. Replace the carbon electrode with the platinum electrode. Bubble nitrogen gas
through the solution for another five minutes. Now, acquire a cyclic voltammogram
of the deoxygenated solution using the platinum electrode.
10. Replace the platinum electrode with the gold electrode. Deoxygenate the solution for
five minutes.
11. Now, acquire a cyclic voltammogram of the deoxygenated solution using the gold
electrode
12. The 7th and last voltammogram to be acquired is the Gold electrode in deoxygenated
H2SO4.Replace the solution with 1.0 M H2SO4. Deoxygenate the solution for ten
minutes. Now, acquire a cyclic voltammogram of the deoxygenated solution using the
gold electrode
Questions
1. Discuss any interference of O2 apparent from series of voltammograms.
2. What considerations for the CV experiment requires choosing the appropriate solvent,
supporting electrolyte, and working electrode?
3. Why isn't the solution stirred when running a cyclic voltammogram?
4. Based on your results, what are the useful potential ranges for each of the four
degassed systems studied here?
5. Why is phosphate buffer used as a background electrolyte? List the characteristics of
a good background electrolyte.

Part II
The electroactive of Dopamine
Electrochemical method had been used to analyze electroactive materials for years. The
aim of this experiment is to use cyclic voltammatry to determine the electroactivity of
dopamine (DA). The measurement involves studying the current flow from and to the
dissolved analyte. The oxidation reaction of dopamine is in the following:

Based on previous work from Part I of this laboratory, you continue the experiment by
using an appropriate solvent, electrode and chemical environment to measure the
electroactivity of DA by CV.
Reagents
100 ml stock solution of 50 mM 4-(2-aminoethyl)benzene-1,2-diol (Dopamine,
DA), prepared in 0.1 M phosphate buffer (pH=7.0)
Prepare 25 ml each of 5, 10, 15, 20 and 25 mM DA solutions in 0.1 M phosphate
buffer from stock solution.
Prepare an unknown DA solution
Procedure
A three electrode system is used for this section.
4. Pt working electrode/area = 2.5 mm2, (black wire)
5. Pt auxiliary electrode (red wire)
6. Ag/AgCl reference electrode (white wire)
1. The top of the electrode holder has four holes to accommodate the three electrodes
and a tube for deoxygenating by bubbling with a stream of N2.
2. The cell is assembled and filled with about 12-13 ml of 0.1M phosphate buffer. The
system is deoxygenated by purging with N2 for 10 min. Following deoxygenation, N2
is allowed to flow over the solution to prevent O2 from reentering the cell for the
remainder of the experiment.
3. While the system is being deoxygenated, the scan parameters can be set. The working
electrode (black wire) should be disconnected during this procedure. The initial
potential is set at 400 mV and the scan limits are based on the optimized condition
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4.
5.

6.
7.

you found in part 1 by using Pt working electrode. All scans are initiated in the
negative direction with a scan rate of 20 mV/s. Use the default value for the
sensitivity.
After allowing the current to attain a constant value (quiet time = 10 s), the potential
scan is initiated and a background CV of the supporting electrolyte solution is
obtained.
After turning off the working electrode, the cell is cleaned and refilled with 15 mM
DA prepared in 0.1 M phosphate buffer. Following the same procedure as above, a
CV of the DA/DA ortho-quinone is obtained. The effect of the sweep rate (n) on the
voltammograms is observed by using this same solution and recording CV's at the
following rates: 20, 50, 75, 100, 125, 150, 175, and 200 mV/s.
Obtaining scans of 5, 10, 15, 20 and 25 mM DA using a sweep rate of 20 mV/s to
construct calibration curve.
Run cyclic voltammatry for unknown DA.

Note:
Make sure that there are no bubbles on the electrodes, and do not stir the
solution when running the cyclic voltammogram.)
Calculations:
1. Determine the diffusion coefficient of the system using Ipa and Ipc for each
concentration at 20 mV/s.
Ip = (2.69 x 105)n 3/2 ADo Cv 1/2
Where:
n = Number of electrons transferred
A = Area of the electrode
Do = Diffusion coefficient
C = Concentration of the solution (mol/cm3)
v = Scan rate (V/s).
2. Plot Ipa and Ipc vs n 1/2 (sweep rate mV/min) 1/2 for your 15 mM data. Obtain the
slope of these plots and calculate the diffusion coefficient
3. Calculate the mean and standard deviation in the diffusion coefficient. How does this
compare to typical diffusion coefficients?
4. What is the evidence indicating the reversibility of the system?
5. Show that Ipa and Ipc are directly proportional to concentration by plotting a graph of
current vs. concentration at 20 mV/s. Does this graph demonstrate this concept well?
6. Determine the concentration of the unknown, if you were asked to perform an
unknown.
7. Why is the Platinum electrode used instead of the carbon or gold electrodes?

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Part III
Effect of Coupled Chemical Reactions
Acetaminophen (APAP), the active ingredient in Tylenol, is commonly used as an aspirin
substitute. This redox system is useful in demonstrating the mechanistic information that
can be obtained from CV's.
Reagents
McIlvaine buffer: (table 1)
500 ml of pH 2.2 McIlvaine buffer (ionic strength = 0.5)
200 ml of pH 6.0 McIlvaine buffer (ionic strength = 0.5)
200 ml of 1.8 M H2SO4
0.070 M APAP stock solution is prepared in 0.05 M perchloric acid
Unknowns: Tylenol tablet
Procedure
1. Using the stock solution, 25 ml of an APAP solution is prepared in each of the three
supporting electrolyte solutions. The concentration of these APAP solutions should
be approximately 3 mM.
2. For the purpose of establishing a calibration curve, four additional APAP solutions in
pH 2.2 buffer are needed (range from 0.1 mM to 5.0 mM); 25 ml of each are needed.
An unknown is prepared from a solid sample by dissolving a tablet in 250 ml of pH
2.2 buffer. A workable concentration is obtained by diluting a 5 ml aliquot of this
solution. If a liquid aspirin substitute is given, a suitable solution can be obtained by
direct dilution.

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Table I.
Preparation of Constant Ionic Strength McIlvaine Buffered Solutions
Desired pH
at 25EC
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
6.0

Na2HPO412H2O
Citric acid,
(g/l)
H3C6H5O7H2O
(g/l)
1.43
20.6
4.44
19.7
7.8
18.7
11.35
17.7
14.7
16.7
17.7
15.8
20.4
15.0
21.5
14.2
25.4
13.6
27.6
12.9
29.7
12.3
31.6
11.7
33.4
11.2
35.3
10.7
36.9
10.2
38.4
9.75
40.0
9.29
41.5
8.72
43.3
8.32
45.2
7.74

Ionic
strength
0.0108
0.0245
0.0410
0.0592
0.0771
0.0934
0.112
0.128
0.142
0.157
0.173
0.190
0.210
0.232
0.256
0.278
0.302
0.321
0.336
0.344

KCl (g/l) to
bring to 0.5 M
ionic strength
37.2
35.4
34.2
32.9
31.4
30.3
28.9
27.6
26.7
25.5
24.4
23.1
21.6
19.9
18.2
16.5
14.8
13.3
12.2
11.6

Using 3 mM APAP solution in pH 2.2 buffer, carbon electrode, scan limits are
established at 1000 mV and 200 mV. Scans are initiated in the positive direction at 0
mV. Cyclic voltammograms of the 3 mM APAP solution in each of the three buffers are
then obtained at a scan rate of 40 mV/s and 250 mV/s. The solutions should be stirred
between each run. Obtain voltammograms of four additional APAP solutions in pH 2.2
buffer and unknown solutions at a scan rate of 50 mV/s.

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Calculations:
1. Give a reasonable explanation to the following oxidation mechanism of APAP, and
how it applies to this experiment.

2. How do you explain the large separation between the anodic and cathodic peak
currents in the pH = 6 cyclic voltammograms?
3. Construct a calibration curve by plotting peak current vs concentration of APAP for
the standard solutions of APAP.
4. From you calibration curve, determine the concentration of APAP in the diluted
unknown solutions that you analyzed.
5. Calculate the weight of APAP in the unknown tablet and/or the concentration in the
liquid unknown. Do your results agree with the expected value?
6. Explain why faster sweep rates are necessary to study electrochemical reaction
mechanisms where the oxidized and/or the reduced species can participate in slower
side reactions.
7. What problems can you anticipate encountering for very fast scan rates (>100 v/s)?
8. Why the carbon electrode is used in part III instead of the gold or platinum
electrodes?

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