Cyclic Voltammetry Experiment
James J. Van Benschoten. J a n e Y. Lewis, a n d William R. H e i n e m a n
University of Cincinnati. Cincinnati, OH 45221
Daryl A. Roston' and P e t e r T. Klsslnger
Purdue University. West Lafayene. IN 47907
Cyclic voltammetry (CV) is a very useful modern elec-
troanalytical technique; its principles and theories have been
discussed by Kissinger and Heineman (I). Despite t h e ad-
vantages of the technique a n d its widespread use, there is a
lack of CV experiments in t h e literature for students. Thus,
this experiment has been designed specifically for introducing
-
CV to students who are a t t h e advanced undergraduate or
-- " maduate level. There are three oarts to this exueriment,
earlv
each of which may be performed independently.
P a r t I uses t h e Fel1I(CN)c3-/Fe11(CN)s4-couule a s a n ex-
ample of a well-behaveb e ~ e i t r o c h e m i c areversible
~i~ system
in aoueous solution. This exoeriment demonstrates deter-
minition of t h e following: t h e formal reduction potential
(E"'): the number of electrons transferred in the redox process
in);the diffusion coefficient (D); electrochemical reveriibility;
and t h e effects of varying concentration and scan rate.
P a r t I1 investigates t h e electrochemical behavior of acet-
aminophen, a n ingredient in many over-the-counter phar-
maceuticals (e.g., Tylenol*, Excedrin*, Nyquil*, etc.). T h i s
organic system is more complex, involving chemical a s well
a s electrochemical reactions. Principles t h a t are illustrated
include: effect of a coupled chemical reaction on t h e appear-
ance of t h e CV; effect of p H on the appearance of the CV and
o n t h e mechanism of reaction; use of scan rate for elucidating
mechanistic information; and quantitative determinationof
acetaminophen in a l'ylenolm tnhlet.
P a r t 111-is designedto introduce t h e student t o practical
considerations in a cyclic voltammetry experiment. Instead
-
of followine recommended conditions t h e student now is
persuaded t o investigate factors ~ u c has: t h e effect of 02 on
~ ~~ ~
.. . electrode: ~srablishinaPO-
the C'Y: choosinr the aoorooriate
tential $can lim& and studying Pt electrode surface waves.
It is honed that. uoon comoletion of this section, t h e student
can effktively design a n eiectrochemical experiment for a n y
particular chemical system of interest.
Part I-Fundamentals of Cyclic Voltammetry
T h e Fe111(CN)6"-/Fe"(CN)$L- couple is known t o be well-
behaved both chemically and electrochemically (2). As such,
i t is often used a s a model system in electrochemical experi-
ments. I t can be used t o determine electrode areas a n d to
diagnose problems associated with new electrochemical cell
designs. In this experiment, t h e couple is used t o clearly
demonstrate s o m e ~ i m p o r t a n tprinciples of cyclic voltam-
metry.
Experimental
Reagents. All chemicals are reagent grade and are used assuch. A
10O-mlstock solution of apprnximateiy 10 mM K3Fe(CNk is prepared
in 1 M KN03. From this, 25 ml each of approximately 2,4,6, and 8
mM solutions in 1 M KN03 are made. In addition, a 25-ml K3Fe(CN)6
solution of approximately 4 mM is prepared in 1 M NazS04.All so-
lution concentrations must be accurately known. An unknown
KsFe(CN)fisolution should be provided by the instructor.
Apparatus. The cyclic voltammetry apparatus consists of a po-
tentiastat with potential sean capability, a voltmeter (optional), a
Current address: Department of Chemistry. Northern Illinois Uni-
versity. DeKalb. IL 60115.
772 Journal of Chemical Education
recorder, and an electrochemical cell (I). The potentiostat used is a
Bioanalyticsl Systems, Inc. CV-1R. Alternatively, any number of
commercially available instruments, or a homebuilt model con-
structed from conventional operational amplifiers can be used ( 3 . 4 ) .
The current versus potential curves are recorded on a Hewlett-
Packard model 7015B XY recorder, As mentioned in reference ( 1 ),
.~
the ootential scan varies linearlv with time. thus it is feasible to use
~
a rrrip chart recorder, even tho&h 11 is not ns wnvenienr as an X ) ' .
I f an <,rcill~mcopeia nvailahlr, i t can be used in place of the rerorder.
The p~trntialoutput is fi~lhwedindependently wwlth n Keithley model
178 digital voltmeter.
A three-electrode system is used for the CV experiment (I). The
electrodes reauired are a Pt warkinc electrode (area = 2.5 mm2),a Pt
auxiliary electrode, and either a A ~ I A ~ CorI a saturated calomel
electrode (SCEI reference electrode. All ootentials in this exoeriment
~~~~ ~
are referenced veraur. %'E The cell used la a H~mnalyticalSystems.
In,. \'('-2 ylaw wal with a t i t m l top. The u,p ha., iour hdes machmed
to nerommudate the three rlectn~desand a t u h for detrxygenating
by bubbling with a stream of Ns.
Procedure. Pretreatment of the platinum working electrode surface
may be required. Simply polishing the surface with powdered alumina
and rinsing thoroughly with distilled water should suffice. The elec-
trode can be sonicated in an ultrasonic bath if available.
The cell, as shown in reference ( I ) , is assembled and filled with 1
M KNOJ just until the ends of the electrodes are immersed (Note:
avoid tilting the SCE; this may disturb the HgIHgnCln and result in
incorrect potentialsl. The system is deoxygenated by purging with
Nz for approximately 10 mi". Following this, N2 is allowed to flow over
the solution to prevent 0 2 from re-entering the eell for the remainder
of the experiment.
While the system is beingdeoxygenated, the scan parameters can
be set. The working electrode should be disconnected or switched off
during this procedure. The initial potential is set at 0.80 V, and the
scan limits at 0.80 V and -0.12 V using the recorder as a monitor. All
scans are initiated in the negative direction with a scan rate of 20
mV/s. These settings will be used unless otherwise specified.
When deoxygenation is complete, the working electrade is switched
on. After allowing the current to attainaeonstant value (in about 10
s), the potential sean is initiated and a background CV of the sup-
porting electrolyte solution is obtained.
After turning off the working electrode, the eell is cleaned and re-
filled with 4 mM KaFe(CNI6 in 1M KNOs. Following the same pro-
cedure as above, a CV of the Fe'1L(CN)i"/Fe1'(CN)8- couple is ob-
tained.
The effect of the sweep rate ( u ) on the voltammoprams is observed
by using this same soiutionand recording CV's at the following rates:
20,50,75,100,125,150,115,and 200mV/s. Retweeneach scan, initial
conditions at the electrodesurface are restored by moving the working
electrode gently up and down without actually removing it from so-
lution. Care should be taken that no buhbles remain on the elec-
trodes.
('wwenrration likewiseaffrcts the magnrtudr of thr penkcurrent.
This i seen by uhtainmg +cansof 2.6.8. and I d m A f K ,l.'t.tC'Fi~fi uang
~~~ ~~
.~
nswwo rate uf 20 mV,s A \r,ltarnmoeram of tne unkn<,wnK8nCN)a
~~~ ~
solution should be ru'n as well.
The affect of the supporting electrolyte on the appearance of the
CV isdemonstrated by recordingvoltammogramsof (1) 4 mM ferri-
cyanide in 1 M KNOs and (2) 4 mM ferricyanide in 1M Na2S01.
Results and Discussion
Using the data obtained, a number of simple calculations
can he done that will yield considerable information about the
ferri-ferrocyanide system. Anodic peak current (i,) cathodic
peak current (iw), E"', and n can be determined as described
 "
0.8 04 00 ;-loL ' I
WTENTIAL V vr SCE 2.0 4.0 6.0 6.0 100
CONCENTRATION mM
POTMTIAL. V rr 5CE
. . Cvcllc
F i a r e 2. IAl -
. voltammmam of KIF~CN). . .. In 1 MKNO*.Scan rate = 20
Figure 1. (A) Cyclic voltammograms of 4 mMKsFe(CN)sin 1 MKNOJ.Pi elec- mVls. PL elechade. Concentration = 2. 4, 6. 8, and 10 mM. (8)Plot of i, versus
bade. Scan rate ( 4 = 20. 50. 75. 100. 125. 150. 175. end 200 mVls. (8)Plot concentration and i, vsrsus concentration horn voltammograms in (A).
01 iw YBTSUI v ' ' ~and ,1 versus uU2 horn voltammogams in (A).

in reference ( I ) using the voltammogram of 4 m M
K3Fe"'(CN)6 in 1M KN03.
The effect of the scan rate, v, on the appearance of the CV
can be seen in Figure 1A. As described by the Randles-Sevcik
equation (I), ,i and ip, i n c r e m as u"~. A plot of this equation
(Fig. 1B) yields a straight line, the slope of which can be used
to determine the diffusion coefficient (D in cm2/s) of the
system. T h e area of the working electrode will either have to
be provided by the instructor or experimentally deter-
mined.
Evidence indicating that the system is electrochemically
reversible (discussed in reference ( I ) ) can he seen in Figure
1A as well. T h e separation of the peak potentials (AEJ is
i n d e ~ e n d e nof
t v. This can he discussed bv the student.
The Kandlrs-Sevcik equation ( 1 ) also indicates that i, and
...i are d i r e d v.. .
oro~urtionalto concentration. The effect of
increasing concentration on the appearance of the CV can be
seen in Figure 2A. A calibration curve (Fig. 2B) can be con-
structed and used to determine the concentration of the un-
known ferricvanide solution.
A formal potential as reported in the literature is a working
number that is dependent on the conditions of the experiment
(5).T h e effect ofthe particular supporting electrolyte used
is demonstrated by comparing CV's of K3Fen1(CN)6in KN03
and Na2SOa.
Part ll-Effect of Coupled Chemlcal Reactions
Acetaminophen (N-acetyl-p-aminophenol, APAP), the
-
active ineredient in Tvlenol". is commonlv used as an a s ~ i r i n
substitute. However, unlike aspirin, it is known to cause liver
and kidnev damaee when administered in laree amounts. I t
is suspectld that :metabolite of APAP is the actual hepato-
toxic agent, thus APAP and its metabolites have been ex-
tensively investigated (6).
Voltammetric studies in aqueous solution have revealed
chemical as well as electrochemical steps (7). The APAP
system therefore is useful in demonstrating the mechanistic
information that can he obtained from CV's.
Experimental
Reagents. All chemicals are reagent grade and are used as such. The
fallowing supporting electrolyte solutions are needed: 500 ml of pH
2.2 and 200 mlof DH6 Mcllvaine bufferwith an ionicstrenethof 0.6
M (8); 200 ml of i.8 M HSSO~.
A stock solution of approximately 0.070MAPAP is prepared in0.05
M perehlaric acid. This should be kept in the refrigerator when not
in use. Using the stock solution, 10-25 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
~ ~
tions should span the range of 0.10 to 5.0 m M ; 10-25 ml of each are
needed.
An unknown solution is prepared by dissolving a Tylenolm tablet
in 250 ml of pH 2.2 buffer. A workable concentration is obtained by
diluting a 5-ml aliquot of this solution to 50 ml.
All APAP solution concentrations need to be accurately known.
Apparatus. The apparatus used in this experiment is identical to
that in Part I with the exception of the carbon paste workii electrode
(area = 9.1 mm2).
~ ~~~ ~ ~
. . as described in
Procedure. The carbon oaste electrode is ~renared
the Hiuanalytirnl Sysrems. Inc. manual. Thw elrrtrc,dt must he
carefully parked tu avoid erroneous resulu and rare ;lhould c,e mken
not to gauge it once it is ready for use.
Using the 3 m M APAP solution in pH 2.2 buffer, scan limits are
established at 1.0 V and -0.2 V. Scans are initiated in the positive
direction at 0.0 V. Cvclic voltammomams of the 3 mM APAP solution
in each of the 3 buffers are then obcined at a scan rate of 40 mV/s and
250 mV1s. The solution should be stirred between each run.
As was demonstrated in Part I, CV's can be used for quantitative
analysis. A standard curve can be constructed using the series of 5
APAP solutions in pH 2.2 buffer. From this, the concentration of
APAP in the Tylenol solution is determined.
Results and Discussion
The oxidation mechanism of APAP is as follows
OH
11 111
I
NAPQI
APAP
APAP is electrochemically oxidized in a pH-dependent, 2-
. . .
electron. 2-proton Drocess to N-acetvl-D-~uinoneimine
(NAPQI') (step 1). ~ i occurrence
e of follow-up chemical re-
actions involving NAPQl. is .
pH dependent. Bv . varving
. the pH
- .
of the media and the scan rate ofthe cyclic voltammetry ex-
periment, chemical reactions involving NAPQI can be
"mapped-out." At p H values 26, NAPQI exists in the stable
unprotonated form (11). Cyclic voltammograms recorded for
N A P a t pH 6 are shown in Figure 3. Reasonably well-defined

mM.
For the purpose of establishing a calibration curve, four additional anodic and cathodic waves are evident. The anodic current
APAP solutions in pH 2.2 buffer are needed. These four concentra- represents step 1in the mechanism detailed above while the

Volume 60 Number 9 September 1983 773

 E,VOLTS vr Wepcl
roe // 70.4 r0.z
1

Figure 3. Cyclic voltammogramr of 3.6 mM APAP in pH 6 Mcllvsine buffer.

Carbon paste electrode.

cathodic current represents the reverse of this step. The

similarity in appearance of the p H 6 cyclic voltamm~grams
Figure 4. Cyclic voltammcqramsof 3.6 mMAPAP in pH 2.2 Mcllvaine buffer.
observed with 40 and 250 mV/s scan rates indicates that the
involved species are stable in the time domain of the cyclic Carbon paste electrode.
voltammetrv experiment. The large separation between the
anodic andcathodic peak currents &the pH 6 cyclic vol-
tammograms is a manifestation of sluggish electron transfer
kinetics.
Under more acidic conditions, NAPQI is immediately
protonated (step 21, yieldmg a less itablebut elrctn,cherni-
calls artivr species (1111ahirh rapidlv yields (step ;I) a hy-
clrnted firm- I,IYr, that is elertroch~~micallv
~~~~~~ ~ ~ ~ ~ ~ inactiw at the ex-
~

amined potentials. Cyclic voltammograms shown in Figure

4 are consistent with this mechanism. The DH of the media
was 2.2. A small cathodic wave due to the reduction of pro-
tonated NAPQI " (111)
. . is evident when the scan rate of 250 mV/s
is employed. This wave is even more pronounced when faster
. " .however. faster scan rates reauire the
scan rates are emnloved:
use of an oscilloscope to record thk current-potential rksponse.
With a slower scan rate of 40 mV/s, a cathodic wave for the
reduction of protonated NAPQI is not observed. All of the
protonated NAPQI (111) is converted to the inactive hydrated
form (IV) before negative enough potentials are reached
durinz the reverse scan of the cvclic voltammetrv exoeri-
...-....
Hvdrated NAPQI (IV) converts (step 4) to benzoquinone;
however, the media has to he extreme& acidic for thk rate of
the process to be sienificant enough that reduction of benzo-
qui&ne is observed during the cyclic voltammetry experi-
ment. The media for the cyclic voltammograms detailed in
Figure 5 was 1.8 M HzS04. A poorly defined cathodic wave for
Figwe 5. Cyclic w l i a m w m m s of 3.6 mM APAP in 1.8 M W . . Cmbm psste
the reduction of benzoquinone (V) was observed when a scan electrode.
rate of 250 mV/s was employed. The reduction wave is broad
because the formation of benzoquinone (V) from hydrated
NAPQI (IV) occurs during the reverse scan. When the scan
rate is 40 mV/s, the increased length of time required to reach determining whether 02 is an interference. Generally, this is
negative enough potentials during the reverse scan allows for accomplished by some amount of trial and error. This effort
is justified, however, because as shown in parts I and 11, con-
the accumulation of benzoquinone (V). Consequently, a
well-defined reduction wave was observed for henzoouinone siderable information can be obtained from a relatively simple
experiment. This section demonstrates how these selections
( V ) when the slower scan raw wnsernployrd.The sermd scan
are made, thus giving the student insight on how todesign an
in thr nositive direction virld3 i u ~anodic wave in addition to
effirirnt C V experimrnt for almost anv chemical systtm of
that oE APAP which coriesponds to the oxidation of hydro-
interest.
quinone, the reduction product of benzoquinone.
Part Ill-Dissolved Oxygen, Potential Limlts, Surface Experimental
Elfects Reagents. All chemicals are reagent grade and require no further
purification. Solutions of approximately 25 ml1.0 M H2SO&and 25
When investigating a chemical system for the first time with ml 1.0 M KNOuare required.
cyclic voltammetry, there are several experimental conditions A~oarotus.The electrochemical aooaratus is described in Dart I
that need to be established. Among these are choosing the
appropriate electrode, solvent, and supporting electrolyte; and

774 Journal of Chemical Education

 O1 REMOVED
0.4 0.0 -0.4 -0.8 -1.2
POTENTIAL, V vs SCE
Figure 6. Cyclic volternmqlrams ol 1.0 MKWsshowing effect of OZ.Oxygen
rernovd by deaxygenating wilh N2 fn 10 min. Au electrode. Scan rate = 50
rnV/s.
I .
1.6 00 0.0 -08 -1.6
POTPITIAL, Y vr SCE
F r g ~ e7 Cyclic voltarnmDgrams of 1 0 M <NOs bs.ng d tlerenl wommg slsc-
bmes (Alglassycarbon. IBicaman pase. ICIAU.ID1 Fi Cycilc vohmmogsm
01 1 0 MH,SO. mng IE) Au electrode Scan rate = 50 mVls
9.1 mm2),and an Au electrode (area = 2.5 mm2)are used. Any or all
of these electrodes may he investigated depending on availability.
Procedure. The effect andlor interference of dissolved 01 " in the
~~
supporting electrolyte is readily determined. Using the Au working
electrode (polished as was the Pt electrode in part I) acyclicvoltam-
mogram of 1.0 M KN03 with scan limits of 0.7 V and -1.0 V is run.
This is initiated at 0.40 V in the negative direction with a scan rate
of 50 mV1s. The solution is then deaxygenated for 15 min as described
in part I, and a CV of the oxygen-free solution is recorded.
The potential window for variouselectrodes can be just as readily
determined. At the low current settines.. tvoicallv
. , used in CV.. this is
generally l~m~red m either end hg large offrcnlr wnwz ['ring n 1.0 M
K N h sdutim, n scan rntr oi 50 my s,and a current range of ap-
proxmately hll pA in.. the worknhlr pute~,tialrange can be deter-
mined for eaeh electrode.
Not only is the potential range dependent on the particular elec-
trode used, but alsoon the suppurtingelectrolyteused. This isdem-
onstrated by comparing the potential limits available on an Au
working electrode in 1.0 M KN03 and 1.0 M H2S04.
v' ,
1.2 0.9 0.6 0.3 00 -0.3
POTENTIAL, V vs SCE
Figure 8. Cyclic valtarnmqlram showing R eisctrDMt surface waves in 1 M
H2S0,. Scan rate = 50 rnV/s.
Plntinum makw a very interwing elcctrde i n that several surface
wnves npprar in a 1,ackgmund rean. Thmr wavra ran he investigated
in a dwrygmated solution of 1.0 M HJOI wing a pdirhed electnde.
A voltammogram is obtained by initiating the scan in the negative
direction at 0.30 V with potential limits of 1.425V and -0.225 V. The
positive potential limit is progressively stepped in to 0.825 V (in 0.15
~ ~
~-
V increments) obtainine a CV at eaeh new limit. Leavine this limit
~ ~
at 0.825 V, the negativepotential limit is then likewisestepped in to
~~~~~~~
0.075 V (in 0.075 V increments) obtaining a CV at each new set-
ting.
Results and Discussion
Though a compound is not chemically altered by 0 2 (i.e.,
oxidized, degraded, etc.), the voltammogram of that com-
pound may nonetheless be subject to 0 2 interference. This
results from the fact that 0. is electrochemicallv active (i.e..
reducible to Hz02 and HZO~.These two process"es should h i
amarent from the CV's of oxveenated 1.0 M KNO* (see Fie.
f3j.'1f the compound of i n t e r e z e d u c e s in the samepktential
region.
- . deoxveenation is a necessarv -~rocedure.
.
Choosing the appropriate solvent, supporting electrolyte,
and working electrode for a CV e x ~ e r i m e nreauirest
rtmsiderati(;n.s.The major requirements of the xivent are that
several
the iveries of interest he soluble and stahle in it. The SUI>-
porting electrolyte must provide a relatively high ionic
strength (>0.01 M ) and be compatible with the svstem. A
further consideration is the window that is available.
In aqueous solution, this is often limited on the negative end
by the reduction of HzO to H2 and on the positive end by the
oxidation of Hz0 to 0 2 . It is influenced by the choice of
working electrode, solvent, and supporting electrolyte. Elec-
trolysis of the species of interest must occur within this range
for a CV experiment. Figure 7 (A-D) shows the potential
windows provided by several working electrodes in 1M KNOs.
Figure 7C and 7E demonstrate the influence that two different
supporting electrolytes, 1 M KN03 and 1.0 M H2S04 re-
spectively, can have. These illustrate the pH dependence of
the Hz0 electrolysis waves.
Metals such as Au and Pt are not totallv inert as once
thought ( 9 , l O ) .When used as electrodes, ~ t a n d exhibit~ u
surface waves which limit the usable votential ranee. At an
Au electnde (as shown in Fig. 7 E ) these waves are atrributed
to adiorhed oxide furmation and redurtion at low pH. Figure
H illustrates the numerous l't surface waves. At negative po-
tentials, fmnation and oxidation ol adsurhed Hv UCCUW: in
the positive region, formation and reduction of adsorbed oxide
Volume 60 Number 9 September 1983 775
 14) Kimingcr, P. T., in "Labcrstory T ~ h n i q u e ain E l e c t r 4 y f i c a l ChemhV/."KYsbger.
is observed. These waves have been studied and can be used P. T,and Heineman. W. K. IEditomI Marrel Dakkar, New York, in pma. Chapt.
to determine accurately electrode area (9,10). As demon- E.
strated in Figure 8, if the potential range is sufficientlylimited, (51 ~ d t h o f fI.
. ~ . . ~ n m a i e cW
k ,. J . J ~ h y chem.
s 39.945 (1935).
(fil Miner. I). .I.. Rice. J. H..Rimin. R. M.. Kiasin~or.P. T.. Aml. Chsm.. 53. 2258
a very clean workable background can be obtained. 119811.

Literature Cited
.....-".
171 Preddy, C. A . Miner. D. .I., Meinsma. D. A . Kiasinpr, P. T., Anal. Chem., sub-
-;*.-A
(8) Riving. P. J., Markoulitz. J. M.. Rorenthal. I . . A m i . Chm~.28.1179(1956).
(91 sayer,n. T.. ~ n l x r t aJX..I.
. ~ . . - ~ ~ ~~ ~l ~i t ~m ~h ~t ~forchemista."
r i es tl ~ widey.
11) Kissinwr. P. T.. Heineman, W. R.. 3. CHEM.EDUC..EO, 702 119831. Now York. 1914. pg. -9.
(21 DeAn~e1is.T.P., Heineman, W. R., J. CHBM. BDVC..53.94 11976l. I101 Bsuer. H. H.. "Electrdie: Modern Ideas Concerninr E l r d r d o Reactions." Gwrg
(3) Schwan. W. M.,Shain, I., A n d Chem..35.177011963). Thismr l'uhl~sherr,StutOa~.Gsrmany.1972. ~ p l W . 103.

776 Journal of Chemical Education