Cyclic Voltammetry Experiment
James J. Van Benschoten . J a n e Y. Lewis, a n d William R.
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 an d theories have been
discussed by Kissinger an d Heineman (I) . Despite t h e ad -
vantages of th e 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 earlv
maduate level. There are three oarts to this exueriment, -- "
each of which ma y 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~~
system in aoueous solution. Thi s 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; an d t h
e effects of varying concentration an d 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 o n t h e appear-ance of t h e
CV; effect of p H o n th e appearance of th e CV an d o n t h e
mechanism of reaction; use of scan rate for elucidating
mechanistic information; an d quantitative determinationof
acetaminophen in a l'ylenolm tnhlet.
P a r t 111-is designedto introduce t h e studen t t o practical
considerations in a cyclic voltammetry experiment. Instead of
-
followine recommended conditions t h e studen t now is
persuaded t o investigate factors ~ u c has: t h e effect of 02o n
th e C'Y: choosinr the aoorooriate... electrode: ~srablishin aPO-
tential $can lim& an d studying Pt electrode surface waves. It is
honed that . uoon comoletion of this section, t h e studen t can
effktively design a n eiectrochemical experiment for a n y
particular chemical system of interest.
Part I-Fundamentals of Cyclic Voltammetry
T h e Fe111(CN)6"-/Fe"(CN)$L- couple is known t o b e well-
behaved both chemically an d electrochemically (2). As such, i t
is often used a s a model system in electrochemical experi-ments.
I t ca n b e 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
Heineman
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 ~ C orI a saturated calomel
electrode (SCEI reference electrode. All ootentials in this exoeriment
are referenced veraur. %'E The cell used la a H~mnalyticalSystems.
In,. \'('-2ylaw wal wit h 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 electrode surface 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~fiuang 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 th e dat a obtained, a number of simple calculations can
he done tha t will yield considerable information about th e ferri-
ferrocyanide system. Anodic peak current (i,) cathodic peak
current (iw), E"', and n can be determined as described

POTMTIAL. V rr 5CE
Figure 1. (A) Cyclic voltammograms of 4 mMKsFe(CN)sin 1 MKNOJ. Pi
elec-bade. Scan rate ( 4 = 20. 50. 75. 100. 125. 150. 175. end 200 mVls. (8)
Plot 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 noft 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~urtional.to 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 buffer with 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 mM.
For the purpose of establishing a calibration curve, four additional
APAP solutions in pH 2.2 buffer are needed. These four concentra-
" ' I
0.8 04 00 ;-loL
WTENTIAL V vr SCE 2.04.06.0 6.0 100
CONCENTRATION mM
F i a r e 2. IAl.. Cvcllc. voltammmam of KIF~CN)-.... In 1 MKNO*. Scan rate =
20 mVls. PL elechade. Concentration = 2. 4, 6. 8, and 10 mM. (8)Plot of i, versus
concentration and i, vsrsus concentration horn voltammograms in (A).
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).
Procedure. The carbon oaste electrode is ~renared ..as described
in 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
I
11 111
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 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
anodic and cathodic waves are evident. The anodic current
represents step 1in the mechanism detailed above while the
Volume 60 Number 9 September 1983 773
 E,VOLTS vr Wepcl
//
1
roe 70.4r 0 . z

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
observed with 40 and 250 mV/s scan rates indicates that the Figure 4. Cyclic voltammcqrams of 3.6 mMAPAP in pH 2.2 Mcllvaine buffer.
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 (1111 ahirh rapidlv yields (step ;I) a hy-clrnted
firm I IYr that is elertroch~~micallvinactiw 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
scan rates are emnloved:." .however. faster scan rates reauire the
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 the reduction of
benzoquinone (V) was observed when a scan rate of 250 mV/s Figwe 5. Cyclic wliamwmms of 3.6 mM APAP in 1.8 M W . . Cmbm psste
electrode.
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 negative enough determining whether 02 is an interference. Generally, this is
potentials during the reverse scan allows for the accumulation of accomplished by some amount of trial and error. This effort is
benzoquinone (V). Consequently, a well-defined reduction wave justified, however, because as shown in parts I and 11, con-
was observed for henzoouinone ( V ) when the slower scan raw siderable information can be obtained from a relatively
wnsernployrd.The sermd scan in thr nositive direction virld3 i u simple experiment. This section demonstrates how these
~anodic wave in addition to that oE APAP which coriesponds to
selections are made, thus giving the student insight on how
the oxidation of hydro-quinone, the reduction product of todesign an effirirnt C V experimrnt for almost anv chemical
benzoquinone. systtm of interest.

Part Ill-Dissolved Oxygen, Potential Limlts, Surface Experimental

Elfects
When investigating a chemical system for the first time with
cyclic voltammetry, there are several experimental conditions that
need to be established. Among these are choosing the appropriate
electrode, solvent, and supporting electrolyte; and
Reagents. All chemicals are reagent grade and require no
further purification. Solutions of approximately 25 ml1.0 M
H2SO&and 25 ml 1.0 M KNOu are required.
A ~ o a r o t u sThe. electrochemical aooaratus is described in Dart I
774 Journal of Chemical Education
 O1 REMOVED
0.4 0.0 -0.4 -0.8
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
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 01in 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 either end hg large offrcnlr wnwz ['ring n 1.0
M 9 , l O ) .When used as electrodes, ~ t a n d exhibit~u surface
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.
-1.2
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 several
rtmsiderati(;n.s.The major requirements of the xivent are that the
-1.6
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 H2and 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 (
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

is observed. These waves have been studied and can be used to
determine accurately electrode area (9,10) . As demon-
strated in Figure 8, if the potential range is sufficiently
limited, a very clean workable background can be obtained.
Literature Cited
11) Kissinwr. P. T.. Heineman, W. R.. 3. CHEM.EDUC..EO, 702 119831.
(21 DeAn~e1is.TP. ., Heineman, W. R., J. CHBM. BDVC..53.94 11976l.
(3) Schwan. W. M.,Shain, I., A n d Chem..35.177011963).
776 Journal of Chemical Education
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.
P. T,and Heineman. W. K. IEditomI Marrel Dakkar, New York, in pma. Chapt.
E.
(51 ~ d t h o f fI.. ~ . . ~ n m a i e cWk,. J . J ~ h y chems. 39.945 (1935).
(fil Miner. I). .I.. Rice. J. H..Rimin. R. M.. Kiasin~or.P. T.. Aml. Chsm.. 53. 2258
119811.
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 .. Ami . Chm~.28.1179(1956).
(91 sayer, n. T.. ~nlxrtaJX...I. ~ . . - ~ ~ ~~ ~l ~i t ~m ~h ~t ~forchemistaeis tl ~
." widey.
Now York. 1914. pg. -9.
I101 Bsuer. H. H.. "Electrdie : Modern Ideas Concerninr E l r d r d o Reactions."
Gwrg Thismr l'uhl~sherr,StutOa~.Gsrmany1972.. ~ pl W. 1 0 3 .