CYCLIC VOLTAMMETRY The following attached articles pertaining to cyclic volt- ammetry have been taken from the Journal of Chemical Educa- tion: G. A. Mabbott, "An Introduction to Cyclic voltam- metry," J. Chem. Educ., 60, 697-702 (1983). P. T. Kissinger and W. R. Heineman, "Cyclic volt- amnetry," J. Chem. Educ., 60, 702-706 (1983). J. J. Van Benschoten, J. ¥. Lewis, W. R. Heineman, D. A. Roston, and P. T. Kissinger, "Cyclic Voltam- metry Experiment," J. Chem. Educ., 60, 772-776 (1983).{An Introduction to Cyclic Voltammetry Gary A. Mabbott Department of Chomistry and Geology, Clomson University, Clemson, SC 25631 Cyclic voltemmetzy has become a popular tool in the last “fifteen years for studying electrochemical reactions. Organic ‘Rhemisis have applied the technique to the study of biosyn- thetic reaction pathways (1) and to studies of electrochemi: ‘eilly generated free radicals (2). An increasing number of ‘Sorganic chemists have been using cyclic voltammetry to evaluate the effects of ligands on the oxidation/reduction ntial of the central metal ion in complexes and multinu- Sclear clusters (3). This type of information plays an integral pert in many of the approaches directed toward solar energy ‘Zeoaversion (4) and in model studies of enzymatic catalysis (5). Knowledge ofthe electrochemistry of a metal complex can be “useful in the selection ofthe proper oxidizing agent to put the metal complex in ai'intermediate oxidation state (6). Blec- rochemical methodology hes also been exploited as ¢ novel means of introducing functional groups end removing blocking agents (7). "There are several good texts that deal with the theory and practice of modern voltammetry in depth (8-10). Also, many instrumental anelysis textbooks give avery brief overview of the method. However, the needs ofa researcher interested in applying the technique for the first time are somewhre be thieen these two extremes, Instructors of instrumental analysis ‘who want to teach modern electrochemistry are faced with a similar dilemma due to the lack of suitable background ma- terial forthe students to read. This artile is intended to help meet those needs. The CV Experimont ‘The voltage applied to the “working” electrode is scanned linearly from an initial value, B, toa predetermined limit, Ey, (known as the switching potential) where the direction of the scan is reversed (see Fig. 1a). The operator can halt the scan ‘anywhere or let the instrument cycle between Ex and some other preselected value, Ea. The current response is plotted ‘5. function ofthe applied potential. Often there is very litle Gifference between the first cycle and successive scans. However, the changes that do appear on repetitive cycles are important keys to unlocking information about reaction mechanisms (as will be shown leter in this paper) Figure 1b shows a current-voltage curve (or voltammogram) for Fe(CN)s*. As the potential is scanned in the negative di- rection the current rises to a peak and then decays in a regular manner. The current depends on two steps in the overall process, the movement of electroactive material to the surface and the electron transfer reaction. The electron transfer rate constant for a reduction process is a function of potential and can be described theoretically. beak exe [Se —e)} 0 the standard heterogeneous electron-transfer rate con- stant. (Its value is a property of the reaction between the particular compound and the electrode surface used.) The number of electrons transferred per molecule is n; F is the Faraday; R is the universal gas constant; T is the Kelvin temperature; and 6°" is the formal reduction potential. (The primo signifies that the effect on the free energy of the reac- tants and products embodied in activity coefficients has been combined with the thermodynamic reduction potential to form a term that is directly measurable but subject to solution @) +05 To5 appLicd volts. [ APPLIED VOLTAGE Figs 1.5) Applied potontl program. Ey ard Exe ae svtclog potetas Typical ete voltammogram of tmMKgFei ata platinum elckoda a ‘gusus 0-1 MKC olan, Tha scan rate wes 100 mec and evonce ‘locvode was Ag/AGCIin 0.1 MKT elution conditions.) The term avis known as the transfer coefficient. It arises because only a fraction of the enezry thats put into the system (in the form of the applied potential) lowers the activation energy bartie. Its value varies from zaro to unity (often ~0.5) depending on the shape ofthe free energy sur- faces for the reactants and products.) ‘The exponential depandence of kron the applied potential accounts for the steep rise inthe current. However, the elec- trolysis of the reactant depletes its concentration near the surface. Since the experiment is performed at a stationary ‘electrode in an unstirred solution, diffusion is the prin means of moving the reactant to the surface. This relatively slow mode of mass transport eannot maintain asteady-state concentration profile in the region close to the electrode. ‘Therefore, the depletion zone grows. Ina sens, the average distance that the reactant molecules must travel to reach the surface increases. Consequently, the rate of mass transport , decreases. The dependence on mass transport, and the fact that a finite rate for the reverse electron transfer process is possible, prevent the current from increasing exponentially 1 This sa simpliicauon, For a welbwriton and much more detailed explanation ofthe signiieance of tho vansfr cooticint and symmetry factors se0 pp. 917-929 of rot27.with potential. Eventually the mass transport step becomes rate determining and the current reaches a maximum. Since the concentration gradient continuss to decrease, the rate of ‘mass transport continues to decrease causing the current to decay. Beyond the peak the current is actually dependent on time and independent of the applied potential. In this diffu- sion-limited region the current is proportional to ¢"22 An advantage of the cyclic voltammetry experiment is the fact that a significant concentration of product (in this case, the reduced form) has been generated near the electrode on the forward scan. When the scan direction is reversed, the reduced form is oxidized back to the original starting material and the current for the reverse process is recorded (see Fig. 1b). The electron transfor rate constant for the reverse (or oxidation) process is similarly controlled by the applied po- tential, «p= og wo(fe-m — « Determination of the Formal Reduction Potential tis common practice to report the average of the forward. and return pealepotentials as the formal reduction potential for the redox couple. This is an approximation that is most accurate when the electron transfer process is reversible and the diffusion coefficients for the oxidized and reduced forms are the same. Ifthe reaction is reversible, then the separation in the peak potentials, AF, will be clase to58/n mV (at 25°C). (This relationship can be used to evaluate n.) By reversible, electrochemists mean that the reaction i fast enough to maintain the concentrations of the oxidized and reduced forms in equilibrium with each other at the electrode surface. The proper equilibrium ratio at a given potential is, determined by the Nernst Equation: aT (i e-er— fy we oy where O is the oxidized form and R is the reduced form. ‘How fast is fast enough? Many systems look reversible when the voltage is scanned slowly but at higher sean rates AE, appears greater than $8/n mV. Reversibility is, then, amatter of degree and depends on the stress that is applied to the system. Matsuda and Ayabe indicated that for scanning vol- tammetry any deviations from roversible behavior will be imperceptible ifthe value of f° (in em/sec) is greater than the numerical value of 0.30"? (where. is the scan rate in V/see)® (11). Voltammograms recorded at scan rates up to 10 V/see are common. Some instruments are capable of scanning up to 1000 V/sec. Therefore, electron transfer reactions with rate ‘constants greater than 10 ex/sec will be reversible even in the very fastest experiments. Redox, couples whose peaks shift farther apart with in- ‘creasing Seai rate are categorized a3 quasi-reversible. (Some authors merely say irreversible.) There are some cases in which the peaks are so widely separated (K° = 2X 10-4? cm/aee) that po parts of the two peaks overlap on the potential axis at all: These are generally known as “totally irreversible” sys- tems. A subset of this class are those reactions that yield products that cannot be recycled electrochemically to give back the original reactants (for example, those that involve extensive bond breaking and/or loss of substituents to solu- tion). These are “chemically ireversible” reactions, and many ‘yield nf return peak at all. Ahother characteristic of reversible systems is the depen. dence of the peaks height on the square root of thescan rate! At 25°C the peak current is Fp = (269 x 1wynRanyPoIAC; 6 ‘The current will be in amperes when A is in cm?, Dg is in em?/sec, vig in volts/sec, and Cy is tho bull concentration in ‘moles/em. The poak current for a quasi-reversiblesyetam is not proportional tov! except when the peaks are so widely separated that the aystem is more appropriately described as, totally irreversible. Although the average of the peak potentials can be a good estimate of the E* for a reversible redox reaction, one must bbe careful not to attribute high accuracy to the determination. In Nicholson and Shain’s classic paper on the theory of vol. tammetry at stationary electrodes (12), they point out that, the position of the return peak, even for a reversible system ‘ean shift as much a3 5 mY depending on the choice of the switching potential, Z,, (The farther Bis from Ep, the mor nearly symmetric about the reduction potential the peaks vl, be.) Also their work indicates that the midpoint between the peaks is really an estimate of En (Ey isa term from po- larography that was given to the potential where the Gurrent, {ishalf the value of that on the current plateau.) Fortunately, the diffusion coefficients have asmall effect. Even if Do/D = 2, the error introduced by assuming Ey» = B®" would be only ~9iaV for a single electron exchange process. ‘Some workers have found that the broad point at the top of the current peak makes it difficult to determine the true, position of the peak precisely. They prefer to read the po- tential where the curront is half the value of the peak current. ‘This half-peak potential (for a reversible redox couple at 25°C) is related to the polarographic Bz value by the fol- lowing equation: Eya= Ein o (The sign is positive for a reduction process.) Estimating formal reduction potentials from quasi-re- vversible.voltanmograms isles reliable the farther the peak separation deviates from the reversible case. Theoretical work shows that a the scan rate is increased, slow electron transfer kinetics can make the peak potentials shift in such a manner that they are no longer symmetric about the Bj» for the redox ‘couple. The problem is worse the farther the electron transfer ‘coefficient i from 0.5. rough indication of the magnitude of the error that may be introduced by averaging the pair of cathodic and anodic peak potentials for a quasi-reversible voltammogram can be derived from graphical data prepared bby Matauda and Ayabe (17). For an a-value of 0.3 and peak. separations of 108, 912, and 592 mY, the midpoint between, the peas would be on the negative side of the actual Ey» value. by 2,44, and 104 mV, respectively. (For an a-value of 0.7 the. Grror would have the same magnitude with the opposite: sign.) ee = RFADLEC/B Aho ‘ ‘Ais the elactrode area: Ds the difson coofficient ofthe oxidized ‘Species; tis timo; and xs tha elstancs ftom the olactrode surtace. AN== ‘experiment in which the votago is stepped instoad of scanned out Oak ‘2 potentlal whore the currents difusion contoliod ls much eadlor ts: ‘medel mathematically. (This Is croncamporometry.) In that ease ° "2 i z 0 ofPrinos = Cis VFB ore whore G5 the concentration of the oxkized matertal inthe buk 201 ‘ion tn olor) sean rcronble, ton Sat scanning 068! ‘sao votlage wou also cause be caren to fall as =" a $'Rates of hoterogenecus reactions gr referenced to unit surat! ‘area and have unis of mol soe" em-® inca tha rates expresso a tho producto AG. to rale constant, kmusthave unt of om S667 won concentration i given ia mal on> i "Equation (6) asumes a planar eoeroce, Fora spherical lack (ouch as aranging meres Sep! = lian (0.782) FADS CAI ore ro te ral off lace, See eee te ie E‘The point to remember is that one should use conditions that give the most reversible behavior possible. For quasi reversible systems the scan rate should he slowed down to minimize AE,, There is a lower limit for the sean rate, how. ever. This lint is set by our ability to maintain a convee. =tion-free solution. Convection often sets in after times as short as 90 seconds, unless special precautions against stray vibra- tions and other sources of convection are taken. ‘The type and condition of the working electrode surface can make a difference in the electron transfer kinetics, Often solid ‘electrodes need to be polished and/or cleaned by exposing ‘them to oxidizing agents. In some cases workers advocate activating” the electrode surface (particularly carbon elec- ‘Exodes) by application of a sequence of extreme positive and ‘Znegative potentials. (For more discussion about surface effects and pretreatment procedures see references (13-15). “Speak Currents and Coupled Chemical Reactions ©The height ofthe current peak can be used to determine the ‘toncentration of the reactant in the bulk solution. However, other electrochemical methods (such a differential pulse voltammetry) are better suited for this task. The real forte of this technique is thé analysis of homogencous chemical re- actions that are coupled to the electron transfer process, Di- agnosis of coupled chemical reactions is often based on the ~ relative heilts ofthe anodie and eathodic peaks. For example, consider areversible charge transfer followed by an irzovers ible chemical reaction (entry Il in the table). Ifthe conversion of Rto Z is fast and the potential is scanned slowly, some of R will be lost to Z. Less R will be available for the oxidation back to 0 on the return scan and, therefore, the anodic peak will be smaller. In the extreme case, k may be 50 fast relative to the scan rate, that all of R will be converted to Z and the return peak will be absent entirely. Figure 2 illustrates how the voltammograms change depending on the ratio of the chemical rate constant to the scan rate. (Note that the y-axis i the normalized current as given by the function: in®2FADY"Cw'),) ‘Nicholson and Shain have deroonstrated that the ratio of the anodic to cathodic peak currents can be predicted from the rate constant for the chemical step, k, and the time, +, spent between Ey, and the switching potential, By (15). (Ey willbe the midpoint between the peaks at very high san rates where the following chemical reaction does not have time to consume a significant amount of R.} The theoretical rele- k Ot nest R eZ Ka = 5000, g & CURRENT FUNCTION 8 L & f s 8 wo 120 600-60 (-Eygn, mV Figwe 2, Cycle volarmogams er a raversibesiacironanstrolowed by ‘st eroversible chemical step or vious fatios ofthe enema! ate constant {oscanrate, ya whore a= nF ¥/ATand vi volle/sacond, (Adapted whe "ision om Anal Chem, 96, 705-723 1964) tionship is plotied in Figure 3, Experimentally we ean use the graph to obtain an estimate of k for the chemieal step. (For experimental values of ipaipe, find the corresponding theo: retical value of log (kr). Solve for kr and divide by the ex- perimental value of 7.) Other electrochemical mechanisms can be identified A list of some of the more common ones is given in the table. Figure os| Figaro 3. Ratio of anode o cabs (or revere to forward) peak crrent s a ‘uneton of i for a reversibl elacron vans fotowed by chemical step. (Acad wih prmision trom Ana. Chom, 98, 705-729 (1364)), Electrochemical Mechanisms Involving Coupled Chemical Rosctions en |. Rovorsible electron ranstor, no enemies complications Ot moma I Reversible eign transfor fotowes ya reverb chemical reaction -E,C, mocharlam Ot me aoe Ii. Reversible electron transor flowed by an travertine chemical reaction EC; mechan +m. atz IW. Reversible chemical reaction precang anctor—G., mecraniom zo OF man \V._ Reversible chemical action precotiag an Weversibl elacton| ‘ransfor—G. mocaniem zsto Ot mR Vi Reverse olacron transfor folowod by a averse regeneration ‘of stating materiat—catatle mocanism Oma Rtz>0 Yi kroversiie electron transtor flowed by an Froversbaregenstion ot starting materia! Ot mk ntze0 vu lecton tanetor wh Iterering chemical easton ECE7p (enodie) oo oi 10 1 10 SAN RATE Figur 4. Ratio of anode to eather rovers o forward) poak current 38 8 funeton of rate of veto scan for various eloctochernval mechanisms, + 30% Aber Tew 30% SCAN RATE Figure 6. ato of sof potent sanction of cana for varios electrode ‘mectanisms. (Aaapied witt pernsslon tem Anel. Chern, 98, 706-723, (36) 4 shows the general trend that the peak current ratio follows 9 a function of scan rate for each of the cases involving re- versible electron transfer listed in the table. Also of some di- ‘agnostic value is the rate at which Ey shifts aa a function of ‘can rate. These trends are presented in Figure 5. (Reference (12) gives a detailed development of esch of these eases, Pol- cyn and Shain also described multistep charge-transfer re- actions where an intermediate oxidation state is formed (16). ‘Treatment of a multi-electron reaction with an intervening chemical step has also been given (17, 18). Data from other types of electrochemical experiments is often needed to evaluate rate constants for reactions with coupled chemical stepa.) ‘Measurement of the peak current ia fairly simple for the forward sean. The proper baseline can be obtained by re- cording the background current fora scan without the analyte under the same conditions (same electrolyte, surface pre- treatment, etc.). The roverse scan is more complicated since the electrolysis for the forward process still contributes to the total current until the scam as passed the foot ofthe (forward) wave again. The generally accepted approach is to assume that, the contribution of the forward process to the total current. Continues to decrease with the square root ofthe time during the reverse scan. The baseline curve for the return scan can be obtained by stopping the forward scan at the switching Potential with the recorder sweeping along the x-axis a3 a function of time. This is shown in Figure 63. A second approach is to stop the scan at a convenient spot (at least 35 mV past Bp for the forward sean) and hold the potential until the current is relatively constant. The appro- priate baseline is shown in Figure 6b (13), (a) (B) Figure 6. Maths for datannning to proper baseline for meesurement of be ‘ak current for no reverse scan. a) Recording the signal versus lms end stopping the fst scan at Eb) Using an X-Y recorder and stopping to sean at E, unl Fappreacnes a stoacy stato bore scanning back (c) Pavesi ‘sed for calculation ofthe current rato using Nenolse's method, ean (10 ‘There are occasions when neither of these two methods is, convenient. Nicholson (19) has indicated that the proper current ratio can also be calculated using the following equation. (izaa , 0485(59 “ie + cose oe In eqn. (8), ges the peak current for the forward proces; (so is the absolute current at the switching potential; and (ipglo the uncorrected return pea: current measured from the eurrent aris. (See Fig. 6e) ‘There are some systems in which a coupled chemical reac: tion yields electroactive by-products. In these cases multipled? scans can be benefiial. For example, the product of electron! transfer in the oxidation of aniline is thought to be a freee’ radical that very rapidly dimerizes (13). a Oe = OF +e Ob -SO# = OF Ore oo ‘The p-aminodiphenylamine (I11) that is formed ig much!) ‘more easily oxidized at the applied potential and a further two electron oxidation occurs. Qh = Qe pi aMize I-te> rmezHt eI +2H* Figaro 7. GV of antng at a sassy carbon elaczod in 0.1 MCI end 0.05 M assum hycogen pela soon (it) Sean ate ie 60 mV/ee AGIAGC! 0.1 MKGI reterencs, Dot ine cates second scan, ‘This last reaction isa reversible process and the reduction step is observed (Fig, 7) at 0.2 V on the return sean, The oxidation of the p-aminodiphenylamine appears as a new peak on the second scan (dotted line). The appearance of the new peak: was an important clue to the identity of the product of the oxi- dation reaction. ‘The Calculation of Formation Constants ‘The formation constants for complexes in both the oxidized and reduced forms are useful in evaluating the v-donor and ‘-acceptor properties of the ligands (20, 21). The shift in the formal reduction potential for the complex from the reduction potential for the aquo-complex is dependent on the ratio of ‘he formation constants for the reduced and oxidized forms, For example, consider the reactions below. MIGHO}y + pL Mitty + ptO ~f | MUCHO), + pL <== MUL, + pio EOL AML.) = £°"(NE3(H0) MH: 0) 5) RT +p in KulKnd) Often the formal potential can be evaluated by eyclic vol- tammetry when one of the complexes is too unstable to permit 4 direct determination of E% by potentiometric measurement of an equimolar solution of the two form, If either Kim or Kt an be evaluated independently (22), then the other can be calculated from E* data, Practical Conslderatlons ‘Most modern equipment uses a three-electrode cell in which, counter or auxiliary electrode provides the current that is needled at the working electrode (23, 24). Therefore, virtually ho current flows through the reference electrode and its po- ‘ential remains constant. (For discussion of reference elec: trodes see references (25) and (26).) A three-electrode system also permits one to minimize voltage errors due to obmic (or R) loss through solution by placing the reference electrode: close to the working electrode surface. The voltage represented bby the product of the current and uncompensated resistance (mainly the solution resistance between the reference and working electrodes) is wasted and does not appear across the electrode/solution interface. Since the peak current increases with the square root of the scan rate, the voltage error in- creases at the same rate. In cases where the errr is of the order of millivolts, the peaks from even a totally reversible redox couple will appear to separate as though the system wore ‘quasi-reversible. Therefore the experimenter should be cau- tious about drawing conclusions concerning electron transfer kinetics when either the current or uncompensated resistance is large. Some manufacturers incorporate a positive feedback uit in their equipment to compensate for iR loss. ‘Another source of error in the applied voltage arises from the variation in the rates at which ions diffuse across the ion bridge separating the reference electrode from the sample solution. ‘The net difference in the movement of cations compared to anions results in a charge separation and, therefore an electrochemical potential difference. These junction potentials can be minimized by choosing supporting clectrolyte ions with similar diffusion coefficients (such as K* and Cl"). Mercury working electrodes are limited to the negative potential range. Platinum and various carbon electrodes are popular for performing oxidations. However, solid electrodes. are susceptible to adsorption, or surface fouling, and surface oxidation. For example, platinum forms an oxide film that shows a large reduction peak near +0.8 V in 0.5 M H,SO, versus the normal hydrogen electrode. Fortunately, a surface current can be identified easily as such since the peak height is directly proportional to the acan rate. Often, judicious choice of solution conditions and electrode pretreatment can mi mize this problem. In summary, eyelic voltammetzy is a convenient tool for obcaining qualitative information about electron transfer processes. It is also a rapid method for obiaining good est tates of formal reduction potentials, formation constants and, sometimes, the number of electrons transferred per reactant molecule and rate constants, ifthe user is aware ofits limita- tions. ‘Acknowledgment ‘The author gratefully acknowledges the helpful comments land encouragement of Dr. James C. Fanning end Dr. John D. Petersen in the preparation of this article. Literature Cited (a Bobi Mand Wy Soe Org Chen 5, 1574 198, © Niges Suph Re Ca, Ben Gnd ant Wank Pak J Ore Pciuchonal Tecligr fr forgtie Chen” Aces "Pec adoe an en Yor. 96, (0) al 2 Panini coco Ana” Jab Wey & Sa New Yor, (nt Mra Hand Aya. 2. Bleeker 88 458, [22 Mbt Sand Shu, Anal Cans st 13) Ada ph "each ot Sd coor aral De ew Yor. 124 Gina, lecyonal Cher 2311 (95D, {it East Racal 2 Sta (Go) Kishin Gand mse Cou Amer Che Sc 98689057) {GU Tower Menuet Cath Fore. Chote CFT (G8 Far eta ee he pcp md enn ‘Arn Went 8M. “Pandastait heagie Cei Bakcadputbcerearenaro Pete, S210 seen, White Pla, NY: Stra See itn, done Ba ht Bove o4 A217 7) SS er man ‘ndemic Pros, New York, 1961 ms nae 1 SEES nae ct Cyclic Voltammetry Peter T. Kissinger Purdue University, West Lafayette, IN 47907 William R. Heineman University of Cincinnati, Cincinnati, OH 45221 Cyclic voltammetry (CV) is perhaps the most versatile electroanalyticaljechnique for the study of electroactive species, Iis versatility combined with ease of measurement has resulted in extensive use of CV in the fields of electrochem- istry, inorganic chemistry, organic chemistry, and biochem- istry. Cyclic voltammetry is often the first experiment per- formed in an electrochemical study of a compound, a biolog- ical material or an electrode surface. The effectiveness of CV results from its capability for rapidly observing the redox behavior over a wide potential range. The resulting voltam- ‘mogram is analogous to a conventional spectrum in that it conveys information asa function of an energy scan. In spite of the wide usage enjoyed by CV, this technique is rot generally well understood in comparison to other instra- ‘mental methods such as spectroscopy and chromatography. tis not uncommon for the experimenter who is performing CY to have a poor understanding of the basic concepts of the technique, such as why the voltammograms have their pecu- liar shapes. The brief treatment afforded CV in most instru- ‘mental analysis textbooks is insufficient to convey an in-depth understanding of this powerful technique. tis the purpose ofthis article to provide a description of CV end its capabilities. The authors intend this to be suitable for a supplement to an undergraduate course in instrumental analysis oras an “intial reference” for anyone embarking on ‘a CV experiment for the first time. This article is accompanied by an experiment which hes been developed to demonstrate important features of CV. Fundamentals of Cycllc Votiammetry CV consists of eycling the potential of an electrode, which is immersed in an unstirred solution, end measuring the re~ sulting current. The potential of this working electrode is controlled versus a reference electrode such as a saturated calomel electrode (SCE) ora silver/silver chloride electrode (Ag/AgCl). The controlling potential which is applied across these two electrodes can be considered an excitation signal, ‘The excitation signal for CV isa linear potential scan with a ‘triangular waveform os shown in Figure 1. This triangular potential excitation signal sweeps the potential of the elec- trode between two values, sometimes called the stitching potentials. ‘The excitation signal in Figure 1 causes the po- tential first to scan negatively from +0.80 to ~0.20 V versus ‘SCE at which point the scan direction is reversed, causing a positive scan back to the original potential of +0.80 V. The Scan rate, as reflected by the slope, is 50 mV/s. A second cycle is indicated by the dashed line. Single or multiple eyeles can "The exporiment to accompany tis atic appears on page 72 of i isu. POTENTIAL, V versus SCE o 20 “6080 Fig 1. Typical excation sal for cyte vtarmein—a tlangulrpotnt swavetonn with withing potential tO. nd 0.2 V versus SOE. be used. Modern instrumentation enables witching potentials and scan rates to be easily varied. ‘A cyclic voltammogram is obtained by measuring the cur- rent at the working electrode during the potential sean. The ‘current can be considered the response signal to the potential. ‘excitation signal. The voltammogram is a display of current. (vertical axis) versus potential (horizontal axis). Because the ~ potential varies linearly with time, the horizontal axis can also be thought of a a time axis. This is helpful in understanding ~ the fundamentals of the technique. ‘A typical cyclic voltammogram is shown in Figure 2 for a platinum working electrode in a solution containing 6.0 mM= KgFe(CN)s as the electronctive species in 1.0 M KNOs ima watoras the supporting electrolyte. The potential excitations, signal used to obtain this voltammogram is that shown ins: Figure 1, but with a negative switching potential of ~0.15 Vea ‘Thus, the vertical axis in Figure 1 is now the horizontal axisait for Figure 2. The initial potential (E;) of 0.80 V applied at (aA is chosen to avoid any electrolysis of Fe(CN)s~ when electrode is switched on. The potential is then scanned ne#= ‘tively, forward scan, as indicated by the arrow. When th potential is sufficiently negative to reduce Fe"(CN)!~, cong Thode current is indiated at (b) due to Ube electrode pro-Sy Famenya- +e FetHONet Oa ‘Thgeletrae snow a sufficiently strong reductant to reduce KCN);2~. The cathodic current increases rapidly (b — a) tl the concentration of Fe!"(CN)? at the electrode surface is substantially diminished, causing the current to peak (d)- ‘The current then decays (d > ) as the solution surroundingcathedie CURRENT, nA, 08 06 ae 02 0 a2 POTENTIAL, V versus SCE Fete Folens Lo Fyre 2. Oycic votammogram of 8 mM KyFlCNe Ia 1 MKNOs. Gen nite 310.8 Vvorsus SCE ln naga diepcion at 50 mis, Platinum eloctodo, rea = 254mm the electrode is depleted of Fe! (CN) due to its electrolytic conversion to Fe!l(CN)g*~. The scan direction is switched to positive at ~0.16 V (f) for the reverse scan. The potential is still sufficiently negative to reduce Fet¥(CN),°-, so cathodic current continues even though the potential is naw scanning in the positive direction. When the electrode becomes a su- ficiently strong oxidant, Fell(CN)gt", which has been accu- ‘mulating adjacent to the electrode, can now be oxidized by the electrode process FellCN)gt~ -- Fell(CN) I" + 6 e This causes anodie current (i—~ k). The anodic current rap- idly increases until the surface concentration of Fell(CN)g* is diminished, causing the current to peak (The current then Gecays (j —~ ik) as the solution surrounding the electrode is Gopleted of Fe!'(CN)st-. The first cycle is completed when the potential reaches +0.80 V. Now that the cyclic voltammogram 's obtained, itis apparent that any potential positive of ~ +0.4 V would be suitable as an initial potential in that reduction of Fell(CN)g° would not occur when the potential is applied, ‘This procedure avoids inadvertent electrolysis as a result of applying the initial potential. ‘Simply stated, in the forward scan Fe!"(CN),'~ is electro- chemically generated from Fel!(CN),°~ as indicated by the cathodic current. In the reverse sean this Fe!!(CN)¢¢~ is oxi ized back to Felll(CN),5~ as indicated by the anodic current. ‘Thus, CV is capable of rapidly generating a new oxidation state during the forward scan and then probing its fate on the reverse scan. This Very important aspect ofthe techy be illustrated in the section on coupled chemical reactions. Amore detailed understanding ean bo gained by consi ing the Nernst equation and the changes in concentration that occur in solution adjacent to the electrode during elec- trolysis. The potential excitation signal exerts control of the ratio of Fel!(CN),3~/Fe!(CN)st~ at the electrode surface as described by the Nernst equation for a reversible system 5 = B‘ncre-patmennse + 225 fg AMEND] B= Bw ranemnesaterne +E tog eR} where E*"is the formal reduction potential ofthe couple. An initial value of £ which is sufficiently postive of E*’ maintains 4 ratio in which Fell(CN)_°~ greatly predominates, Thus, ‘application of +0.80 V asthe initial potential eauses negligible current. Howover, as Eis scanned negatively, conversion of Felll(CN)™~ to Fell(CN)g*~ by reduction is mandatory for satisfaction of the Nernst equation. The ratios of iron redo states that must exist at the electrode surface at several po tentials during the sean are shown on the lower horizontal axis in Figure 2. The logarithmic relationship between E and [Fel(CN)¢8-]/[Fe"(CN)¢¢-] is reflected by a rapid rate of change in the region where E = E*, Le,, {Fel(CN)_°-]/ [et(CN) ot] is causes the dramatic rae in eathodic current (b> €) di ‘The physical situation in the solution adjacent tothe elec- trode duting the potential scan is ilustrated by the concen. tration-distance profiles (C-x profiles) in Figure 3 for sslocted potentials from Figure 2. A C-r profile is a graphical illus- tration of how solution concentration (C) varies as a function ‘of distance (x) from the electrode surface. ‘The C-z profiles in Figure Sa are for Fe!(CN),!~ and Fel¥(CN)t~ atthe initial potential. Note that the application of Ey does not measurably alter the concentration of Felll( CN)0.01 M) and be compatible with the system. A further consideration is the potential window thet is available, In aqueous solution, thisis often limited on the negative end by the reduction of H_0 to Hy and on the positive end by the oxidation of H;0 to Op. It is influenced by the choice of working electrode, solvent, and supporting electrolyte. Blec- trelysis ofthe 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 1 M KNOs. Figure 7C and 7E demonstrate the influence that two different supporting electrolytes, 1 M KNOs and 1.0 M H:S0, re- spectively, can have. These illustrate the pH dependence of the H,0 electrolysis waves. Metals such as Au and Pt are not totally inert as once ‘thought (9, 10). When used as electrodes, Ptand Au exhibit surface waves which limit the usable potential range. At an ‘Au electrode (as shown in Fig. 16) cove waves are altributed to adsorbed oxide formation and reduction at ow pH. Figure B illustrates the numerous Pt surface waves. At negative po tentials, formation and oxidation of adsorbed I, occurs the pasitve egion, formation and reduction of adsorbed oxide 15is observed. These waves have been studied and can be used to determine accurately electrode area (9, 10). As demon- strated in Figure 6, if the potential range a sufficiently limited, a very clean workable background can be obtained. Literature Cited |) singe PT. Hegre WR. Cu fount 702889) (2) Dearei TP, Mercman WK) Ce Eve. S800 (8) Sar WM Shai tat ham 0 (5, (0 a8 i enn Teco in casi Cai A ator) Maret Ben, Wow Yorn fea CO (9) Kode 1M Toma, Phy, Chem 38,95 (150. (6) Bing BSR Ws Rig fe Mi Ringe PFs al Chem. 53, ia, (Peg Mies, D Maina DAs Kinng, P.T Anal Chea (@) vine Fd, Mahi. 1.8, Hees Anal Chem 38 178 {Soe BE ran rere try Ci Wig (1 Bag HH eter Noe a Cntig Hace Reig 16