Cyclic Voltammetry Principle

Cyclic Voltammetry PrincipleCyclic voltammetry is the most widely used technique for acquiring qualitative reading intimately electro chemic replys 34, 35. The power of cyclic voltammetry results from its ability to provide considerable information on the thermodynamics and energizings of heterogeneous negatron absent replys 47, 48, and linked chemical substance receptions 36, 37. It likewise provides mathematical analysis of an negatron transfer suffice at an electrode 41, 49, 50.Basic Principle of Cyclic voltammetryAn electron transfer process with a single quantity whitethorn be represented asO + ne R (2.1)where O and R ar oxidized and trim back form of electoractive species respectively, which both is alcohol-soluble in solution or absorbed on the electrode surface and atomic number 18 transported by spreading alone.Cyclic voltammetry consists of exhaustning linearly the la hug drugt of a unmoving on the job(p) electrode (in an unstirred solution), using a triangular emf waveform. Depending on the information sought, single or multiple cycles send away be used. During the achievable sweep, the potentiostat measures the genuine resulting from the applied possible. The resulting plot of present-day(prenominal) vs. probableity is termed as cyclic voltammogram.The excitation signal in cyclic voltammetry is given in Fig. 2.1a. Initially the electric potential of the electrode is Ei. indeed the potential is swept linearly at the enume consec swan of volts per second. In cyclic voltammetry reversal technique is carried out by reversing direction of scan after a certain time t = .The potential at any time E (t) is given byE (t) = Ei t tE (t) = Ei 2 + t t (2.2b)Here is scan rate in V/s.The shape of the resulting cyclic voltammogram can be qualitatively explained as followsWhen potential is change magnitude from the region where oxidized form O is stable, cathodic current starts to flow as potential approaches E0 for R/O coupl e until a cathodic apex of the suns way is reached. After traversing the potential region in which the reduction process takes place, the direction of potential sweep is reversed.The response-taking place in the send on scan can be expressed asO + e- RDuring the reverse scan, R molecule (generated in the forward half cycle, and accumulated near the surface) is reoxidized back to O and anodal confidential information results.R O + e-In the forward scan as potential moves past Eo, the near-electrode concentration of O falls to zero, the locoweed transfer of O reaches a uttermost rate, in unstirred solution, this rate then declines as the depletion of O further and further from electrode takes place. Before dropping again current passes by means of a maximum. Reversal of scan repeats the above sequence of events for the oxidation of electrochemically generated R that now predominates in near-electrode region.The continuous change in the surface concentration is coupled with an expansion of the diffusion layer thickness (as expected in the quiescent solutions). The resulting current steers thus reflect the continuous change of the concentration gradient with time, hence, the adjoin to the pointedness current corresponds to the achievement of diffusion control, while the current drop (beyond the peak) exhibits a t-1/2 dependence (independent of the applied potential). For the above reasons, the reversal current has the resembling shape as the forward one.Electrochemical CellElectrochemical cell is a sealed vessel which is designed to prevent the entry of air. It has an inlet and button to allow the saturation of solution with an inert gas, N2 or Ar. Removal of O2 is usually necessary to prevent currents due to the reduction of O2 interfering with response from system low study. The monetary standard electrochemical cell consists of three electrodes immersed in an electrolyteWorking electrode (WE)Reference electrode (RE)Counter electrode (CE)Working Electrode (WE)The performance of the voltammetric procedure is strongly influenced by the working electrode material. Since the reaction of interest (reduction or oxidation) takes place on working electrode, it should provide high signal to noise characteristics, as well as a reproducible response. Thus, its survival of the fittest depends primarily on two chemical elements the redox behaviour of the target analyte and the background current over the potential region required for the measurement. Other considerations include the potential window, electrical conductivity, surface reproducibility, mechanical properties, cost, availability and toxicity. A range of materials learn found application as working electrodes for electroanalysis, the most popular are those involving mercury, nose candy or noble metals (particularly platinum and gold).Reference Electrode (RE)This functional electrode has a eternal potential so it can be used as reference standard against which potential of other electrode present in the cell can be measured. Commonly used reference electrodes are silver-silver chloride or the calomel electrode.Counter of ancillary Electrode (CE)It is also termed as auxiliary electrode and serves as source or sink for electrons so that current can be passed from external circuit through the cell.The potential at WE is monitored and controlled very precisely with respect to RE via potentiostat. This may be controlled in turn via interfacing with a computer. The desired waveform is imposed on the potential at the WE by a waveform generator. The potential drop V is usually measured by the current flowing between the WE and CE across a resistor R (from which (I=V/R), the latter connected in series with the two electrodes. The resulting I/V trace, termed as a voltammogram is then either plotted out via an XY chart recorder or, where possible, retained in a computer to allow any desired data manipulation prior to gravid copy being taken.Single Electron Transfer ProcessThree types of single electron transfer process can be studied. correctable processIr correctable processQuasi- reversible processBased on comforts of electrochemical parameters, i.e. peak potential Ep, half peak potential (Ep/2), half wave potential (E1/2), peak current (ip), anodic peak potential Epa, cathodic peak potential Epc etc, it can be ascertained whether a reaction is reversible, irreversible or quasi-reversible. Ep is the potential corresponding to peak current ip, Ep/2 is the potential corresponding to 0.5 ip, E1/2 is the potential corresponding to 0.85 ip. Theseelectrochemical parameters can be graphically obtained from the voltammogram as shown in the Fig. 2.2.two-sided ProcessThe heterogeneous transfer of electron from an electrode to a reducible species and vice versaO + ne Ris a form of Nernstian electrode reaction with assumption that at the surface of electrode, rate of electron transfer is so rapid that a dynamic offset is established and Ner nstian condition holds i.e.CO(0,t) CR(0,t) = Exp(nFRT)(Ei-t-Eo) (2.3)In equality (2.3), Co and CR are concentration of oxidized and reduced species at the surface of electrode as a function of time, Eo is the standard electrode potential, Ei is the initial potential and is the scan rate in volts per second. Under these conditions, the oxidized and reduced species involved in an electrode reaction are in equilibrium at the electrode surface and such an electrode reaction is termed as a reversible reaction.Current ExpressionDue to variation in concentration of electroactive species at the surface of electrode and the concentration in the bulk, diffusion controlled mass transport takes place. Ficks second law can be applied to obtain time dependent concentration distribution in one dimension of expanding diffusion layer.Ci(x, t) t = Di2Ci(x, t) x2 (2.4)Peak current is a characteristic quantity in reversible cyclic voltammetric process. The current expression is obtained by solving Ficks law 51.i = nFACo*(Doa)1/2 (at) (2.5)where i = current, n = number of electrons transferred, A is the area of electrode, Co* is the bulk concentration of oxidized species, Do is the diffusion coefficient, (at) is the current function and a = nF/RTAt 298K, function (at) and the current potential curve reaches their maximum for the reduction process at a potential which is 28.5/n mV much controvert than the half wave potential i.e. at n(Ep-E1/2) = 28.50 mV, 1/2(at) = 0.4463 ( Table 2.1). Then the current expression for the forward potential scan becomes(2.6)where ip is the peak current or maximum current.Using T=298K, Area (A) in cm2, Diffusion coefficient (Do) in cm2/s, concentration of species O (Co*) in moles dm-3 and Scan rate () in volts sec-1, equation (2.6) takes the following form,(2.7)Equation (2.7) is called Randles Sevick equation 39, 40.Diagnostic Criteria of ReversibilityCertain well-defined characteristic values can be obtained from the voltammogram, for a reve rsible electrochemical reaction.relationship between peak potential (Ep) and half wave potential (E1/2) for a reversible reaction is given by,(2.8a)(2.8b)Where E1/2 is potential corresponding to i = 0.8817ip 41.At 298 K(2.8c)From equations (2.8a) and (2.8b) one obtains,(2.9a)At 298K(2.9b)The peak voltage position does non alter as scan rate varies. In some cases, the precise mark of peak potential Ep is not easy because the observed CV peak is somewhat broader. So it is sometimes more convenient to report the potential at i = 0.5ip called half peak potential, which can be used for E1/2 stopping point 52.(2.10a)At 298 K(2.10b)(2.10c)From equations (2.8a) and (2.10a) we obtain,(2.11a)At 298K(2.11b)The diagnostic criterion of single electron transfer reversible reaction is often sufficient to get qualitative as well as quantitative information about the thermodynamic and energizing parameters of the system.For a reversible system, should be independent of the scan rate, however, it is found that generally increases with . This is due to presence of finite solution resistance between the reference and the working electrode.Irreversible ProcessFor a totally irreversible process, reverse reaction of the electrode process does not occur. Actually for this type of reaction the charge transfer rate constant is quite small, i.e. ksh 10-5cm sec-1, hence charge transfer is extremely low and current is mainly controlled by the rate of charge transfer reaction. Nernst equation is not applicable for such type of reaction.The process can be best described by the following reactionO + ne RDelahay 51 and posterior on Mastuda, Ayabe 48, and Reinmuth 53 described the stationary electrode voltammetric curves of the irreversible process.Irreversibility can be diagnosed by three major criteria.A shift in peak potential occurs as the scan rate varies.Half peak width for an irreversible process is given by(2.12)Here is transfer coefficient and na is the number of electrons invo lved in rate determining step of charge transfer process.At 298K(2.13)Current expression is given as,i = nFACo*(Dob)1/2 (bt) (2.14)The function (bt) goes through a maximum at 1/2(bt) = 0.4958.(Table 2.2).Introduction of this value in equation (2.14) yields the expression (2.15) for the peakcurrent.A plot of ln ip vs. (Ep-Eo) for different scan rate would be a straight line with a slope proportional to -naF and an intercept proportional to ks,h.Quasi-reversible ProcessQuasi-reversible process is termed as a process which shows mediocre behaviour between reversible and irreversible processes. Both charge transfer and mass transfer control current of the reaction. For quasi-reversible process value of standard heterogeneous electron transfer rate constant, ks,h lies between 10-1 to 10-5 cm sec-142. Cyclic voltammogram for quasi-reversible process is shown in Fig. 2.3.An expression relating the current to potential dependent charge transfer rate was first provided by Matsuda and Ayabe 48.(2.17)where, ksh is the heterogeneous electron transfer rate constant at standard potential Eo of redox system,is the transfer coefficient and = 1- .In this case, the shape of the peak and the various peak parameters are functions of and the dimensionless parameter , defined as 54(2.18)For quasi-reversible process current value is expressed as a function of.(2.19)where is expressed as(2.20)is shown in Fig. 2.4. It is observed that when 10, the behavior approaches that of a reversible system.It is observed that for a quasi-reversible reaction, ip is not proportional to 1/2. For half peak potential we haveat 298K (2.21)This implies,These parameters attain limiting values characteristic of reversible or totally irreversible processes as varies. For 10, (,) = 2.2 which gives Ep-Ep/2 = 56.5mV (value characteristic of a reversible wave). For mutation of with and is shown in Fig. 2.5.For three types of electrode processes Matsuda and Ayabe 48 suggested following zone boundarie s.a) Reversible (Nernstian)15 ksh 0.3 1/2cm s-1b) Quasi-Reversible15 10-2 (1+) 0.3 1/2 ksh 2 10-5 1/2 cm s-1c) wholly Irreversible Source Bard, A.J. Faulkner, L.R. Electrochemical Methods, Fundamentals and Applications, John Wiley, New York, 1980, pp 225.Source Bard, A.J. Faulkner, L.R. Electrochemical Methods, Fundamentals and Applications, John Wiley, New York, 1980, pp 227.Multi Electron Transfer ProcessMulti-electron transfer process usually takes place in two separate steps. deuce-steps mechanism, each step characterized by its own electrochemical parameters is called EE mechanism.Stepwise reversible EE mechanism is given by following reaction,A + n1e B (E10) (2.22a)B + n2e C (E20) (2.22b)where, A and B are electroactive species and n1 and n2 are the number of electrons involved in successive steps. If A and B react at sufficiently separated potentials with A more easily reducible than B, the voltammogram for overall reduction of A to C consists of two separated waves. The first wave corresponds to the reduction of A to B with n1 electrons and in this potential range the substance B diffuses into the solution. As potential is scanned towards more cathodic values, a second wave show ups which is made up of two superimposed parts. The current related to substance A, which is still diffusing toward electrode increases since this species now is reduced directly to substance C by (n1+n2) electrons. In addition, substance B, which was the product of the first wave, can be reduced in this potential region and a portion of this material diffuses back towards the electrode and reacts.Each heterogeneous electron transfer step is associated with its own electrochemical parameters i.e. ks,hi and i, where i =1, 2 for the 1st and 2nd electron transfer respectively.Based on the value of Eo, we come across three different types of cases 50 as shown in the Fig. 2.6.Types of Two Electron Transfer Reactions 50 topic 1 Separate PeaksWhen Eo -150mV the EE mechanism is termed as disproportionate mechanism 55. Cyclic voltammogram consists of two typical one-electron reduction waves. The heterogeneous electron transfer reaction may simultaneously be accompanied by homogenous electron transfer reactions, which in multi-electron system leads todisproportionation. Each disproportionation reaction can be described as,2R1 O+ R2 (2.23)The equilibrium constant K (disproportionation constant) is given by(2.24)It can be derived from the difference between the standard potentials using (2.25)Case 2 In this case, the item-by-item waves merge into one broad distorted wave whose peak height and shape are no longer characteristics of a reversible wave. The wave is broadened similar to an irreversible wave, but can be distinguished from the irreversible voltammogram, in that the distorted wave does not shift on the potential axis as a function of the scan rate.Case 3 = 0mV Single peakIn this case, in cyclic voltammogram, only a single wave would appear with p eak current intermediate between those of a single step one electron and two electron transfer reactions and Ep-Ep/2 = 21 mV.Case 4 E1o If the energy required for the first second electron transfer is less than that for the first, one wave is observed having peak height equal to 23/2 times that of a single electron transfer process. In this case, Ep E1/2 = 14.25 mV. The effective E0 for the composite two electron wave is given by 50.Source Polcyn, D.S. Shain, I. J. Anal. Chem. 1966, 38, 370.Cyclic Voltammetric Methods for the Determination of Heterogeneous Electron Transfer Rate ConstantCyclic voltammetry provides a systematic approach to solution of diffusion problems and determination of different kinetic parameters including ks,h. Various methods are reported in literature to determine heterogeneous rate constants. Nicholson 41, 42, Gileadi 56 and Kochi 37 developed different equations to calculate heterogeneous electron transfer rate constants.Nicholsons Method 41, 42Nicholson derived an expression for determination of heterogeneous electron transfer rate constant ksh. This method is based on correlation between and ks,h through a dimensionless parameter by following equation,(2.26)where is scan rate.for different values of Ep can be obtained from the Table 2.3. Hence, if Ep (Epa-Epc) is determined from the voltammogram, can be cognize from Table 2.3. From the knowledge of, , ksh can be calculated using equation (2.27).If D o= DR then =1(2.27)This method is applied for voltammograms having peak dissolution in the range of 57mV to 250mV, and between this range, the electrode process progresses from reversible to irreversible. With increasing scan rate, the peak separation and hence decreases.It can be seen from the Table 2.3, that for reversible reactions i.e. for the current voltage curves and is independent of . For totally irreversible reaction i.e. for the back reaction becomes unimportant, anodic peak and is not observed. For quasi-reaction i.e. fo r 0. 001Separation of cathodic and anodic peak potential as a function of the kinetic parameter in the cyclic voltammogram at room temperature.Kochis MethodKochi and Klinger 37 formulated another correlation between the rate constant for heterogeneous electron transfer and peak separation.The expression for ksh given by Kochi was(2.28)The standard rate constant ksh can be calculated from the difference of peak potentials and the sweep rate directly. This equation applies only to sweep rates which are large enough to induce electrode irreversibility. The relation derived by Kochi is based on following expressions derived by Nicholson and Shain 41.(2.29a)(2.29b)where = 1- , and is the scan rate.Equations (2.29a) and (2.29b) yield(2.30)This expression is used for the determination of the transfer coefficient. Assuming that (for reversible reaction).We have,(2.31)Gileadis MethodGileadi 56 formulated a more civilise method for the determination of heterogeneous electron transfer rate constant, ks,h, using the idea of slender scan rate, c. This method can be used in the case where anodic peak is not observed.When reversible heterogeneous electron transfer process is studied at increasing scan rates, peak potential values also vary and process progresses towards irreversible. If are plotted against the logarithm of scan rates, a straight line at low scan rates and ascending curve at higher(prenominal) scan rate is obtained. Extrapolation of both curves intersects them at a point known as toe. This toe corresponds to the logarithm of sarcastic scan rate, c. as shown in Fig. 2.7. Hence critical scan rate can be calculated experimentally.ks,h can be calculated as,(2.32)where c is the critical scan rate, is a dimensionless parameter, called transfer coefficient and Do is the diffusion coefficient.Coupled Chemical ReactionsAlthough charge transfer processes are an important part of entire spectrum of chemical reactions, they seldom occur as isolated elementary step s. Electron transfer reactions coupled with new bond formation or bond breaking steps are very frequent. The occurrence of such chemical reactions, which directly affect the available surface concentration of the electroactive species, is common to redox processes of many important organic and inorganic compounds. Changes in the shape of the cyclic voltammogram resulting from the chemical competition for the electrochemical reactantor product, can be extremely useful for elucidating the reaction pathways and for providing reliable chemical information about reactive intermediates 35.It is convenient to classify the different possible reaction schemes in which homogeneous reactions are associated with the heterogeneous electrons transfer steps by using letters to signify the nature of the step. E represents an electron transfer at the electrode surface, and C represents a homogenous chemical reaction. While O and R usher oxidized and reduced forms of the electroactive species, other non electroactive species which result from the coupled chemical complication are indicated by W, Y, Z, etc 57. The order of C with respect to E then follows the chronological order in which the two events occur 58. So match to sequence of step, the systems are separate as EC, ECE, CE etc. These reactions are further classified on basis of reversibility. For example, subclasses of EC reactions can be distinguished depending on whether the reactions are reversible (r), quasi-reversible (q), or irreversible (i), for example Er Cr, ErCi, EqCi, etc.Two Steps Coupled Chemical ReactionsIn two steps reactions, a variety of possibilities exist, which include chemical reactions following or preceding a reversible or an irreversible electron transfer 59, 60, 61, 62. The chemical reactions themselves may be reversible or irreversible.a) Preceding Chemical Reactions (CE)In a preceding chemical reaction, the species O is the product resulting from a chemical reaction. Such a reaction influenc es the amount of O to be reduced so forward peak is perturbed. For a preceding chemical reaction, two mechanisms are possible, depending on whether the electron transfer is reversible CrEr or irreversible CrEi 58.Reversible Electrode Process Preceded by a Reversible Chemical Reaction(CrEr Reaction)The process in which a homogeneous chemical reaction precedes a reversible electron transfer is schematized as follows(2.33)where Y represents the non electroactive species and O and R are the electroactive congeners.Since the supply of electroactive species O results from the chemical reaction, it is important to know that how much of O is formed during the time scale of cyclic voltammogram. In this connection, it mustiness be noted that the time scale of voltammetry is measured by the parametera = nF/RT for a reversible processand b = naF/RT for a quasi reversible or an irreversible processIt means that the time scale of cyclic voltammetry is a function of the scan rate, in the sense th at higher the scan rate, the higher is the competition of the voltammetric intervention with respect to the rate of chemical complication.The limit at which the chemical complication can proceed is governed either by the equilibrium constant K or the kinetics of the homogeneous reaction (l = kf+kr). In this regard, it is convenient to distinguish three limiting cases depending on the rate of chemical complication 41. dense preceding chemical reaction (kf+kr When K is large (i.e. K 20) most of O testament already be present in solution, the response is plain not disturbed by the latter, i.e. it appears as a simple reversible electron transfer.When K is small, the small electron transfer again appears as a simple reversible process except that the peak current will be smaller than is expected on the basis of quantity of Y in the solution. This results because the concentration of the electroactive species CO, being determined by the equilibrium of the preceding reaction is equal to a fraction of species Y placed in the solution.where C* = CO (x,0) +CY(x,0) firm preceding chemical reaction (kf+kr nF/RT)When K is large, once again the response appears as a simple reversible electron transfer, but the measured standard potential Eo/* is shifted toward more negative values compared to the standard potential Eo/ of the couple O/ R by a factor of .When K is small, because of the fast continuous maintaining of the small equilibrium amount of O, the complete depletion of O at the electrode surface will never be reached, so that the forward profile no longer maintains the peak shape form, rather assumes a sigmoidal S-shaped curve, the height of which remains constant at all scan rates. intermediate preceding chemical reaction (kf+kr = nF/RT)In this case, the kinetics can be studied using the ratio between the kinetic and the diffusive currents according to the relationship(2.34)Irreversible Electrode Process Preceded by a Reversible Chemical Reaction(CrEi Reaction)Thi s process is schematizes as.(2.35)In this case, not only the thermodynamic K (kf / kr) and kinetic (kf + kr) parameters of preceding chemical reaction but also the kinetic parameters of the electron transfer (, k0) play a role. Obviously the lack of reverse peak is at a time apparent, due to the irreversibility of the charge transfer. The curves are also more drawn out because of the electron transfer coefficient, .Slow preceding chemical reaction (kf+kr In this case, the process appears as a simple irreversible electron transfer. The peak height of the process depends on the equilibrium constant because, as mentioned in the former case, the concentration of the active species CO is a fraction of the amount C* put in the solutionFast preceding chemical reaction (kf+kr nF/RT)If instead the reaction kinetics is fast, there are two possibilitiesIf K is large, again the response appears as if the preceding chemical reaction would be absent. However, the peak potential is shifted towa rds more negative values than those that would be recorded in the absence of the chemical complication by a factor equal to .If K is small, as in the preceding case, an easily recognizable S-like curve voltammogram is obtained having a limiting current independent from the scan rate(2.36)Intermediate preceding chemical reaction (kf+kr = nF/RT)Here again, the kinetics can be studied using the ratio between the kinetic and diffusive currents according to the relationship(2.37)b) by-line Chemical Reactions (EC)The process in which the primary product of an electron transfer becomes involved in a chemical reaction is indicated by EC mechanism. It can be represented byO + ne RR Z (2.38)where O and R are the electroactive congeners and Z represents the non electroactive species.Several situations are possible depending on the extent of electrochemical reversibility of the electron transfer and on the reversibility or irreversibility of the chemical reaction following the electron trans fer.As a general criterion, in cyclic voltammetry, the presence of a following reaction has little influence on the forward peak, whereas it has a considerable effect on the reverse peak.Reversible Electrode Process Followed by a Reversible Chemical Reaction(ErCr Reaction)ErCr mechanism can be written as(2.39)Once again the voltammetric response will differ to a greater or lesser extent with respect to a simple electron transfer depending on the values of either the equilibrium constant, K, or the kinetics of the chemical complication (kf+kr) 58.Analogously to that discussed for preceding equilibrium reactions, three limiting cases can be distinguished.Slow following chemical reaction (kf+kr If the rate of chemical reaction is low, it has a little effect on the process, thus reducing it a simple reversible electron transfer.Fast following chemical reaction (kf+kr nF/RT)If the rate of the chemical complication is high, the system will always be in equilibrium and the voltammogram wi ll apparently look like a non complicated reversible electron transfer. However, as a consequence of the continual partial removal of the species R from the electrode surface, the reduction occurs at potential values less negative than that of a simple electron transfer by an amount of .Due to the fast kinetics of the chemical complication, the potential will remain at this value regardless of the scan rate.Intermediate following chemical reaction (kf+kr=nF/RT)If the kinetics of the chemical reaction are intermediate with the scan rate the response gradually shifts from previous value for a fast chemical reaction which was more anodic by w.r.t. to value of the couple O/R towards the Eo/ value assuming more and more the values predicted by the relationship(2.40)In other words, the response (which for the fast kinetics is more anodic compared to E0/) due to the competitive effects of the potential scan rate moves towards more cathodic values by 30/n (mV) for every ten fold increase in the scan rate. However, it is noted that at the same time, the reversible peak tends to disappear, in that on increasing the scan rate, the species Z does not have time to restore R. This is demonstrated by the current ratio which is about one at low scan rates, but it tends to zero at high scan rates.Reversible Electrode Process Followed by an Irreversible Chemical R