PCII Praktikum Gruppe Fermn

Basics of Dynamic Electrochemistry

1.-Summary The present practical is devoted to illustrate the most basic techniques to evaluate the kinetics of electrochemical responses, namely cyclic voltammetry and impedance spectroscopy. The dynamic responses of the systems to be studied can be described in terms of the rate of electron transfer and mass transport to the electrode surface. The experiments will illustrate the complementarities of both techniques as well as the diagnostic criteria for determining the rate determining step in the electrochemical processes.

2.- The electrochemical system The present study will compare the behaviour of the redox couple

ferricyanide/ferrocyanide in aqueous solution employing Pt and carbon electrodes. The solution also contains Na2SO4 as supporting electrolyte.

3.- Instrumentation The experiments will be carried out in a -Autolab electrochemical system. A single compartment glass cell will be used, fitted with a Pt counter-electrode and a standard Calomel reference electrode.

4.- Laboratory and general structure of the session The lab session will be carried out at the lab 619 assisted by Ms. Evren Aslan. The session will start with a brief introduction on the theoretical aspects of cyclic voltammetry and electrochemical impedance. The introduction will be followed by an exercise for instrument calibration. The second day will be dedicated to the experimental work, while the third day will involve analysis of the results.

5.- Basic relationships for analysing Cyclic Voltammograms and Impedance Spectra This section provides a short introduction to the mathematical expressions for the analysis of the electrochemical responses at planar electrodes under semi-infinite diffusion conditions. For a thorough complete description of these electrochemical techniques, it is strongly recommended to consult textbooks available in the library [1,2]. 5a. Cyclic Voltammetry (CV). This technique is widely employed in many field of chemistry as it provides a simple access to the formal redox potential of electroactive species. Standard CV experiments consist of measuring the current flowing through the working electrode (WE) during a triangular potential perturbation. The applied potential is measured against the reference electrode (RE), while the counter-electrode (CE) closes the electrical circuit for the current to flow. The experiments are performed by a potentiostat that effectively controls the voltage between the RE and WE, while measuring the current through the CE (the WE is connected to the ground). In these experiments, the key parameters to fix are: 1.- The initial potential (EI): the applied potential when the circuit is closed. 2.- The first (E1) and second (E2) potentials vertex: the two limits potentials of the triangular cycle. 3.- The potential scan rate ( ): the rate of the potential sweep (units V s-1). Considering a reversible process, the characteristic CVs at various scan rates are exemplified in figure 1. In equilibrium (at open circuit), the potential of WE is determined by the Nernst equilibrium potential of the redox species,
* RT CO E=E + ln * nF CR '

(1)

where E ' is the formal redox potential, and C* corresponds to the bulk concentration of the oxidised (O) and reduced (R) species. Upon closing the potentiostatic circuit and the potential sweep is activated,
E ( t ) = EI t

(2)

40

20 i /A

5 mVs _1 10 mVs _1 20 mVs _1 40 mVs _1 60 mVs _1 80 mVs _1 100 mVs

_1

Ep E1/2 Ep/2

0 Ep/2 -20
-3

E1/2 Ep 0.0 0.2 E / V vs SCE 0.4

-40x10

figure 1. Cyclic voltammograms of the Ferri/ferrocyanide redox couple at various potential scan rate.

the concentration of the redox species at the electrode surface (C(0,t)) is altered, nF = f ( t ) = exp EI t E ' RT CR ( 0, t ) CO ( 0, t )

(3)

where the derivation of the parameter f(t) involves non-trivial mathematical developments. The corresponding derivations can be found in full in the recommended textbooks. In this section, we shall summarise the most useful expressions that can be derived for reversible and quasi-reversible electron transfer processes. It is important to realise that reversibility, in the electrochemical context, referred to as reactions controlled by the mass transport of the reactants to the electrode surface. In other words, the electron transfer takes place at a time scale shorter than the acquisition time for a given measurement. In this case, the characteristic peak current (ip) in the CV is given by:

F3 ip = 0.4462 RT

12 1 * n3 2 ADO 2CO 1 2

(4)

where A is the area of the electrode surface and D is the diffusion coefficient. At 25C, A in cm2, D in cm2/s, C in mol/cm3 and in V/s, ip in amperes is simplified to:
1 * ip = 2.69 105 n3 2 ADO 2CO 1 2

(5)

An interesting consequence of eq. (5) is that the peak current is directly proportional to the square root of the scan rate. A plot of ip vs 0.5 will then give a straight line with a zero intercept and a slope proportional to the diffusion coefficient of the reactant. Under the same conditions, the difference between the half-peak (Ep/2) and peak (Ep) potentials is determined by:
Ep Ep 2 = 2.20 RT = 56.5 n mV nF (6)

Although eq. (6) provides a useful criterion for determining whether the electrochemical reaction is reversible, the important potential to be determined is the half-wave potential (E1/2), Ep = E1 2 1.109 RT = E1 2 28.5 n mV nF (7)

This potential is related to E ' by the expression: RT DR E1 2 = E + ln nF DO

'

12

(8)

Expressions (4) to (8) allow determining the diffusion coefficients of the redox species and the formal redox potential for reversible processes, providing that CVs are measured at several scan rates. In the case that the rate of electron transfer is finite (quasi-reversible reactions), the previous expressions are not readily applicable. In particular, slow electron transfer processes induce a separation between the peaks of oxidation and reduction in the voltammogram. The dependence of the peak-to-peak separation on the scan rate can be used for determining the rate constant of electron transfer. However, the presence of a finite resistance between RE and WE can also produce the same effect and can lead to erroneous interpretation of the voltammograms. In such cases, impedance spectroscopy provides direct access to the various parameters affecting the dynamic electrochemical responses.

5b. Electrochemical Impedance Spectroscopy (EIS). This technique provides a powerful approach to kinetic responses at electrode surfaces. However, as most electrochemical technique, EIS is rather non-specific to the nature of the electrochemical response. From this point of view, EIS requires prior knowledge of the mechanism of the electrochemical reaction in order to be fully and unambiguously interpreted. The same argument is applicable to CV and other techniques based on current-voltage measurements (electrons are not different if they come from one species or another). In a broad sense, the term impedance is used for the ratio between of an intensive over an extensive function. The opposite of this ratio is known as admittance, while the ratio between two intensive parameters (or between two extensive one) is defined as a gain. Obviously, in electrochemistry the intensive and the extensive quantities are voltage and current respectively. The term spectroscopy arises as the measurements are performed as function of the frequency of a periodical perturbation. The most common, type of perturbation is a sinusoidal voltage with relative small amplitude (e.g. 10 mV rms). The use of small amplitude of perturbation allows the linearization of the current potential relationships in electrochemical systems. This will become clearer after a quick revision of the characteristic impedance of linear elements such as resistors and capacitors. Let assume a sinusoidal potential perturbation of the type: E = E sin(t ) E E sin (t ) = R R (9)

applied to a resistor R. The ac-current flowing to the resistor will be given by i= (10)

consequently, the current response is in-phase with the ac voltage perturbation. In the oscilloscope, the results of the experiment will be as in figure 2a. If the experiment is performed with an ideal capacitor, the situation is different as the voltage is proportional to the charge ( q = CE ),
i = C E d ( sin (t ) ) = C E cos (t ) = E sin t + (11) 2 dt XC

Signal

Signal

(a)
an ideal resistor (a) and an ideal capacitor (b)

(b)

Figure 2. AC current responses generated by sinusoidal potential perturbation to

1

where the term X C = (C )

is commonly referred to as the capacitive reactance. As

displayed in figure 2b, the current response for an ideal capacitor is 90 out-of-phase with respect to the voltage perturbation. This phenomenon expands the responses into a complex plane, where the 90 out-of-phase (or imaginary) component is assigned to the ordinate and the in-phase (or real) component to the abscissa. In the case of a resistance and a capacitor in series, the impedance Z corresponds to:
E = ER + EC = i ( R jX c ) = iZ

(12)

consequently, the impedance is a complex quantity graphically represented by figure 3.

R Z

j Xc
Figure 3. Complex notation of the electrical impedance response of a system at a

given frequency. The angle indicates the phase shift between the current and the ac-voltage.

Let us consider how the evolution of the impedance as the frequency is varied for a series and parallel connection of resistance and capacitance. In figure 4a-b, the amplitude and phase shift of the impedance as a function of the frequency of modulation for typical equivalent circuits are displayed. This representation is commonly referred to as Bode

plots. The complex representations of the frequency response analysis based on the phasor notation are shown in figures 4c-d. This representation (also known as Nyquist plot) is rather useful as parallel RC combinations are clearly identified by a semicircle. In electrochemical systems, parallel RC combinations are generally associated with time constants of processes (e.g. rate constant of electron transfer). However, as opposed to the Bode plots, the frequency of the potential modulation is not actively included in the representation. Consequently, both representations are highly complementary. Electrochemical systems are not composed of ideal resistance and capacitors, but more physical entities that are highly non-linear. A detailed study of the structure of electrochemical systems is beyond the scope of this practical and basic descriptions must be consulted in textbooks. Here, we shall briefly mention that the interfacial region between the electrode surface and the electrolyte is composed of an electrical double layer, which is formed by the organisation of the ions in the electrolyte and the charges at the electrode. In the simplified model sketched in figure 5, the charges at electrode surface are screened by ions located at the outer-Helmholtz layer, defined as the plane of closest approach for the solvated ions. At high concentrations of the electrolyte, the impedance associated with the double layer can be modelled as a capacitor of parallel plates Cd. In addition, there is always a finite resistance between the working and reference electrodes often called uncompensated resistance element (Ru). In the absence of redox species, the impedance of the electrochemical cell is described by the series combination of the uncompensated resistance and the double layer capacitance. In this case, the impedance response approached the behaviour shown in figs.
4a-c.

In the case of quasi-reversible electron transfer reactions, two other impedance elements should be considered. The first element is associated with the kinetics of electron transfer, which can be represented in terms of the so-called charge transfer resistance. From a phenomenological point of view, the current exhibits an exponential dependence on the applied potential near the potential of equilibrium as indicated by the Butler-Volmer equation. However, as the EIS experiments introduce small amplitude of potential perturbation, the exponential dependence of the current response can be expanded in a Taylor series, and the first harmonic provide a linear relationship between

current and voltage. The charge transfer resistance is associated in parallel to the double layer capacitance. Consequently, if the electron transfer is the rate determining step of the electrochemical response, then the impedance spectra will describe a semicircle as in case d in figure 4.

C = 106 F
R = 1000
10
6

R1 = 100

C = 106 F

R2 = 2000
2

a
10
5

80 1000

60 50

|Z|

|Z|

60

7 6 5 4 3

40 30 20

40 10
4

|Z|
10
3

20

|Z|
0
-1

10 0
3 5

10

10

10

10

100 -1 10

10

10

10

Log f
2000

Log f
c
2000

1500

-Zim/

1000

-Zim/

1500

max = 1 R2C

1000

500

500

R1
500

R1 + R2
1000 1500 2000

0 0

500

1000

1500

2000

0 0

Zre/
Figure 4. Impedance spectra of linear circuit elements

Zre/

Inner Helmholtz plane Metal Plane Outer Helmholtz Plane

Solvated Anions

Figure 5. Simplified representation of the electrical double layer, defining the

position of the inner and outer Helmholtz planes.

In the case that the concentration of the reactant is consumed at the surface, the electrochemical process will be controlled by the mass transport of the redox species. In the case of planar diffusion geometry (large electrodes in the absence of mechanic stirring), the mass transport will generate an extra impedance response commonly referred to as the Warburg impedance. Finally, the faradaic impedance (Zf) is determined by the series connection of the charge transfer resistance Rct and the Warburg impedance (ZW),
Z f = Z ct + Z W = Rct +

+ j

(13)

where ZW is an element 45 out-of-phase with respect to the potential modulation. This amplitude of this element is given b,

Z W = +
2

1 22

(14)

where the parameter is dependent on the bulk concentration and the diffusion coefficients of the redox species:

1 1 + 1 * * F 2 A 2 DO 2CO D1 2CR R RT

(15)

The equivalent circuit including the contribution of elements mentioned so far, namely Ru, Cd and and Rct, is depicted in figure 6. In this circuit, the faradaic impedance composed of Rct and the Warburg elements is arranged in parallel to the double layer capacitance. The characteristic responses for this circuit are illustrated in figure 7 for different values of Rct. It can be seen at low frequencies that the dominant element is Warburg component as the complex impedance exhibits a straight line with 45 phase shift. As the frequency is increased, and for high values of Rct, a semicircle is observed indicating that the electron transfer is the dominant component. It is also shown that for reversible electron transfer, i.e. Rct ~ 0, only the Warburg element contributes to the impedance spectrum. This figure exemplified the power of this technique for selectively addressing the kinetics of the various processes by tuning the frequency of modulation.

Eq. 12

Ru

Eq. 17

Eqs. 14-15

Figure 6. Randles equivalent circuit commonly employed for describing

electrochemical responses for processes controlled by the planar diffusion of the redox species and the rate of electron transfer.

10

1000

9 8 7 6 5 4 3

Rct
400 200

Log |Z|

20
100 -1 10 50 40 30 20 10
1

10

10

Rct

400

200
10

20
0 -1 10 10
1

10

10

Log f
300

Rct
200 20

-Zim/

200 100 0 0

400

100

200

300

400

500

600

Zre/
Figure 6. Bode and Nyquist plots of the Randles equivalent circuit for various

charge transfer resistance. The concentration and diffusion coefficient of the reduced and oxidised species were taken as 10-3 mol dm-3 and 10-6 cm2 s-1 respectively.

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6. Experimental Section.

The experiments to be performed in this practical will allow studying the electrochemical kinetics involving the redox couple ferricyanide/ferrocyanide employing Pt and C electrodes. The kinetics will be investigated by CV and EIS. The first part will be devoted to test calibration of the potentiostat. 6a. Calibration of the impedance responses. Connect the calibrated resistance and capacitors in the various configurations in figure 5 and run the FRA routine of the potentiostat (consult the assistant). The WE will be connected to Ru, while RE and CE will be connected to the other side of the equivalent circuit. The frequency limits will be set between 0.1hz and 50 khz, while the amplitude should be fixed to 10 mV rms. Examine the Nyquist and other representation of the impedance and fit the experimental results to the appropriate equivalent circuits. Details of the fitting routines will be given by the assistant. Verify that the values provide by the fitting are in agreements with the values of the calibrating elements. 6b. Preparation of the solutions and electrodes. The electrolyte solution will contain 1 mM of K4(Fe(CN)6) and 1mM of K3(Fe(CN)6), as well as 100 mM Na2SO4. The solutions
must be prepared with ultrapure milliQ water. Details of the preparation of the working

electrodes will be provided by the assistant. 6c. Cyclic voltammetry. Assemble the electrochemical cell starting with the Pt WE. The RE electrode should be handled carefully and rinsed with purified water before put in and taken out of the electrolyte. Introduce a solution of the supporting electrolyte, in the absence of the redox couple and purge it with N2 for 15 min. In the meantime, run the GPES programme and set the experimental parameters for the CV measurements: EI= 0.18 V E1= 1.2 V E2= -0.75 V = 0.1 V/s After purging the electrolyte, run CVs with varying from 10 mV to 200 mV/s. Examine the main features of the CVs. Replace the Pt WE by the C WE and repeat the same routines.

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Replace the electrolyte and introduce the solution containing ferri/ferrocyanide. Repeat the voltammetric experiments with both WE electrodes using the following parameters: EI= 0.18 V E1= 0.45 V E2= -0.10 V = 0.1 V/s Compare both set of data. Identify which for which electrode a reversible electron transfer is observed. In this case, estimate the equilibrium potential. 6d. Electrochemical Impedance Spectra. Close the GPES programme and run the FRA one. Set the frequency range from 13 khz to 0.13 hz, and the 10 mV amplitude. The dc potential is set initially at the equilibrium potential and run the frequency sweep. Measure the impedance spectra at various dc potentials in a range of 120 mV around the equilibrium potential. Collect the impedance spectra for both WEs.

7. Analysis of the results and reporting.

The CVs and the EIS spectra will be analysed with the provided software. In the case of the CVs, a discussion should be presented including:
Q1.- Is the electron transfer is reversible or quasi-reversible, on the basis of the relations

described in figure 5a? Is the same behaviour observed for both electrodes?
Q2.- Estimate the diffusion coefficients of the reduced and oxidised species from the

peak current dependence on scan rate.

Q3.- Estimate the Formal electron transfer E of the redox couple. Q4.- Is the redox process taking place at a Pt or at a PtOx surface?

The impedance spectra should be fitted to the appropriate equivalent circuit at

E. The capacitance of the double layer is introduced as a Constant Phase Elements

(CPE). The general expression of CPE is:

Z CPE =

( j K )

(16)

where the parameters K and are adjustable. In the case of an ideal capacitor, = 1, and the parameter K is equal to the capacitance. Depending of the structure and chemical

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properties of the double layer, the impedance responses may not fit to the ideal capacitor limit and will adopt values smaller than 1. In the current experiment, the fits of the impedance data should provide values higher > 0.9.
Q5.- Estimate the initial value for from the diffusion coefficients (step b) and the

concentration of the redox species.

Q6.- Fit the impedance data to the Randles equivalent circuit at the formal transfer

potential, taking as initial parameters the Ru = 10 , Cd = 10-6 F, =1 (double layer), W= and Rct = 500 . Verify the quality of the fit for both electrodes.
Q7.- Estimate the value of the phenomenological electron transfer rate constant (k0) at the

formal transfer potential using the Rct value obtained from the fits. The relationship between Rct and the apparent rate constant of electron transfer (k0) is given by,
Rct = RT RT = 2 nFi0 nF Ak 0C

(17)

where i0 is the exchange current and C is the concentration of the redox species (eq. (17)
* * is strictly valid only when CO = CR ). Report the rate constants for both electrodes.

Q8. Simulate the voltammetric responses employing the Nicholson-Shain formalism. The

GPES software can simulate the voltammetry data and compare it to the experimental one. For the simulation, the normalised electron transfer rate constant (ks) should be calculated,
ks = k 0 RT nF D

(18)

where is the scan rate in V s-1. The coefficient will be taken as 1.

Q9.- Is the ferri/ferrocyanide couple fully reversible for both electrodes. The Pt

electrode shows a reversible behaviour in the voltammograms as concluded from the analysis in steps a-d. However, the impedance data provided a quasi-reversible behaviour. Are these two measurements compatible?

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8. Reference.

1.- A.J. Bard and L.R. Faulkner, Electrochemical Methods Fundamental and Applications. 2nd Edition, John Wiley & Sons, 2001, Chapters 6 and 10. 2.- C.M.A. Brett and A.M.O. Oliveira Brett, Electrochemistry, Oxford Science Publications, ISBN 0-471-05542-5

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