Experiment 7: Study the Nature of the Cyclic Voltammogram for a One Electron

Transfer [FeIII(CN)6]3-/[FeII(CN)6]4- System and Calculation of the Formal Potential

and Diffusion Coefficient of the Ion for the Given System

Theory: A simple potential wave form that is often used in electrochemical experiments is the
linear wave form i.e., the potential is changing continuously as a linear function of time. The rate
of change of potential with time is called the scan rate (ν). The simplest technique that uses the
wave form is linear sweep voltammetry (LSV). The potential range is scanned in one direction,
starting at the initial potential and ending at the final potential. A more commonly used variation
of this technique is Cyclic Voltammetry (CV) in which the direction of the potential is reversed at
the end of the first scan (see Figure 1). Thus, the wave form is usually in the form of an
isosceles triangle. This has an advantage that the product of the electron transfer reaction that
occurred in the forward direction can be probed again in the reverse direction. Hence, CV is a
non-destructive technique. In addition, it is a powerful technique for the determination of the
formal redox potential, determination of chemical reactions that proceed or follow the
electrochemical pathway and evaluation of electron transfer kinetics.

Figure 1: Cyclic potential sweep in cyclic voltammetry (CV). Different isosceles triangles show
different scan rates for CV. Blue and green triangle represent slow and fast scan rate
respectively.

In this experiment, the basics of CV will be illustrated by looking at the one electron ox idation of
ferrocyanide to ferricyanide and vice versa. This redox couple exhibits nearly a reversible
electrode reaction without any complications of proceeding or post chemical reactions. Thus,
ferricyanide/ferrocyanide couple has been a popular choice through the years to use as a standard
to demonstrate CV. The waveform of the voltage applied to a working electrode in CV is a triangular
shaped (i.e., theforward and reverse scan, Figure 1). Since this voltage varies linearly with time,
the scan rate is the slope (V/s).

For a reversible electron transfer reaction where redox species are dissolved in solution, the
peak current (Ip ), is governed by the Randle-Sevcik equation
I = 2.69 x 105x n3/2 x A x D1/2 x c x v1/2 (1)
p

where n, A, D, C, are the number of electrons transferred, area of the electrode in cm2, diffusion
coefficient in cm2/s, concentration in mole/cm3, and scan rate of voltammetry in V/s. Hence, a
plot of Ip vs (ν)1/2, can provide the diffusion coefficient for the dissolved redox species provided
n, A, and C are known.
According to the Nernst equation, formal potential is the potential where the concentration of
the oxidized and reduced species is same under an equilibrium condition. Formal potential can
be determined by taking the average of peak
potential for cathodic and anodic peak potential (Eq. 2).

Eo'= (E p,a + E p,c )/2 (2)

Equipment:

• Potentiostat
• Electrochemical cell and electrodes
• Platinum working electrode
• Pt counter electrode
• Ag/AgCl reference electrode
• Volumetric flasks (100 mL)
• Pipette (10 mL)
• Beaker (100 mL)
• Dropper

Chemicals:

5mM K 3[Fe(CN) 6] and 5 mM K 4[Fe(CN) 6] in 100 ml of 1.0 M KCl.

Procedure

(i) Prepare 100 mL of (5 mM K3[Fe(CN)6] + 5 mM K4 [Fe(CN)6) in 1.0 M KCl solution.

(ii) Take the solution in an electrochemical cell.

(iii) Wash the all electrodes with deionized water and dry it using Kimwipe or tissue paper.

(iv) Dip three electrodes in the solution.

(v) Connect the three electrodes with potentiostat. (Green: Working, Red: Counter and White
Reference)

(vi) Turn on the potentiostat. Click on CH instrument software on the desktop.

(vii) Click on “setup” and then “Hardware test”.

(viii) Software should show “ok” for all the parameters. If any error is displayed, contact
lab instructor immediately.

(ix) If the instrument anytime shows “Link Failed”, close the software, then restart the software
and try again.

(x) Click on “Set up” and then “system”. Do not change Communication port (Com 3).

(xi) Choose Line Frequency “60 Hz”, Potential Axis “positive right”, Current axis “positive up”,
Current polarity “Anodic Positive”.

(xii) Click on “Set up” and then “Parameters”.

 (xiii) Choose potential Range (-0.2 V to + 0.6 V). Potential range can be increased if complete
CV is not displayed. ( Increasing potential window on negative side is not recommended since
oxygen reduction start to occur at that potential).

(xiv) Choose initial scan polarity “positive”, Sweep segment “2”, Sample interval “0.001 V”,
quite time “2 sec”, sensitivity “1e-005”. If current overflows then increase the sensitivity.

(xv) Now set the scan rate as 0.01 V/s and click on run to obtain the cyclic voltammogram.

(xvi) Click on data to get the values of Ep,a and Ep,c and ic and ia. Write down these values in your
lab note book in Table 1.

(xvii) Now save your data in D drive in CHM 426-22. Create a sub folder with your roll number/
group number. Each data should be saved in “.bin” and “.csv” format. “.csv” format data later
can be plotted in Origin.

(xviii) Now repeat steps (xv - xvii) with scan rates of 0.02, 0 .0 3 , 0.04, 0.05, 0.06, 0.08, V/s

(xix) Do not forget to save the data after each scan.

(xx) Discard the solution and take 1 M KCl in the electrochemical cell.

(xxi) Dip the three electrodes in KCl solution and obtain background peak current (i c and ia) at
each of the above scan rates and record in table 2

TABLE 1:
Segment 1 Segment 2
Scan rate Ep,a (V) Ip (A) Ep (V) Ip (A)
(V/s)
0.01
0.02
0.03
0.04
0.05
0.06
0.08

Calculations:
(i) Determination of Formal potential:
Formal potential of the following reaction can be determined by taking the average of peak
potential for anodic and cathodic reaction (Eq. 2) preferably at the slowest scan rate.

(ii) Determination of the diffusion coefficient:

Plot peak current obtained after background subtraction versus (scan rate)1/2 The plot should pass
through origin according to eq. 1. From the slope, determine diffusion coefficient for K3[Fe(CN)6]/
K4[Fe(CN)6] couple since other parameters are known. Compare the calculated diffusion coefficient
with literature value.

Note- Radius of Pt working electrode is 0.1 cm.