Cyclic Voltammetry using a LabVIEW-based Acquisition System

(Feb. 06, 2004 revision)

Supported by an Academic Partnership grant from National Instruments, Inc. Introduction Cyclic voltammetry is an attractive method for teaching a number of concepts in electrochemistry. Students usually come to the study of this technique with some familiarity with potentiometric measurements using pairs of chemical electrodes. Such measurements might be described as passive electrochemical analyses because the voltage of the system simply responds to changes in the concentration of one or more analyte, e.g. H+ in the case of a pH probe. Electrolysis, cyclic voltammetry, amperometry and several other techniques might be described as active electrochemical methods because the experimenter drives an electrochemical reaction by incorporating the chemistry into a circuit and then controlling the reaction by circuit parameters such as voltage.

6 4

current signal

2 0 -2 -4 -6 -8 -0.2

oxidation peak

finish start reduction peak

0.0

0.2

0.4

0.6

0.8

cycle voltage
Figure 1. A typical cyclic voltammogram showing reduction and oxidation current peaks.

In typical cyclic voltammetry, a solution component is electrolyzed (oxidized or reduced) by placing the solution in contact with an electrode surface, and then making that surface sufficiently positive or negative in voltage to force electron transfer. In simple cases, the surface is started at a particular voltage with respect to a reference half-cell such as calomel or Ag/AgCl, the electrode voltage is changed to a higher or lower voltage at a linear rate, and finally, the voltage is changed back to the original value at the same linear rate. When the surface becomes sufficiently negative or positive, a solution species may gain electrons from the surface or transfer electrons to the surface. This results in a measurable current in the electrode circuitry. However, if the solution is not mixed, the concentration of transferring species near the surface drops, and the electrolysis current then falls off. When the voltage cycle is reversed, it is often the case that electron transfer between electrode and chemical species will also be reversed, leading to an inverse current peak. These features are illustrated in Figure 1. A discussion of electrochemical concepts and chemical applications may be found for cyclic voltammetry in standard analytical chemistry texts. There are also a number of excellent teaching journal sources, illustrated by references (1-4). Principles and concepts illustrated by the results may include: 1) quantitation of concentrations; 2) diffusion effects; 3) irreversibility; 4) study of reaction intermediates; 5) identification of electron transfer steps; and 6) relationships to the Nernst equation. The focus of this module is on the use of LabVIEW software to control the driving voltage cycle and to measure the current responses. Earlier versions of these ideas are presented in references (5,6). The voltage cycle is defined by four parameters: the maximum and minimum voltages, the starting voltage, and the initial direction of scan (to more + or to more voltage values). The cycle consists of 1000 voltage steps, and the fastest scan rate is set by the time required for the output of these 1000 values and input of 1000 current readings. There is no screen updating during a scan since that might significantly slow some computer systems. A three-electrode system design is an essential feature of all cyclic voltammetry systems, and this is incorporated in the present experiment. One of the electrodes is a reference electrode, and the three-electrode design locks the voltage of an auxiliary electrode, e.g. Pt, to the reference electrode using a voltage follower circuit. Most of the actual current flow is between the auxiliary and working electrodes, leaving the reference electrode essentially unchanged. Experimental Circuit construction Cyclic voltammetry requires two simple operational amplifier (op amp) circuits. We employ inexpensive and robust 741 op amp chips available from any electronic supply house. The circuits described below are meant to introduce some basic op amp principles, and therefore are not designed to minimize electronic noise, to provide a large variable range for the current response signal, or to provide unusually fast response times. A pin diagram of the 741 chip is shown below (7).

Figure 2. Top view of a 741 operational amplifier chip. The pins are numbered 1 8 as indicated. Unlabeled inputs are not used in this application. Figure 3 shows the two op amp circuits required for the cyclic voltammetry experiment. The standard triangle notation for each op amp has connections corresponding to the pins 2, 3 (inputs) and 6 (output) of Figure 2. A 15 V power supply, not shown in Figure 3, must supply 15 V to pin 4 and +15 V to pin 7 on each 741 chip. The top circuit has the 741 output pin (6) connected directly back to the input pin (2). This direct feedback circuit is called a voltage follower circuit1. The purpose is to insure that the voltage difference between the working electrode, also wired to the op amp output, and the reference elctrode is exactly the same as the computer-controlled output voltage, independent of IR changes in the cyclic voltammetry system as currents ebb and flow. Very little current is actually drawn from the

Figure 3. Cyclic voltammetry circuit layout. AE, RE and WE refer to the auxiliary, reference and working electrodes. Op amp 1: voltage follower circuit: output (pin 6 of Fig. 2) goes to the auxiliary electrode, e.g. Pt. + and inputs correspond to pins 3 and 2 of Fig. 2 Op amp 2: current-to-voltage converter: R = 51 kohms, C = 47 pf. The voltmeters are recommended options for checking that the driving voltage between the reference and working electrodes is correct, and that the voltage output from op amp 2 is not too large.

reference electrode wired to the + input of the op amp, so this reference voltage remains very stable. It is important to note the magnitude of the voltage follower output is identical with the input, but the sign is reversed. The computer program takes this into account in setting up the driving voltage cycle for the experiments. The second op amp circuit of Figure 3 has a resistor/capacitor combination wired between op amp input and output. This arrangement is called a current-to-voltage converter because the output voltage of the op amp, also wired to a computer input channel, is proportional to the current between the working and auxiliary electrodes. Both of the op amp circuits in Figure 3 are widely employed in solid-state electronic circuitry. The op amp circuits may be assembled on a breadboard with mechanical connections, such as the Radio Shack Experimenter Socket, PN 276-175, but the current response signals are often quite noisy as a result. It is strongly recommended that components in the op amp circuits be soldered to a standard 8-hole mounting base for the 741 chips. These chips can then be readily replaced if needed. Our soldered unit consists of a small Radio Shack breadboard inside a 2" x 3" Radio Shack project box. The box has eight banana jack posts for the external connections to the electrodes and computer IO ports via alligator clip wires. We also recommend using voltmeters across the output and input ports to monitor the behavior of the system. Electrodes and other equipment A glassy carbon electrode is a good choice for the working electrode. We purchased this, along with a special calomel reference electrode, from Bioanalytical Systems, Inc. The working electrode surface often requires careful prior polishing with a very fine pad, also available from Bioanalytical Systems, for good results. The special calomel electrode has a porous quartz connector between electrode and the solution to be studied. The electrical resistance of this junction is lower than that of many standard reference electrodes used, for example, in pH measurements. Higher reference electrode resistances interfere with the correct operation of the 741 chip in our experience. We store the calomel upright in a saturated KCl solution in a small dessicator to avoid problems with a dried-out junction. Any reasonable Pt electrode will serve as the auxiliary electrode. Chemical systems About 20 mL of solution are required for the measurements described in this module. We first present a simple system which is widely used to teach cyclic voltammetry principles and to check on the operation of the equipment. This involves the reduction of Fe(III) in potassium ferricyanide, K3Fe(CN)6 as the drive voltage makes the working electrode more and more negative, followed by the re-oxidation of Fe(II) to Fe(III) in the cyanide complex as the voltage is returned to its starting value. reduction: [Fe(CN)6 ]3- + e- [Fe(CN)6 ]4-

oxidation: [Fe(CN)6 ]4- [Fe(CN)6 ]3- + e-

The potassium ferricyanide2 is prepared by dissolving a carefully weighed sample of the crystalline material in 100 mL of stock 1.0 M potassium nitrate. Typical results are shown in the following figure (and in Figure 1):

Figure 4. Cyclic voltammogram for the reduction of 0.010 M potassium ferricyanide K3Fe(CN)6 in 1.0 M KNO3 as a supporting electrolyte. The voltage profile on the left is the actual computer output. This voltage is then inverted by the voltage follower circuit. The scan shown on the right begins at 0.8 V, and the red part of the cycle shows a reduction peak as the drive voltage applied to the system reaches about 0.18 V. As the voltage returns from the minimum of 0.20 volts, the iron species is reoxidized when the blue upper curve reaches about 0.27 V. Computer and IO hardware The results presented here were obtained using LabVIEW 5.1 running on a 400 MHz Pentium II system with 128Mb RAM. Signals are acquired using a National Instruments PCI 6024E IO board. The Type SH6868 connector cable links the IO board to a CB-68LP connector block inside a Radio Shack 20 cm x 11 cm x 6 cm project box. Banana jacks on the box are wired to three input and two output channels on the connector. It is often useful to monitor the output and signal voltages at the IO jacks with standard digital voltmeters. Since the signals into the IO board are floating with respect to ground, we wire all inputs in the differential mode recommended by the manufacturer, using 1M resistors in the bias current return path between the + and signal lines and analog ground. (9)

The maximum input voltage rating for the 6024E IO board is +/- 45 V and is unlikely to be exceeded even if the circuits of Figure 2 malfunction. The most common problem we have

encountered is a bad connection to or within one of the electrodes, resulting in output voltages as high as +/- 14 V, close to the power supply values. The possibility of excessive voltages is an excellent reason for monitoring the actual current-to-voltage output with a voltmeter! The IO board has 10 bit resolution, meaning that if the output voltage range is 1V, the output steps can be as small as 1 mV. This practical lower limit is what drives the choice of a 1000 step voltage loop. Finally, it should be noted that the vertical scale of the voltammograms is in volts. The voltage from the current-to-voltage converter is a function of the feedback resistor and capacitor in Figure 2. The program can be easily altered to include this conversion, given by: V = iR feedback For the system described here, the typical R value is 51 K so that 1 V corresponds to about 20 A.
Software The LabVIEW program runs the voltage ramps (one output channel) and collects the resulting current response of the system using a current-to-voltage op amp circuit (one input channel). The pairs of output voltages and response signals are stored in spreadsheet format for more sophisticated analysis. The front panel of the CV virtual instrument permits the user to select starting voltage, the voltage range, and the direction of ramp scan. When the program is operated, the output channel moves to the initial voltage and holds that for a selectable time so that initial capacitance effects can die out. The panel also displays the voltage ramp profile and the final cyclic voltammogram. Since the scan direction and corresponding current response are not always obvious in the final presentation, we display the first and second halves of the scan in different colors.

The most important part of the program is the creation of the voltage ramp. For simple experiments, it is common to start at a either a high voltage or a low voltage, ramp the voltage to the other limit, and then return to the original value. This was illustrated in the example of Figure 4. In more complex examples, one may wish to start at any point in the cycle and run the cycle in either direction. We accomplish this in LabVIEW by first creating an array of 1000 values which start at the high voltage limit, descend in 500 equal steps to the low limit, and then return in 500 equal steps to the upper limit. If an intermediate starting voltage is selected, the two array positions closest to this value are easily selected. The position in the descending voltage sequence is the appropriate position for an initial "- scan" and the position in the ascending sequence would be the starting point for an initial "+ scan". A panel "+ scan" or "scan" logic switch is used to make the correct choice of initial position. The original array is then split into two arrays of unequal size at the reference position. For the "- scan", these arrays are simply swapped and then recombined into the final voltage ramp array. For the "+ scan", the larger array must be reversed, and then the two arrays are again swapped and recombined. The elements of the final rearranged voltage value array are now used in a 1000-step loop to create the voltage cycle. The time duration of each loop is set by the desired overall time for the cycle scan, also selectable on the front panel. (Note that there is a lower limit set by the inherent time required for each loop we do not plot the final cycle during a run in order to minimize loop cycle time). Each step in the loop creates a new output voltage defined by the voltage array element. The response current is also measured in each step. The ramp voltage array and the

response current array provide the "x" and "y" coordinates for the cyclic voltammogram. The initial array creation, the array rearrangements, and the final loop for running the cycle are shown in the following two diagrams:

Figure 5. This part of the program divides the voltage range into 500 incremental steps and then creates a 501 pt. array of these voltages using the loop structure. The original output array is also inverted. The original and inverted arrays are then combined to produce a 1000-point voltage array for the cycle. The high, low and starting voltages are also used to locate the array positions for the start of the voltage cycle. One position corresponds to an initial voltage scan in the + direction, and the other to an initial scan in the direction.

Figure 6. This step in the program brings in the original 1000 pt. voltage array and uses the starting voltage index to split and rearrange the array into the final array of output voltage values. The splitting position appropriate for up or down initial scans is selected by the True/False case structure.

Figures 5 and 6 are the first two of six LabVIEW sequence steps. Subsequent steps use LabVIEW AO ONE PT and AI ONE PT routines to set the initial voltage in the cycle, hold that voltage for a selectable number of seconds, and then start the voltage scan, reading the response current signal just before each new voltage step. This produces a 1000-point array of current response values. Finally, the voltage cycle array and the current response array are used to plot the cyclic voltammogram on the Panel of the computer screen, and are then stored in spreadsheet format for possible later analysis.
Additional illustrations 1. The oxidation of ascorbic acid. May organic molecules are electrochemically reactive, and there are often quite interesting differences in redox reversibility, stability of reduced and oxidized forms, and pH effects. (3,4). Ascorbic acid (Vitamin C) is one such example.

O HO

CH2OH OH

O O

CH2OH OH
+ + 2H + 2e

OH

Ascorbic Acid

Dehydroascorbic Acid

The following portion of a LabVIEW panel shows the voltammogram of 6 mM ascorbic acid in a 1M KNO3 matrix. It is well known that ascorbic acid (Vitamin C) can be easily oxidized, and in this experiment, the scan starts at 0.00 V (red) and the working electrode voltage is then increased to +0.80 V. A strong maximum at 0.35 V relative to SCE) indicates oxidation to dehydroascorbic acid. There the very weak peak at about 0.18 V on the blue curve shows may be due to the instability of dehydroascorbic acid (it might decompose before the reduction cycle can convert it back). It may also be due to slow kinetics of the reverse half-reaction at this pH, particularly since a source of H+ is required.

Figure 7. Cyclic voltammogram of 6 mM ascorbic acid in a 1.0 M KNO3 matrix. The scan cycle time is 30 seconds, and the reference electrode is SCE. The red curve shows the first half of the scan, from 0.00 V up to 0.80 V and back to 0.50 V. The blue curve shows the second half of the cycle. This CV takes advantage of all of the start/range/direction scanning features of this LabVIEW program.

2. The reduction of methylene blue (MB). This intensely blue compound is easily reduced to colorless leucomethylene blue.
H N (H3C)2N S + 2H + 2e N(CH3)2
+ -

N (H3C)2N S NH(CH3)2

Methylene Blue (blue)

Leucomethylene Blue (colorless)

Leucomethylene blue can also be re-oxidized by dissolved oxygen. The system has been widely studied and is the subject of several blue bottle lecture demonstration/exploration studies (1012). Solutions of this dye are normally quite dilute, and Figure 8 illustrates some of the issues involved in studying weak CV signals. This figure uses Excel to combine data from two cycles,
2
current signal

1 0 -1 -2 -3 -0.6

-0.4

-0.2

0.2

0.4

0.6

cycle voltage

Figure 8. Cyclic voltammograms for 0.7 M KNO3 (green, mostly inner, curve) and for 0.7mM methylene blue in a 0.7 M KNO3 aqueous solution. (red, mostly outer, curve). Scan directions are counterclockwise, starting at 0.60 V.

both starting on the lower curves at 0.60 V. The slightly larger red cycle is for 0.7 mM MB in 0.7 M KNO3, and it shows two possible peaks near 0.2 V on the lower reduction scan, and near 0.1 V on the oxidation scan. The smaller green cycle is for 0.7 M KNO3 alone. Figure 9 shows the result when the green values are subtracted from the red value, thus eliminating much of the background of the potassium nitrate scan. Even though the result is much noisier, it is now clear that the two MB peaks can be easily identified.

0.6 0.4 0.2 0 -0.2 -0.4 -0.6 -0.8 -1 -0.6 -0.4 -0.2 0 0.2 0.4 0.6

Figure 9. 0.7mM Methylene blue cyclic voltammogram, with background subtraction.

Detection limits are imposed by the noise in the signal, and by possible contaminants in the solution matrix. This educational system has no special electronic features for noise suppression, and some of the noise is undoubtedly due to the mechanical contacts in the electrical connections. The resulting voltammograms will typically be noisier than a good commercial system. For slower cycle times, it is possible to modify the program to read and average several current signal values for each step in the cycle. This would be one way of reducing the signal noise somewhat. One of the more likely contaminants is dissolved oxygen, and the examples shown here have all used air-saturated systems. This has no significant effect on the more concentrated systems shown in Figures 4 and 7. Deoxygenation is most easily accomplished by purging the matrix solution with a nitrogen bubbler for a few minutes.

Footnotes

1. Details on these applications of operational amplifiers may be found in several textbooks on practical electronics, such as reference (8). 2. The cyanide present in this compound is so tightly bound to the iron that it poses minimal hazard, particularly at relatively low concentrations. Exposure to strongly acidic conditions could conceivably be hazardous, but there is no reason to carry out the measurements described here in anything other than neutral aqueous solutions.
References:

1. Kissinger, P.T.; Heineman, W.R. J. Chem. Educ., 1983, 60, 702. 2. Van Benschoten, J.J.; Lewis, J.Y.; Heineman, W.R.; Rosten, D.A.; Kissinger, P.T. J. Chem. Educ., 1983, 60, 772. 3. Mabbott, G.M., J. Chem. Educ. 1983, 60, 697. 4. Baldwin, R.P.; Ravidhandran, K.; Johnson, R.K. J. Chem. Educ., 1984, 61, 820. Check names! 5. Ontko, R.J.; Russell, R.N.; Ogren, P.J. J. Chem. Educ. 1986, 63, 325. 6. Ogren, P.J.; Jones, T.P. J. Chem. Educ., 1996, 73, 1115-1116. 7. Taken from: "Linear Integrated Circuits", p. 2-173, National Semiconductor Corp., Santa Clara CA, 1973. 8. Diefenderfer, A.U. Principles of Electronic Instrumentation, W.B. Saunders, Philadelphia, Pa. 1972, p. 552. 9. PCI E Series User Manual, National Instrument Corporation, 1999, pp. 4.16-4.18. 10. Zhang, Y.; Field, R.J. J. Phys. Chem. 1991, 95, 723. 11. Mowry, S.; Ogren, P.J. J. Chem. Educ., 1999, 76, 970. 12. Campbell, J.A. J. Chem. Educ. 1963, 40, 578.