CV Operation Procedure

I. Preparation of Solutions Before using the CV, prepare the analyte and electrolyte (if using nonaqueous reference electrode) as follows: 1) Prepare ~50ml 0.1M electrolyte solution (Solution 1). The concentration of solution 1 should be at least 100 times higher than that of analyte solution. Common electrolytes include: Bu4NPF6, Bu4NClO4 or Bu4N+B(C6F5)4- (only the first two are commerciallyavailable). 2) Prepare ~25 ml of 0.1M electrolyte solution with 0.01M AgNO3 (Solution 2). Solution 2 is for the nonaqueous reference electrode. 3) Prepare 10~15ml of 0.001M analyte solution using the electrolyte solution as the solvent (Solution 3). Therefore, 3 will contain 0.001M analyte/0.1M electrolyte/solvent. 4) Prepare 10~ 15ml of 0.001M ferrocene solution using the electrolyte solution as the solvent (Solution 4). This will be the reference solution to standardize the potential of your reference electrode. NOTE: The choice of solvent is very important to get good result. MeCN is the most common solvent because it has a wide potential window (+/-3V). THF (only for reduction) or CH2Cl2 (only for oxidation) also can be used as a solvent although their range is limited compared with MeCN. Suitable organic solvents for the reference electrode include MeCN, DMSO, MeOH, EtOH and THF. Ag ions are reduced by DMF and are insoluble in CH2Cl2; MeCN can be used as the reference electrode solvent when one of these two solvents is used. If using a concentration other than 0.001M for your analyte solution, adjust the concentration of the electrolyte and ferrocene solution accordingly.

II. Preparation of Electrodes Three electrodes are used for CV experiment. The role of each electrode is described in reference paper. In this instruction, only the experimental aspect will be mentioned. 1) Working electrode: Pt disk. Cylinder shape, covered with black plastic. Also available: Au disk. Check to see if the surface looks scratched. If so, please follow polishing

procedures in the BASi handbook included with the polish kit. Else gently wipe the surface with a Kimwipe soaked with MeOH. 2) Auxiliary electrode: Pt wire. Needs to be fitted inside a glass body. See below for instructions. 3) Reference Electrode: 2 types available a) Aqueous Ag/AgCl(3M NaCl). Use only with analyte solution that is not watersensitive. Already assembled and ready for use. b) Nonaqueous Ag/AgNO3 electrode. Needs to be assembled before use. To prepare the auxiliary electrode and reference electrodes, two glass bodies are fitted with a piece of the cut-plastic tubing. Then the vycor frit tip is inserted and held in place against the end of the glass body by melting the tubing with a heat gun.
Glass Body Frit Glass Body Heat with heatgun to make it tight

Electrolyte Solution (e.q. 0.1M NBu4PF6)

Glass Body

Electrolyte Solution (e.q. 0.1M NBu4PF6)

Immerse the glass body in the electrolyte solution for ~ 1 hr to thoroughly wet the frit (the inside of the body is also filled with electrolyte solution). After a certain time (0.5~ 1 hr) passes, the reference electrode only is soaked again with electrolyte solution containing AgNO3.

III. Device Assembly

1) Add the analyte solution into the 3-neck CV flask.

2) Secure the three electrodes using the screw caps and septa. Make sure to put the working electrode in the center. 3) Connect the alligator clips to the corresponding electrodes: black = working electrode; red = auxiliary; white = reference. 4) Before running any measurements, Argon gas should be bubbled into the solution to remove the oxygen completely (very important!!). But when the experiment is being carried out, it should be turned off (why? See the reference).

IV. Running the Program 1) Go to Method and click General Parameter. Change the scan rate, range, number of scans and sensitivity to find the best condition. 2) Go to Control and click Start run. 3) Measure the potential of solution 4 containing ferrocene. Check the spectrum for a Nernstian, reversible oxidation spectrum. 4) Second, measure the potential of your analyte solution.

V. Low-Volume Setup For experiments using <1ml of analyte solution, use the LowVolume Setup (Figure 3) 1) Prepare the different solutions as listed in part I, except in smaller volume. 2) Same electrodes can be used in this setup, except no glass body is required for the auxiliary electrode. The sample chamber will have to be fitted with a vycor and wetted with electrolyte solution before use. 3) Assemble the chamber as shown in Figure 2. Blank electrolyte solution should fill the cell vial to keep the vycor tips wet. 4) Run the experiment as listed in part IV. Use a new sample chamber (new frit) for each different analyte to avoid cross contamination.

Reference 1. Heinze, J. Angew. Chem. Int. Ed. 1984, 23, 831-847 2. Kissinger, P. T.; Heineman, W. R. J. Chem. Ed. 1983, 60, 702-706 3. D. H. Evans et al. J. Chem. Ed. 1983, 60, 290-298