1. Cyclic Voltammetry

2. Current-Potential-Time Space
Reversible System

3. A New Waveform
Potential waveform: E Ei 

4. Diffusion Condition For the reversible case have the standard
Semi-infinite diffusion conditions plus:

5. Solution
1948
Sevick, “Oscillographic Polarography with Periodic Triangular Voltage”, Collection of Czech. Chem. Comm., 13, 349 (1948).
Randles, “A Cathode Ray Polarograph”, Faraday Society, 44, 327 (1948).

6. Problem
There is no analytical solution to Fick’s second law when the boundary is time dependent. Sevick and Randles solutions was to approximate the integral with a series. While this works for the reversible case, it is not very pragmatic for more complex mechanisms.
New Solution:
Wait for a high speed computer (IBM main frame University of Wisconsin at Madison)
Nicholson and Shain, “Theory of Stationary Electrode Polarography”, Analytical Chemistry, 36, 706 (1964)

10. Reversible CV Continued

11. Don’t Miss this Table
Myth: A reversible wave will have a 60mV peak to peak separation.

12. N&S Diagnostics

13. Two KEY Points Should use all three diagnostics
MUST go over three orders in magnitude in scan rate to reliably use a diagnostic!
Implication: A single CV scan doesn’t tell you much, don’t over interpret it!

14. The Baseline Issue Three solutions Guess Record i-t over i-V
Nicholson:
Nicholson, Anal. Chem. 38, 1406 (1966)

15. More On Baselines

16. Hydrazine (N2H4)Oxidation

17. eg(s*)
Bpy p*
t2g e–
eg(s*)
Bpy p*
t2g

19. ClRe(CO)3phen in acetonitrile (CH3CN) + tetrabutylammonium perchlorate
An EC Mechanism
ClRe(CO)3phen in acetonitrile (CH3CN) + tetrabutylammonium perchlorate
Luong, Nadjo and Wrighton, JACS, 100, 5790 (1978)

20. Charge Transfer Communication