Exercise 1: Cyclic Voltammetry.

Oxidation / reduction of

Jesus Arroyo Condori Studen Number : 83461

1. In general:
a) Describe shortly cyclic volatmmetry

In cyclic voltammetry a triangular waveform is applied, and cathodic and

anodic processes are observed in sucession. Cyclic voltammetry is an
electrochemical measurement.

The electrochemical measurements measure the relationship between current

(I) and potential (E) through the use of a potentiostat. The current is
measured as a function of superimposed potential, or vice versa. The final
result is obtained plotting [I] vs. [E]. We start from a known potential which
is modified with a constant rate.

b) Why do current peaks occur in the cyclic voltammograms?

When the solution is oxidized (one electron is 6 → Fe(CN)

6 +1e) ,and it
4- 3-
delivered, Fe(CN) achieve
a peak and when it is reduced 6 + 1e- → 6 ) it will show another peak in
3- 4-
(Fe(CN) Fe(CN) the other
position of the graph. So in this way they will become sufficienly negative

or positive charged. c) Why does the current increase with higher

scan rates ?

The current increases with increasing scan rate, this can be relationed by
considering the size of the diffusion layer and the time taken to record the
scan. The size of the diffusion layer of the electrode surface will be different
depending upon the voltage scan rate used. In a slow voltage scan the
diffusion layer will grow much further from the electrode in comparison to a
fast scan. Consequently the flux to the electrode surface is considerably
smaller at slow scan rates than it is at faster rates. As the current is
proportional to the flux of the electrode the magnitude of the current will be
lower at slow scan rates and higher at high rates.
 4,00E-05

3,00E-05

2,00E-05

scan rate
1,00E-05
5 scan
Current

rate 25
(A)

scan rate
0,00E+00 50 scan
rate 100

-300,000 -200,000 - 0,00 100,00 200,00 300,00 400,00 500,00 600,00

100,000 0 0 0 0 0 0 0 scan rate
200

-1,00E-05

-2,00E-05

-3,00E-05
Potential (mV)
b) give in a form of a table , What conclusions can you make
about the
reversibility of the electrode reaction based on the table?.

Scan 5 mV/s 25 mV/s 50 mV/s 100 150 200

Rate mV/s mV/s mV/s
5 25 50 100 150 200

2,24 5 7,07 10 12,25 14,14

17 18 17 17 16 162
8 2 5 0 7
25 26 27 27 27 277
4 0 0 1 1
76 78 95 10 10 115
1 4
2,6 6,5 9,4 13, 16, 19
9 7 3 5 6
4,4 9,9 14 20, 25 29
9 4 1

On the basis of the table we can say that the reaction is almost reversible.

The catodic and anodic ( , respectively ) is of the same size

(experiment failed, it is not our case).
Epa-Epc = (RT)/nF = 59, 0mV/n (in our case is n=1, it is not consistent with
our
experiments)
Ip is proportional to v½ ( it is consistent with our
experiments) Ep is independent of v (it is
consistent with our experiments)
On the basis of the graph we could say that the reaction is reversible.