CHAPTER 6

CYCLIC VOLTAMMETRY
DETERMINATION OF DIFFUSION COEFFICIENTS
Electrochemical transient techniques were used in determining the diffusion
coefficients of electrochemical active species. The key to extracting information from
electrochemical data is to use a system where the mass-transfer is well described in terms
of operating parameters. The techniques that meet this criteria and that will be used to
determine the diffusion coefficient of Fe(CN)6-3 in 1 M KCl are Linear sweep
voltammetry and Limiting current studies at a rotating electrode.
The reduction reaction of interest is
Fe(CN)6-3 + e- Fe(CN)6-4
Below is the description of two techniques.
6.1 Linear Sweep Voltammetry
Linear sweep voltammetry (LSV) is a transient technique in which the
potential difference between the working and reference electrode is changed linearly with
time. The competing effects of an increasing potential driving force and an increasing
diffusion layer thickness results in a peak current (see figures 1 and fig 2).
For fast Charge-transfer kinetics, the peak current is related to the sweep rate by the
following equation .(Randles-sevcik equation)

ip = 0.4463NFAC0* nfD0

(1)

where ip is the peak current , n is the number of electrons transferred in the

electrochemical reaction , F is the Faradays constant, A is the electrode area, C0* is the

bulk concentration of the oxidized species, f F/RT, is the sweep rate, and D0 is the
diffusion coefficient of the oxidized species . Equation (1) indicated that a plot of the
peak current versus the square root of the sweep rate would result in a straight line. The
slope of the line can be used to extract the diffusion coefficient of Fe(CN)63-.

Required Equipment and Supplies

1. Scanning Potentiostat
2. X-Y recorder or data acquisition facility
3. K3Fe(CN)6 and KCl
4. Deionized (DI) water
5. 250 mL Beaker
6. Pt-disc (working) and Pt- gauze (Counter) electrodes
7. Ag/AgCl electrode
8. Polishing material
Procedure
1. Use DI water to prepare a 0.01 M solution of K3Fe(CN)6 IN 1 M KCl
2. Deoxygenate the solution by passing Nitrogen gas through a sparging tube for 10
minutes.
3. Transfer approximately 150mL to 250mL beaker and deoxygenate for another 2
minutes.
4. Polish the Pt disc to a mirror finish and thoroughly rinse it with DI water.
5. Connect the three electrodes to the potentiostat and apply 0.75 V to the working
electrode relative to the Ag/AgCl reference electrode.
6. Repeatedly scan the potential (i.e cycle) between 0.75 V and 0.15 V versus Ag/AgCl
at a sweep rate of 100 mV/s .
7. Shake the working electrode in order to destroy the diffusion layer , set the initial
potential to 1 V versus Ag/AgCl , and sweep the potential in the negative direction at
225 mV/s.

8. Repeat item 7 at different convenient scan rates (196,169,144,121.9).

9. Plot ip versus and obtain D0 from the slope of the resulting straight line.
10. Draw conclusions on the reversibility of the system.

2. Limiting Current at a Rotating -Disc electrode

Introduction
Limiting current at a rotating -disc electrode is a steady state technique in which
the potential is held at a value where the current has reached a limiting value. The
limiting current is related to the electrode by the following equation.
iL = 0.620NFAC0*D02/3 1/2

1/ 6

(2)

Where iL is the limiting current, is the rotation speed of the electrode, and is the
viscosity of the electrolyte. Equation (2) indicates that a plot of the limiting current
versus the square root of the rotation speed will result in a straight line. The slope of the
line can be used to extract the diffusion coefficient of the ferricyanide ion.

Required Equipment and supplies

Same as previous with a Rotating -disc Assembly .

Procedure

1. Repeat items 1-5 of the LSV experiment.

2. At 10 mV/s and 400 rpm, scan the potential from 0.75 V versus the Ag/AgCl
reference electrode towards more negative values until the current reaches a
plateau.
3. Choose a potential in the plateau region and hold the potential at the value.
4. Lower the rotation speed to 64 rpm and record the steady state current.

5. Repeat item 4 at convenient scan rates (100,144,196784) and 900 rpm

6. Plot iL versus

and obtain D0 from the slope of the resulting straight

line.

DIAGNOSTIC TESTS FOR REVERSIBILITY:

1. EPA - EPC = 59/n mV

2. EP - EP/2 = 59/n mV
3. IpA/IpC =1
4. Ip is proportional to
5. EP is independent of

DIAGNOSTIC TESTS FOR IRRREVERSIBILITY:

1. No reverse peak
2. IpC is proportional to 1/2
3. EpC shifts -30/cn for each decade increase in
4. Ep - Ep/2 = 48/cn mV