Date: 2018-02-14

Experiment 3: Determination of the Diffusion Coefficient of

Ferrocenemethanol using Rotating Electrode Technique

ABSTRACT
In this laboratory experiment, a rotating disk electrodes was operated at different speeds to vary the
effective thickness of the diffusion layer, δ of the oxidation of ferrocenemethanol at an electrode to
calculate the diffusion coefficient of the electrochemical reaction which was found to be 1.53E-6cm2*s-1.
Keywords: rotating disk electrodes, diffusion layer, ferrocenemethanol, cyclic voltammetry, diffusion coefficient,
Levich plot

1.INTRODUCTION

Diffusion is a physical process that occurs when there is a difference in chemical potential of a species in a
given area. An important type of diffusion is that of the thin layer adjacent to an electrode in a
electrochemical reaction. The flow of species from the area of highest concentration, or flux, will be directly
related to the current flowing through the electrode. When the reaction is proceeding at a fast rate, the
concentration of reactants at the electrode will effectively be 0, as their turnover rate is very high. Therefore,
the current through the electrode will be dependent on the overall rate of diffusion of the species in the cell.
When the concentration of the reactants is 0, the current has been maximized, and this value can be
manipulated to find the overall concentration in the cell, and the diffusion constant, D. Under normal
circumstances, it is challenging to perform this calculation, as another factor to take into consideration is
the thickness of the diffusion layer, which is proportional to time. However, with the use of a rotating disk
electrode (RDE), it is possible to minimize the thickness of the diffusion layer to just the reaction electrode,
as its constant motion keeps the concentration in the cell consistent. A diffusion layer will still form but
will be much smaller, and dependent on the rate of rotation.

2. EXPERIMENTAL

The experiment consisted of a potentiostat, rotator and electrochemical cell. The potentiostat provided a
voltage and measured the current in the cell. The rotator provided the rotation for the RDE, and the cell
contained the molecule of interest, Ferrocenemethanol, with a concentration of 0.21606g in 2L and KCl,
with a concentration of 14.91 g in 2L to aid provide electrical conductivity. The potentiostat was
connected to a computer and allowed for voltage parameters, at -0.200V, 0.500V, -0.2V and 1mV. The
current-voltage dependence was measured with no rotation, and then rotation speeds at 400, 800, 1200,
1600, and 2000 rpm.

The following graphs were generated from the potentiostat readings:

 0.00001

0.000008

0.000006
Current (μA)
0.000004

0.000002

0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.000002

-0.000004

-0.000006

-0.000008
Voltage (V)

Figure 1: Current-Voltage Dependence in stationary cell

0.00002

0.000015

0.00001
Current (μA)

0.000005

0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6

-0.000005

-0.00001
Voltage (V)

Figure 2: Current-Voltage Dependence at 200rpm

 0.000025

0.00002

0.000015

Current (μA)
0.00001

0.000005

0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.000005

-0.00001
Voltage (V)

Figure 3: Current-Voltage Dependence at 400 rpm

0.000035
0.00003
0.000025
Current (μA)

0.00002
0.000015
0.00001
0.000005
0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.000005
-0.00001
Voltage (V)

Figure 4: Current-Voltage Dependence at 800 rpm

0.00004
0.000035
0.00003
0.000025
Current (μA)

0.00002
0.000015
0.00001
0.000005
0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.000005
-0.00001
Voltage (V)

Figure 5: Current-Voltage Dependence at 1200 rpm

 0.00005

0.00004

0.00003

Current (μA)
0.00002

0.00001

0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.00001

-0.00002
Voltage (V)

Figure 6: Current-Voltage Dependence at 1600 rpm

0.00005

0.00004

0.00003
Current (μA)

0.00002

0.00001

0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6
-0.00001

-0.00002
Voltage (V)

Figure 7: Current-Voltage Dependence at 2000 rpm

3. RESULTS AND DISCUSSION

The reaction that took place at the electrode was:

C11 H12 Fe2+ O  C11 H12 Fe3+ O + 1e-,

There was 1 electron participating in the electrochemical reaction. Ferrocenemethanol has excellent
redox properties due to its structure, the central Fe3+ can be reversibly reduced to Fe2+ and vice versa
because the Fe ion is so well protected by the cyclopentadienyl rings.
Since the concentration of C11 H12 Fe2+ was 0.21606g in 2L, the molarity was found to be 5E-4 M or
5E-7 mol/cm3.

0.21606g x 1mol x 1000 cm3

2L 216.06g 1L = 5E-7 mol/cm3

Since only 1 electron participates in this reaction, the concentration of e- is also 5*10-7mol/cm3.

When examining the graphs for the Current-Voltage dependency at different rotation speeds, it is evident
that there is a current at which the relationship evens out. This is called the limiting diffusion current or
IElectrochem.The stationary cell has a different shape as the diffusion area is not controlled by the RDE and it
increases with time.
Table 1. Limiting Diffusion Current recorded at 0.4V for different rotation speeds/angular velocities.

Rotation Speed (rpm) Angular Velocity (Rad/s) IElectrochem (μA)

200 20.944 1.548 × 10-5
400 41.888 2.153 × 10-5
800 83.776 2.877 × 10-5
1200 125.664 3.309 × 10-5
1600 167.552 3.830 × 10-5
2000 209.440 4.220 × 10-5

Though the data was recorded by taking the rotation speed, for calculations, it is more convenient to
convert this variable into rad/s measuring the angular velocity.
Sample Calculation:
1 rpm = 9.549 rad/s
200 rpm * (9.549 rad/s)/(1rpm) = 20.944 rpm

Rotation speed and IElectrochem have a direct relationship which can be viewed linearly as a Levich Plot.

y = 3E-06x
0.00005 R² = 0.9923
0.000045
Limiting Current (µA)

0.00004
0.000035
0.00003
0.000025
0.00002
0.000015
0.00001
0.000005
0
0 2 4 6 8 10 12 14 16
ω-1/2 (Rad/s)

Figure 8. Levich plot, linear relationship between limiting current and the square root of rad/s.
From the slope of the Levich plot, m, 3E-6, it is possible to calculate the diffusion coefficient by using the
following equation:
IElectrochem.= 0.62 × nFA × D 2/3 × ν -1/6 × ω ½ × C0 (1)
where, n = number of electrons participating in the electrochemical reaction
F = Faraday constant, 96485 C mol -1
A = electrode area, 5mm
C0 = bulk concentration of the diffusion compound, 5E-7 mol/cm3.
ν = kinematic viscosity of the solution, 8.425 E-7 m2*s2

D was found to be 1.53E-6cm2*s-1.

After calculating D, it was possible to calculate the diffusion layer thickness’ with the following equation
δ= 1.61 x D 1/3 x v 1/6 x ω -1/2 (2)
Table 2. Diffusion Layer Thickness at different rotation speeds.

Rotation speed (rpm) Diffusion Layer Thickness

(cm)
200 0.002684441
400 0.001898187
800 0.001342221
1200 0.001095919
1600 0.000949093
2000 0.000848895

As the rotation speed increased, the diffusion layer thickness decreased as the liquid in the cell was
moving faster, therefore minimizing the layer around the electrode.

The diffusion layer at the stationary electrode was 14.69 µm ± 0.9 using the equation:

I = nFAD (c0/δ) (3)

This is because since there is no rotation that can effectively control the diffusion layer, it will grow with
time. This is also the reason for the difference in shape of the voltammetric curves, as the rotation will
cause the concentration of ferrocenemethanol to drop to 0 at the electrode. When it does, we notice
smoothening out of the relationship.
 4. CONCLUSION
Upon completion of this laboratory experiment, it is evident that the coefficient of diffusion can be
calculated by adding RDE to the electrochemical cell. This was found to be 1.53E-6cm2*s-1. This allows
for the concentration of the molecule to be effectively 0 at the surface of the reaction electrode as the
reaction is proceeding quickly. Additionally, the diffusion layer thickness can also be controlled by
increasing the rotation. Through these manipulations, it is possible to calculate the diffusion layer
thickness in stationary cells, which is not very easily done as it constantly increases with time. It was
found to be 14.69 µm ± 0.9.

References:
[1] Semenikhin, Oleg. Chemistry 2384B Laboratory Manual; University of Western Ontario: London,
ON, 2018; p 30-38.