Rotating Disk Electrode

-a hydrodynamic method

Fei Lu
May 31, 2011
Center for Electrochemical Engineering Research
Department of Chemical and Biomolecular
Engineering
Rotating Disk Electrode

• A rotating disk electrode (RDE) is

a hydrodynamic working electrode used in
a three electrode system.
• The RDE is one of the few convective
electrode systems for which the
hydrodynamic equations and the
convective-diffusion equation have been
solved rigorously for the steady state.

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 Construct of RDE

Brush
contact RDE (Rotating Disk Electrode )
Shaft
(brass) RDE is constructed from a disk of
electrode material imbedded in a rod
of insulating material. The electrode is
attached to a motor and rotated at a
certain frequency.
Insulator
(Teflon)
Disk Insulating material : Teflon, epoxy
resin or other plastic[1].
Bottom View

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Velocity Profile
At Disk Surface, ( y  0), vr  0 , v y  0 and
v  r . The solution is dragged along at the
surface of the disk at the angular velocity ω. In
the bulk solution ( y  ), vr  0 , v  0 and
v y  U0.

For electrochemical studies, the important

velocity is vr and v y , Near the surface of the
rotating disk ( y  0) , these velocities are given
by: v  0.51 3 / 2 1 / 2 y 2
y

vr  0.51 3 / 2 1 / 2 ry
For ( y  ) , the limit velocity in y direction,
U0 is: U0  lim v y  0.88447( )1/ 2
y 
Hydrodynamic boundary layer thickness yh (At

  ( )1/ 2 y  3.6 ), v y  0.8U0 , yh  3.6( / )
1/ 2


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Convective-Diffusion Equation

Steady-state convective-diffusion equation in terms of cylindrical

coordinates:
CO v CO CO   2CO  2CO 1 CO  1  2CO 
vr ( ) ( )  vy ( )  DO  2     2 
2 
r r  y  y r 2
r r  r  

Limit current condition:

CO  2CO
vy ( )  DO
y y 2
    
convection diffusion

Substitution of the value of vy :

v y  0.51 3 / 2 1/ 2 y 2

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Solution of Convective-Diffusion Equation

CO  2CO
 0.51 3/ 2 1 / 2 2
y ( )  DO
y y 2
Boundary condition:
CO ( y  0)  0

CO ( y  )  CO
*

Current is the flux at the electrode surface, that is:

CO
i  nFADO ( ) y 0
y
Under limit conditions:
i  il ,c
Solution of convective-diffusion equation:
il ,c  0.62nFADO2 / 31/ 2 1/ 6CO*

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Diffusion Layer Thickness
Levich equation:
il ,c  0.62nFADO2 / 31/ 2 1/ 6CO*

For simple steady-state diffusion layer model:

DO
il ,c  nFAmOCO*  nFA( )CO*
O
For RDE:
DO
mO   0.62 DO2 / 31/ 2 1 / 6
O
O  1.61DO1/ 3 1/ 2 1/ 6

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General Current-Potential Curves at RDE

CO  2CO
 0.510 y 2
(
3
)  DO
y y 2
Boundary condition:
CO ( y  0)  CO ( y  0)

CO ( y  )  CO
*

Current is the flux at the electrode surface, that is:

CO
i  nFADO ( ) y 0
y
Solution of convective-diffusion equation:
i  0.62nFADO2 / 31/ 2 1/ 6 [CO*  CO ( y  0)]

Combine with Levich equation:

i
CO ( y  0)  CO* (1  )
il ,c
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Koutecky-Levich Equation
For Levich equation, il ,c is proportional to  . A deviation of a
1/ 2

plot of i vs. 1/ 2 from a straight line intersecting the original

suggest a kinetic limitation is involved in the electron-transfer
reaction. For totally irriversible one-step one-electron reaction, the
disk current is : i  FAk ( E )C ( y  0)
f O

Where : k f (E ) is forward reaction rate at E.

i
i  FAk f ( E )CO* (1  )
il ,c

With rearrangement and defining: iK  FAk f ( E )CO*

Koutecky-Levich equation:
1 1 1 1 1
   
i iK il ,c iK 0.62nFADO2 / 31/ 2 1/ 6CO*

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Koutecky-Levich Equation
1 1 1 1 1
   
i iK il ,c iK 0.62nFADO2 / 31/ 2 1/ 6CO*

Variation of і with ω1/2 at an RDE for an

electrode reaction with slow kinetics
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 Advantages of RDE

A steady state is attained rather quickly and measurements can be made

with high precision at RDE[2].
RDE gives good reproducibility and stable polarization curve. In
stagnant solution, diffusion layer thickness is the same as boundary
layer thickness, it is easy to be disturb by external disturbance. But for
RDE:
 O 1.61 DO 
   ( )1 / 2 y
 h 3.6  

The diffusion layer thickness is far less than boundary layer thickness,
the diffusion layer is protect by boundary layer which makes the
polarization curve stable and has good reproducibility.
[2] L.H. Mendoza-Huizar, C.H. Rios Reyes, M. Rivera and C.A. Galán-Vidal, A Voltammetric Study Of The Underpotential
Deposition Of Cobalt Onto A Glassy Carbon Electrode, AZojomo (ISSN 1833-122X) Volume 3 January 2007

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 Applications of RDE
I. Measure Fe2+/Fe3+ Concentrations

From the Levich equation, Levich current il ,c , is directly proportional to

the concentration:
il ,c  0.62nFADO2 / 31 / 2 1 / 6CO*  aCO*
a  0.62nFADO2 / 31 / 2 1/ 6
Consider a reaction:
Fe3  e  Fe 2
if the il ,c is known, the concentration of Fe2+/Fe3+ can be calculated by
linear regression using the following model [3]:
il ,c  0.62nFADO2 / 31/ 2 1/ 6CO*  aCO*  b

[3] Xin Jin, Gerardine G. Botte, Electrochemical technique to measure Fe(II) and Fe(III) concentrations simultaneously, J Appl
Electrochem (2009) 39:1709–1717

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 Applications of RDE
II. Determine Diffusion Coefficient

Levich equation:
il ,c  0.62nFADO2 / 31/ 2 1/ 6CO*
Plotting іl,s vs. ω1/2 yields straight
line with slope:
slope  0.62nFADO2 / 3 1/ 6CO*
Diffusion coefficient can be
calculated by:
3
 Slope 
D   
1 / 6 * 
Plots of іl,s vs ω1/2. Working solution:  0.620nFA CO 
K3Fe(CN)6 (10 mM) + K4Fe(CN)6 (20 mM) in
Na2SO4(0.1 M) at a vitreous carbon RDE.

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 Application for current research
III. Determine kinetic parameters

0.12
y = 1.0271x + 0.0428
0.1

0.08 Koutecky-Levich equation:

1/i

0.06
1 1 1
0.04  
1/iK i iK 0.62nFADO2 / 31/ 2 1 / 6CO*
0.02

0 1 / iK is the intercept at y axis.

0 0.02 0.04 0.06 0.08

ω-1/2

Plots of і-1 vs ω1/2. Working solution: 0.33 M

Urea and 5 M KOH with Ni base RDE at 0.52V.

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 Thank You!

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