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Ring-Disc Electrodes
Part 1.-A New Approach to the Theory

BY W. J. ALBERY

Physical Chemistry Laboratory, Oxford

Published on 01 January 1966 on http://pubs.rsc.org | doi:10.1039/TF9666201915

Received 8th December, 1965

Hitherto the theory of transfer from the disc to the ring of a ring-disc electrode has only been
approximate. A new approach involving Laplace transformations and Airy functions is described.
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General relations are derived from the basic differentialequation which will be applied in subsequent
papers to particular problems.

The rotating disc electrode is a powerful technique for investigating the speed of
electrode processes and of homogeneous reactions in solution. A more complicated
but more versatile system is the rotating ring-disc electrode 1 in which the central disc
is surrounded by an insulating gap which in its turn is surrounded by a ring electrode.
With this system a reactant can be generated on the disc and its effects measured on
the ring electrode. While the theory of transport to the rotating disc electrode and
the effect of homogeneous kinetics is well established, less progress has been made for
the more complicated ring-disc system. An approximate solution 2 has been found
which describes the size of the ring current when an intermediate is generated on the
disc and an estimate 3 has been made of the effect of any homogeneous decomposition
of the intermediate, as it is transported from the disc electrode to the ring electrode
by radial convection and diffusion.
This series of papers will describe a new mathematical approach which enables
an exact solution to be derived for the problem of diffusive and convective transfer
from the disc to the ring. Approximate solutions are obtained for cases where the
intermediate is consumed by first- and by second-order kinetics. This first paper
deals with the differential equation which is common to the whole approach and it
derives general relationships used in the subsequent papers.

BASIC DIFFERENTIAL EQUATION

Expressed in cylindrical co-ordinates the general equation for the production and
consumption of a chemical species in the vicinity of a rotating disc electrode is 4 :

In each case this equation is reduced to the form,

where u, 5, and y are respectively functions of concentration, the radial coordinate,

and the normal coordinate. Furthermore, u is chosen so that as
y+m, u-to. (2.3)
1915
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1916 THEORY OF R I N G - D I S C ELECTRODES

We assume a second boundary condition that at

[ = 0, u = uo,
where uo is a known function of and y .
The third boundary condition necessary for the solution of the differential equation
describes the conditions on the surface of the disc, i.e., the value of u or du/ay at
y = 0. It is different for different parts of the disc. For instance, in the insulating
gap, since nothing can react on the surface, the boundary condition is
(au/ay)y=o= 0. (2.4)
Published on 01 January 1966 on http://pubs.rsc.org | doi:10.1039/TF9666201915

While on the ring electrode, when the limiting current is being passed,
u,=o = 0.
Hence, the differential equation has to be solved for two different zones, the gap and
the ring electrode. The boundary condition u = uo at [ = 0 is the link between the
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various zones ; the solution for u from an inner zone provides the boundary condition
for the adjacent outer zone.2
To solve the differential equation (2.2) we take the Laplace transform with respect
to 5 and write
1 a2u
S G - U , = --
Y BY2 ’
and then letting
z = s‘fy,
we have
a2u - zuo
a22 = zu --S *
The solution to this equation may be written in the general form :
u =Alfl +B,f,+fp,
wherefi andf2 are functions which satisfy

A1 and B1 are constants andf, is the particular integral satisfying

a 2 f p / a z 2= z f p - f o ,
where
fo = zu,/s.
From their definitionsfi andfz are modified Bessel functions of order 4.
Let
f1 = z+I&z+); fi = z+I-+(*z+),
and
fp = Pfi +Q f 2 ,
where
P’fi + Q’f2 = 0, (2.9)
the primes indicating differentiation with respect t o z. Then, differentiating eqn.
(2.8) twice and using eqn. (2.6), (2.7) and (2.9),
P‘ = -fof2l(fif;-fi’fi) and Q’ = f0fi/(f2fl-f2’f1>.
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W. J . ALBERY 1917
Also 5

Hence

where 8 = $z%, and A2 and B2 are constants.

When
y + a , e + w , I+e+I-+e, ii+o
Published on 01 January 1966 on http://pubs.rsc.org | doi:10.1039/TF9666201915

and
(2.11)
Now
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Multiplying eqn. (2.10) by 3+z-C38/2n, and eqn. (2.12) by 3%-1I+8/2n, subtracting,

and using the relationship 6 that
I-+ei-+e-+eI+e = 3 " ~ e = P p n ~ 3 ,
then
B, + J ' fOi,elde,
0
= zI-,eii - z*I+eau/az.
Similarly,
A, - 1*
0
j-oI-+elde, = - Z i, e ii +z+il_,eaiqaz.
Using eqn. (2.1 1) and the relations 7
z+(i-+e-I+e) = 3Ai(z),
z(r-,e -13e) = - 3Ai'(z)

and 1B, (I-+el -I+e,)de, = 3

J: Ai(z,)dz,,

we have
foAi(z,)dzl = -Ai'(z)ii +Ai(z)dii/az. (2.13)

Ai ( 2 ) is the Airy function.7 It is a solution of the differential equation,

UII = zu.
On the electrode surface y and z tend to zero hence we can derive an important
relationship at y = 0 between the value of 4 and its gradient :

zur,,Ai(z)dz = (2.14)

where
p = Ai(0) = [331'(+)]-', (2.15)
and
= ~ i y o=
) [PI-(+)]
- (2.16)
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1918 THEORY OF R I N G - D I S C ELECTRODES

On the electrode we usually either know ii and wish to find dzljdy, or vice versa.
However, in the gap between the disc and ring we need to find u at some particular
value of (1 to provide the boundary condition uo at <2 = 0 for the zone of the ring
electrode. This requires that we solve the differential equation (2.13). To do this,
we integrate U” = zu to give

Also
s z,A’i(z,)dz, = Ai’(z,). (2.17)

s
Published on 01 January 1966 on http://pubs.rsc.org | doi:10.1039/TF9666201915

Ai‘(z,)dz, = Ai(z,),

and since as z-+ co , both A @ ) and Ai’(z)+O, we can integrate repeatedly by parts to
obtain the relation :
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Eqn. (2.13) becomes

This equation is solved by

(2.19)

where the integration “ constant ” A3 may be a function of s.

If we apply the particular boundary condition which is usual in the gap, viz., that,
(aiipz), = = 0 we find

(2.21)

where as before
= p+r(+)]-l.
Thus this equation gives Q as a function of y and the transformed variable s. The
application of these equations and the inversion of the transforms are peculiar to each
particular problem.
In the succeeding papers they are applied to the calculation of first, N for a ring-
disc electrode, secondly, the description of the complete current-voltage curve at the
ring of a ring-disc electrode, thirdly, the complete shape of the titration curve in
ring-disc titrations,* fourthly, the size of the ring current when the intermediate
produced on the disc is destroyed by either first- or second-order homogeneous
kinetics, and finally the effect of electrochemical and homogeneous kinetics at the
ring electrode.

This work was carried out at the University of Minnesota and I should like to
express my gratitude to Prof. Bruckenstein for his advice and encouragement and to
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W. J. ALBERY 1919
the School of Chemistry of the University of Minnesota for their hospitality. This
work was supported by the National Science Foundation.

1 Frumkin, Nekrasov, Levich and Ivanov, J. Electroanal. Chem., 1959/60, 1, 84.

2 Ivanov and Levich, Doklady Akad. Nauk S.S.S.R., 1959, 126, 1029 ; Levich, Physicocheinical
Hydrodynamics, (Prentice-Hall, 1962), p. 329.
3 Bruckenstein and Feldman, J. Electroanal. Chem., 1965, 9, 395.
4 Levich, Physicochemical Hydrodynamics, (Prentice-Hall, 1962), p. 65.
5 Albery, Trans. Faraday SOC.,1966, 62, 1575.
6 Watson, Theory of Bessel Functions, (Cambridge, 1952), pp. 77-79.
7 Handbook of Mathematical Functions, (National Bureau of Standards, 1969, pp. 446, 447.
Published on 01 January 1966 on http://pubs.rsc.org | doi:10.1039/TF9666201915

8 Bruckenstein and Johnson, Anal. Chem., 1964, 36, 2186.

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