J. Electroanal, Chem.

, 69 ( 1 9 7 6 ) 1--105 1
© Elsevier S e q u o i a S.A., L a u s a n n e - - P r i n t e d in The N e t h e r l a n d s

ROTATING DISK ELECTRODES

F R A N T I S E K O P E K A R and P R E M Y S L B E R A N
Department of Analytical Chemistry, Charles University, Albertov 2030, 12840 Prague 2
(Czechoslovakia)
(Received 15th May 1975)

CONTENTS

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1. I n t r o d u c t i o n . . . . . . . . . . . . . . . . . . . . . . . 2
2. T h e o r y . . . . . . . . . . . . . . . . . . . . . . . . . 4
2-1. General relations for h y d r o d y n a m i c e l e c t r o d e s . . . . . . . . . . 5
2-1(a) The c o n v e c t i v e - d i f f u s i o n e q u a t i o n . . . . . . . . . . . . 5
2-1(b) E q u a t i o n s for fluid flow . . . . . . . . . . . . . . . . 6
2-1(c) The diffusion b o u n d a r y layer . . . . . . . . . . . . . . 7
2-2. Fluid flow t o w a r d a r o t a t i n g disk . . . . . . . . . . . . . . . 9
2-2(a) Laminar flow . . . . . . . . . . . . . . . . . . . 9
2-2(b) T u r b u l e n t flow . . . . . . . . . . . . . . . . . . 14
2-3. Mass t r a n s p o r t t o w a r d the R D E . . . . . . . . . . . . . . . 17
2-3(a) Mass t r a n s p o r t t o w a r d the R D E u n d e r laminar flow c o n d i t i o n s 17
2-3(b) Mass t r a n s p o r t t o w a r d the R D E u n d e r t u r b u l e n t flow c o n d i t i o n s 20
2-3(c) R D E t h e o r y in binary e l e c t r o l y t e s . . . . . . . . . . . . 22
2-3(d) Mass t r a n s p o r t t o w a r d the R R D E . . . . . . . . . . . . . 24
2-3(e) N o n - s t a t i o n a r y convective d i f f u s i o n . . . . . . . . . . . . 30
2-4. Verification o f the t h e o r y . . . . . . . . . . . . . . . . . 33
3. Practical a p p l i c a t i o n s o f disk e l e c t r o d e s . . . . . . . . . . . . . . 34
3-1. S t u d y o f diffusion . . . . . . . . . . . . . . . . . . . . 34
3-2. S t u d y o f e l e c t r o d e r e a c t i o n k i n e t i c s . . . . . . . . . . . . . . 38
3-2(a) S t u d y of e l e c t r o d e r e a c t i o n kinetics using t h e R D E . . . . . . 38
3-2(b) S t u d y o f e l e c t r o d e r e a c t i o n kinetics using the R R D E . . . . . . 47
3-3. S t u d y o f volume r e a c t i o n kinetics . . . . . . . . . . . . . . 51
3-3(a) S t u d y o f p r e c e d i n g chemical r e a c t i o n s using the R D E . . . . . . 53
3-3(b) S t u d y o f parallel chemical r e a c t i o n s using the R D E . . . . . . 56
3-3(c) S t u d y o f follow-up c h e m i c a l r e a c t i o n s using the R D E . . . . . . 60
3-3(d) S t u d y o f first-order v o l u m e r e a c t i o n s using t h e R R D E . . . . . 63
3-3(e) S t u d y o f s e c o n d - o r d e r r e a c t i o n s using the R R D E . . . . . . . 64
3-4. O t h e r a p p l i c a t i o n p o t e n t i a l i t i e s o f disk e l e c t r o d e s . . . . . . . . . 68
3-4(a) Use o f the R D E for s o l u t i o n o f o t h e r e l e c t r o c h e m i c a l p r o b l e m s . 68
3-4(b) F u r t h e r uses o f t h e R R D E . . . . . . . . . . . . . . . 73
4. C o n s t r u c t i o n o f e l e c t r o d e s and auxiliary devices: F u r t h e r e x p e r i m e n t a l f a c t o r s 75
4-1. E l e c t r o d e s . . . . . . . . . . . . . . . . . . . . . . 75
4-2. The r o t a t i o n s y s t e m . . . . . . . . . . . . . . . . . . . 81
4-3. O t h e r devices . . . . . . . . . . . . . . . . . . . . . 84
5. A c k n o w l e d g e m e n t s . . . . . . . . . . . . . . . . . . . . . 87
6. List o f m o s t c o m m o n l y used a b b r e v i a t i o n s and s y m b o l s . . . . . . . . . 87
7. R e f e r e n c e s . . . . . . . . . . . . . . . . . . . . . . . . 89
PREFACE

Rotating disk electrodes and rotating ring-disk electrodes have recently

found increasingly extensive use in electrochemistry. Owing to their advan-
tages over other types of solid electrodes and to the rigorous theory describing
their behaviour, comparable to the theory for the dropping mercury electrode,
these electrodes have been employed for the study of a great variety of electro-
chemical problems. This fact is documented by the hundreds of original publi-
cations which can be found in international chemical literature, as well as by
several reviews [4,493,522,599] and monographs [26,568].
It is evident that disk electrodes have acquired an important position, not
only in electrochemistry, but also in the solution of non-electrochemical prob-
lems, such as mass transport, heat transfer, hydrodynamics and so forth.

1. INTRODUCTION "

Electrodes made of solid materials have been used for a long time. How-
ever, their application has been complicated by many problems such as pas-
sivity of the electrode surface, decrease of the effective surface area by inter-
mediates formed in surface reactions, formation by various undesirable reac-
tions of surface oxides and films capable of affecting the measurements,
and difficulties in cleaning the surface, during which the character of the sur-
face and the electrode geometry are frequently changed. For these and other
reasons, it is frequently impossible to obtain reproducible results and the mea-
sured values can vary with time. With most solid electrodes, it is also difficult
or even impossible to describe the mass transport by a rigorous equation.
A number of workers have tried to maintain the cleanliness of the electrode
surface, i.e. to eliminate the effect of the electrode history, by developing
various methods for continuous renewal of the electrode surface during the
measurements, e.g. by dipping the electrode into mercury [164,438,635],
wiping it with scrapers made of various materials [ 540,695], by adding
carborundum powder to the solution [650], by constructing so-called "resting"
electrodes [212,263], etc.
However, these methods do not achieve the required effect and, moreover,
necessitate the use of rather complicated apparatus. Since electrochemical
processes characteristic of the particular electrode material take place on the
electrode surface [4,110,381,706], various methods for obtaining a "clean"
electrode surface have been devised, involving cleaning the products of pre-
vious electrochemical reactions from the electrode surface and chemical or
electrochemical pretreatment of the surface.
Chromic acid or hot nitric acid have been recommended for cleaning elec-
trodes. The following pretreatment depends on the character of the reaction
to be studied. Surface oxide layers or adsorbed hydrogen can be removed by
immersing the electrode for several minutes in a solution of a reductant (Fe 2+,
As 3÷) or of an oxidant (Fe 3÷, Ce a÷, bromine water), respectively [381]. How-
ever, electrochemical pretreatment is often more suitable [ 4], The clean elec-
trode is polarized to a potential close to that of hydrogen evolution (for a Pt
electrode ca. --0.2 V (SCE) in an acid medium), thus reducing the surface
oxide. After a sufficiently long time (when the cathodic current approaches
zero), the potential is shifted to a low positive value (about +0.05 V (SCE) for
a Pt electrode in an acid medium), thus freeing the surface from adsorbed hy-
drogen (the anodic current decreases to zero). The resulting electrode surface
is virtually free from oxide layers and adsorbed hydrogen and is suitable for
most measurements. Reduction of surface oxides by gaseous hydrogen with
vacuum pretreatment is used only rarely [680].
For special applications, electrodes covered with oxide layers or with ad-
sorbed hydrogen are sometimes useful. They can be prepared by polarizing the
electrode at the potentials of oxygen or hydrogen evolution, respectively; the
potential values depend on the character of the electrolyte and of the electrode
material [ 110].
The rotating disk electrode (RDE) solves many problems connected with
the use of solid electrodes, both from the experimental and from the theoretical
point of view. The easy cleaning of the electrode surface by polishing without
changing its geometry, and simple changing of the experimental conditions by
variations in the rotation rate are very important experimentally. A relation-
ship between the measured value and the quantity to be determined can often
be expressed by plotting the measured value against the rotation rate. From
the electrochemical point of view it is important that processes at the RDE
proceed under steady state conditions and that the mass transport can be ex-
plicitly formulated (even if the electrode reaction is complicated by a hetero-
geneous or homogeneous chemical reaction). The flux of the liquid and of
the electroactive species to any point on the disk is independent of the dis-
tance of the point from the axis of rotation and therefore electrochemically
important quantities such as the thickness of the diffusion layer and the cur-
rent density have with rare exceptions the same values over the whole surface
area of the disk. Suitable hydrodynamic conditions are thus established in
the vicinity of the electrode.
RDE theory was described by Levich [425] as early as 1942 and was ex-
perimentally verified by Siver and Kabanov [633] in 1949. The first practical
applications appeared several years later and n o w this electrode is successfully
replacing classical types of solid electrodes (rotating wire electrodes, vibrating
electrodes, etc.). Although some attempts were later made to find more
rigorous expressions for the theoretical dependences (for example, for the
thickness of the diffusion boundary layer), the original Levich t h e o r y has n o t
been altered substantially.
The RDE does not enable unambiguous identification of the products of
more complex electrochemical reactions. In 1959, papers by Frumkin,
Nekrasov and others [ 248,249,325] were published describing a new type of
disk electrode that has a conductive ring placed around the disk. The advan-
tage of this electrode is based on the fact that the reaction products are hydro-
dynamically transported from the disk to the ring where they can be directly
monitored electrochemically, provided that they are electroactive. The first
application [248] verified the suitability of the design of this sensor and the
theory has been developed [ 325], enabling quantitative interpretation of the
measured results.
The original approximate theory of the rotating ring-disk electrode (RRDE),
in the development of which Levich and his co-workers again participated,
was later treated mathematically in detail by Albery and co-workers, both for
steady-state and non-steady-state measurements, In addition to these analytical
solutions, numerical calculations of the necessary dependences have been
carried out by Bard and co-workers.
The first reports of applications of the R R D E came from Soviet institutes,
and only more than five years later did papers by other authors appear; groups
of co-workers have gradually formed around authorities such as Kiss and Farkas
in Hungary, Bruckenstein, Bard, Bockris and Miller in the United States, Albery
in Britain, Mfiller in the German Democratic Republic and others.
The present review presents the theoretical background for the RDE and
R R D E and emphasizes their application to the study of the kinetics of electrode
and volume reactions, and to the study of diffusion. These fields of application
have not been chosen at random; disk electrodes meet a number of necessary
requirements in these particular measurements.
Disk electrodes belong to the group of so-called convection or hydrodynamic
electrodes; i.e. mass transport at their surfaces, and consequently the magni-
tude of the current passing during simple electrode reactions, are controlled
by convection of the electroactive species, caused by electrode rotation or by
stirring of the solution. Hence certain methods and laws of hydrodynamics
are employed in the theory of these electrodes. The principal factors affecting
the performance of the electrodes are the liquid flow and the mass transport.
These two factors can be considered separately and then suitably combined
to obtain equations describing the properties of the electrodes. This procedure
was followed during the development of the theory.

2. THEORY

The basic modes of mass transport in stirred solutions are convection and
diffusion. The equation describing these transport processes -- the convective-
diffusion equation -- can be solved explicitly if the dependence of the velocity
vector for the flowing fluid on the coordinates of a selected coordinate system
is known.
Below, some relationships holding generally for hydrodynamic electrodes
will be given and then applied to a specific hydrodynamic system -- the RDE.
The theoretical considerations contained in the present paper are based on
Riddiford's review [ 599] and on the works of Levich [429], Pleskov and
Filinovskii [568] and of Albery and Hitchman [26].
2-1. General relations for h y d r o d y n a m i c electrodes

(a) The convective-diffusion equation. If the solution is not in t h e r m o d y n a m i c

equilibrium, transport phenomena occur. Assuming that no chemical reactions
take place in the solution and that the solution is isothermal, the material flux
for the i-th particle of concentration ci and with diffusion coefficient D i to-
wards the electrode is described by the equation
(Jd)i = (Jd)i, dif + (]d)i,conv + (]d)i, migr = - - D i grad c i + civ + ViciE (2-1)
where ]d is the flux for a kinetically uncomplicated process (if the material
flux value contains a kinetic contribution, it is termed j; similarly, ia and i are
the corresponding current densities), E is the electric field intensity in the solu-
tion, Ui is the ionic mobility and v is the velocity vector for the flowing fluid.
Assuming that
(i) ci -- f ( x , y , z ) is different at various points and depends on time;
(ii) a steady-state is established, d v / d t = 0;
(iii) the dependence of D i on the concentration is neglected;
(iv) the fluid is incompressible;
the number of particles, Qi, entering volume element V enclosed by area S in
one second equals Qi = - ~ (Jd)i dS (the direction of the normal vector to the
surface in an outward direction is taken as positive). If 8ci/~ t equals the change
in the number of particles in a unit volume per second, then the change in the
number of particles in element V is given by integral Qi = f (8ci/St) dV. When
these relationships are compared
f d V = - - f (Jd)i dS
and the Gauss-Ostrogradski theorem is employed, the equation
f ( ~ci/~ t) d V = - - f div(j d)i d V
is obtained, from which it follows t h a t
~ C i / ~ t ---- - - div(j d)i
or, taking into account equation (2-1),
~ci/8 t = div(Di grad ci) -- div civ -- div(UiciE) (2-2)

As Di is assumed to be independent of the concentration, it is valid that

div(D i grad ci) = Di div grad c i = Di Ac i

div(civ ) = v grad c i + c i div v

Div v = 0 (the liquid is incompressible), so that the material balance is de-

scribed by the equation
~ei/~ t = DiAc i -- V grad ci -- Ui div(ciE) (2-3)
This is the general equation for convective diffusion. It is simplified when the
concentration is independent of time, when the solution is not stirred (Fick's
second law), or when the transport is not affected by the electric field (un-
charged particles, excess base electrolyte).
Equation {2-3) or its simplified forms can be solved in connection with a
system of boundary conditions, the choice of which depends on the character
of the system studied or on the character of the dependence followed. They
are usually formulated as follows: The concentration in the bulk of the solution
equals the overall analytical concentration, ci = ci(¢¢), for y -~ ~, where y is the
perpendicular distance from the electrode surface. At the electrode surface, for
y = 0, the equation D i ( ~ c i / ~ n ) y = 0 = k Ci{0) # holds, where k is the heterogeneous
rate constant and p is the reaction order, ci(0) is the surface concentration and
the differential term, ~ci/~n, expresses the number of molecules transported to
a unit electrode surface at steady state. The latter boundary condition depends
on the character of the surface reaction. For rapid electrode reactions, ci = 0,
while for very low reaction rates (~ci/~n) ~ O. When substances are stripped
from the electrode surface, the condition ci = 0 holds for y -~ oo and if the
stripping rate is greater than the rate of transport into the bulk of the solution,
the condition c i = (Ci)sa t holds for y = 0.

(b) Equations for fluid flow. Equation (2-3) with the appropriate boundary
conditions can be solved if the dependence of the fluid velocity vector, v, on
the coordinates is known. A system can be considered, consisting of a solid
phase (a plate) with characteristic dimension l (e.g. the length of the plate in
cm), around which a fluid of dynamic viscosity p and density p flows at veloc-
ity v (e.g. in cm s - l ) . The movement of the fluid can be expressed by equa-
tions that have the following form in Cartesian coordinates
p [dv/dt + v grad v] = -- grad p + p a y + f (2-4)
div v = 0 (2-5)

Relationship (2-4) is the Navier-Stokes equation, describing the movement of

a fluid element (1 cm 3) due to the effect of various forces. The left-hand side
of the equation gives the effect of the mass of this element on its acceleration
and the right-hand side specifies the forces acting on it: pressure p, external
forces f and viscosity p or the forces of internal friction, p a y . The internal
friction forces act between layers of the fluid moving at different velocities if
so-called Newtonian fluids are involved, i.e, isotropic fluids for which p is con-
stant at the given temperature and pressure.
Due to the internal friction between neighbouring fluid layers, the distance
between which, at right angles to the direction of fluid flow, is dy and the
difference in velocity dv, tangential tension r develops, described by the equa-
tion
T = p dv/dy (2-6)
Equation (2-5) is the equation of continuity, expressing the law of conservation
of mass.
In addition, a dimensionless parameter, the Reynolds number, R e , must be
defined:
R e = ul/v (2-7)
where v = p / p is the coefficient of kinematic viscosity. If p [cm -1 g s-1 ] and
p [g c m - 3 ] , then v [cm 2 s - l ] . R e is a critical value that characterizes the qual-
ity of the flow. For low R e < Recrit , the flow is laminar and for large R e >Recrit,
turbulent flow occurs.
It is convenient to divide the whole system into two regions:
(i) The region located far from the surface of the solid phase;
(ii) the region in close vicinity to the solid phase.
In the former, viscous forces are without effect for R e >> 1 and the Navier-
Stokes equation is converted into the Euler equation on neglecting the terms
containing viscosity, i.e. into the equation describing the behaviour of an ideal,
non-viscous fluid. Solution of this equation assumes the following form for
stationary flow and for external forces given by f = grad u
v grad v = - - g r a d [ p / p + u / p ]
This is the Bernoulli equation, expressing the law of the conservation of energy
in an ideal fluid

u2/2 + p / p + u / p = const.

In real fluids, a specific region is formed in close vicinity to the solid phase
{region ii), within which viscosity forces play a predominant role. In this re-
gion a fluid velocity gradient is formed at right angles to the surface of the
solid phase, with velocities ranging from that of the flow of the bulk of the
fluid to that of the solid phase. This region is more important than the bulk
of the fluid from the h y d r o d y n a m i c point of view and is termed the (Prandtl)
boundary layer. The viscosity terms cannot be neglected in equation (2-4); if
the dimension of the solid phase is much larger than the thickness of the
boundary layer, ~o, then the latter is given by the relationship

~o ~ l / R e l l 2 (2-8)

The Navier-Stokes equation can be solved rigorously for only a few cases
under these conditions. One of them is the rotating disk system (see below);
otherwise approximate methods must be employed.

(c) T h e d i f f u s i o n b o u n d a r y layer. A simplified convective-diffusion equation

for stationary concentration distribution, ~ c i / ~ t = 0, and for zero electric
field assumes the form
v grad ci = D i A c i (2-9)
The left-hand side of this equation expresses convective transport; the right-
hand side corresponds to transport by diffusion.
Analogous to the definition of the number R e , characterizing the mode of
flow, another dimensionless parameter, the Peclet number, Pe, can be defined
to characterize the mass transport properties
Pe = v l/Di (2-10)

Transport by diffusion is negligible for large P e values and predominant for

small values. The P e / R e ratio gives the Schmidt number, S c
P e / R e = v/Di = Sc (2-11)

(Some authors call this ratio the Prandtl number; however, this name is usually
reserved for heat transfer).
Since aqueous solutions have values of v ~ 1 0 - 2 c m 2 s - 1 and D i ~ 10-Scm 2
s- 1 , the value of S c is ca. 103. It can be seen from the equation, Pe -- R e X S c ,
that for R e ~ 10 - 2 and S c ~ 103, the P e value is sufficiently large for mass
transport to be effected mostly by convection (moreover, practically attained
values of R e are usually several orders higher than the above value, see below).
Hence, the diffusion terms in equation (2-9) can be neglected with respect to
convection and the solution of the simplified equation, v grad ci = 0, leads to
the result, ci = const,
If the solid phase considered is an electrode on which a surface reaction
proceeds at a sufficient rate, the above result is n o t correct within a certain
distance, 5, from the solid phase surface, when a concentration gradient is
established. Diffusion plays an important role within this layer and hence the
D i A c i term becomes comparable to the convection term. Therefore, the con-
vection-diffusion equation must be solved without simplification for this re-
gion.
This thin layer, termed the diffusion boundary layer, is substantially thinner
than the boundary layer 50 since D~ < v, and its thickness is given by

5 ~ ( D / v ) 113 5o = 5 o / S c 113 (2-12)

Hence, 5 is about ten times thinner than 50 in aqueous solutions.

In the above text a certain analogy between fluid flow to a solid phase and
mass transport towards an electrode in a stirred solution is evident. In both
cases the characteristic property of the system, e.g. the viscosity or diffusion
coefficient, is not important in the bulk of the solution and the velocity of
fluid flow or mass transport is independent of it. However, this property becomes
very important in the vicinity of the solid phase. The processes of mass trans-
port and heat transfer are also very similar; a number of theoretical conclu-
sions for mass transport have been made on the basis of the study of heat
transfer. The similarity of the two processes is documented in Table 1, which
summarises the important parameters and shows that the mathematical for-
mulae are also formally analogous.
2-2. Fluid flow toward a rotating disk

(a) Laminar flow. The rotating disk electrode can be described theoretically as
a system of a circular conductive plane with infinitely large radius, placed
horizontally in a solution of an electrolyte and rotated along the vertical axis
with an angular velocity of ¢0. Equations (2-4) and (2-5) can be solved explic-
itly for this system [271]. Because of the axial s y m m e t r y of the system, it is
suitable to transfer these equations into polar coordinates (r, ~0, y) [ 160,355].
It is assumed that:
(i) the flow is non-turbulent, dv/dt = 0;
(ii) the flow is independent of coordinate ~, because of the axial symmetry;
(iii) the fluid is incompressible and the b o u n d a r y layer is horizontal;
(iv) variations in the pressure in the boundary layer are d e p e n d e n t only on y;
(v) a sufficient angular velocity generates strong convection, so that contri-
butions from extraneous forces are eliminated, i.e. f = 0 (the gravitational force
is included in the pressure);
(vi) the infinitely large radius of the disk allows edge effects to be neglected.
The resulting equations for the individual c o m p o n e n t s of the fluid flow ve-
locity vector (see Fig. 1) and the equation of continuity then assume the form
c]Vr U2 + Vy = /: + + --
vr ~ r - - 7 -~ [_aN2 ~r 2 r~r

vrv
v~ ~ + + Vy =v [ + + -- ~j (2-13)
r -~ Lay 2 ~r 2 r~r

~Vy ~Uy p ~ = [~2Vy ~2Vy ~Vy-]

v~ ~ + v, -~- + v t_ ay2 + ar 2 + r-SVJ

~Vr Vr ~Vy
--~r + --r + ~-y = 0 (2-14)

The components of the fluid velocity and the pressure can be c o m p u t e d from
this set of equations, employing the b o u n d a r y conditions
v~ = 0 v~=cor vy=0fory =0 (2-15)
v~=0 v~=0 vy=const, fory-*
and using the integration methods of K&rmfin [355] and Cochrane [160], ob-
taining
vr = rooF(7)
v~ = r ~ G ( 7 )
vy = (coy) 1/2 H(7) (2-16)

p = pvwP(7)
10

TABLE 1
Survey of some parameters that characterize mass and heat transport

Mass transport or flux Heat transfer Symbols

of liquid

Reynolds number Reynolds number v - - f l u i d v e l o c i t y [ c m s -1 ]

l -- the solid phase dimension [cm]
Re = vl/v Re = vl/v
v - - k i n e m a t i c v i s c o s i t y [ c m 2 s- 1 ]
Sherwood number Nusselt number Jd material flux [mol cm--2s -1 ]
- -

D - - d i f f u s i o n c o e f f i c i e n t [ c m 2 s- 1 ]
S h = j d l / D [ c ( c ~ ) - - c( O ) ] N u ~ q l / h [ T - - T ( O) ]
c(~) -- bulk concentration
c ( 0 ) - - c o n c e n t r a t i o n at t h e s o l i d
phase surface
Schmidt number Prandtl number q - rate of heat transfer
[cal c m - 2 s - 1 ]
Sc = v/D Pr = vpslX
)~ t h e r m a l c o n d u c t i v i t y
- -

[cal c m 1 d e g - - 1 s--1 ]
Peclet number T -- solution temperature
T(0) -- temperature at the solid
Pe = vl/D phase surface
s -- specific heat of the fluid
[cal g--1 d e g - - 1 ]

where 3' is a dimensionless distance f r o m the disk surface

3`= (co~v) 112 y (2-17)

On substituting into e q u a t i o n s (2-13), (2-14) and (2-15), a set o f differential
equations with the appropriate boundary conditions are obtained

Vr

Fig. 1. T h e r o t a t i n g d i s k c o o r d i n a t e s y s t e m .
 11

F2-G 2+F'H=F''

2 F G + G ' H = G"
H H ' = P' + H" (2-18)

2F+H'=0
F=0 G=I H=0 forT=0 (2-19)

F=0 G =0 H = - - c o n s t / ( c 0 v ) 1/2 f o r ~ , - + ° °

(the p r i m e d s y m b o l s d e n o t e d i f f e r e n t i a t i o n o f the given f u n c t i o n with r e s p e c t

to y).
F u n c t i o n F describes the centrifugal m o v e m e n t o f the fluid, f u n c t i o n G t h e
r o t a t i o n a l m o v e m e n t and f u n c t i o n H the m o v e m e n t at right angles t o the sur-
face o f the disk. These f u n c t i o n s , d e t e r m i n i n g the a p p r o p r i a t e c o m p o n e n t s o f
the fluid velocity, can be c a l c u l a t e d f r o m e q u a t i o n s (2-18) and (2-19). F o r
small values o f 7 it holds t h a t
b2
1 2 - - ~1b ' , / 3 -- ,~4 . .
F = a7 ~7 ~ •

1 3 ( a b - - 1) 74 (2-20)
G =l+b 7+~a7 + 12 "'"

H = --aT 2 + ~1 73 + ~b 74 . . .

and for large values o f 7,

A 2 +B 2
F = A exp(--aT) exp(--2aT) + . . .
2a 2

G = B exp(--aT) B(A2+B2) exp(--3aT) + . . . (2-21)

12a ~

H=--a+2Aexp(--aT) A2 + B2 e x p ( - 2 a 7 ) + . . .
c~ 2a3

w h e r e a = 0.510, b = - - 0 . 6 1 6 , ~ = 0 . 8 8 6 , A = 0 . 9 3 4 and B = 1.208. More accu-

rate values o f these c o e f f i c i e n t s were f o u n d b y S p a r r o w and Gregg [ 6 4 5 ] , ~ =
0 . 8 8 4 4 7 , a = 0 . 5 1 0 2 3 , Rogers and L a n c e [ 6 0 1 ] , ~ = 0 . 8 8 4 4 6 , a = 0 . 5 1 0 2 3 3 ,
b = - - 0 . 6 1 5 9 2 2 and B e n t o n [ 8 5 ] , A = 0 . 9 1 7 7 2 , B = 1 . 2 0 2 1 1 . F u n c t i o n s F, G
and H are r e p r e s e n t e d in Fig. 2 a n d their values for various values o f 7 are
given in Table 2.
It can be seen t h a t for 7 = 3.6 the value o f G is ca. 0 . 0 5 G ( 0 ) a n d H ~ 0.8H(oo).
This value o f 7 was t a k e n b y Levich as the t h i c k n e s s o f the b o u n d a r y layer, i.e.
the distance f r o m the surface at w h i c h t h e fluid begins t o be carried b y t h e ro-
12

i I i i I I I I i
1

0.8

0.6

0,4

0,2

0,4 0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6

Fig. 2. T h e s h a p e of f u n c t i o n s F, G a n d H a c c o r d i n g to t h e d i s t a n c e f r o m t h e r o t a t i n g disk.

TABLE 2
T h e values o f f u n c t i o n s F, G, H a n d P for various values o f 3~
F r o m ref. 568

7 F G --H P

0.2 0.084 0.878 0.018 0.167

0.4 0.136 0.762 0.063 0.275
0.6 0.166 0.656 0.124 0.340
0.8 0.179 0.561 0.193 0.377
1.0 0.180 0.468 0.266 0.395
1:2 0.173 0.404 0.336 0.403
1.4 0.162 0.341 0.404 0.406
1.6 0.148 0.288 0.466 0.405
1.8 0.133 0.242 0.522 0.403
2.0 0.118 0.203 0.572 0.401
2.2 0.104 0.171 0.617 0.398
2.4 0.091 0.143 0.656 0.396
2.6 0.078 0.120 0.690 0.395
2.8 0.068 0.t01 0.721 0.395
3.0 0.058 0.083 0.746 0.395
3.2 0.050 0.071 0.768 0.395
3.4 0.042 0.059 0.786 0.394
3.8 0.031 0.042 0.815 0.393
4.0 0.026 0.035 0.826 0.393
4.4 0.018 0.024 0.844 0.393
¢¢ 0 0 0.886 0.393
 13

tating disk because of its viscosity. Hence, the thickness o f the b o u n d a r y layer
is given, according to equation (2-17), by

~0 = 3.6 (v/a~) 1/2 (2-22)

The numerical value of ~ 0 differs in accordance with the value of 7 that the
particular author considers to be critical. For example, Riddiford [ 599] con-
siders distance 7 = 2.8 to be the thickness of the boundary layer, for which it
holds that G ~ 0.1G(0) a n d H ~ 0.72H(~o).
Thickness ~ o is independent of coordinate r, i.e. is identical over the entire
surface of the disk and increases with decreasing rotation velocity. For aqueous
solutions, ~o = 0.36 cm for I rev s- 1 , ~0 = 0.11 cm f o r 1 0 rev s- 1 , ~0 = 0.036
cm for 100 rev s-1 and a0 = 0.011 cm for 1000 rev s- 1 .
The shape of the above functions also provides a picture of the fluid flow;
according to yon K ~ r m ~ , the fluid flows at right angles to the surface of the
disk at a constant velocity at a large distance from the disk (7 -~ ~). From a
certain distance from the surface of the disk (equation (2-22)), the fluid begins
to be carried tangentially, its angular velocity increases with decreasing distance
from the surface and at the surface of the disk (7 = 0) equals its angular veloc-
ity (Fig. 3).
For rotating disks, c o m p o n e n t vy is most important, since the electroactive
material is transported toward the surface only in this direction. With the ro-
tating ring-disk electrode, the radial c o m p o n e n t of the fluid velocity vector,
vr, is also important. Considering the values of functions H and F (equation
(2-20)) and using equations (2-16), the important components of the fluid
velocity vector can be expressed in the form

vy = --0.886 (¢0v) 1/2 for 7 -~ oo (2-23)

vy =--(¢ov)lJ2 [ 0 . 5 1 7 2 - - 0 . 3 3 3 73 + 0 . 1 0 3 7 4 .... ] f o r 0 < 7 < ~o (2-24)

vr = r ¢ o [ 0 . 5 1 7 - - 0 . 5 7 2 + 0 . 2 0 5 7 3 - . . . ] for0<7<Oo (2-25)

As can be seen from these equations, the normal c o m p o n e n t of the fluid ve-

\\
A
B

Fig. 3. Scheme of fluid flow toward a rotating disk. (A) in the immediate vicinity of the
disk, (B) below the disk.
14

locity is, in contrast to the radial component, independent of coordinate r

and is the same at any point on the disk.
The mode of fluid flow is characterized by a dimensionless quantity, the
Reynolds number, R e (see equation (2-7) above), which for a rotating disk of
radius rl0, is given by

R e = ¢Or2o/V (2-26)

At a certain value, Recrit , the fluid flow changes qualitatively from laminar to
turbulent. Conversion is gradual. First, the edge of the disk is affected by
turbulence and this gradually extends toward the centre with increasing veloc-
ity of rotation. The range of this conversion is wider for smaller S c values.
Critical R e values have been determined by m a n y authors; laminar flow
changes to turbulent at R e ~ 105. The Recrit values obtained by various mea-
surements are given in Table 3. An orientative R e value can be f o u n d for an
electrode of a given diameter d [mm], rotated at rate f [rev m i n - 1 ] , from the
intercept nomogram given in Fig. 4.
Turbulence sometimes appears at R e values below Recrit when the disk vi-
brates axially or radially and when the surface is uneven, which causes supple-
mentary stirring of the solution [171,648].
Another extreme occurs for R e ~ 10, when the thickness of the boundary
layer, ~ 0, becomes comparable with the dimensions of the disk and natural
convection in the solution begins to play a role. Therefore, the condition

3.6 ( v / c o ) l / 2 / r l o ~ O, i.e. 3 . 6 2 / R e ~- 0 (2-27)

must be fulfilled. Then the thickness of the b o u n d a r y layer is sufficiently

smaller than the radius of the disk and R e is sufficiently large to make natural
convection negligible. The effect of the vessel walls on the flow is thus also
eliminated (it is impossible to employ a disk w i t h an infinitely large radius in
an unlimitedly large medium), as well as the effect of other parts of the
apparatus immersed in the solution.

(b) T u r b u l e n t f l o w . Owing to friction between the surface of the disk and the
neighbouring layers of the fluid, a tangential tension appears (equation (2-6)),

TABLE 3
The Recrit values obtained in various measurements

Recrit Ref. Recrit Ref.

2.4 x 105 159 1.8 x 105 286

2.2 × 105 669 2.1 x 105 399
2.7 X 105 170 3.1X 105 636
 15

--105
70st - S.lO4 .,~

-- 2.104 "~o~

r~L.3"103/ -8.1o3 R e
--5,10 3 ('~ =lO-2cm2s"1)

--2.10 3

2.130 1

--~103 ~.,,.A.S
--800
--4
1.5.1 -- 600

-- 3.5
-- 400

--200
L~

-2.7

--100 "2.5
-- 80

-- 60 j 2.2
-- 50
-- 40 2

-- 30
-- 20 / 7"8

%
--10 i,~

--5

ml

Fig. 4. A nomogram for the determination of the Recrit value for electrodes of the given
geometric parameters.

which is given by the relation [ 5 6 8 ]

r~ = p ( a v ~ / a y ) ~ = o = r p v 112 co3/2 G'(0) (2-28)

for a rotating disk and laminar flow.

The m o m e n t of viscosity forces M acting on a disk with radius r 10 is given
by the relation
rl0
M = f rry~ 27rr dr = - - 0 . 3 0 8 ~rpv 1/2 w 3]2 r~o
0

Instead of M, a dimensionless coefficient of the m o m e n t of medium resistance,

16

CM, is often employed and has the value

CM =--M/pco2r5o = 3 . 8 7 / R e °'5 (2-29)

for a rotating disk and laminar flow. Thus CM ~ R e - ° ' 5 for laminar flow.
At R e > Recrit laminar flow changes into non-stationary chaotic movement;
only average values of the appropriate quantities can be used for description
of the fluid movement, since the fluid velocity fluctuates non-uniformly
around a certain average value. With laminar flow any turbulent pulsations dis-
appear rapidly, while with turbulent flow chaotic movement of the fluid per-
sists. The tangential tension for turbulent flow is given by [357]
--t--t --t
r y ~ = U( ~v~/~ Y ) - - p ( v ~vy ) = p ( v - - Vturb) ~V~/~ y (2-30)
where v' is the average velocity of the turbulent pulsations. The quantity
Pturb i s , in contrast to v, determined n o t by the properties of the fluid b u t
by the character of the pulsations. Far from the disk Vturb >> V and the viscos-
ity forces in the fluid play no role. At the boundary of a solid phase and
turbulently flowing fluid, a turbulent boundary layer, ~o, is formed, within
which Vturb decreases linearly with decreasing distance from the surface of
the solid phase, i.e. Vturb ~ y. There are t w o sub-layers in the vicinity of the
solid phase:
(i) a viscosity sub-layer within which turbulent pulsations disappear and
it holds that Pturb ~ yC~, where a ~> 3;
(ii) a laminar sub-layer corresponding to a thin layer immediately at the
surface of the solid phase, where Vtu~b ~ V.
The velocity profile for turbulent flow is given by KSxm~n [355] as

v~ = const r c o ( y / ~ o ) 1/7 [1 -- (Y/~o)]

v~ = rco[1 -- ( y / 8 o ) :17 ]

The thickness of the turbulent boundary layer is given by

Bo = 0.525 r (v/r2o co) 1/2 (2-31)

The coefficient of the m o m e n t of the medium resistance is given by the rela-

tion [355,356]
CM = O . 1 4 6 / R e °'2 (2-32)
Therefore, the dependence of CM on R e is CM ~ R e - ° ' 2 . (The logarithmic
form of the relationship between CM and R e was found by Goldstein [ 2 7 0 ] ,
1/c~/2 = f [log Re/c 112] .) Equations (2-29) (laminar flow) and (2-32) (turbu-
lent flow) are plotted in Fig. 5 (from Dorfman [198]). The break on the plot
around R e ~. 105 corresponds to transfer from laminar to turbulent flow. The
boundary layer thickness for turbulent flow depends on coordinate r (equa-
tion (2-31))and hence is n o t identical over the surface of the disk:
 17

7
6

o 4
o

3~

2~

0.5 -

I f I
104 105 106 Re

Fig. 5. T h e dependence o f c M on Re. (1) A c c o r d i n g to e q u a t i o n (2-g9), (2) a c c o r d i n g to

equation (2-32).

2-3. Mass transport toward the R D E

(a) Mass transport toward the R D E under laminar flow conditions. If the depen-
dence of the components of the fluid velocity vector on the coordinates is
known, the convective diffusion equation (2-3) can be solved. It has the follow-
ing form in polar coordinates (assuming zero electric field, i.e. transport of un-
charged particles or the presence of excess base electrolyte):

~ e + v r ~c ~ ~c+ ~c ra2c a2c l a c 1 ~2c~

~--t ~+r~-~ vy ~ = D + +---+- (2-33)
Lay2 ~r 2 r ~r r 2 ~ 2 j
This equation was solved by Levich [425--427,429] for the RDE. The fluid
flow conditions must be fulfilled; moreover, the equation for the RDE can be
simplified assuming that:
(i) a steady state is established, ~c/5 t = 0;
(ii) the diffusion coefficient is independent of the concentration;
(iii) c is independent of coordinate ~ because of the axial s y m m e t r y ;
(iv) c is independent of coordinate r, since the concentration varies along a
line normal to the surface of the disk and the substance cannot be transported
18

beyond the diffusion layer with a disk of sufficiently large radius (theoretically
infinitely large);
(v) the surface of the disk is smooth and homogeneous.
The convective-diffusion equation for the RDE is simplified to give

vy dc/dy = D d2c/dy 2 (2-34)

which can be solved for the boundary conditions

c = c(oo) for y -+ oo (2-35)
c=0 for y = 0 (2-36)
A general boundary condition containing the effect of the surface reaction,
D(~c/~y) = kc ~, will be introduced below.
Equations (2-34)--(2-36) can be solved in the form c = f(y). Double integra-
tion of equation (2-34) yields the expression

e=al /
o
exp ~
o
vy(z) dz ] dt +a2 = a l I ' +a2 (2-37)

where a 1 and a2 are integration constants. From boundary condition (2-36)

it follows that a2 = 0 and from (2-35) that

¢(~)=a 1
/
o
exp ~
0
vy(z) dz
1 d t = a l I = a l ( I 1 +I2) (2-38)

In order to calculate integral I, the integration range, <0, ~ ) is separated into

two parts: I1: <0, ~) and I2: <O, ~). Outside the diffusion boundary layer,
equation (2-23) is valid for vy, while equation (2-24) is valid inside the diffu-
sion layer.
It was shown in section 2-1c that basic changes in the concentration take
place in a thin layer at the electrode surface for large Se values (D ~ v); hence,
it can be concluded that the value of integral I2 is negligibly small compared
with the value of I1. Integrals 11 and I2 have been calculated by Levich using
the value

Vr = __0.51C03/2 p - - l / 2 y2

corresponding to the first term of expansion (2-24):

I1 = co1/2 0.8934 = 1.61 (2-39)

1 D

Comparison of these integrals for c o m m o n D/v ~. 10 a leads to the inequality

 19

I2 < I1, confirming the above assumption. The I1 value is the diffusion layer
thickness at the RDE.
The value of integration constant al can be determined from equations
{2-38) and (2-39); on substitution into (2-37), the concentration distribution
is given by

c= c(oo) I' (2-41)

1.61 (D/v) 1/3 (V/W) 1/2
Hence the limiting material flux to a unit surface equals
(de) _ De(c') (2-42)
Jd = D ~-~ y=0 1.61 (D/v)113(v/co) I/2
where

0 = 1.61 ~ 0.5 Se 1/~

is the thickness of the boundary diffusion layer. At Se = 103, 0 = 0.015 cm for

1 rev s- I , 0.005 cm for 10 rev s - 1 , 0.0015 cm for 100 rev s- 1 and 5 X 10 - 4 cm
for 1000 rev s- 1 .
Both the material flux (equation (2-42)) and the diffusion layer thickness
(equation (2-43)) have the same values at all points on the RDE surface. This
property -- the uniform accessibility of the surface [ 241] -- is a specific prop-
erty of the RDE, leading to the particular suitability of this electrode for
studying various electrochemical and non-electrochemical problems. It should
be noted that this property is encountered only with homogeneous, smooth
disks, under conditions far from the extremes (very low current densities, well
below the limiting value, and strong polarization, see below).
The concentration distribution in the diffusion layer is evident from Fig. 6,
where C = [c(~) - - e ] / e and ~ = y/~. The Nernstian distribution, for which

c-C(°°)--c-[lo--~c for0<y<~
for y >
is also given for the sake of comparison.
When the limiting material flux value (equation (2-42)) and the Eucken
relationship for the limiting current density at a rotating solid electrode [222]
are employed, the limiting current density at the RDE is given by the equation

id = -+0.620 nFD213p--116 w l l 2 C(OO) = ±B(.v¢)l/2 (2-44)

Hence the limiting current is a linear function of the square root of the elec-
trode rotation rate (w = 27rf).
A number of workers have attempted to make the Levich theory more
rigorous, namely Gregory and Riddiford [285], Newman [527] and Kassner
[359]. The results of Gregory and Riddiford are cited especially frequently;
 2O

i I • I

0.5

0
i 0.5
%
I

Fig. 6. Scheme of the concentration distribution in the diffusion layer. (1) According to
equation (2-41); (2) the Nernstian distribution.

they calculated integral I1 taking into account higher terms in the vy expan-
sion (see equation (2-24)). Their solution, considering the third order terms
of the expansion, gives

a = 1.61 (D)I/~ ( ~ ) 1/2 I1 + 0.3539 (D)°'s61 (2-45)

for the thickness of the diffusion layer. The difference between this value and
that given by equation (2-43) amounts to about 3--5%, with a correspondingly
lower value of the material flux. However, it has been shown [429] that this
correction is compensated to a large degree by a number of factors, such as
edge effects, contributions from natural convection, turbulence, the migration
component of the material flux, etc. The significance of the Gregory and Riddi-
ford correction increases for Sc numbers in the interval, 10 < Sc < 102, where
the difference from the Levich theoretical value reaches values of up to 17%
[568].
For the sake of comparison, examples of other hydrodynamic systems dis-
cussed by Levich [429] are given in Table 4.

(b) Mass transport toward the RDE under turbulent flow conditions. The ma-
 21

TABLE 4
S o m e i m p o r t a n t r e l a t i o n s h i p s for h y d r o d y n a m i c e l e c t r o d e s of various s h a p e s

System R o t a t i n g disk Plate a r o u n d w h i c h Tubular electrode

fluid flows

tY x
l,
Convective- dc d2c dc dc 2v0 dc d2c
diffusion vy ~yy = D - dy "-R- Y-~x = D - -
equation dy 2 Vx ~ + Vy -
dy 2

= Fd ÷d cl
Ldx 2 dy2J
Material Dc ( oo ) Dc ( oo ) D c ( ~o )
flUX Jd
Dtl/3 ( p tl/2 [ DRx'~ 1/3
.01 .49t- o

layer a = 0.5 a0 a = 0.6 a0 a = 1.49 --

\Vo/
thickness

terial flux toward a rotating disk under laminar flow can be expressed by the
dimensionless S h number (see Table 1)

S h = 0.62 R e 1/2 S c 1In (2-46)

For material flux under turbulent flow, the equation [ 568]
Jd : --(D + Dturb ) dc-/dy
is valid, where d-~/dy is the mean concentration gradient and Dturb is the
turbulent diffusion coefficient, characterizing substance transfer in a turbulently
and chaotically moving fluid. It differs from the diffusion coefficient D, charac-
terizing molecular diffusion, in all except the dimensions [cm 2 s-l]. Since
turbulent pulsations change with changing distance from the solid phase, Dturb
also changes in dependence on coordinate y. This diffusion coefficient is deter-
mined by the same mechanism as ~2turb and in the vicinity of the solid phase it
holds that Dturb ~ Pturb; it is larger than D by several orders of magnitude.
Analogously to turbulent fluid flow, with turbulent substance transfer the
22

whole system can be divided into several regions with different properties. F a r
away from the solid phase, within the region of well developed turbulent pulsa-
tions, the transfer is determined b y the magnitude of Dturb and molecular diffu-
sion is unimportant. In the vicinity of the solid phase -- an electrode -- three
characteristic regions can be distinguished:
(i) the turbulent diffusion layer, where transfer by turbulent pulsations
predominates, Dturb >~ D;
(ii) the viscosity diffusion sub-layer, in which Dturb decreases with the
fourth power of the distance from the surface, down to the region where
Dturb ~ D ;
(iii) the laminar diffusion sub-layer, where the transfer is determined by
molecular diffusion and Dtu~b is unimportant.
The equation for material flux under turbulent flow has the dimensionless
form

S h = 0.02 R e ~ S c • (2-47)
where coefficient 7 characterizes the rate of disappearance of turbulent pulsa-
tions in the viscosity sublayer. The 7 and fl values were determined and some
of the results are given in Table 5; present experimental methods are incapable
of determining the coefficients 7 and/3 more reliably than shown in the Table.
It is thus possible to consider, in agreement with Levich's work [428,429],
that material flux for turbulent flow is given by the equation

S h = 0.02 R e 4/5 S c 1/4 (2-48)

Material transfer in turbulently stirred media has been discussed by several
other workers [62,70,226,468].

(c) R D E t h e o r y in b i n a r y e l e c t r o l y t e s . The equations for the material flux

(2-42) and the current density (2-44) at the RDE hold for transport of un-
charged particles or for transport in a base electrolyte solution. If charged
species are transported, the migration c o m p o n e n t contributes to the material
flux. If the solution contains an ion with charge zi, concentration ci and diffu-

TABLE 5
The values of coefficients 3' and/~ in equation (2-47)

7 Ref. /3 Ref.

Large Sc 0.8 159, 184

0.25 429,!241 0.9 429,166
0.33 166, 360 0.78 360
0.5 190, 580 0.92 190
Small Sc
1 159,429
 23

sion coefficient Di, then the ion moves in an electric field with intensity E
under the action of force z i e E (e is the charge of one electron), and the flux
of the migrating species equals the third term in equation (2-1). Then the
concentration distribution must be described by the general equation (2-3),
combined with the condition of electroneutrality of the solution as a whole,
Y, cizi = O. One of the cases for which equation (2-3) can be solved is for a
binary electrolyte. The convective-diffusion equation assumes the form
v grad c = D e f A c (2-49)

where De~ = D + D _ (z÷ + Jz_ L)/{z+D+ + Iz_ ID_ ) is the effective diffusion co-
efficient and c is the overall concentration (molar), given by c = c÷/]z_ J =
C/Z+.
When the concentration distribution is known, the potential distribution
can be determined. Using the Eucken procedure, the equation for the E - - i
curve in a binary electrolyte can be derived

{
i = i0 1 - - e x p z . + [z_[ (gv--Eohm)
1} (2-50)

where Uv is the voltage applied to the electrodes, Eohm is the ohmic drop in
the solution and id is the limiting current density at the RDE, for which it
holds in a binary electrolyte solution that

id = Fz+D+
I1 -- ~z+I 1.61
c+(~)¢°i12
n l / 3 vl/6
(2-51)
~ef

A more complex dependence of the current density on the diffusion coeffi-

cient is encountered here. For a binary electrolyte, i d ~ D ~ 1/3 and D+
In addition to Levich [429], many other authors [149,362,523,528,529,
606,638] have studied RDE theory in binary electrolytes. Attempts have also
been made to calculate the potential distribution in solutions containing three
kinds of ions [9,244,722,723,727]. The effect of the indifferent electrolyte
concentration on the current values was investigated in a number of publica-
tions [205,206,276,446,447,524,711,712].
The ohmic voltage drop that appears in the vicinity of the RDE is a linear
function of the distance from the disk, assuming infinite disk radius. In real
electrochemical systems the rotating disk has finite dimensions and the poten-
tial distribution has a different character. This distribution close to a disk with
radius rio placed in an insulator was calculated by Newman [525] for currents
considerably below the limiting current, so that the concentration distribution
need n o t be considered and the potential gradient is purely ohmic. The equi-
potential planes under disks placed in insulators of various shapes were deter-
mined experimentally by Angell et al. [35] ; some of their results are given in
Fig. 7. It follows from these investigations that the greatest potential gradient
connected with ohmic resistance is formed in close vicinity to the disk sur-
24

/ /
0.251 Y

1 ¢rn
I- I 0.2157V

Fig. 7. The potential distribution for disks with variously shaped insulating mantles. From
ref. 35. r 1 0 = 0 . 2 0 5 c m , l M K I + 3.5X 10--2MI2, I = 0 . 3 4 7 mA.

face. It has been shown [525] that the ohmic drop in the voltage cannot be
neglected at distances greater than 5 X 10 - 2 cm from the surface of the disk.
Therefore the orifice of the reference electrode must be placed as close to the
surface of the disk as possible, unless a circuit eliminating the ohmic drop is
employed. Changes in the potential gradient at greater distances from the disk
are negligibly small and the effect of the shape of the electrode insulator is
unimportant.
A number of publications have been devoted to the current distribution on
the RDE [13,30,126,452,506,525,526]. It has been found that for currents
much lower than the limiting value, when the concentration distribution is
neglected, the current density differs at various points on the disk (hence the
surface of the disk is n o t uniformly accessible); analogously, all points on the
surface of the RDE are not at the same potential during strong polarization
[269]. According to Newman [ 525], the current density under these condi-
tions is given by

i Uv~/Tr(r~o - - r2) 1/2 at 0 < r < rl0 (disk surface)

i=
at r > rz0 (beyond the electroactive surface of the
disk)
where ~ is the specific conductivity. Newman's theoretical conclusion has been
verified experimentally by measuring the thickness of a copper film deposited
at very low current densities at various points on the surface of the disk [452].
An experimental procedure for the measurement of the ohmic drop has been
described by Newman [531] and by McIntyre [467].

(d) Mass transport toward the R R D E . A schematic diagram of an R R D E is

shown in Fig. 8. It can be seen that the R R D E is a disk electrode with radius
 25

I i , ,

Fig. 8. S c h e m e o f a n R R D E .

rio made from a suitable material, around which is placed an insulating gap
made of teflon, polyethylene, epoxy resin, etc. A ring electrode (usually plati-
num or gold), with an inner radius of r2o and an outer radius of r30, is placed
around the disk in a centrally symmetrical position. The ring is usually sur-:
rounded by teflon insulation, which prevents access of the solution to parts
of the electrode other than the b o t t o m circular area.
The R R D E is characterized by two important functions, the collection
efficiency, N, and the shielding efficiency, S. If the reaction
A -+ n D e -+ B (2-52)
proceeds on the surface of the disk electrode, intermediate B being generated
26

by constant current ID, a constant flux of this species is obtained. Product B

is carried from the disk electrode into the bulk of the solution under convec-
tive diffusion transport (its concentration in the base electrolyte is zero), and
a certain number of particles of B reaches the ring, where they can undergo
the reverse reaction at a suitably selected potential:
B + n R e -+ A (2-53)

The ring current, IR, will then be a certain fraction of the disk current. The
value of this fraction is termed the collection efficiency, defined by
N = I R rl D / I D rt R {2-54)
The dependence of the collection efficiency on the geometric and other
parameters of the RRDE was first determined by Ivanov and Levich [325].
Later, Albery [10] and Albery and Bruckenstein [15] determined these depen-
dences rigorously, on the basis of the solution of transport equation (2-33), in
which c = c2 is now the concentration of substance B. The equation was
solved using the following assumptions:
(i) a steadyzstate is established, ~ c 2 / ~ t = 0;
(ii) c is independent of coordinate ~, due to the axial symmetry;
(iii) the diffusion coefficient is independent of the concentration;
(iv) radial diffusion can be neglected with respect to radial convection [26].
Therefore, equation (2-33) can be rewritten in the form

~C 2 ~C 2 ~2C 2
vr ~ + vy ~ = D-- (2-55)
~y2

vy and v~ are given by equations (2-24) and (2-25). During calculations, only
the first term of expanded equation (2-55) is taken into account for v~ {or for
vy), i.e.

Vr = 0 . 5 1 r CO3/2 p--1[2 y

In order to solve this equation, boundary conditions must be specified for

the three basic zones of the RRDE (Fig. 8):
(i) the concentration of substance B is zero in the bulk of the solution for
all three zones
c2 = 0 f o r y - ~ oo; (2-56)

(ii) for constant current passing through the disk, r < rio,
(~ce/~r)r=o = 0 (2-57)

( ~ c 2 / ~ y ) y = 0 = --ID/~r210 n F D (2-58)
{iii) the condition for the insulating gap, rio < r < r20, states t h a t no reac-
tion t a k e s ~ a c e between the disk and the ring, provided that only convective-
 27

diffusion transport w i t h o u t volume-kinetic processes is considered

(~c2/~Y)y=o = 0 (2-59)
(iv) the condition for the limiting current holds for the ring, r20 < r < r3o ,
Ce=0 fory=0. (2-60)
The solution of equation (2-55) for the above b o u n d a r y conditions gives
the expression for the collection efficiency N in the form [ 15]

N = 1 --F((~/fl) + fl2/3 [1 - - F ( ~ ) ] - - (1 + ~ + fi)2/3 { 1 - - F [(~/fi)(1 + ~ +fi)]}

(2-61)
where ~ characterizes the thickness of the gap

= (r2o/rlo) 3 -- 1 (2-62)
and fi characterizes the thickness of the ring

fl = ( r 3 o / r l o ) 3 - - ( r 2 o / r l o ) s (2-63)
The concentration distribution close to the R R D E is shown in Fig. 9. The lines
under the electrode surface indicate the concentration distribution of substance
B, in accordance with boundary conditions (2-57)--(2-60). The values of func-
tion F(0) in equation (2-61) have been calculated and tabulated [ 15 ]. The con-
ditions
F(0)=0 for0=0
F(0)=I for0-~

Do

Fig. 9, Concentration distribution under an RRDE.

 b~
O0

TABLE 6
Collection e f f i c i e n c y values, 104 N, for t h e m o s t c o m m o n R R D E radii
F r o m ref. 120

r30/r2o r2o/rlo

1.006 1.008 1.010 1.012 1.014 1.016 1.018 1.020 1.030 1.040 1.050 1.060 1.070 1.080 1.090 1.100

1.020 1090 1076 1063 1051 1040 1030 1021 1012 0976 0947 0922 0902 0884 0869 0855 0843
1.030 1378 1363 1349 1336 1324 1313 1302 1292 1250 1215 1186 1162 1140 1121 1104 1089
1.040 1620 1604 1589 1576 1563 1551 1539 1529 1483 1444 1412 1385 1360 1339 1320 1302
1.050 1830 1814 1799 1785 1772 1759 1747 1736 1687 1647 1612 1582 1556 1533 1512 1493
1.060 2018 2002 1987 1972 1959 1946 1934 1922 1872 1829 1793 1761 1733 1708 1686 1665
1.070 2189 2172 2157 2142 2129 2116 2103 2091 2039 1996 1958 1925 1896 1896 1846 1824
1.080 2345 2328 2313 2298 2285 2271 2259 2247 2194 2149 2110 2076 2046 2019 1994 1972
1.090 2490 2473 2458 2443 2429 2416 2403 2391 2338 2292 2252 2217 2186 2158 2133 2110
1.100 2624 2608 2592 2578 2564 2551 2538 2526 2472 2426 2385 2350 2318 2289 2263 2240
1.120 2870 2854 2838 2824 2810 2797 2784 2772 2717 2670 2629 2593 2560 2530 2503 2479
1.140 3089 3073 3058 3044 3030 3017 3004 2992 2938 2890 2849 2812 2778 2748 2720 2695
1.160 3288 3272 3257 3243 3229 3216 3204 3192 3138 3090 3048 3011 2977 2947 2919 2893
1.180 3470 3454 3440 3426 3412 3399 3387 3375 3321 3274 3232 3194 3161 3130 3101 3075
1.200 3638 3622 3608 3594 3581 3568 3556 3544 3490 3443 3402 3364 3330 3290 3271 3245
1.220 3793 3778 3764 3750 3737 3725 3713 3701 3648 3601 3560 3523 3489 3458 3429 3403
1.240 3939 3924 3910 3896 3883 3871 3859 3847 3795 3749 3708 3671 3637 3606 3577 3551
1.260 4075 4060 4046 4033 4020 4008 3996 3985 3933 3887 3847 3810 3776 3745 3717 3691
1.280 4203 4188 4175 4162 4149 4137 4126 4114 4063 4018 3977 3941 3907 3877 3849 3822
1.300 4324 4310 4296 4283 4271 4259 4248 4236 4186 4141 4101 4065 4032 4001 3973 3947
1.320 4438 4424 4411 4398 4386 4375 4363 4352 4302 4258 4218 4183 4150 4119 4092 4066
1.340 4547 4533 4520 4508 4496 4484 4473 4462 4413 4369 4330 4294 4262 4232 4204 4178
1.360 4650 4637 4624 4612 4600 4588 4577 4567 4518 4475 4436 4401 4369 4339 4311 4286
1.380 4749 4736 4723 4711 4699 4688 4677 4667 4619 4576 4538 4503 4471 4441 4414 4389
1.400 4843 4830 4817 4806 4794 4783 4772 4762 4715 4673 4635 4600 4568 4539 4512 4487
 29

are i m p o s e d o n F(0). T h e solution shows t h a t the c o l l e c t i o n e f f i c i e n c y is a

f u n c t i o n o f the g e o m e t r i c p a r a m e t e r s o f the e l e c t r o d e alone; h e n c e it can be
calculated and t a b u l a t e d for various (r3o/r2o) and (r2o/rl0) ratios. T h e N values
for c o m m o n values o f these ratios axe given in Table 6.
T h e Ivanov and Levich solution yielded a s o m e w h a t simpler f o r m for func-
tion N, which can be r e w r i t t e n e m p l o y i n g A l b e r y ' s s y m b o l s in the f o r m
NIL = 0 . 9 6 7 4 {1 - - F [(a + 0.25)/fi] } (2-64)

The d i f f e r e n c e b e t w e e n N and N, L is p r o n o u n c e d w h e n the c o l l e c t i o n effi-

ciency is d e t e r m i n e d f o r the e x t r e m e cases:
(i) a -+ :¢ (an infinitely wide gap)

N = 1 - - F(0 -+ oo) + fl2/a [1 -- F(0 ~ oo)] -- (1 + a + f~)2/3 {1 ...... F(0 -+ oo)}

= 1 .... 1 + / 3 2 / 3 [ 1 ..... 1 ] - - ( l + a +fi)2/3 { 1 - - 1 } =0

NIL = 0 . 9 6 7 4 (1 ..... F(0 -+ ¢¢)} = 0 . 9 6 7 4 {1 .... 1} = 0

(ii) B -+ 0 (an infinitely n a r r o w ring), analogous t o t h e previous case,

N = 0 , NIL=0
F o r these t w o limiting cases b o t h e q u a t i o n s indicate t h a t the c o l l e c t i o n
e f f i c i e n c y is zero for an infinitely wide gap or a ring o f zero w i d t h . In t h e
o p p o s i t e case, w h e n the ring is very wide, it can be a s s u m e d t h a t all o f inter-
m e d i a t e B will be d e t e c t e d on the ring, yielding a c o l l e c t i o n efficiency of
unity.
(iii)/~ -~ ~ (infinitely wide gap)
N = 1 NIL = 0 . 9 6 7 4
(iv) a ~ 0 (infinitely n a r r o w gap)

N = 1 + fi2/a .... (1 +fi)2/3 N m = 0 . 9 6 7 4 {1 - F ( 0 . 2 5 / ~ ) }

In the latter case the t w o e q u a t i o n s differ. F o r (iii) the Ivanov and Levich solu-
tion is o n l y a p p r o x i m a t e and for (iv) t h e r e is a significant d i f f e r e n c e in the t w o
functions. Below, the N values calculated b y A l b e r y and B r u c k e n s t e i n f r o m
e q u a t i o n (2-61) will be used. A simpler relationship f o r the c o l l e c t i o n e f f i c i e n c y
holds for e l e c t r o d e s with a v e r y thin ring and a v e r y thin gap [26] :

N " = - 2 / 3 o ~ ' - 2/3 ,~' + 2/3(a' + ,G')F(o~'/,6') + (/~,)2/3 ..... (~/Tf) (fl,)2/3 (0~,)1/2
(2-65)
where
~' = 3 l o g ( r 2 o / r l o ) (2-66)
[3' = 3 l o g ( r a o / r l o ) (2-67)
T h e o t h e r i m p o r t a n t f u n c t i o n c h a r a c t e r i z i n g the R R D E is the shielding
30

efficiency, S. In practice, it often cannot be assumed that the concentration

of the substance undergoing reaction on the ring is zero in the solution. If it
is assumed t h a t reaction (2-52) takes place at both electrodes at the same po-
tential, then current (Id) ° will pass through the ring when the disk electrode
circuit is open, i.e. I D = 0. On closing the disk electrode circuit, current
(Id) R < (Id) ° will pass through the ring, since the a m o u n t of substance A trans-
ported to the ring is diminished by the a m o u n t which has reacted on the disk.
The shielding efficiency S is defined by the ratio of the two currents
S = (ld)R/(Id)O (2-68)

It follows from h y d r o d y n a m i c calculations [429] that

(Id)O = (Id)D/32/3 (2-69)

On substitution for the disk current, (Id)D, from equation (2-44), the relation-
ship for the ring current with an open disk electrode circuit is obtained:

-20,~2/3 cl (00)02/3 12--1/6 501/2

(Id) ° = 0.620 n F r (r~o __r3 (2-70)

where c1(~°) is the concentration of substance A in the bulk of the solution.

Since

(Id)a = (Id) ° ---N(Id)D (2-71)

and, taking into account equations (2-69) and (2-71), function S is given by

S - (Id)R _ 1 - - N (ld)D _ 1 --Nt 3-2/3 (2-72)

qd) °

From this equation it follows that function S is also dependent on the geometric
parameters of the RRDE alone. In order that the differences in the ring currents
at various disk potentials be readily measurable, an electrode with as low an S
coefficient as possible should be employed. This condition is best met by an
RRDE with both a thin gap and a thin ring, where N -~ •2/3.
(e) Non-stationary convective diffusion. Stationary convective diffusion, with
~c/O t = 0, has so far been discussed. During abrupt changes in the electrode
rotation rate or in galvanostatic and potentiostatic circuits, and during electrode
polarization by time-dependent potentials (linearly increasing or varying peri-
odically), non-stationary phenomena occur and a certain time interval is re-
quired for re-establishment of steady-state in the fluid flow and the mass trans-
port.
When the electrode is set into motion abruptly, the fluid layers adjacent to
the disk surface are forced to rotate due to viscosity forces (see section 2-1b).
This rotation is gradually transferred to more distant layers. The character of
the fluid movement will also change; at a sufficient distance from the disk, the
fluid begins to flow perpendicularly to the surface of the disk and steady-state
 31

is established. The time elapsed from the beginning of rotation to the establish-
ment of steady-state flow is ro ~ ~ oe/v.
When a current or a voltage are suddenly applied to the electrode system,
the electrode reaction will be purely diffusion-controlled without respect to
the electrode rotation rate for times from the beginning of the reaction, given
by the relation t ~ ~2/D. After a certain time, T ~ ~2/D, steady-state is estab-
lished. As To/r ~ Sc -1/3, stationary fluid flow is established more rapidly than
stationary mass flux at high Sc values. For small Sc values (diffusion in gases)
a stationary state is established at an approximately identical rate in the two
cases.
For potentiostatic and galvanostatic circuits, equation (2-33) containing the
term, ~c/a t, which has a value other than zero, was solved using various meth-
ods and more or fewer simplifying assumptions. The simplest solution is that
of Levich [429], based on the fact that, at the beginning of the reaction, the
effect of convection is negligible and therefore the convection terms in equa-
tion (2-33) can be omitted. Later, the effect of convection was introduced
into the resulting relationships as a correction; however, this solution is, in
practice, only illustrative. More rigorous relations have been given b y Filinovskii
and Kiryanov [233], Bruckenstein [130] and Buck and Keller [132].
Siver [634] solved the problem of steady-state establishment in stirred solu-
tions much more generally, also considering the electrode reaction kinetics on
the basis of a model assuming the existence of non-stationary effects within
region ~ alone while the concentration is constant everywhere due to intense
convection. Siver's results agree within 8% with those of Hale [294,295] ob-
tained numerically. Filinovskii and Podgaetskii solved the problem for mixed
kinetics [ 234]. These publications give relationships describing the time re-
quired for establishment of stationary mass transport for electrode reactions
of various degrees of reversibility and discuss methods for determining kinetic
parameters of electrode and volume reactions.
Non-stationary convective diffusion was employed for the study of various
problems, e.g. passivation of gold and copper [346], zinc [579], electrodeposi-
tion of nickel [401], chronopotentiometric stripping determination of thallium
[200], cyclic c h r o n o p o t e n t i o m e t r y [ 405], the dependence of material flux
on the concentration in solution varying with time [436] and similar problems
[27,122,150--152,311,361,404,505,536,537].
Non-stationary diffusion during electrode polarization by a potential increas-
ing linearly with time, has been studied by several authors [242,266]. With
high potential scan rates, ( n F / R T ) (a/D)a 2 >> 1, where a is the scan rate [V s - l ] ,
the I--E curves exhibit maxima, since stationary diffusion cannot be established.
The peak current value is proportional to a 1/2, and obeys the ~evSik-Randles
equation and consequently is independent of the rotation rate (a diffusion-con-
trolled process [242]). On the other hand, steady-state diffusion can be estab-
fished for low potential scan rates, ( n F / R T ) {a/D)~ 2 ~ 1; the I--E curves have
the usual shape with limiting currents and obey the Levich equation (a convec-
tion-controlled process) [242]. From the I = f(a 1/2) plot, the critical a value
32

can be found, at which non-stationary diffusion changes into stationary diffu-

sion at a given rotation rate (this is schematically depicted in Fig. 10).
Other investigations were devoted to the study of non-stationary processes
during electrode polarization by a potential varying linearly with time [153,
243,277,687]. Matsuda [461] dealt with a.c. polarization. Potential applica-
tions (e.g. to double-layer structure studies, impedance measurements etc.)
have been treated in a number of papers [161,193,215,217,218,220,422--424,
471,530].
Great attention is at present being paid to non-stationary processes at the
RRDE during a sudden change in the disk potential or current. It can be ex-
pected that this will be very important in the study of electrode reaction inter-
mediates and of adsorption. The first contributions to this field were the works
of Albery [11] and Bruckenstein and Feldman [123]. The time, ~R, required
for a particle formed at the disk to reach the edge of the ring was f o u n d to be
given by the expression [123]
fTR = 43.1 Vlog( r2°l~ 2/3
[_ \rl0/J

where f is the electrode rotation rate in rev min -1. This relationship has been
verified for the reduction of silver ions [129] ( f Z a = 17.5 S rev min -1 was
found, the theoretical value being 15 s rev min -1). Similar results were ob-
tained by Albery and Hitchman [27]. Non-stationary processes at the RRDE
were also studied theoretically and practically in a series of papers by Albery
et al. [12,22--25]. A.c. methods were employed for the study of the reduc-
tion of ferricyanide [25]. The use of non-stationary methods for the study of
adsorption with the RRDE was described by Bruckenstein and Napp [129]

I J
0( ~
Fig. 10. Conversion of stationary diffusion into non-stationary for various r o t a t i o n and
potential scan rates.
 33

and by Gonz et al. [272]. Prater and Bard [585] used a digital c o m p u t e r for
modelling non-stationary processes.

2-4. Verification of the theory

The RDE theory was verified by comparing the measured and theoretical
currents (equation (2-44)); this involved comparing the diffusion coefficients
determined from the measured limiting currents with those determined by
other methods and by monitoring the id = f(¢~1/2) dependence.
The Levich RDE theory was first verified by Slyer and Kabanov [633], who
followed the limiting diffusion currents of 02 and H ÷ on silver and copper
amalgamated disks 2.5 cm in diameter, in an Re range of ~500--60,000. They
obtained direct proportionality between the current and the square root of
the angular velocity and verified the relationship, id = f(D 2/3). The measured
and calculated currents were equal within +3% for Do ~ (0.025 M H2SO4,
20°C) = 1.98 × 10 - 5 cm 2 s-1 and v = 10 -2 cm 2 s-1. They found t h a t the
ratio

DH+]2/3 2(id)H+CO2 (oo)

=

has a value of 2.48, while the theoretical value, obtained from conductivity
measurements, is 2.42.
Aykazyan and Fedorova [ 7] measured hydrogen ionization currents on a
platinum disk in an Re range of ~ 4 9 - 1 4 3 0 . For the DH2 value in an acidic
medium, the value, 3.83 × 10 - 5 cm 2 s-1, was calculated from equation
(2-44), and is in excellent agreement with the value, 3.90 × 10 -~ cm 2 s-1,
calculated from the measurement of the diffusion of hydrogen in silica gel
[6591.
Hogge and Kraichman [314] followed the reduction currents of IF ions in
potassium iodide on a platinum disk electrode in an Re range of ~850-- 4650.
Their measurements were repeated by Gregory and Riddiford using zinc [285]
and copper [284] disks and by Newson and Riddiford [533] on a platinum
electrode; the results agreed very well with the theory. Good agreement of the
original Levich theory as well as of the more rigorous Gregory and Riddiford
theory with experimental results was later demonstrated by a n u m b e r of other
authors [ 169,211,213,366].
The uniform accessibility of the disk surface was verified by Beacon [ 79],
who measured the thickness of a copper deposit on the electrode with an inter-
ference microscope and showed that it was the same over the entire surface of
the disk within a measuring error of -+5%; the same result was obtained by
Kassner [359]. These conclusions do not contradict the measurements per-
formed by Newman [452,525] (see section 2-3c), since very low current den-
sities were not involved in Beacon's measurements. The thickness o f the diffu-
sion layer can be measured directly employing laser interferometry [539].
34

A number of papers have reported deviations of the dependence of the

current density on the square root of the rotation rate from theoretical linear-
ity; the dependence was found not to pass through the origin on extrapolation
to co = 0 [98,326,363,384,577], so that the i = f(~1/2) dependence corre-
sponded to the equation, i = a + b (¢o1/2). This deviation can be caused by
several factors:
(i) natural convection at low co values or additional stirring of the solution,
e.g. by bubbles of a gas evolving at higher current densities [191] ;
(ii) simultaneous occurrence of two processes on the electrode [566], one
controlled by convective-diffusion (depending on the stirring rate) and the
other by the kinetics of a surface or volume reaction;
(iii) inhomogeneity of the electrode surface; at surface irregularities (often
only gas bubbles or particles of deposited metal), changes in the rate of mass
transport can occur [321,564,643] ;
(iv) the occurrence of turbulence either at surface irregularities, leading to a
decrease in R e c r i t , o r turbulence at the edge of the disk at high rotation rates
[171,286,333];
(v) radial and axial vibrations that also contribute to additional stirring of
the solution and thus decrease the R e c r i t value.
The RRDE theory was verified by comparing the theoretical and experi-
mental values of collection efficiency coefficients. For this purpose, electro-
chemical systems yielding stable products of the electrode reaction on the
disk must be employed. Frumkin et al. [248,249] verified the RRDE theory
using the reactions of quinone and of oxygen in an alkaline medium and of
cupric ions in a chloride medium. The reaction products were reoxidized at
the ring at a suitable potential. The N values were determined using the de-
fining equation (2-54) and compared with the theoretical values obtained from
the geometric parameters of the electrode. The experimentally f o u n d collection
efficiency values were 0.37, 0.38 and 0.41 for the reduction of oxygen, quinone
and copper, respectively, the theoretical value being 0.39.
Albery and Bruckenstein [ 15,121] verified the theory using electrodes with
various r2o/rlo and r30/r20 ratios. They also employed the divalent copper
system, in a KC1 solution, as well as bromide in sulphuric acid and ferricyanide
in sulphuric acid. They also stripped silver from a silver-coated disk and reduced
the resulting Ag ÷ ions at the ring. The theoretical and experimental values of
the collection efficiency were again in very good agreement.

3. PRACTICAL APPLICATIONS OF DISK ELECTRODES

3-1. Study of diffusion

The rotating disk electrode is very suitable for measuring diffusion coeffi-
cients. Defined h y d r o d y n a m i c conditions at the e l e c t r o d e - s o l u t i o n interface
preclude the onset of the fluctuations in fluid flow observed with other solid
electrodes [380,688]; further, D is proportional to i~/2, while at the dropping
 35

mercury electrode D ~ id2 (see the Levich and Ilkovich equations). T h e r e f o r e

errors arising during recording of the current will be less pronounced when D
is c o m p u t e d from experimental values obtained from the RDE and very accu-
rate D values are thus obtained, with errors as low as +0.25% [533].
The equation for the limiting current at the RDE
I d = 0.62rtFAD2/3p-1/6¢ol/2c(~¢) = B ' W l / 2
where Id is the limiting current and A is the electrode electroactive area, can
be readily rewritten in a form convenient for the calculation of diffusion co-
efficients:
[ 1)1/6 ]3/2 g,3/2 (3-1)
D = [_0.620 n F A c ( ~ ) J

where c(oo) is the bulk concentration in mol m1-1, in order that D shall have
its usual dimensions. The value of constant B' is given by the slope of the
straight line I d = f ( ~ l / 2 ) (see Fig. 11, p. 39). Diffusion coefficients calculated
in this way are n o t subject to random errors stemming from inaccurate mea-
surement of the limiting current, as might occur if they are calculated directly
from equation (2-44).
The Ubbelohde viscometer is suitable for the measurement of the kinematic
viscosity coefficient. It holds for v that v = GT, where T is the flow-through
time. The viscometer constant, G, is readily determined by measuring T for a
fluid with known density p and dynamic viscosity t~ and applying the equa-
tion, G = ~ / p T .
The diffusion of electrolytes has been studied in detail by Arvfa and co-
workers [ 53,57,78], in a series of papers dealing with the diffusion of ferri-
and ferrocyanide in various media and in a paper on the diffusion of cupric
ions in media of various viscosities [ 54]. The authors studied the dependence
of the diffusion coefficients on the temperature, the concentrations the com-
position of the base electrolyte and the viscosity of the medium. F r o m the
temperature dependences they determined the activation energies of diffusion
and viscosity, given by

DT = Do exp
[ R
(1
. T = ;'o e X p L -

where AE~erro = 17 +- 1 kJ mo1-1 (4.1 -+ 0.7 kcal t o o l - l ) , AE~em = 16 -+ 1 kJ

mo1-1 (3.8 -+ 0.6 kcal mo1-1) and AE~ = 14.0 -+ 1.1 kJ mo1-1 (3.35 -+ 0.25 kcal
tool-l). It has been found that the factor D p / T is independent of the tempera-
ture from 20 to 40°C and it was employed for the calculation of the Stokes
ionic radii. The effect of a non-Newtonian medium of potassium chloride and
carboxymethyl cellulose on the diffusion of ferro- and ferricyanide was also
studied.
36

The accuracy of the determination of the diffusion coefficient using the

RDE is demonstrated in Table 7. Table 8 surveys diffusion coefficients deter-
mined in this way and shows that the RDE has been employed very frequently
for a great variety of molecules and ions in various media.
In aqueous solutions the diffusion coefficients of Ag ÷ ions [ 569], hydrogen
[7,431], h y d r o x o n i u m cations [111,279,409,633], triiodide anions [213],
oxygen [633], hydroxyl ions [259,409], complexes of neptunium [572,574],
zincate in concentrated solutions of sodium hydroxide [731], o-dianisidine
[479], etc. have been measured. Diffusion was also studied in non-aqueous
solutions by Minc et al. [481] and by Lohman [434] in DMFA and nitro-
methane using an anthracene electrode.
Many papers deal with the measurement of diffusion coefficients of various
ions in melts [96,97,156,189,554--557,627]. Shurigin [632] measured diffu-
sion coefficients during dissolution of metals in fused copper and Krichevskii
and Tsechanskaya [400] determined them from non-electric quantities during
dissolution of some solid organic acids pressed into the shape of a disk. Ravdel
and Moskevich [ 594] calculated the concentration dependences of diffusion
coefficients.
Vielstich et al. [279] accurately measured the diffusion coefficient of hy-
drogen ions in KC1 (1 M) in a temperature range of 12--40 ° C; they employed
both the Levich equation (2-44) and the equation corrected by Gregory and
Riddiford. The ratio of the diffusion coefficients calculated from the two
equations w a s D ( : ; R / D L 1.096. -~

Hitchman and Albery [ 313] pointed out that diffusion coefficients could
be measured using the equation

D 7rr20 1
Id(t) =Id(t = 0) exp O V t

TABLE 7
C o m p a r i s o n o f t h e d i f f u s i o n c o e f f i c i e n t values f o r s o m e m o l e c u l e s o b t a i n e d w i t h t h e R D E
a n d f r o m t h e m e a s u r e m e n t o f t h e m o b i l i t y in a c a p i l l a r y
F r o m ref. 4 2 9

Oxygen Hydrogen Quinone Hydroquinone

RDEmeasure- 1 . 9 3 × 10 - 5 3 . 8 3 × 10 - 5 1 . 2 7 × 10 _ 5 0 . 8 5 × 10 - 5
merit e m 2 s- 1 e m 2 s- 1 c m 2 s- 1 c m 2 s- 1
0.025 M H2SO 4 0.5 M H 2 S O 4 2 MKC1
20°C 23°C 26°C 16°C
D i f f u s i o n in 1 . 9 8 × 10 - 5 3.90 × 10 - 5 1.30 X 10 - 5 0 . 8 7 × 10 - 5
capillary c m 2 s- 1 c m 2 s- 1 c m 2 s- 1 c m 2 s- 1
0.025 M H2SO 4 2% agar phosphate buffer water
20°C 23°C p H = 6.8 2 7 ° C 16°C
 37

TABLE 8
A survey of d i f f u s i o n c o e f f i c i e n t values d e t e r m i n e d using t h e R D E

Diffusing Medium T/°C 1 0 5 D / c m 2 s- 1 Notes Ref.

species

Ag + 0.025 M 25 1.4 398

KNO 3
[Ag(SO3)2] 3 - 0.025 M 25 0.56 DAg+ in K N O 3 a n d 344
Na2SO 4 + HCIO 4 was also mea-
0.925 M sured a n d t h e e f f e c t
NaNO 3 of o x y g e n a n d gelatine
followed
[AuC14]- 0.1 M N a N O 3 20 1.2 72
Br 2 0.4 M 25 2.93 S t o k e s radii: r(Br2) = 1.8 A 327
Br-- LiClO4 1.17 r ( B r - - ) = 4.5 A
Br~- in A c N 1.97 r(Br~-)--- 2.8 A
Cd 2+ 1 M KCl 25 0.772 The concentration depen- 711
d e n c e o f D; c o r r e c t i o n was
m a d e for t h e m i g r a t i o n
component
C12 1 M HCI 25 1.74 281
Cl-- 7.6 M H2SO 4 1.77 667
Cl-- 0.4 M 0 0.81 A c t i v a t i o n e n e r g y of t h e 623
Cl 2 LiC10 4 0 2.76 d i f f u s i o n process, A E * =
in A c N 6.3 k J tool - 1 (1.5 kcal
mol- I )
Cu 2+ 1.4 M H2SO 4 25 0.446 S t o k e s radius: r ( C u 2+) = 54
Cu 2+ 0.5 M KC1 20 0.68 3.28 A 130
CO 1 M HC104 1.46 649
Ce 4+ 1 M HClO 4 22 0.4 282
Fe 2+ 1 M KClO 4 25 0.57 Also d i f f u s i o n o f ferro- a n d 329
Fe 3+ 1 M HClO 4 25 0.65 ferricyanide
Fe(CN6) 3 - 1 M NaOH 30 0.65 Activation energy of the 707
Fe(CN6) 4 - 1 M NaOH 30 0.56 diffusion process
A E * -- 15 k J m o 1 - 1 (3.6
kcal m o 1 - 1 )
H2 1 M HClO4 30 4.24 Activation energy 707
A E * = 18,2 k J m o 1 - 1
( 4 . 3 5 kcal m o 1 - 1 )
H+ extrap. 25 9.3 D i f f u s i o n in LiCl, NaC1, KC1, 267
c--*0 NaClO 4 ; t e m p e r a t u r e depen-
dence
H+ 1 M KC104 30 0.24 S t o k e s radius: r ( H +) -- 2 . 3 5 A 542
in DMSO
I-- 0.1 M H N O 3 25 2.0 259
38

TABLE 8 (continued)

Diffusing Medium T/°C 105D/cm 2 s-1 Notes Ref.

species

12 0.4 M 25 1.91 S t o k e s radii: r(I2) = 2.80 A 440

I-- NaC104 1.68 r(I--) = 3.17 A
I~- in A c N 1.4 r(I~-) = 3.89 A
MnO42- 1 M KOH 20 0.83 411
02 extrap. 25 2.0 D i f f u s i o n in K O H 185
c-~0
02 0.1 M N a 2 S O 4 25 1.14 729
OH-- 0.1 M N a 2 S O 4 20 5.6 111
SO 3 Oleum 25 0.006 Stokes radius: r(SO3) = 1 3 . 7 A 145
14.8% SO 3
Pb 2+ 1 M'KCI 25 0.895 E x t r a p o l a t e d to c = 0. F o r 711
T1+ 1.53 small KC1 c o n c e n t r a t i o n s
Z n 2+ 0.730 c o r r e c t i o n was m a d e for t h e
migration component
Quinone 2 M KC1 21 1.10
Hydroquinone 2 M KC1 21 0.91 Activation energy of the
d i f f u s i o n process, A E * =
15.9 k J tool - 1 (3.8 kcal
tool - 1 )
o-Dianisidine 1 M H2SO 4 25 0.366 257

where t is the time and V is the solution volume. This is practically constant-
potential coulometry. The diffusion coefficient of ferrocyanide calculated by
this method, (0.634 + 0.002) × 10 - 5 cm 2 s-1, agrees excellently with the
value, (0.632 -+ 0.003) × 10 - 5 cm 2 s- 1 , measured by Stackelberg et al. [646].
The m e t h o d does not require knowledge of the number of electrons exchanged
in the electrode reaction nor knowledge of the concentration. The same authors
[313] have also proposed use of the RRDE for the determination of diffusion
coefficients, employing a m e t h o d and relationships developed for the study of
second-order volume reactions (coulometric titrations in the diffusion layer,
see below).

3-2. Study o f electrode reaction kinetics

(a) Study o f electrode reaction kinetics using the RDE. In section 2-3a it was
assumed during the solution of the convective-diffusion equation that the rate
of the electrode reaction is sufficiently high to prevent its participation in con-
trolling the overall reaction rate. In general, the rate of the surface reaction can
participate in controlling the overall rate or can be the controlling step in the
overall process and then the boundary condition for the disk surface (equation
 39

I I [ I I I I

Id
/
~A

80 m

2/3 %
D ~ c(®):B
60 --
Fe(lll)--,Fe(ll) ot Pt RDE

/ ;~ : 0.90?cm 2 s ~
c(®)=5×16~t4
40 ~

20

/
/ R I I I i I ~
0 2 4 6 8 10 12
(,~1" 2 / s - 1/2

Fig. 11. The I d = f(co1/2) linear dependence, suitable for the calculation of diffusion co-
efficients.

(2-36)) m u s t be c o n s i d e r e d in steady-state in a m o r e general f o r m

j= D (~c.l = kc(O) ~ (3-2)

kUy/ y=O

where k is t h e h e t e r o g e n e o u s rate c o n s t a n t and p is the r e a c t i o n o r d e r with

respect to the a p p r o p r i a t e r e a c t a n t .
The s o l u t i o n o f e q u a t i o n (2-34) is t h e n c h a n g e d as follows [ 4 2 9 ] : f r o m
e q u a t i o n (2-37) it follows t h a t a2 = c (0) (for a process c o n t r o l l e d solely b y
mass t r a n s p o r t , a2 = 0) and f r o m e q u a t i o n s (2-38) and (2-39),
al = (c(,~) -- c(O))/~ (3-3)

Since c o n s i d e r i n g e q u a t i o n s (3-2) and (2-37) leads t o the r e l a t i o n s h i p

D (~c/~y)y= o = Da 1 = ka~ (3-4)

the surface c o n c e n t r a t i o n , c(0), can finally be e x p r e s s e d b y

c(O) ~' = D c ( ~ )/kO - - D c ( O ) / k O (3-5)

This e q u a t i o n gives t h e relationship b e t w e e n the surface c o n c e n t r a t i o n and t h e
bulk c o n c e n t r a t i o n , p r o v i d e d t h a t the stirring c o n d i t i o n s , i.e. 0, are specified.
40

It is important t h a t a be independent of the character of the heterogeneous

reaction kinetics and of the coordinates.
Equation (3-5) is usually solved graphically. For this purpose, dimensionless
parameters are introduced

C(O) = c(O)/c(~o), g = ~kc(°~)~-l/D (3-6)

and equation (3-5) assumes the form

C(0) ~ = (1 -- C ( O ) ) / g (3-7)
The graphical solution yields a nomogram [241], given schematically in Fig. 12.
The curves with the origin at C(0) = 0 give function C(0) ' for various p values
and the straight lines with origin at C(0) = 1 represent function [1 -- C(0)]/K
for various K values. The coordinates of the intercepts of these curves give
concentration C(0), which is the solution of equation (3-5). When C(0) is known,

2=o

- c(o)
c (0}~ K

o c(o) 1

Fig. 12. Graphical solution of equation (3-7) for various values of p and K.
 41

the material flux toward the surface of the disk can be found

j = (Dc(oo)/~) [1 --C(0)] = ( D c ( ~ ) / O ) KC(O) ~ (3-8)

It is evident from the nomogram in Fig. 12 that, for K >> I (k >>D/Sc(~o) ~ - 1 )
i.e. for very rapid electrode reactions, C(0) -+ 0 and it follows from equation
(3-8) that
J = Jd = Dc(,~)/O process controlled by mass transport

and the corresponding current density obeys equation (2-44). On the other
hand, for K ~ 1 (k ~ D / 5 c(oo)u-1), i.e. for slow electrode reactions, C(0) ~ 1
and from equation (3-8) it follows that

] = Jk = kC(OO)~' process controlled by the kinetics of the surface reaction

and the corresponding current density obeys the equation i k = n F k c ( ~ ) u .

If the diffusion and kinetic flux are comparable, the reaction exhibits mixed
kinetics, which is manifested by a more complex dependence of the current on
the square root of the rotation rate, since the diffusion current is a linear func-
tion of co1/2, while the kinetic current is independent of the r o t a t i o n rate. The
character of the dependence of the current on the rotation rate for mixed
kinetics is depicted in Fig. 13.
From this experimental dependence, the reaction order, p, and the rate con-
stant, k, can be readily determined. It follows from equations (3-2) and (3-4)

i q

A
/

__~ W1/2

Fig. 13. S c h e m e of t h e i = f(¢o 1/2) d e p e n d e n c e for m i x e d k i n e t i c s .

42

[568] that

- j~ ~ w h e r e De(M) 1
Jd (3-9)
k c ( ~ )"
If t h e material flux for t w o d i f f e r e n t e l e c t r o d e r o t a t i o n rates is k n o w n , the
value o f p can be calculated f r o m e q u a t i o n (3-9), since

p log [1 - - J l / ( J d ) l ] Jl
[ 1 - - j 2 / ( J d ) 2 ] = log ~ (3-10)

E q u a t i o n (3-10) can easily be t r a n s f o r m e d into a f o r m f r o m which t h e reac-

t i o n o r d e r g can be d e t e r m i n e d b y measuring the a p p r o p r i a t e segments o f a
p l o t o f t h e c u r r e n t d e n s i t y versus t h e square r o o t o f the r o t a t i o n rate (see
Fig. 13).

log J2/Jl log F E / C B

P - log((jd ) l / [ ( J d ) i -- Jl ] } -- log((Jd)2/[(Jd)2 - - J 2 ] } -- log C A / B A -- l o g E D / E D
(3-11)
In o r d e r t h a t this m e t h o d be practicable, the p o i n t s d e t e r m i n i n g t h e lengths o f
the a p p r o p r i a t e segments m u s t be selected in the region c o r r e s p o n d i n g t o
m i x e d kinetics. O t h e r special l o c a t i o n s o f p o i n t s o n t h e i = f(col/2) curve are
p o i n t e d o u t in the papers b y R i d d i f o r d [ 4 2 0 , 5 9 9 ] and F r u m k i n [ 2 5 0 , 2 4 7 ] .
F o r e x a m p l e , the r e a c t i o n o r d e r can be d e t e r m i n e d a c c o r d i n g t o R i d d i f o r d
using the e q u a t i o n
log ik -- log i
P = log i d -- 1og(i d -- i)
which follows f r o m e q u a t i o n (3-11) (FD = ED, F E = ik).
If the r e a c t i o n o r d e r is k n o w n , the rate c o n s t a n t k can be d e t e r m i n e d . It
follows f r o m e q u a t i o n (3-9) t h a t

k = j [C(°°) (1 - - j / j d ) v ] - 1 = i [c(~o)nF (1 -- i/id)~] - 1 (3-12)

T h e id value m u s t be d e t e r m i n e d or calculated f o r the same co as t h a t at which i

was measured.
T h e a b o v e relationships are simplified for first o r d e r reactions. F r o m equa-
t i o n (3-12) it holds t h a t

1 1 1.61 v 1/6 1
T = nFkc(~) + (3-13)
n F D 2/3 c ( ~ ) col/2

T h e p l o t o f 1/i = f(1/co 1/2) is a straight line which, o n e x t r a p o l a t i o n t o 1/co 1/2-~ 0

(i.e. co -~ ~ ) , permits the d e t e r m i n a t i o n o f the value o f ik = n F k c ( ~ ) f r o m the
i n t e r c e p t on the y-axis and t h e n t h e r a t e c o n s t a n t (a linear 1/i vs. 1/co I/2 p l o t
indicates a first o r d e r r e a c t i o n [ 2 1 4 ] ) can be f o u n d .
 43

Equation (3-13) is applicable only to potential regions sufficiently removed

from the equilibrium potential of the system, Ee, in order that the effect of the
reverse reaction be negligible, i.e. for ~? = ( E - - E e ) >> R T / c ~ n F . For rapid reac-
tions, where the rate of the process is controlled by mass transport even at low
overvoltages, equations including the effect of the reverse reaction must be
used. For the general reaction [207]
Ox + n e ~ Red

with rate constants kf and kb it holds that

i = io ~ expL--~--~ C(OO)red
where io is the exchange current density. The equation i = n F D [c(°°) -- c(0)]/~
can be substituted for the c ( O ) / c ( o o ) ratios in equation (3-14), giving the rela-
tionship [568]

1 b~ +t 1 b } 1.61 v116 1 (3-15)

i - = ( 1 - - b ) i 0 [ Box
513 oo
c( )ox
where b = exp[(nF/RT)~7]
It is evident from the latter equation that the 1 / i = f(co 1/2) dependence is a
straight line for a constant E. The intercept on the y-axis corresponds to the
first term on the right-hand side of the equation and io and a can be deter-
mined from measurements at several potentials. For a typical system, where
D / 5 ~ 10 - 2 cm 2 s -1 (the rotation rate is 120 rev s - l ) , rate constants k ~< 0.1
cm s-1 can be determined. The precision of the determination increases with
decreasing rate constant values [ 329].
The kinetics of the electrode reactions of m a n y organic and inorganic sub-
stances have been studied using the RDE, for example, the ionization or re-
duction of hydrogen under various conditions [6,7,58,94,191,194,245,247,
301,431,443,496,611,624,640], of oxygen [5,246,484,512,518,630,664,665,
680,730] and of chlorine [115,250,281,623] have been followed. The kinetics
of the redox reactions of iodine were studied in aqueous [259,414,533,534,567,
679] and non-aqueous [68,264,440] media, bromine in aqueous [224,486] and
non-aqueous [327] solutions, hypochlorite [488,622], chlorite [621], persul-
phate [227,240,489,490,607], sulphur trioxide [ 56,145], nitrite and nitrate
[459,616,617,700], NO + and NO~ cations [142,258], manganate [409,416],
thiocyanate in AcN [ 558] and DMSO [458], uranium [406], cobalt [ 74],
cerium [435], vanadium [37,39], rhodium [304], titanium [36,37], chromium
[38], iron [3,60,256,275,329] (Angell and Dickinson [ 33,34] studied the
Fea+/Fe 3+ system from the point of view of the effect of the surface pretreat-
ment of the electrode and the overvoltage on the charge-transfer coefficient
- - t h e Marcus theory), silver [237] and gold in cyanide complexes [ 303].
Among organic substances, the redox reactions of methyl- and dimethyl-
44

aniline [255], aniline [107,108,203], hydrazine [236,300,520] and its deriva-

tives [210], h y d r o q u i n o n e and ethanol [8], aromatic nitro compounds [315],
formaldehyde [158], benzyl alcohol [118] and ascorbic acid [115] were
studied. The decomposition of hydrogen peroxide on a silver disk was followed
[495] as were the kinetics of the redox reactions of chloride [233] and thio-
cyanate [55] in melts. The kinetics of electrode reactions at the RDE under
various conditions have been treated in a number of other publications [81,
173,214,221,494,642,702,725]. Some papers also dealt with the effect of the
quality of the electrode surface, double-layer structure and adsorption on
the electron transfer kinetics.
Various metals have different tendencies to form surface oxides; hence,
it can be expected that the same reaction will proceed differently on different
metals. The i vs co1/a dependence then has an anomalous character and de-
pends on the surface properties of the electrode, i.e, on the n u m b e r , size and
distribution of active centres [ 582]. A series of papers by Landsberg and co-
workers has been devoted to this subject, see section 3-4a.
The effect of the double-layer structure on the electrode process is con-
nected with the state of the electrode surface. Fedorovich et al. [227] mea-
sured the kinetic parameters for the reduction of persulphate on disk elec-
trodes made of various metals (Cd, Sn, Pb, Bi) and monitored the effect of
the double-layer structure (the ~-effect) on the character of the log i--E
polarization curves. The results have shown that the charge-transfer coeffi-
cient is the same, although the electron work function into a vacuum differs
for the individual metals if the coefficient is determined using the corrected
Tafel plot (CTP), l o g [ / - - nF ~/2.3RT] vs. E -- ~ (this means that the elec-
tron work function into the electrolyte is independent of the character of
the metal at a constant potential; this assumption was verified by study of
photoemission into an electrolyte solution [571]).
In a series of papers by Koryta, B~ezina et al., dealing with the electrode
reactions of oxygen and hydrogen peroxide on disk electrodes made of plati-
num [388], silver [116] and glassy carbon [112], emphasis was placed on
the state of the electrode surface and on the effect of the electrode pretreat-
ment on the electrode reaction kinetics.
The activity of the surface of a silver electrode is increased by prepolariza-
tion at the potential of hydrogen evolution. Without activation, the overvolt-
age for peroxide reduction increases and the two oxygen reduction waves be-
come perceptibly separated. The effect of activation of the silver electrode is
also documented by measurements performed with the RRDE. The oxygen
reduction current at the ring decreases with time if the disk electrode on
which the peroxide is reduced is n o t activated [114].
Glassy carbon electrodes contain centres which are inactive or specifically
inactive for the reduction of oxygen; this is manifested by a lower oxygen
reduction current compared with the theoretical value. These are sites at
which diamond-type bonds are present on the surface of the glassy carbon,
so that oxygen is n o t adsorbed. Active participation of surface oxides in the
 45

reduction of hydrogen peroxide is indicated by a decrease in the current at

potentials at which the electrode surface is oxide-free.
Hydrogen peroxide yields an anodic-cathodic wave, corresponding to
simultaneous reduction of peroxide to water, HO2 + 2e + H 2 0 -~ 3 O H - ,
and its oxidation to oxygen, HO2 + O H - - ~ 02 + 2e + H 2 0 . To this anodic--
cathodic wave an equation of the form [116]
RT i+ id
E = Em ---- In .
flF ld -- i

can be applied where Em is the mixed potential at zero current and fl is a

function of the charge-transfer coefficients and the numbers of electrons ex-
changed in the two reactions.
Biezina et al. [ 117] studied the decomposition of hydrogen peroxide on a
large silver disk (d = 2 cm) in the absence of an applied voltage. The loss of
peroxide was monitored polarographically. The effect of the electrode pre-
treatment on the rate constant of the peroxide decomposition was also studied
in this work (the disk was soaked for 12 h in various electrolyte solutions
prior to the measurement). B~ezina [113] also studied the formation of the
superoxide ion, 0 2 , on a graphite electrode. He assumes that this ion is stabi-
lized in the paraffin oil in which the graphite was soaked for impregnation.
The character of the polarization curves is significantly affected by adsorp-
tion of ions from solution or of products of surface reactions. Adsorption
causes passivation of the electrode and, at certain potentials, transfer from a
convective-diffusion controlled process to an adsorption-controlled one is
encountered, manifested by a decrease in the current (the current ceases to
depend on the electrode rotation rate). Polarization curves of this t y p e have
been observed, e.g. during the study of hydrogen ionization [6,7,94,624], of
the reduction of persulphate [240,607] and of tetraphenylborate [681] and
in some other works [ 552,605]. During the study of the oxidation of iodide,
tiny crystals of deposited iodine have even been observed on the electrode sur-
face [59,268]. Miiller's papers [490--492] were devoted to the problems of
electrode reaction kinetics when the electroactive species is adsorbed. The
author has proposed a method, by means of which the type of adsorption
isotherm can be determined (the Langmuir isotherm for ideal surface and the
Temkin isotherm for energetically inhomogeneous surfaces). Further, it is
possible to distinguish simple and dissociative adsorption by comparing the
theoretical and experimental i--¢o 1/2 curves. Evaluation of the kinetic data
for charge-transfer reactions (the order, and the kinetic current) when ad-
sorption occurs has also been described. This topic was also discussed by
Filinovskii [ 575].
McIntyre [465] has developed a m e t h o d for the study of the kinetics of
electrode reactions complicated by a parallel heterogeneous chemical reaction.
An intermediate in the electrode reaction decomposes on the electrode surface
regenerating the electroactive species, which is manifested by curvature of the
i vs. ¢o1/2 dependence. The analysis of the problem was directed to elucidating
46

the kinetics and mechanism of the phenomena occurring on the oxygen elec-
trode, where hydrogen peroxide is the intermediate undergoing the heteroge-
neous decomposition. According to the author it is possible, using his equa-
tions (based on the Levich equation corrected by Newman [ 527] ), to deter-
mine the rate constants of parallel first-order heterogeneous reactions in the
range 10 - 3 < kh < 1 0 - 1 c m s - 1 , o r of second-order reactions in the range
1 0 4 ~< k h ~< 1 0 6 c m 4 mo1-1 s- 1 . The author also treated follow-up and parallel
electrochemical reactions and gave a theoretical treatment of the problem for
the RRDE.
An interesting method for distinguishing between t w o parallel electrode
reactions has been proposed by Pleskov [ 566]. The method is applicable to
systems where one reaction is diffusion-controlled, and hence the correspond-
ing current depends linearly on the square root of the rotation rate, and the
other reaction is controlled by the surface reaction kinetics, and consequently
the corresponding current is independent of the rotation rate (i.e. the hetero-
geneous charge-transfer rate constant of the former reaction is much higher
than that for the latter). The net current density then equals i = (Q)I + (ik)2.
At co -+ 0, the current density is i ~ ( i k ) 2 . Therefore, from the dependences of
the current on the square r o o t of the electrode rotation rate recorded at differ-
ent potentials and extrapolated to co = 0, ( i k ) 2 c a n be determined for the in-

iL i Es
TI / T
f
f

[-4

1 E1

I I
,/ I"
-I- ~-q /
I I /

•-E El E2 E3 E4 Es ---.. ~1/2

Fig. 14. S c h e m e o f t h e s e p a r a t i o n o f t w o reactions taking place s i m u l t a n e o u s l y on the

e l e c t r o d e surface.
 47

dividual potentials and subtracted from the net current, thus yielding separate
polarization curves for the two processes (Fig. 14). This m e t h o d has been em-
ployed by many workers [201,343,439,502,565,570,724]. Miiller and Wetzel
[501] studied a similar problem.
Taylor and Humffray [666] studied the rate of electrode reactions on elec-
trodes made of various forms of carbon and compared the charge-transfer rate
constants with the values obtained on platinum and mercury. They arrived at
the conclusion that the rate constants decrease in the series Pt > glassy carbon >
wax impregnated graphite > carbon paste.

(b) Study o f electrode reaction kinetics using the RRDE. The R R D E is often
employed for studying the kinetics of complex electrode reactions. The t w o
indication systems, yielding t w o suitably selected current values, enable simpler
determination of the kinetic parameters of various electrode reaction types.
Therefore the R R D E has generally been used for the study of oxygen electrode
reactions, which are rather complicated.
Among the first papers dealing with the electrode reactions of oxygen were
those of Soviet authors, chiefly Nekrasov et al. [63,131,248,249,289,364,498,
499,500,509,510,513,515,576,610,641,660,661], and the works of Bockris
et al. [93,174,176--178,261,262]. Tarasevich [661] considers the probable
reactions of oxygen to be as follows:

(O2)sol ~ (O2)ads ~ (H202)ads -~ (H202)sol

lk~ k' lk 8
H20 H20

Oxygen in the solution is first adsorbed on the electrode surface and only then
can it be reduced either directly to water or to hydrogen peroxide. The peroxide
is reduced to water, passes into the solution or undergoes heterogeneous chem-
ical decomposition to form elemental oxygen (for a quantitative t h e o r y of this
decomposition process, see reference [ 465]).
The works of Bockris et al. agree with those of the Soviet authors; Bockris
[175] further generalizes a number of results obtained during study of oxygen
ionization and formulates criteria for determination of the character of electro-
chemical reactions. Using these criteria it is possible to assess whether a direct
reaction occurs at the electrode or whether parallel reactions take place. The
author considers the general reaction scheme
disk reaction A -~ D
k
A-* B-*C

so~lution
ring reaction B -~ E
48

F o r the ratio o f the disk and ring c u r r e n t s it holds t h a t [ 1 7 5 ]

ID _ X + 1 + (X + 2) k' ~ (3-16)
IR N N co1/2

w h e r e k' = 1.66 D - 2 / a v 1/6 k and x = flux A -~ D / f l u x A -~ B, i.e. t h e f a c t o r

t h a t d e t e r m i n e s w h e t h e r parallel r e a c t i o n s o c c u r or n o t (for d i r e c t r e a c t i o n s
x = 0, for parallel reactions x ~ 1). T h e I D / I R = f ( c o 1/2) d e p e n d e n c e is linear;
the i n t e r c e p t on the I D / I R axis equals (x + 1 ) / N and the slope is (x + 2)k'/N.
When this test is applied, five d i f f e r e n t r e a c t i o n c o m b i n a t i o n s can b e con-
sidered at the disk:
(i) o n l y r e a c t i o n A -~ D p r o c e e d s , n o i n t e r m e d i a t e is f o r m e d and IR = 0;
(ii) o n l y r e a c t i o n A -~ B p r o c e e d s , k = 0 and it follows f r o m e q u a t i o n (3-16)
t h a t I D/iTR = 1/N. T h e d e p e n d e n c e is linear and t h e straight line is parallel with
the r o t a t i o n rate axis, Fig. 15A;
(iii) r e a c t i o n A -~ B -~ C p r o c e e d s w i t h o u t a n y parallel reactions; x = 0.
F o r the ! D / I R ratio it follows f r o m e q u a t i o n (3-16) t h a t ID/IR = 1/N + 2k'/N col/2;
the I D / I R = f(co -1/2) d e p e n d e n c e is a straight line intersecting a segment
equal t o 1IN o n the I D / I a axis, w h o s e slope yields the k' value (Fig. 15B);
(iv) reactions A -~ D and A -* B take place, k = 0. E q u a t i o n (3-16) assumes
the f o r m , I D / I R = (X + Z ) / N . The c u r r e n t ratio is i n d e p e n d e n t o f the r o t a t i o n

ID

t
11N

A B

T. r,
t t

C D
i
Fig. 15. Scheme of the I D/1 R = f(co 1/2) dependences e m p l o y e d for testing the character
of the reaction on the surface of the disk.
1
 49

rate and the plot is parallel with the (.O- 1 / ' 2 axis (Fig. 15C). The x-value depends
on the potential of the disk electrode;
(v) all the reactions considered take place and equation (3-16) c a n n o t be
simplified. The I D / I R = f(o9 -1/2) plots are straight lines whose slopes are depen-
dent on the disk potential (Fig. 15D).
In a manner similar to that adopted for the classification of electrode pro-
cesses, the rate constant for individual reactions taking place on the disk elec-
trode can be determined directly. By way of example, calculation of the rate
constants can be shown for the reaction [ 568]
kl k2
A + n l e --->B+/22 e ~ C
Intermediate B is monitored at the ring
B + nRe~ E
(Quantities related to substance A will be denoted by subscript 1, those re-
lated to substance B by subscript 2). The disk current is given by the relation

(/d)D,1 I n2 ]
ID = (/21 + n2) (1 + D 1 / k l ~ l ) nl + (1~+ D J k 2 ~ 2 ) (3-17)

where (Id)D,1 is the limiting diffusion current at the disk electrode flowing
with transfer of (/21 +/22) electrons, i.e. (Id)D,1 = A ( n l + n2)FDlCl (°°)/61. The
ring current is given by
nRN(Id)D,1 D2/k2~2
IR = (nl + n2)(1 + D 1 / k l a l ) (1 + D2/k2~2) (3-18)

Combination of the two equations gives the relationship for the ID/IR ratio
[nl + (/21 + rt2) k2a2/D2]
ID/IR = N/2R (3-19)

and, on substitution for 8 from equation (2-43)

ID/IR
F-1 + (/21 +
L" n2)1.61 k2D-2/av-l'Sl_Il
091 ]2 Nn R
(3-20)

The ID/I R = f(09 -1/2) dependence is linear, the intercept on the ID/I R axis
equals nl and the constant h 2 can be determined from the slope.
In order to determine the constant k 1 and the number of electrons ex-
changed in reaction B -* C, n2, it is suitable to plot [(Id)D,l --ID]/IR against
o01/2; this plot is described by the equation
[(Id)D,1 --/D] [ (/21 + n2)Dlk2al (nl+n2)D17 1
IR = [_n2 + + (3-21)
D2hl~2 kl~l J NnR
It is again possible to substitute for a, obtaining a linear dependence with inter-
50

cept on the [(Id)D.1 --ID]/IR axis equal to ne, from the slope of which k 1 can
be determined.
Therefore, for the determination of the kinetic parameters of the above
reaction it is sufficient to measure the I D and IR values for at least two rota-
tion rates, thus obtaining nl, n2, kl and k 2. The (Id)D,1 values can be measured
directly or calculated from the appropriate data.
For parallel electrochemical reactions at the disk
nl, kl
~D
A n2, k 2 nR
~ B---~ E

the equations

ID/I R = (nlk 1 + n2k2)/NnRk 2 (3-22)

and
[(Id)D,1 - - I D ] nl--n 2 n 1 D 2 / 3 ~ 112
- I- (3-23)
IR NnR 1.61 nRNk2 p-l~6 '
are valid [ 568], where (Id)D.1 is the limiting current at the disk for the transfer
of nl electrons. The values of kl and k 2 can be determined from these equa-
tions, analogously to the previous case.
The above-mentioned work dealing with the kinetics of oxygen electrode
reactions was performed in both acidic and alkaline media on a great variety
of metals (platinum [249,287,364,499,500,515,663], palladium [287,641],
nickel [63,289,610], gold [ 576,662], tungsten [662], rhodium [ 513,592],
amalgamated gold in a non-aqueous medium [ 510] and pyrolytic graphite
[660]).
The work of Johnson et al. [342], who investigated the surface of a plati-
num disk electrode in acid media, is also related to the study of the oxygen
reduction mechanism. During the reduction cycle, the PtO2 formed at con-
siderably more positive potentials is reduced to Pt(II). However, an a t t e m p t
to identify the species formed during the oxidation of the electrode was un-
successful.
Honz et al. [317] studied chemisorption of hydrogen on the platinum elec-
trode. Problems connected with electrochemical reactions accompanied by
evolution of gaseous products were studied by Kadije and Naki5 [349,350].
Johnson and Bruckenstein [340] investigated the anodic oxidation of
bromide. Bromide adsorbed on the reduced sites of the platinum electrode
is oxidized to h y p o b r o m i t e and the platinum surface is simultaneously oxi-
dized.
McClure [464] studied the electrochemical reactions of IrC12" using an
optically transparent ring electrode; the redox behaviour of chromium and
cobalt was also studied [335--337]. Shurig and Heusler [631] applied the
R R D E to the study of the reduction of permanganate in an alkaline medium.
 51

The reduction involves three steps, Mn(VII) -~ Mn(VI) -~ Mn(V) -~ Mn(IV).

It is assumed that the last step involves dimerization of the product with a
rate constant of 2 × 10 - 5 1 mo1-1 s- 1 . The kinetics of the anodic oxidation
of aniline in AcN were studied by Breitenbach and Heckner [106]. Miller et
al. [473,478] studied the kinetics of the anodic dissolution of copper and
indium, and Nekrasov and Berezina [ 511] investigated the kinetics of the re-
duction of cupric ions.
So far it has been assumed that the reaction at the disk is first order. If this
is n o t so, knowledge of the reaction orders of the individual reactions is neces-
sary for complete elucidation of the electrode reaction mechanism; determina-
tion of the reaction order was discussed by Filinovskii [231]. For the reactions
kl k2
disk plA + nle -~ B P2B + n2e -* C
ring B + nR e -~ E

where/21 and P2 are t h e appropriate reaction orders, which can be determined

from the equation [ 568]

11-- [IID + IIRn2/nRN] [l(Id)D'l~} 1 IID + IIIcn2/nRN

log 1 -- [2ID + 2iRn2/naN ] [2(Id)D,11] =~--11log 2ID + 2IRn2/naN (3-24)

where 1I are the corresponding currents measured at 091 and 21 are those mea-
sured at c02 and (Ia)D,1 = A(nl + n2)FDxcl(~)/~l. On substitution o f the mea-
sured currents, the order of the first reaction,/2x, is determined. Analogously
for P2

l i e 2~2 1 liD -- lIRnffnRN

log - - - log (3-25)
2/R 1~ 2 122 2/D -- 2IRnffnRN
where the notation of the currents is the same as in equation (3-24).

3-3. Study of volume reaction kinetics

Another important application of the RDE lies in the study o f volume chem-
ical reactions of species participating in the system of electrode processes. The
properties of the RDE permit the solution of transport equations for relatively
complicated reactions, under both stationary and non-stationary conditions.
When the electroactive species is supplied from volume reactions, the con-
vective-diffusion equation must be supplemented with the appropriate kinetic
terms. If a single chemical reaction takes place in the solution, in which sub-
stances A1, A 2 , ...... A n participate,

0 = ~ RkAk
k=l
52

where vk are the corresponding stoichiometric coefficients. For the equilibrium

of this reaction can then be written

1-I k = o
k

where o is the equilibrium constant. If some of substances A~--An (e.g. sub-

stance A1) undergo electrode reaction A~ + ne -~ products (the reaction prod-
uct can be one of substances A2--An), the equilibrium in the vicinity of the
electrode is disturbed and the departure from equilibrium can be expressed
by the equation [568]

Pf(cl, Ce...,Cn) =
p 1--I CkVk - - p o l-I C--Vk
k (3-26)
vk~O Vk~O

where p is the rate constant of the volume reaction and c k the concentration
of substance Ak close to the electrode surface. The expression
V k p f ( c l , C2 . . . . Cn) = Qk

is sometimes called [395] the strength of the volume source, Qk.

The chemical reaction taking place in the solution causes an increase or
decrease in the concentration of electroactive species A1 in the vicinity of the
electrode and hence the diffusion-convective equation must be modified ac-
cordingly. The stationary mass transport equation is thus formulated for the
given reaction

D k d2ck/dy 2 = vy dck/dy + Qk (3-27)

with the following boundary conditions:

Since the non-equilibrium process takes place close to the surface of the elec-
trode, the expression
Ck =ck(¢¢) fory-+ (3-28)

is valid and, for rapid electrode reactions,

cl = 0 for y = 0 (3-29)

Substances Ak¢ 1 do not enter into the electrode reaction, so that

(3-30)
d y /y=o ~ dy/y=o ":'" \ d y :y=o

A brief survey of the solutions of equation (3-27) for various types of chem-
ical reactions participating in the overall electrochemical process is given below.
Methods for treating some types of reactions have been described by Kouteck:~
and Levich [395]. For the sake of simplicity, the diffusion coefficients of all
reactants will be considered equal, thus enabling use of a single value for the
 53

diffusion layer thickness. Some types of reactions were treated by Dogonadze

[196] assuming different diffusion coefficients. The effect of the volume reac-
tion kinetics on steady-state establishment was investigated by Hale [295] and
Chernenko [ 150,151] for galvanostatic conditions.
The behaviour of electrochemical systems with parallel volume reactions
has been studied very systematically, both theoretically and practically, with
the dropping mercury electrode. The basic works in this field were published
by Brdi~ka, Koryta, K0uteck~ and Wiesner. The problem of polarographic
currents controlled by the kinetics of homogeneous chemical reactions was
originally solved using approximate methods, based on the reaction layer con-
cept [ 103,104,704,705]. The rigorous solution of the transport equations
was later given chiefly b y Kouteck:~, who introduced a correction for the
growth of the drop, first into the resulting equations [389,391] and later di-
rectly into the initial equations [390]. A number of monomolecular and pseudo-
monomolecular reactions were handled in this way.
A survey of the results of the study of polarographic kinetic currents is given
in the works of Hanu~ [296] and Brdi6ka [101] ; the theoretical dependences
have been verified experimentally [ 9 1 , 1 0 0 , 1 0 2 , 1 1 5 , 3 8 7 , 3 9 2 - - 3 9 4 , 5 8 1 ] . It
should be pointed out that the results obtained for the dropping mercury elec-
trode and rapid volume reactions are often identical with those for the RDE.
The use of the R R D E for following volume reaction kinetics has been
chiefly studied by Albery et al. [16--19,26,28,29], who have also developed
a theory for studying the kinetics of heterogeneous chemical reactions. In
order that the R R D E be successfully applicable to these problems, two assump-
tions must be fulfilled:
(i) it must be possible to generate one of the reactants on the disk electrode
and no other species present in the solution may interfere with the generation;
(ii) all of the intermediate in the disk reaction that reaches the ring must
undergo a reaction on it and no other substances in the solution (including
the products of the homogeneous reaction) may interfere with this reaction.
These conditions can be met e.g. by choosing a suitable electrode material;
this is one of the advantages of solid electrodes.

(a) Study o f preceding chemical reactions using the RDE. Chemical reaction
(3-31a) is assumed to proceed in the solution and rapid charge-transfer reac-
tion (3-31b) occurs on the electrode
p
A2 ~p A1 (3-31a)

A1 + ne--~ Products (3-31b)

Reaction (3-31a) is quasimonomolecular in as much as the rate constant p can

depend on the concentration of an arbitrary species in the solution. The deple-
tion of electroactive form A1 through the electrode reaction leads to distur-
54

bance of the bulk equilibrium

c2(~) -- a c l ( ~ ) = 0 (3-32)
The system of equations describing stationary mass transport and the appro-
priate boundary conditions is given, in accordance with relationships (3-27)--
{3-30), in the form
d2Cl dcl
D - = vy - ~ - - p (c2 - - (~cl) (3-33)
dy 2

d2c2 dc 2
D -~ = vy ~ + P(c2 - - (/el) (3-34)

cl = c 1 ( ~ ) c2 = c i ( ~ ) for y - ~ (3-35)
c1 = 0 (dc2/dy)y= o = 0 (3-36)
where vy is given by equation (2-24). The solution of equations (3-33)--(3-36)
is analogous to that for the dropping mercury electrode and was carried out
by Kouteck:~ and Levich [ 395]. The resultant relationship expresses the mate-
rial flux toward the electrode

D [ c l (~) + c2(~)]
]= =

Jd
- , (3-37)
u IP D 71/2
_ (1 + o)J +1
where Jd is the pure convective-diffusion material flux, given by equation
(2-42). The term [ D / p ( 1 + a)] 1/2 has the significance of the kinetic layer, Ok.
At a distance y/> Ok, i.e. outside the kinetic layer, equilibrium is preserved.
For the disk electrode, Ok has the same value over the whole disk, similar to
and a0.
The solution was given for a rapid chemical reaction, i.e. when the inequal-
ity

p(1 + o) ~ 1 (3-38)

is valid. Using equation (3-37) the kinetic currents can be expressed in rela-
tion to the limiting current densities of substances A1 and A2 :
i = (id)l o/(1 + o ~k/~) (3-39)
This equation holds for o >> 1, i.e. for negligibly small concentrations of sub-
 55

stance A1 in the solution. In the opposite case, when o < 1, kinetic effects
will not be perceptible and the current density will equal i ~ (id)l. The kinetic
current for a preceding reaction is lower than the diffusion current correspond-
ing to electroinactive substance Az (in the given potential range) and, provided
that condition (3-32) is met,

i = (id)2 (1 + o ~ k / ~ ) - 1 (3-40)
This equation can be written in the form
1 -- i/(id) 2 ak 1 -- i/(id) 2
i/(id) 2 = G" a , i/(id) 2 -- f ( c o 1/2) (3-41)

which corresponds to a straight line, from the slope of which the rate con-
stant p can be determined.
For practical purposes equation (3-41) is often written in the form

i / w 112 = B + C i / p 112, where C = - - o 1 / 2 D l l S / 1 . 6 1 v 1Is (3-42)

For the value of B, see equation (2-44). Equation (3-42) is the equation of a
straight line, i/co 1 / 2 = f(i) and p can be obtained from its slope. When this
m e t h o d is employed, concentration c2(~) need n o t be known. When the non-
equilibrium process is absent (the chemical reaction is very rapid, ~k -* 0), this
dependence is expressed by a horizontal line (see the schematic representation
in Fig. 16).
The rate constants for the dissociation and recombination of weak acids
were determined employing this m e t h o d [647,691--693]. For pseudomono-
molecular reaction H ÷ + A ~ HA it was found from the graphical plot for
p
acetic acid that p = 3 × 10 s s-1 and op = 1 × 101° l mo1-1 s-1. More accurate
measurements of the currents using two synchronously rotating disk electrodes

Fig. 16. Scheme of the i/co 1/2 = f(i) dependence, according to equation (3-42).
56

connected in a bridge circuit [14] yielded p = 9.1 X 105 S- 1 and op = 5.2 X 101°
1 mo1-1 s-1 for this acid. For the dissociation and recombination rate constants
of trinitromethane in AcN it has been found [378] that p = 4.5 X 102 s-1 and
op = 8 X 109 1 mo1-1 s-1 . The precision of the determination of rate constants
was found to be 10%. The effect of the electric field in the diffusion part of
the double layer and of migration on the measured values of dissociation con-
stants was considered by Albery [9].
The bimolecular reaction

A2 G 2A1. (3-43)
op

can also occur as a preceding reaction [395]. Reaction (3-31b) takes place on
the electrode. Equilibrium is established in the bulk of the solution, so that

c2(°°) -- oct(~o) = 0 (3-44)

and the convective-diffusion equation must be supplemented with the terms

Q1 = --2p(c2 -- oc 2)
(3-45)
Q2 = p(c2 -- 0c2)

Boundary conditions (3-35) and (3-36) remain the same. Assuming a rapid
chemical reaction, 3k ~ 3, and c2(oo) >> c1(o~), the appropriate system is solved
obtaining the relationship between the kinetic current density and the elec-
trode reaction rate in the form [568]

[ 1 - - i / ( Q ) 2 ] 3/4_ c1(°°) 3k
i/(id) 2 x/~C2(Oo) 3 ' (3-46)

where bk = xFD~2pa c1(°~) and (id)2 = 2nFDc2(~)/3. It is evident t h a t the rela-

tionship between the current and the rotation rate is more complex than for
monomolecular reactions. This solution has not yet been experimentally
verified.

(b) Study of parallel chemical reactions using the RDE. The rapid reaction
A 1 -+ ne-+ A2 (3-47)

takes place on the electrode and reaction (3-31a) occurs in the solution. The
mass transport is described by the system of equations (2-33)--(2-35). The
boundary condition for the surface of the disk must be formulated anew

cl o, (dcq = _
/de2]
\ d y /y=o \ dy ]y=o (3-48)

In a manner analogous to that considered with the previous reaction types,

 57

the equation for the current density passing through the electrode with rapid
volume reaction (3-31a) is obtained [395]
[ pD ~I/2
i= nF[Cl(°°) + c2(°°)] \1+--o] (3-49)

This equation indicates that the catalytic current is independent of the elec-
trode rotation rate when the other assumptions are fulfilled, i.e. when inequal-
ity (3-38) is valid.
As examples of catalytic reactions which have been studied, the decomposi-
tion of hydrogen peroxide [291,547] and tert-butylhydroperoxide [ 547] by
ferrous ions can be mentioned. The peroxides were present in a large excess,
so that reaction (3-31a) has a pseudo-monomolecular character. It can be seen
from the i = f(co 1/2) dependence (Fig. 17) that for small rotation rates (a is
large) the catalytic current is independent of the electrode rotation rate. At
high rotation rates inequality (2-38) ceases to be valid, i.e. ak ~ a and the cur-
rent becomes a function of the electrode rotation rate.
For practical purposes the solution of the system of transport equations
can be modified, provided that reaction (3-31a) is not very rapid. This modifi-
cation was carried out by Haberland and Landsberg [291], who solved mass
transport equations for chemical reactions participating in the overall electro-
chemical process in the interval, (0, e), where e is a parameter that determines
when equilibrium of the chemical reaction is attained (the previous solution
was carried o u t in the interval, (0, oo)). The resulting equation describes the
dependence of the current density on the electrode rotation rate in a practical

I I ! I f 1

80

v~'~l I ! [ I i
0 2 4 6 8 10 12

Fig. 17. The i = f(co 1/2) dependence for the Fe(II) reaction with H202. From ref. 547.
(1) id; (2) the dependence according to equation (3-49); (3) the experimental dependence.
58

form
i 0p 1/2 0p 112
- cotanh - x cotanh x (3-50)
(id)l D 1/2 0 1/2

where x = 1.61 (v/D) lls (p/co) 1/2. It follows from this equation t h a t
x = {//(id)l} tanh x : (3-51)
Therefore, it is sufficient to determine the current densities (id)l for the corre-
sponding co values (in the absence of a kinetic process) and i (in the presence
of the kinetic process), to obtain x from equation (3-51) and the rate constant
p is found from the slope of linear dependence x = f(1/co1/2).
In general it is convenient to evaluate the f r a c t i o n / / i d in the relationship
for the calculation of rate constants, since quantitative determination of the
concentration of the electroactive species is then often unnecessary. The con-
centration must be maintained constant during the measurements in the pres-
ence and absence of a non-equilibrium process.
A relatively simple m e t h o d for handling kinetic processes is the m e t h o d
of moments of Bruckenstein and Prager [130], which was used during the
study of the iodate reduction with iodide [87] and hydroperoxides with
ferrous iron [547]. T h e method is based on the Nernstian concept of a linear
concentration gradient in the diffusion and kinetic layers and yields results
comparable with those obtained by rigorous solution of the transport equa-
tions.
An example of the use of this m e t h o d is the calculation of the rate constant
of the catalytic reaction
p
A2 --+ A1 A1 + ne--> A2 (3-52)
The convective diffusion equation for electroactive species A1 assumes the
form

D1 d 2 c l / d y 2 = vy d c l / d y - - p c 2 (3-53)

It follows from the concept of linear concentration gradients within 0 and 0 k

that
Cl = c1( ~ ) y/O for 0~<y~<0,0k=0 (3-54)

cl = c l ( ~ ) y / 0 k for 0~<y~<0k, 0 k * 0 (3-55)

C2=C2(0)[1--Y/0k] for 0~<y~<0k, 0 k ~ 0 (3-56)

The integration of equation (3-53) over the interval, <0, Ok>, yields

dcl ~ k dcl r~ k
-- j vy dy -- j pc2 dy (3-57)
--D1 ~ - o o
 59

From equations (3-55) and (3-56) we obtain

dcl/dy = Cl(°°)/0k dc2/dY = --c2(0)/Ok (3-58)
Since the relationship
D1 d c l / d y = --D2 d c 2 / d y

is valid and taking into account equations (3-58), the surface concentration
is given by
c2(0) = ( D 1 / D 2 ) c 1 ( ~ ) (3-59)

On substitution into equation (3-56) the expression

C 2 ----( D 1 / D 2 ) Cl(OO ) [ 1 - - y/Ok] (3-60)

is obtained. The relationships for d c l / d Y and c2 can be substituted into (3-57),

the expression for vy in this equation can be substituted from (2-24) and the
equation is integrated for the second time, giving

C1(°°) 0 . 5 1 09 3/2 P'--l]2 C1(°° ) D1

--D1 O----k--= -- 3 O~ -- 2D~ p c1(°°) Ok (3-61)

After multiplying equation (3-61) by the term O k / D l c l ( : ¢ ) , the first term on

the right-hand side is equivalent to the ratio (Ok/O)a and the resultant relation-
ship can be written in the form

O~ 1 O2 O~
- - + - - -- 1 -- 0 (3-62)

Or

R 3 + xPR 2 -- 1 = 0 (3-63)

where R = ak/a = ( i d ) l / i l and × = 1.61 D 213 v l l ~ / D 2 ¢ o . Equation (3-63) corre-

sponds to a straight line:

(1 - - R 3 ) / R 2 = X.P
the slope of which gives rate constant p.
Using the RDE, the catalytic reactions of iodide with iodate [292], the re-
duction of chromic acid in sulphate solutions [133] and the oxidation of
methanol with octavalent osmium [238] have been studied. The theory of
catalytic currents was also examined by Milyavskii [480].
Some attention has been paid to disproportionation reactions of the t y p e
P
2A2 ~ A1 A1 + ne ~ A2 (3-64)
op
60

The mass transport equations then include the terms

V l = - p ( c2 -- o c l )
(3-65)
Q2 = 2 p ( c 2 - ac x)

The boundary conditions are given by equations (3-35) and (3-48). The result-
ing expression is [568]

i/2(id)l = 12~ 1/2 2C1(°°) a

(3-66)
[1 -- i/2(id)l] 3/2 ~] C2(~) bk

where ~k = (D/Po) 1/2. With high disproportionation reaction rates, the maxi-
mum current density, i = 2(id)1, is observed.
Ulstrup [684] has given an analytical solution to the problem of regenera-
tion of the electroactive species by disproportionation. His method enables
the determination of rate constants of disproportionation reactions for which
the relationship k >~ 10 s 1 mo1-1 s- 1 holds, corresponding to ratios of i/id ~ 2;
hence, this method is only applicable to almost complete disproportionation.
Holub [316] solved this problem numerically for all possible ratios of (i - - Q)/
id = J from 0 to 1. The author tabulated the values of t~ = [ 2 c 1 ( ~ ) p / 0 . 5 1 2 / 3 co]-
[v/D] against J for ~ ~< 50. Ulstrup's analytical solution ~ = 1.809(1 + j ) 2 /
(1 -- j)3 is suitable for K > 50.
Disproportionation reactions were also studied using the RDE by Olander
[544] and Geisler et al. [260]. Kfita and Yeager [407] studied the dispropor-
tionation of U(V) and e m p l o y e d Holub's solution [316] for the determina-
tion of the disproportionation rate constant.

(c) S t u d y o f follow-up chemical reactions using the R D E . The reversible reac-

tion
A3 + ne ~ A1 (3-67)
takes place on the electrode and the chemical reaction
pa
A1 ~- A2 (3-68)
p
occurs in the vicinity of the electrode. The effect of the latter reaction on the
kinetics of the electrode process will be stronger the smaller the concentration
of substance A1 in the solution, i.e. when a >> 1, The system of transport
equations for substances A1 and Ae is identical with equations (3-33) and
(3-34) and for substance A3 it holds that

D d2c3/dY 2 = vy d o w d y (3-69)
 61

The boundary conditions are given by the equations

Cl = c1(°°), c2 = c2(°°), c3 = ca(°°) for y ~ oo (3-70)

tic31
dY / y=o
=_~del~ ~dc2 i
\ dY ] y=o' \ dy ] y=O = 0 ,
e3(O)=cl(O)exp[~T(E--EO)]f o r y =0
(3-71)
The solution of this system of equations can be expressed in the form [568]

1 - - i ( i d ) 3 _ ak [ nF --E°)]
i/(Q)3 0 exp ~ (E (3-72)

where ~k = (D/Pe) 1/2 and E ° is the standard redox potential of the system.
From equation (3-72) it follows for the half-wave potential in the presence
of kinetic process (3-68) that

(El/2) k = E ° + (RT/nF) ln[(po/D)l/2~ ] (3-73)

It can be seen that, due to the follow-up chemical reaction, the half-wave
potential shifts compared to the value, E1/2 ~ E 0, obtained in the absence
of reaction (3-68). The same dependence was found by Galus and Adams
[254], who employed the reaction layer concept for the solution of the trans-
port equations. The same authors also dealt with reaction 2A1 ~ A2.
From the shift in the half-wave potential the rate constants for reactions
of the products of the electrode reaction of N-alkylphenyldiamines with O H -
ions were calculated [562,675]. These are reactions of the t y p e

R2 N NR 2 " ~ 2N NR + 2OH- : ~ O O

Equations for i--E curves on the RDE when the electron transfer is followed
by a first-order homogeneous reaction were also given by MSller and Heckner
[485] ; Gray and Harrison [280] used the RDE for the study of electrochemi-
cally-initiated polymerization reactions. Ko~fnek et al. [383] studied the oxi-
dation of hydrazine on the dropping mercury electrode and on gold and silver
RDEs. They found that a shift in the half-wave potential occurs on gold and
mercury electrodes and explained this p h e n o m e n o n by assumption of a fol-
low-up chemical reaction of a hydrazine reaction p r o d u c t with O H - ions in
the solution. For the reaction
o --e p --3e
N2H4+H20~N2H~-+H30 ÷ -~N2H3-*X -*N 2
an equation for the polarization curve was derived, which has the following
form for a gold RDE

E =E° +
_R_FT I
In [H
~0+] RT
+ - ~ In
----ln]
Ln a~
--N2n3v
D 2/3 , - - 1 ] 6 ,.,112
. . . . . N2H4 v ~.~
62

The hydrazine oxidation reaction belongs to reactions of the type

pa
A3 + r i l e - * A1 -~ A2 + n 2 e -> A4 (3-74)
This is the so-called e.c.e, reaction mechanism (electrochemical-chemical-elec-
trochemical), which has been studied by a number of workers [230,444,451,
455,456,538]. When identical diffusion coefficients and numbers of electrons
exchanged are assumed (n 1 = n2 = n) and substance A2 is considered to be
more readily changed electrochemically than A3, the current density is given
by [444]

i = (id)3 [2 -- e x p ( - - p o ~ 2 / T r D ) ] (3-75)

(the authors employed an analogy between the potentiostatic m e t h o d for the

study of the e.c.e, mechanism and the RDE method.) It can be seen from
equation (3-75) that for very rapid chemical reactions when pa > D / 8 the ex-
ponential term becomes zero and the net current corresponds to an exchange
of 2n electrons. On the other hand, for p o ~ 0 the current corresponds to an
exchange of n electrons. Inside this rate constant interval, the apparent num-
ber of exchange electrons,/'lapp, varies from 2n to n. Therefore equation (3-75)
leads to the expression

//(id)3 = r/app/rt = 2 -- exp(--pa52/~D) (3-76)

from which a constant pa value can be determined. More rigorous treatment
of this reaction was carried out by Karp [ 538], while Filinovskii [230] solved
this problem for unequal numbers of exchanged electrons nl #= rt2. The e.c.e.
mechanism was studied for the oxidation of a series of aromatic amines [444,
451,455,456], also for solution volume reactions of the type 2A1 P~ A2. For
example

,c.Hs 2N© + H

+ H -2e
2 (C6Hs)2N:=~. e~r ~ ( C 6 H s ) 2 N ~ N ( C 6 F I s ) 2

(C6Hs)2N N(C6H5)2

Other works dealing with the use of the RDE for both theoretical and prac-
tical study of volume reactions include e.g. hydrogenation of methylstyrene
[703], hydrolysis of acetyl salicylaldehyde [629], electrochemical dimeriza-
tion and cyclization of organic molecules [32,503], etc. [656].
 63

(d) S t u d y o f first-order volume reactions using the R R D E . The presence of a

volume reaction, for example
disk reaction A + riDe --> B
solution reaction B ~ products
ring reaction B + nRe--> A
is manifested by a change in the collection efficiency N. The p r o d u c t of the
disk electrode reaction, B, diffuses into the solution where it undergoes a
chemical reaction; unreacted species B can be detected on the ring. It is ob-
vious that, with increasing rates of the chemical reaction (higher p), less of
species B reaches the ring and the kinetic collection efficiency Nk is corre-
spondingly lower. The range of rate constants determinable by this m e t h o d
is chiefly determined by the parameters of the measuring apparatus. Slow
chemical reactions do n o t cause a measurable difference between N and N k ,
since only a negligible part of B reacts during the transport from the disk to
the ring; i.e. Nk ~ N (this limitation is imposed by the limited sensitivity of
the instrument). On the contrary, very rapid reactions change the B species
into electroinactive products before it can cross the gap between the electrodes
and Nk ~ 0 (this limitation is imposed by the particular electrode construc-
tion).
The solution of the transport equation for a first-order volume reaction
(or pseudo-first-order, where p = kcx(o¢), Cx being the concentration of a sub-
stance present in a large excess in the solution)

D a 2 c 2 / ~ y 2 = v r ac2/ar + vy a c 2 / a y + p c 2 (3-77)

where c2 is the concentration of substance B, leads to the expression for the

kinetic collection efficiency, Nk = ( i R n D ) / ( i D n R ) , from which rate constant p
can be determined. If it is valid that
j¢ = (p/D) 112 (D/C) 1Is (3-78)

and
C = 0.51 w 8/2 v-1/2 (3-79)
where C is the convective constant, then it holds for the kinetic collection
efficiency, assuming that ~ < 1 and t h a t both the gap and the ring are very
narrow [26], that

N k' = N " -- (/~,)213 (1 -- A i - l c , ) + 1/2 A i -1A~ ~2 c. (fl,)4/3 _ 2 A 2 E 2 T2 (3-80)

where N " is given by equation (2-65), fl' by equation (2-67) and

A1 = 3½ F (4/3) = 1.288

A2 = 0.643 v 1/6 D 1/3

64

c. = K- 1 tanh(A1K) f o r g ~ 0.3

c. = A1 [1 - - 0 . 3 7 2 ( A 1 ~ ) 2 + 0 . 1 4 6 ( A 1 ~ ) 4 ...] f o r ~ < 0.3

c. are the d i m e n s i o n l e s s c o n c e n t r a t i o n variables d e t e r m i n e d b y Hale [ 2 9 5 ]

and T2 is a f u n c t i o n o f t h e g e o m e t r i c p a r a m e t e r s (see ref. [ 2 6 ] ) .
Since t h e c o n d i t i o n t h a t N ~ N " is rarely m e t in practice, a c o r r e c t i o n f o r
u p t o a 20% d i f f e r e n c e b e t w e e n N a n d N " can be i n t r o d u c e d b y t h e e q u a t i o n
[26]

N k = (1 + [1 - - t a n h 2 ( A l ~ ) ] (N/N"--1)} N~' (3-81)

T h e a b o v e e q u a t i o n s s h o w t h a t N k d e p e n d s solely on t h e g e o m e t r i c p a r a m e t e r s
o f t h e e l e c t r o d e and the ~ value. H e n c e it is possible t o p l o t NR = f ( ~ ) f o r an
e l e c t r o d e w i t h c e r t a i n g e o m e t r i c p a r a m e t e r s , d e t e r m i n e t h e ~ value f r o m t h e
Nk values m e a s u r e d w i t h t h e s a m e e l e c t r o d e using d e f i n i t i o n e q u a t i o n (2-54),
and t o d e t e r m i n e t h e r a t e c o n s t a n t .
F o r values of ~ ~ 1 t h e analytical e q u a t i o n
logN k --logN = - - a ~ + b - - log[1 + 1/(~ + c)] (3-82)

is valid. C o e f f i c i e n t s a, b, and c in this e q u a t i o n are t a b u l a t e d in t h e m o n o -

graph b y A l b e r y a n d H i t c h m a n [ 26] f o r the m o s t c o m m o n ratios o f r2o/rl0
and r3o/r2o.
Using this m e t h o d , r a t e c o n s t a n t s f o r v o l u m e r e a c t i o n s can be d e t e r m i n e d
w i t h i n a range o f 0.2 < ~ < 5 c o r r e s p o n d i n g t o r a t e c o n s t a n t s in t h e interval
3 × 10 - 2 s - 1 < p < 10 s - 1 f o r r o t a t i o n rates o f 2 t o 100 rev s - 1 f o r first-
o r d e r r e a c t i o n s a n d c o n s t a n t s o f 3 × 10 - 2 1 m o 1 - 1 s - 1 < k ( 107 1 m o 1 - 1 s - 1
f o r p s e u d o - f i r s t - o r d e r reactions, w h e r e p = kcx (o~ ).
T h e s e t h e o r e t i c a l d e p e n d e n c e s h a v e b e e n verified b y m e a s u r i n g t h e rate con-
stants f o r t h e b r o m a t i o n o f anisol a n d m - f l u o r o a n i s o l a n d f o r t h e r e a c t i o n o f
f e r r o u s iron with v a n a d a t e [ 2 8 ] .

(e) S t u d y o f s e c o n d - o r d e r reactions using the R R D E . F o r s e c o n d - o r d e r reac-

tions,
disk r e a c t i o n A + nDe --> B

solution reaction B + X ~ products

ring r e a c t i o n B + n R e -~ A

the t r a n s p o r t e q u a t i o n s m u s t be solved f o r species B a n d X, w i t h kinetic t e r m s

Q = - - p c2c x.
L i n e a r l y increasing c u r r e n t I D passes t h r o u g h t h e disk e l e c t r o d e , g e n e r a t i n g
species B. I f an i n f i n i t e l y rapid v o l u m e r e a c t i o n is first c o n s i d e r e d (p -~ oo),
t h e c o n c e n t r a t i o n o f B at the surface o f the disk will be zero until I D is large
 65

enough to generate more of substance B than the a m o u n t of X t ransport ed to

the electrode by convective diffusion. This critical value of the disk current,
M, is given by

M = ITr2o n D F D 2/3 C 1 / 3 c x ( ~ ° ) / 1 . 2 8 8 (3-83)

When I D = M, the flux of B from the electrode equals the flux of X from the
bulk of the solution toward the electrode. For I D > M a layer containing pre-
d o m in an tly B is formed. With a further increase in I D the zone containing
p r e d o m i n a n t l y substance B will widen and will finally reach the edge of the
ring, causing an increase in the ring current {point a in Fig. 18); this occurs for
I D = - - M / { 1 -- F ( a ) } (3-84)

IR
t

O< rt,< [t / III

III

l ~o
V////////////////7//A /
I
B \ I
I
I
I
/
J
JJ

Fig. 18. A t i t r a t i o n curve for c o u i o m e t r i c t i t r a t i o n s in t h e d i f f u s i o n layer a n d t h e c o n c e n -

t r a t i o n d i s t r i b u t i o n u n d e r t h e R R D E for a rapid s e c o n d o r d e r r e a c t i o n .
66

On a further increase in I D , the zone containing substance B widens again until

it includes the whole ring and the ring current becomes a linear function of
the disk current (point b in Fig. 18).

IR = _ _ N I D __ M~2/3 (3-85)
It is important that no substance B can penetrate into the region in which
there is a predominance of substance X (due to the high rate of the chemical
reaction). The t w o regions are sharply separated by the reaction layer (repre-
sented by the d o t t e d line in Fig. 18).
The above-described curve, shown in Fig. 18, can be utilized for the deter-
mination of the concentration of substance X. Extrapolation of the linear
portion of the curve to IR = 0 gives the I D value corresponding to I D in equa-
tion (3-85). From this equation M can be calculated and the concentration
of substance X in the solution is then given, according to equation (3-83), by

Cx(~) = 1.288 M/Irr2onD F D 2/3 C 113 (3-86)

These dependences were utilized by Albery et al. [19] and Bruckenstein and
Johnson [125] for determination of As(III) by titration with bromine gener-
ated on the disk, and were called coulometric titrations in the diffusion layer.
By solving the transport equations for substances B and X, it has been found
for the region between points a and b in Fig. 18, i.e. for 0 < fij </3, that

N'= 1 --F(a/fij) (1 + ~
1+o~~j)l/3
+
{
1 --F
[.(1 +- -~+; ~)~]/j (3-87)

M 1--F(a) 1--F (3-88)

ID (1 + (~ + ~j)1/3 ~j

where
~j = ( r j / r l O ) 3 - - ( r 2 0 / r l o ) 3 (3-89)

and rj specifies the place on the ring electrode to which the reaction zone ex-
tends.
For more precise determination of I D for IR = 0, the following procedure
is recommended [ 19,26]. The N ' values are calculated for various fii values in
the interval (0, fi) using equation (3-87) and the corresponding ID/M values for
the same fli are calculated from equation (3-88). Straight lines with slope N '
are superimposed on the experimental IR--I D c u r v e s . The intercept of these
straight lines with the IR--ID c u r v e then determines the point (ID)exp" The
(ID)exp values thus obtained are plotted against the corresponding ID/M values.
The plot is a straight line with slope M which is substituted into equation
(3-86). In this way concentrations of As a+ down to 10 - 7 M were determined.
To obtain a sharp break on the titration curve from zero IR to a linear IR--I D
 67

dependence, RRDE's with wide gaps and narrow rings are suitable.
Very rapid chemical reactions have so far been considered. When the volume
reaction is slower, substance B penetrates into the zone corresponding to sub-
stance X and vice versa. The reaction boundary is not as sharp as for reactions
with infinitely large rates. This fact can be utilized for the measurement of the
rate constant for the reaction between B and X. The generation current I D c a n
be adjusted to a value such that the reaction zone, where c2 = cx, is exactly
at the inner edge of the ring. For infinitely rapid reaction no IR current is
measured, whilst for finite rates I s is proportional to the a m o u n t of B which
has penetrated into zone X and thus also to the rate of the volume reaction.
Albery and Bruckenstein [17] derived relations for the kinetic ring current,
(Ik)a and the kinetic collection efficiency for this situation, N~, by solving the
transport equations (see also ref. 29).

(Ik)R = 0.21 7r r~o n F D co 3/2 v -1/2 p - 1 (3-90)

0.339 r22oD1/3[1 - - F ( a ) ] co
N~ = (3-91)
r2o Vl/3 p c×(°°)

The p value can be determined in practice as follows: The I R - I n curve has a

shape analogous to that of the titration curve discussed above. The disk cur-
rent, (Ik)D, corresponding to the value at which the reaction zone reaches to
the edge of the ring, is given by equation (3-84), i.e. (/k)D = - - M / [ 1 - - F ( a ) ] .
The M values can be obtained from the ! R - - I D curve, as has been shown above
using equation (3-87) and equation (3-88). The appropriate values of M can
be substituted into equation (3-84), giving the value of (Ik)D. Conversely, from
experimental I R - - I D curves the corresponding (Ik)R value can be determined
for the given (Ik)D value and the ratio of the two currents gives N~, from
which the rate constant can be calculated employing equation {3-91), or (Ik)R
can be substituted directly into equation {3-90). The theory has been verified
by measuring the rate constant for the bromination of anisol [ 29] ; it can be
employed for the determination of rate constants up to 109 1 mo1-1 s- 1 .
The kinetics of volume reactions have also been studied by Bard, Prater and
co-workers [448--450,585--587,589,590], who numerically solved the prob-
lem of mass transport complicated by a volume reaction. For example, dimeriza-
tion reactions [ 589,590] and reactions accompanied by chemiluminescence
[448--450] were studied. The two approaches -- Albery's analytical and Bard's
numerical methods -- were compared [ 21] and good agreement was f o u n d
between them. The analytical solution is especially suitable for electrodes with
a thin gap and thin ring, the numerical solution for electrodes with a wide gap
and wide ring (Bard employed a graphite paste RRDE for verification of his
results, Albery a platinum or gold RRDE with a teflon gap, using which, rela-
tively narrow rings and gaps can be obtained). Some general principles of pro-
gramming during solution of transport processes were discussed e.g. by Feld-
berg [ 228].
68

Problems in the measurement of rate constants with the R R D E were also

examined by Adams and Prater [445]. The disproportionation of U(V) was
studied by Nekrasov et al. [516]. The effect of chemical reactions on the
transition time was also investigated [11,123]. For other uses of the R R D E
for the study of chemical reactions in solution, see for example refs. 341 and
591.

3-4. Other application potentialities of disk electrodes

(a) Use of the RDE for solution of other electrochemical problems. Disk elec-
trodes have very frequently been used for various electrochemical and non-
electrochemical measurements, because of their suitable properties which are
discussed above, and often replace traditional solid electrodes. Below, uses of
the RDE for various electrochemical measurements will be briefly surveyed.
In connection with the voltammetry of inorganic and organic depolarizers,
the following investigations should be mentioned in addition to the papers al-
ready cited in sections 3-1 and 3-2: voltammetry of the Fe3+/Fe 2÷ system in
aqueous solutions [273,283] and in acetonitrile (complexes of the phenanthro-
line type, with dipyridyl, phenanthroline and ferrocene) [609], of the Mn3÷/
Mn 2÷ system [274], of titanium in solutions of acids [ 143], of osmium in an
alkaline medium (with a discussion of the possibility of its analytical determi-
nation) [71], of the TlS÷/T1 + system in acidic media [330,683], the reduction
of persulphate in acidic and alkaline solutions [676], the behaviour of iridium
[397], m o l y b d e n u m [545], complexes of neptunium (using a glassy carbon
electrode) [ 572--574] and r u t h e n i u m [302], the I 2 / I - and Br2/Br- systems
using two disk electrodes [332], mercury halides in a suspension on an amal-
gamated electrode [180,181] and oxidation of zinc in 10 M KOH [551]. The
cathodic behaviour of 85--100% H2SO4 on various metals was studied by
Beck [80]. Polarization of amorphous Se was studied by Abrarov et al. [1].
Among organic substances, the oxidation of resorcinol [ 598], N,N-dimethyl-
4-aminoazobenzene and its metabolites [ 460], alizarine S and benzidine on
graphite and platinum [ 596], aliphatic nitro c o m p o u n d s [379] and phenyl-
hydrazine in AcN [146] were studied as well as the electrochemical behaviour
of 9,10-di(a-naphthyl)anthracene [457] and others [109,265,454,597]. The
electrochemical oxidation of NADH and its derivatives was studied using RDEs
made of various materials [ 290,421].
A number of the papers cited also supply data for possible use of the RDE
for the quantitative determination of the substances studied. Some papers
dealt primarily with the analytical use of the RDE. Landsberg et al. [409,411,
415,416] determined MnO 2 - from 5 × 10 - 4 to 10 - 2 M with a precision of
1--2% (excess permanganate does not interfere). For analytical determination
of ions which are readily adsorbed on platinum, an electrode was made from a
mixture of azobenzene (or diphenyl) and graphite, with which iodide, bromide,
nitrite and chlorite can be determined without difficulties [621]. For analysis
of noble metals (Au, Pt, Pd, Rh, Os) a microdisk electrode was constructed
 69

[71--73] by sealing a platinum wire in glass (an electroactive area of 0.78 mm2).
Kabanova [347] also determined gold. Davenport and Johnson [182] deter-
mined nitrite and nitrate voltammetrically.
Analytical applications of glassy carbon RDEs have been described by Vydra
et al. [382,561,652,697,699]. The authors used the RDE as a sensor in the
biamperometric titration of iron with EDTA [697], in which the glassy carbon
electrode exhibits a number of advantages, such as easy pretreatment by polish-
ing with metallographic papers, wide potential range and the possibility of
working in the presence of dissolved oxygen. Another advantage is the low
cost of glassy carbon. The main drawbacks are higher residual currents and the
possibility of recrystallization of glassy carbon at high currents. The same
authors employed the RDE for stripping analysis, using both the conventional
d.c. method [382], determining silver in concentrations down to 10 - 9 M and
copper down to 10 - 8 M in acidic, neutral and alkaline solutions and a.c. meth-
ods. They also proposed a method for the determination of silver (10 - 7 M)
in the presence of copper (10 - 3 M) b y depositing silver from an ammoniacal
buffer (from which copper is not deposited at the potential employed), and
dissolving the silver into pure base electrolyte. Employing a.c. methods [652,
699], they attained increased selectivity, determining silver in the presence of
copper without exchanging the electrolyte. The sensitivity can be increased
by using the second harmonic a.c. voltammetric method, thus reducing the
charging current; in this way Hg 2÷ (10 - 1 ° M) can be determined. The authors
further determined mercury by stripping [651], copper voltammetrically
[653] and described the stripping determination of some metals in the presence
of mercury [437]. Temmerman and Verbeek [668] described the stripping
determination of silver in cadmium; Kabanova [ 348] determined lead and
Florence bismuth [239]. Bakanov et al. [65,66] used a mercury-coated RDE
for stripping analysis. Copper [ 588] and gold [288] were determined coulo-
metrically using RDEs. Bezuglyi and Beylis [ 90] determined some organic sub-
stances. Various analytical potentialities of the RDE were summarized by
Muzgin et al. [487].
Various ions (Ag, Pb, Cd, T1, Ni) were determined in melts [154,186,715].
The RDE was also used for the study of the electrode processes of a great va-
riety of electrolytes in melts [98,99,155,187,192,334,628,677,714,716,717].
In some investigations [307,354,535,553,658] a graphite RDE combined
with spectral analysis was employed for analytical purposes.
The RDE has further been used to study the kinetics of the electrodeposi-
tion of metals from solutions. The deposition of the metals from complex
salts of copper, cadmium, zinc, palladium, gold and nickel [694] and the de-
position of bismuth [278], iron [310,439] and copper [119,323,625] are
diffusion controlled, as is even the more complex reduction of copper. The
effect of electrodeposited platinum on the activity of a Ti electrode was
studied by Weber and Pos[fil [701]. The electrodeposition of zinc [608],
copper from a suspension of Cu20 on amalgamated RDE [179], lead [298],
palladium [299] and mercury [483] has also been studied.
70

A separate group of publications deals with the effect of some substances

(coumarin, thiourea) on metal electrodeposition processes [119,216,322,331,
401--403,602,603,682]. It has been found that organic substances exert a
levelling effect during the electrodeposition; they are adsorbed on the high
spots on the electrode surface, thus decreasing the amount of metal deposited
and the metal preferentially fills the pits.
The deposition of calcium and potassium from non-aqueous solutions was
also studied [76]. Dorsch [202] investigated the simultaneous deposition of
nickel and evolution of hydrogen on the RDE.
The anodic dissolution of metals and non-metals and the corrosion of
various materials have also been studied using the RDE. The dissolution of
aluminium [167], cadmium [368] and zinc [43] is controlled by mass trans-
port, while the dissolution of titanium in fluoride baths [ 144] exhibits mixed
kinetics. The anodic dissolution of copper in dilute solutions of phosphoric
acid [721] is controlled by the rate of transport of non-dissociated H3PO4
molecules toward the electrode. Armstrong et al. [45] studied the dissolution
of tungsten in alkaline solutions by non-stationary, stationary and a.c. methods.
During the dissolution of nickel in sulphuric acid, the material flux is diffusion-
controlled, provided that the dissolution does not take place in the passivation
region [ 219] ; by contrast, in the passivation region, the mass transport is in-
dependent of the stirring rate and is controlled by the surface kinetics [183,
208,579]. The passivation of iron and cobalt in H2SO 4 and HC104 [208] and
of iron in Na2CO3 and NaHCO3 [44] were studied. Armstrong and Henderson
investigated the transfer from the active to the passive state for nickel in sul-
phuric acid [ 51] and also investigated chromium in the passive state [ 50].
Schwake and Lfick [619] studied the anodic behaviour of zinc in solutions
of zinc sulphate containing labelled sulphur and zinc.
Among non-metals, the dissolution of graphite in fused metal oxides [95],
of anthracene in solutions of oxidants [434,435], of sulphides in solutions of
cyanides [ 352], silicon in solutions of nitric and hydrofluoric acids (which
has been utilized for electrolytic polishing) [ 559,560], calcium sulphate [75],
solid organic acids (terephthalic, adipic, salicylic) in aqueous amine solutions
[400] and tetraborate and borates in water [595] have been studied. Armstrong
and Harrison [47] theoretically treated the formation and dissolution of pre-
cipitates on the RDE surface during a study of metal passivation.
A number of publications deal with the corrosion of metals. The first use
of the RDE in this field was the study of the corrosion of manganese and
magnesium in hydrochloric, acetic, formic and oxalic acids [204]. The dissolu-
tion rate depends on the character of the metal and is proportional to the acid
concentration and the square r o o t of the rotation rate, i.e. is diffusion con-
trolled (by diffusion of hydrogen ions toward the metal surface). Zembura and
coworkers [719,720,724,726,728,730] studied the dissolution of zinc, copper
and iron in solutions of sodium sulphate at various pH's and temperatures, and
also in the presence of dissolved oxygen. Feller [229] studied the corrosion
of copper and zinc in sulphuric acid, Armstrong [43] the corrosion of zinc,
 71

Vahdat and Newman [686] the corrosion of iron, and Ambrose et al. [31]
the dissolution and passivation of copper. Cadle [136] investigated the oxida-
tion of a thin Pd film on a gold RDE.
Many workers have discussed corrosion in solutions of oxidants: of zirconium
in nitric and hydrofluoric acids [469], zinc in solutions of iodine [285,408],
copper in solutions of sulphuric acid and bichromate [ 284] and in solutions
of ferric iron [ 578], copper and nickel in alcoholic solutions of acids [ 306],
lead and nickel in nitric and trichloroacetic acids [593]. Kakovskii et al. [351]
examined the dissolution of gold in cyanide solutions. It has been f o u n d t h a t
some organic compounds cause depassivation of gold and enhance the dissolu-
tion. The corrosion of steel [ 519,538,577,600,718] and of inhomogeneous
metals [197,626] has also been studied.
An internally heated disk electrode was constructed [655] to study thermo-
diffusion processes [430,654]. The RDE has also been used in systems with
variable physical properties (i.e. in systems where the density, viscosity and
diffusion coefficient are n o t the same at all points), see e.g. refs. 172,283,324,
532,543. Vydra et al. [696, 698] employed the RDE for the measurement
of the rate of sorption processes of iron and copper on silica and of iron on
Dowex 50W X8 cation exchanger.
As has already been pointed out in chapter 2, uniform accessibility of the
disk surface is attainable only with homogeneous disks. The surface of solid
electrodes is generally composed of active and inactive sites, causing a differ-
ence between the geometric and effective electrode surface area. Two limiting
cases can be distinguished:
(i) the active sites are very small, i.e. their radius rl (see Fig. 19) is much
smaller than the thickness of the diffusion layer, and their number is large, so
that the distances between them are also much smaller than the thickness of
the diffusion layer. Then the Levich equation (2-44) is valid. For ~ > 8rl, the
effective area differs from the geometric [504] by a factor of 2 × 10-2%. This
is generally true for c o m m o n , homogeneous, smooth electrodes.
r1 /x~
/ \

G' j\j
f. ,,
" "'~'i- --: - ~-

\
] "~ ..._~

Fig. 19. Schematic illustration of electrodes with inactive sites.

72

(ii) The active and inactive sites are large compared to the thickness of the
diffusion layer; the linear dependence, id = f(co 1/2), is still valid but the propor-
tionality constant is smaller than corresponds to the appropriate diffusion co-
efficient. This is basically a generalization of a rotating disk with an inactive
centre (the ring electrode).
Landsberg et al. [412,413,417,497,612--615,708] and others [320,504,604,
639] have calculated the current passing in the presence of inactive sites uni-
formly distributed over the surface of the disk. It has been shown that the
limiting current passing through an active site with radius r 1 can be calculated
as t h e current flowing through a conductive cone with two electrodes of radii
r I and r2 (Fig. 19A). The net limiting current is then the sum of the contribu-
tions from all the active sites (n parallel cylinders or cones per cm 2); for the
current density it then holds that [417]

1 1.61 v 1/6 1 l ~ A n tanh(xn~/r2)l

-- = + (3.92)
id nFD2/3 e ( ~ ) (2/r)1/2 C01/2 nFDc(~)

For low revolution rates, r2 < ~, tanh(xn5/r2) >- 1 and for high rates tanh(xn~/
r2) ~ (Xn~/r2). The A n and Xn values were tabulated by Smythe [639] for
various values of r 1 and r 2.
For a disk with a blocked central area of radius q (Fig, !9B), the current
density becomes dependent on the distance from the rotation axis and the
corresponding material flux for a diffusion-controlled process is given by [ 568]

(jd)a = jd [l __(\ r rl~ ] _J (3-93)

where Jd is the overall material flux toward a disk with radius rl + Ar (equa-
tion (2-42)). When the process is controlled solely by the kinetics of the sur-
face reaction, it holds that [ 568]

(Jk)R
=Jk [1--~\ r rl~ ] ~2Jl (3-94)

where Jk = k c ( ~ ) ~ is the overall kinetic material flux (see section 3-2). The
material flux cannot be expressed analytically for mixed kinetics; the trans-
port equations are then solved numerically and the results plotted graphically.
The theory for h y d r o d y n a m i c electrodes of the opposite character, where
the electrode is stationary and the fluid moves, has been given by Matsuda
[462,463]. The author found relationships for a stationary disk or ring in
linearly flowing fluid analogous to those for rotating electrodes, except that
the current is proportional to the square root of the fluid translational move-
ment instead of the square root of the electrode angular rotation rate and
that it depends on the radius of the electrode insulation, ro. If stationary elec-
trodes are placed in a fluid rotating at an angular rate of co, the equations for
the current passing are also quite analogous to those for rotating electrodes in
 73

an unstirred fluid; the only difference is in the distribution of the current den-
sity on the disk electrode

iD = f(u, F, c(~°), D 2/3, v- : / 6 , wl/2 r/[r30_ r3]:/3)

This theory has been extended to methods for the determination of diffusion
coefficients and of the parameters of volume reactions.

(b) Further uses of the RRDE. Many workers have studied the anodic dissolu-
tion and ionization of metals and corrosion and passivation. Kiss, Farkas and
coworkers [367,369--376] have developed a general theory for anodic dissolu-
tion and applied it to the study of the dissolution of copper and indium. Miller
et al. also studied the dissolution of copper [473,475], copper alloys [472],
silver [474] and indium [478]. These investigations are notable particularly
in the use of a split ring and an apparatus that enables simultaneous monitor-
ing of two processes on the two halves of the ring.
Armstrong et al. investigated the dissolution of iron [41,42], titanium [48],
chromium [ 52] and vanadium [ 49], using electrodes with disks made of the
particular metals and platinum or gold rings. The dissolution of metals has also
been studied by other workers, e.g. m o l y b d e n u m in acidic and alkaline media
[318], lead in sulphuric acid [40], iron in acetic [710] and sulphuric [308]
acids, nickel in alkaline media [549], indium in perchloric [396] and sulphuric
[377] acids, beryllium [209] and palladium [135]. The corrosion of copper
[563], iron [345], a Ti--Pd alloy [46] and corrosion and passivation of zinc
[ 548,550] were also studied. Anodic dissolution of titanium carbide was
studied by Cowling and Hintermann [ 163].
Interesting considerations were published by Untereken and Bruckenstein
[685] concerning the interpretation of isopotential points, obtained as inter-
cepts of polarization curves recorded several times on the same electrode
without surface renewal (e.g. reduction and oxidation of a platinum electrode).
Bruckenstein and his coworkers have contributed a great deal to the practical
application of the RRDE. They studied the kinetics and the voltammetric
properties of the deposition of copper [ 1 2 9 , 1 3 8 , 5 0 8 , 6 7 0 - - 6 7 2 ] , simultaneous
deposition of copper and silver [673], deposition of silver [674], bismuth
[139,141], mercury [124,305] and the behaviour of tin [689]. Bruckenstein
and Hassan [124] studied the reduction of mercurous ions on a platinum
electrode in great detail. They found that mercurous ions first reduce the oxi-
dized platinum surface and are only then adsorbed on the reduced surface.
In another paper [305], the conditions for the formation of mercury films on
platinum were examined in detail. The authors found that a relatively thick
layer of mercury must be deposited in order that a uniform thickness of liquid
mercury film be present on the electrode surface. First, various layers and sub-
layers of platinum compounds with mercury are formed, which do n o t prevent
further dissolution of platinum, but may hinder the reaction of mercury with
platinum. Therefore, a relatively thick layer of mercury must be deposited in
74

order that the life-time of the mercury-coated platinum electrode be sufficient.

Bruckenstein and Tindall [670--674] studied the behaviour of copper and
silver in detail. They observed three waves during the reduction of cupric ions
and three anodic waves appeared during stripping of the copper film. Two of
these processes involve the formation and removal of a monolayer on the elec-
trode; only then are further layers of copper deposited at potentials more nega-
tive than 0.0 V (SCE). Cuprous ions are simultaneously formed in the vicinity
of the disk electrode. For the determination of the heterogeneous rate con-
stant, copper was deposited on the disk and after opening the disk electrode
circuit the anodic ring current was recorded, corresponding to cuprous ions
formed by oxidation of the copper on the disk by cupric ions from the solu-
tion. The equilibrium constant of the reaction, Cu + Cu 2÷ = 2Cu ÷, o = 5.6 × 10 - 7
is in good agreement with the values obtained by other measurements. Redox
reactions of copper were also investigated by Jacq et al. [328].
Undervoltage deposition of silver was also described [674]. Silver is not de-
posited on a fully oxidized electrode surface, but on a reduced surface, two
monolayers are deposited at potentials more positive than the Nernstian value
(undervoltage). Similar undervoltages were observed by Vincente and Brucken-
stein [689] for the deposition of tin. Cadle and Bruckenstein [138] have also
interpreted the behaviour of copper described by Tindall as deposition at an
undervoltage. The same authors [ 141] then examined undervoltage deposition
of bismuth on a gold electrode, placing particular emphasis on electrode sur-
face pretreatment. The behaviour of bismuth was studied in detail in another
paper [ 139], where chief attention was paid to the formation of bismuth
monolayers and the formation of an alloy on the electrode surface. The for-
mation of alloys was studied using isopotential points, enabling the determina-
tion of the Bi--Pt stoichiometric ratios, which vary with variations in the
electrode potential. The damaged electrode surface also suggests the forma-
tion of alloys. Bruckenstein et al. [137,140,690] studied the behaviour of
gold electrodes in various media and the adsorption of lead on a gold electrode.
Beran and Bruckenstein [86] examined reactions in solutions of iodide,
iodine, iodine monochloride and iodate. The Cu(II)/Cu(I) and ferri/ferrocyanide
redox systems were investigated by Magarit et al. [441]. The reduction of
Mo(VI) was studied by Hull [319] and the reduction of nitrite in HC104 by
Gadde and Bruckenstein [253]. Among organic systems, the reactions of di-
phenylamine [ 309], benzaldehyde and benzophenone [ 386,514], thiophene
[517], anthracene [365] and others [385] have been examined,
The current distribution in the diffusion layer was studied b y Smyrl and
Newman [637] and Neubert et al. [521] and the potential distribution b y
Gabrielli [ 552]. Bruckenstein et al. [ 20,121] experimentally verified the rela-
tionship between the disk and the ring current. Problems of mass transport
were further studied b y Daguenet [161,168] and the relationships between
the size of the R R D E and the rotation rate by other authors [251].
Very few papers have been published on the use of the R R D E for chemical
analysis. Two basic principles can be employed here: coulometric titrations
 75

in the diffusion layer (see section 3-3e) and stripping analysis. The use of the
R R D E for stripping analysis was proposed by Tindall and Bruckenstein [672,
673] and applied analytically by Johnson and Allen [339]. The depolarizer
is deposited on the disk and the ring current is recorded at a suitable poten-
tial during the stripping. The advantage of this procedure compared with
c o m m o n stripping analysis (e.g. with the RDE) lies in the fact that the ring
signal exhibits lower residual current and the curves are evaluated more easily.
The method was applied to the determination of silver (10 - l ° M) in sulphuric
acid, using a glassy carbon disk and platinum ring. Laser and Ariel [ 418,419]
also employed a glassy carbon R R D E for stripping analysis; they described
the determination of Cu, Pb, Cd, and Zn on a mercury-coated electrode.
As far as use of the R R D E for analysis is concerned, a number of practical
applications are needed in order to evaluate the potential advantages of these
methods over classical coulometry and stripping analysis.

4. CONSTRUCTION OF ELECTRODES AND AUXILIARY DEVICES: FURTHER EX-

PERIMENTAL FACTORS

4.1. Electrodes

The precision of measurements with disk electrodes depends primarily on

the quality of their construction and on the uniformity and reproducibility of
their rotation. Most disk electrodes consist of an active disk area and an in-
sulating mantle covering all other parts of the electrode. As insulating materials,
teflon, polyethylene, e p o x y resins, glass and other materials have been used.
The insulating mantle must add the minimum possible contribution to the
stirring of the solution and has three basic functions:
(i) it insulates the sides and the upper parts of the electroactive material;
(ii) it prevents interaction between the fluid flow under and above the disk;
(iii) it eliminates edge effects on disks, which obviously cannot have the
infinite radii required by the theory.
The effect of various shapes of insulating mantles was examined in detail,
chiefly by Azim and Riddiford [61], Blurton and Riddiford [92] and Prater
and Adams [ 584]. Electrodes with the most c o m m o n shapes of insulating
mantles, shown in Fig. 20, were subjected to critical evaluation; the effect
of the shape of the mantle was discussed from the point of view of mass trans-
port [61,584] and of fluid flow [92]. Comparison of various mantle shapes
was made by comparing the measured and calculated values of the current
for a suitable depolarizer. It has been found that the requirements placed on
the insulating mantle are best met by shape B in Fig. 20 (BEL, bell-shaped
electrode), with a suitably selected radius of the curved part and ratio of the
electroactive and electroinactive parts of the disk (Oo >> 2a, r o (the radius of
the insulator) >> ao). With this electrode the interaction between the flow
under and above the electrode is minimal and the electrolyte is stirred only
minimally by the insulating mantle. The deviation from the theoretical current
76

A II C O E

J t Jt
.4 .--

, I
I
' I
? I

Fig. 20. The most common shapes of disk electrode insulating mantles and a scheme of
steady-state fluid flow around these electrodes. From ref. 92; flow at 240 rev rain-1.

was less than 1% at rotation rates of 50--240 rev min - 1 . With electrode shape
A ( " i n f i n i t e " cylinder, CEL) and C, deviations of 2--3% were found. Electrode
shapes D and E ( " f i n i t e " cylinder) have been f o u n d quite unsuitable both
from the h y d r o d y n a m i c and mass transport aspects; complex material flux
occurs around them, a combination of the flux toward the disk and that to-
ward the cylinder, which is manifested even with a = 0.5 m m and a large disk
radius, d = 5.3 cm [61].
Comparison of the results obtained with electrode shapes A and B led Prater
and Adams to the conclusion t h a t in c o m m o n measurements there is no differ-
ence exceeding experimental error. Shape A is most frequently used because
of its simpler construction. According to Perevoshchikov and Gusev [ 560]
the edge effects extend to about 0.1 mm from the edge of the disk.
The principal procedures for the preparation of metal disk electrodes are
based on the work of Bruckenstein and Albery [15] and o f Napp [507]. A
disk of the required material (a cylinder with base of the required radius,
usually 1--10 mm, and height of ca. 2 mm) is soldered onto a machined stain-
less steel shaft. The other end of the shaft is modified according to the way
it is fitted in the rotation system. The teflon insulating mantle with a hole
0.6 mm in diameter smaller than t h a t of the shaft is heated to 200--220°C
and the shaft with the disk is pressed into it (Fig. 21A). After cooling the pro-
truding part of the teflon is removed, the mantle is machined to obtain the
required shape and the surface of the disk is ground and polished by c o m m o n
metallographic techniques. Grinding can be performed using e.g. SIA metallo-
graphic papers (Switzerland) with grain 1F 4/0 and 6/0 or by grinding under
water with C 400 waterproof paper (Czechoslovakia). The latter m e t h o d is
especially suitable for grinding RRDEs, since the metal particles removed are
 77

carried away by the water and are not pressed into the gap between the disk
and the ring (see below). After grinding, the electrode is polished to a mirror-
like finish using e.g. an emulsion of metallographic alumina. The electrode is
then washed with a saponate and polarized several times in a dilute acid
(0.1 M HC104); it is then ready for use.
The m e t h o d preparation described involves the danger of scratching the
inner wall of the teflon during insertion of the axle and the disk; therefore,
the original m e t h o d was somewhat modified [88]. The electrode then con-
sists of two parts: (1) a brass cone with a small angle (ca. 1 °) between the sur-
face and a line perpendicular to the base, which is provided with a thread in
the upper narrower part. To its lower end is soldered the disk, which is cyl-
indrical in order that no change in its diameter will occur during grinding.
(2) The other part is a steel shaft with the upper end modified for fitting in
the rotation system and having an internal thread, corresponding to the cone
with the disk, on its lower end. The teflon is drilled and heated as in the pre-
vious procedure (the hole in the teflon must be larger than the diameter of
the thread on the cone). Then the cone with the disk is pressed into the teflon
from the b o t t o m and the steel shaft from the top and the two parts are screwed
together (Fig. 21 B, C). To improve the insulation at the teflon--disk interface,
the sides of the cone with the disk can be coated with epoxy resin t h a t can
then be fired (see the use of this resin for insulating silver wire electrodes in
oscillographic polarography [470] ). The grinding and polishing of the electrode
is carried out in the same way as previously.
For the constructions of RDEs, see the works of Wojtowicz and Conway
[707], who constructed an electrode for work at elevated temperatures and
Marcoux and Adams [453], who changed the commercial Beckman No. 39272
electrode into a rotating disk electrode. Belyayeva [82] described an all-glass
RDE, containing an internal reference electrode, connected with the electro-
lyte through an opening in the centre of the disk. Bardin et al. [72] constructed
a microdisk electrode (0.78 mm 2) by sealing a platinum wire into glass; they
recommend the use of this electrode in place of less advantageous wire elec-
trodes. Generally, disk electrodes with glass as an insulator are suitable only
for lower rotation rates, since it is difficult to avoid vibrations and glass is in-
sufficiently strong mechanically. For special purposes involving work at a
temperature gradient, internally heated electrodes have been made [655].
The preparation of ring-disk electrodes is somewhat more difficult, which
is apparently the chief reason for their being used far less extensively than
RDEs. The preparation involves the construction of a disk electrode with the
required radius of the electroactive area, rl o. The teflon mantle t h a t insulates
the ring from the disk and the shaft is machined to a radius 0.07 m m larger
than the inner diameter of the ring, r2o. The ring electrode is made from a
brass tube, onto the end of which is soldered a ring made of the required
material, and the inner radius of the tube is adjusted to r2o. The tube with
the ring is heated to 200°C and is inserted over the teflon mantle of the disk
electrode; after cooling, the surface of the ring is machined to radius r30. The
78

A B (3 I)

-7
i

lo
i
Fig. 21. Scheme of RDE preparation.

outer teflon mantle is made using the above-described procedure and the elec-
trode is polished (Fig. 21 D). This preparation procedure has been described
by Johnson [338] and Bruckenstein [15]. Cavalier et al. [147] described a
similar procedure, employing polyethylene insulation between the disk and
the ring.
The following principal problems are encountered when the R R D E is pre-
pared in this way. The teflon gap is subject to distortion with consequent
formation of crevices between the teflon insulation and the disk and/or the
ring. Since teflon is relatively soft, particles of the disk and ring materials
loosened on grinding and polishing can become imbedded in it, which may
lead to undesirable conductive connection between the disk and the ring over
the gap.
To avoid these difficulties, the following procedure for R R D E preparation
can be recommended [89]. The individual phases of the preparation are carried
out using jigs that enable perfect centering of the two parts of the electrode
system. The gap between the disk and the ring (which can be substantially
less than 0.1 mm) is formed by E p o x y - l l 0 resin with AT-50 catalyst (The
Union for Chemical and Steel Products, Czechoslovakia), which is pressed be-
tween the electrodes using another jig with a plunger. The resin is perfectly
inert and has suitable electrical properties. The effectiveness of this procedure
is also one hundred percent, while only some of the electrodes prepared by
the classical procedure can be used.
The individual stages in this RRDE preparation procedure are shown in
 79

B [ I
Fig. 22. Scheme of RRDE preparation.

Fig. 22. The disk electrode is machined from a brass rod to the shape depicted
in Fig. 22A. The ring electrode is prepared by drilling a hole with a radius of
r20 in a brass rod with the ring material soldered onto it, fixed in a jig as de-
picted in Fig. 22B. The t w o parts are assembled together after complete re-
moval of any grease. Since the brass rod with the disk is insulated b y the e p o x y
resin from the jig with the ring, it is possible to check during the assembly that
no conductive connection has developed between the disk and the ring, b y
measuring the electric resistance. If electrical contact between the electrodes
or non-symmetry of the gap is detected, they can be removed b y adjusting
with screws in the upper part of the jig with the ring. The assembled system
(Fig. 22C) is heated to 100--130°C and placed in another jig with a plunger,
on which is placed the required a m o u n t of E p o x y - l l 0 resin thoroughly mixed
with the catalyst and freed of air bubbles by centrifugation and placing in a
vacuum (Fig. 22D). Using the plunger, the resin is pressed into the gap be-
tween the disk and the ring (Fig. 22E). In order that the resin penetrate only
into the gap, a silicone rubber seal with an opening with a radius of r2o < r < rio
is placed between the t w o jigs. Through the central opening in the ring jig a
check can be made that the whole gap is filled with the resin. The jig with the
80

electrodes is then removed and the resin is polymerized at 150°C for ca. 2 h.
Then the electrode is removed from the jig, the outer radius is machined to
r~0, it is fixed to a suitable shaft with contacts for the disk and the ring (e.g.
according to Fig. 22F) and the outer teflon mantle is made. The grinding and
polishing is carried o u t in the same way as in the procedures described above
for disk electrodes.
Some special R R D E preparation procedures have also been described. An
R R D E which can be taken apart has been described by Zhutayeva [733],
Doronin [199] and Harrington et al. [ 2 9 7 ] ; a two-ring electrode was used by
Heusler et al. [309], Vielstich et al. [678] and Zhutayeva [732] (a theory has
been developed for the two-ring electrode [322,442]). Miller and coworkers
[472,644] have described a split-ring-disk electrode. McClure [ 464] constructed
a ring electrode from an optically transparent material, enabling optical moni-
toring of the electrode reaction products.
In some cases, the reverse system, i.e. a stationary electrode and fluid flow-
ing under laminar or turbulent conditions, was employed. In addition to the
already-cited works of Matsuda [ 462,463], some other authors have also
dealt with the problem [70,541].
It has already been mentioned in section 2-4 that irregularities on the disk
surface have an unfavourable effect on the mass transport and the fluid flow.
They decrease the Recrit value and the rate of mass transport changes on the
surface irregularities (see e.g. ref. 602). Therefore, the surface of disk electrodes
must be as smooth as possible, in order that surface irregularities be sufficiently
smaller than the diffusion layer thickness. Several workers have dealt with
transport phenomena on RDEs with surface irregularities, see refs. 67,162,235.
In addition to metal electrodes, various forms of carbon have been employed;
their inertness toward surface oxidation is assumed and the materials are marked
by their wide useful potential range. Wax-impregnated spectral graphite, pyroly-
tic graphite, glassy carbon with low porosity and graphite pastes, made by
mixing high purity graphite powder with a suitable amount of hydrophobic,
non-volatile and sufficiently pure electroinactive diluent, are frequently em-
ployed. Monobromonaphthalene [2,546], carbon tetrachloride, benzene, a
mixture of trimethylbenzenes, ethyl naphthalene, nujol (paraffin oil) [ 546],
silicone oil (methyl silicone, M.W. ca. 60,000) [225], paraffin [482,708,709],
methyl naphthalene [618], azobenzene [410] and other materials have been
used as diluents. These electrodes are usually stationary, but RDEs [148,546,
584] and RRDEs [257] have also been described. Paste electrodes are also
produced commercially, e.g. by Metrohm.
The effective area of a carbon paste disk electrode (Ae~ > A~eor, ) is given
by [157]

Aef = 0.97 ~ r20/d °'z4 (V1/Vs) 1"9 (4-1)

where d is the diameter of the particles in the carbon paste and V1/Vs is the
ratio of the volumes of the liquid and solid phases in the paste.
 81

The preparation of graphite paste electrodes is very simple. The paste is

pressed into a depression with radius rio in an insulating cylinder (usually
teflon), into which a platinum contact protrudes (Fig. 23). The surface of the
paste is smoothed with a spatula. Linquist [432] proposed cutting off the
surface of the paste with a string in order to renew it reproducibly and tested
seven different paste electrodes with various diluents [433]. The RRDE is
prepared analogously. The most suitable paste has proven to be one made
from a mixture of graphite powder with monobromonaphthalene. The paste
yields results reproducible within -+2% after use for several days and storage
in water; for freshly-prepared pastes, a reproducibility of +6% has been re-
ported [546]. A typical paste consists of 6 g graphite and 4 cm ~ bromo-
naphthalene.
Electrodes made from other forms of carbon are usually prepared by in-
serting and sealing a carbon rod into a teflon or glass tube with a suitable
contact. The applicability and properties of electrodes made from various
forms of carbon are surveyed in Tables 9 and 10.

4-2. The rotation system

The following demands are placed on the rotation device driving the elec-
trode:
(i) the electrode must be fixed in a way that avoids radial or axial vibrations;
(ii) the rotation rate must be constant during the measurement;
(iii) the range of rotation rates should be as wide as possible;
(iv) the rotation rate should be measurable as accurately as possible;
(v) good electrical connection must be provided for recording the electric
signal.

i
!
I

I'.', " " "

l't; "-'"
ol i I H
mz...-,i ~.~_
• .o. ,t • io~
i'.o

RDE RRDE

Fig. 23. S c h e m e o f a c a r b o n paste disk e l e c t r o d e .

82

TABLE 9
Anodic potential ranges for carbon paste electrodes with monobromonaphthalene in the
region where the residual current does not exceed 2 pA
From ref. 546

Medium Potential/V(SCE)

1 M KCl 1.10
0.1 M KC1 + HC1 (pH = 2.5) 1.08
1 M HC1 1.02
0.1 M NaAc + HAc 1.27
1 M Na2SO 4 1.28
0.4 M H2SO 4 1.30
Britt. Rob. + 0.2 M Na2SO 4 (pH = 2.4) 1.30
Britt. Rob. + 0.2 M Na2SO 4 (pH ----4.8) 1.30
0.2 M NaOH 0.87

The most suitable way of fixing the electrode in the rotation system is to
use ground self-locking cones' ( c o m m o n with machine tools). The radial vibra-
tions are then suppressed to a minimum, provided that the electrode is made
carefully. For the ratio of the currents of an electrode vibrating with an ampli-
tude Av and an ideally rotating electrode, the relationship [188]

Iv/Iid.,ot. = ((3/2) ~r)lz2 Av/1.9 v - l l 6 D 11s rio (4-2)

has been found. It is evident from this expression that the contribution of
vibration will be smaller the smaller the vibration amplitude and the larger
the disk radius. Bardin and Dikusar also dealt with this problem [69].
A constant rotation rate is achieved by using a robust m o t o r with power
substantially greater than that actually ~equired for rotation of the electrode.
Variations in the rotation rate are obtained using a belt transmission with
wheels of various sizes. Much more reproducible driving of the electrode is
achieved using a generator-powered motor; the rotation rate can be varied in

TABLE 10
Useful potential ranges in 0.2 M KNO3 for electrodes made of various forms of carbon
From ref. 482

Electrode Potential range/V(SCE)

Wax impregnated graphite +0.25 to 0.00

Graphite paste with nujol +0.85 to --0.25
Pyrolytic graphite +0.90 to --0.75
Glassy carbon ÷1.00 to--0.75
 83

a broad range by varying the o u t p u t parameter (frequency, voltage). An appa-

ratus employing this principle was built by Belyanchikov et al. [84], who
could regulate the rotation rate up to 30,000 rev rain -1 ; a similar apparatus
was described by Baucke et al. [77]. At present the rotation rate can be con-
trolled by devices with multilayer semiconductor switching elements (silicon-
controlled rectifiers, diacs, triacs) where the constancy of the rotation is en-
sured by a suitably selected feedback from the motor.
McIntyre and Peck [466] described an electronic device for maintaining
a constant m o t o r rotation rate, based on comparison of the signal from a
t a c h o d y n a m o with a reference voltage using a differential amplifier, the out-
put signal of which adjusts the rotation rate to the preselected value; this regu-
lation method seems to be generally most convenient. The authors state that
the rotation rate is constant within 0.5%.
The dependence of the current on the rotation rate is the basic function
employed when working with disk electrodes. Thus devices have been con-
structed for programming the electrode rotation rate, which permit direct
recording of the current at a chosen constant potential as a function of the
rotation rate or its square root, etc. This measuring technique has been
termed r o t o a m p e r o m e t r y [165,583]. For obtaining high rotation rates, an
air turbine was used [167,312] instead of an electric motor.
For quantitative evaluation of measurements on disk electrodes the perti-
nent rotation rates must be known with sufficient accuracy. An error of 5% is
permissible in current analytical practice, but for calculation of kinetic param-
eters and the measurement of diffusion coefficients, an accuracy of better
than 1% is necessary. The rotation rate can be measured with a hand tacho-
meter if knowledge of the rotation rate within 5--10% is satisfactory. For more
precise measurements a more accurate m e t h o d must be used, e.g. oscillographic
measurement of the frequency of rectangular pulses derived by sliding contacts
from a split collector placed on the electrode shaft, to which a small d.c. voltage
is applied [707]. Measurement of the frequency of pulses produced by a
photodiode on which light falls either after reflection from a shiny plate fixed
on the electrode shaft or after being interrupted by suitable shutters placed
on the electrode shaft, employing a digital pulse counter, seems to be more
accurate and easier. Stroboscopic methods enable very accurate measurement
of the rotation rate (an error of less than 1%) [84].
The electrical signal is most frequently taken from the electrodes using carbon
friction contacts pressed by steel springs on to a copper or bronze ring fixed on
the electrode shaft. The shaft must, of course, be conductively connected with
the ring or the disk. The " n o i s e " caused by varying resistance at the carbon--
copper interface is n o t large and amounts to about 10 - 4 V at 40,000 rev min -1
according to Hintermann and Suter [312]. For low rotation rates, a platinum
wire immersed in a drop of mercury placed in a depression in the upper part of
the electrode shaft can also be used. It should be noted that the electrode and
the contact must be insulated from other parts of the apparatus, especially
from the electric motor.
84

4.3-Other devices

The shape of the electrolytic vessel is not particularly important. The vessel
must have a sufficiently large volume and must contain a sufficient a m o u n t of
the electrolyte in order that the electroactive species shall not be depleted (the
active surface areas of disk electrodes are often rather large). All boundaries
other than the disk--fluid boundary, i.e. air--fluid, fluid--vessel wall and walls
of other parts immersed in the solution can theoretically affect the results
when they are not infinitely far away (y -~ oo). According to Gregory and
Riddiford [285] no effect can be observed when y / > 0.5 cm. However, it has
been shown [ 584] t h a t identical results can be obtained with an electrode
immersed 2 cm deep in the fluid and an electrode that just touches the surface
of the electrolyte; hence the authors conclude that the depth of immersion
of the electrode is insignificant. The effect of the electrolyte--vessel lower
boundary is more likely to be important. To ensure that forced fluid flow of
a defined character be established, the surface of the disk must be at least 0.5
cm above the b o t t o m of the vessel. From the h y d r o d y n a m i c point of view, it
is also desirable that the b o t t o m and walls of the vessel be rounded. Greater
demands are made on the placement of the capillary orifice of the reference
electrode salt bridge. The best position for the capillary appears to be at the
centre of the disk (ring) surface, parallel to the lines of flow of the fluid [281,
343]. The reference electrode bridge orifice is mostly placed at the level of the
disk (y = 0), and at one side almost touching the disk. It has been shown that
in this arrangement the RDE potential against the reference electrode is in-
dependent of the position of the capillary. Only when the orifice is below the
level of the disk and very close to it can a change in the potential be observed
on changing the capillary position (see section 2-3c).
Zambonin [713] constructed a special cell for work in melts with a con-
trolled atmosphere. The cell is hermetically closed and the electrode is rotated
by means of a permanent magnet fixed on the electrode shaft, which corre-
sponds to a similar magnet placed~on the axle of an electric m o t o r outside the
vessel. Complete equipment for work with disk electrodes has been described,
for example in the works of Sonner et ah [644] and others [106,293,734].
Disk electrodes can be employed in connection with c o m m o n polarographic
instruments. However, it is more suitable for all types of electrodes to be em-
ployed with instruments assembled from operational amplifiers, combined
with an XY or XYY' recorder. The field of application of operational ampli-
fiers in chemical instrumentation is surveyed, for example, in the new book by
Kalvoda [353] where the most c o m m o n circuits useful in chemical measure-
ments are briefly discussed.
In conclusion, a circuit for three-electrode voltammetry and a bipotentiostat
required for measurements with the RRDE, which can easily be assembled
from operational amplifiers, can be mentioned. Commercial bipotentiostats
are often not easily available. The whole circuit is depicted in Fig. 24.
A circuit for work with an RDE (a three-electrode polarograph, depicted
 85

0 •

r--II--~
I I
L°
0

i - -

I
1
v

I I .,1 T o IR
0

L ER
.l.

Fig. 24. The electronic circuit of a bipotentiostat.

in the box in Fig. 24) consists of voltage follower F1, potentiostatic amplifier
P1 and current follower CF. The potentiostat maintains the potential difference
between the disk and the reference electrode at the potential, Esi~ + Einit, when
Rz = R 2 = R 3 , hence
E D - - E r e f = Esig + Einit (4-3)
Integrator INT can be used as a source of Es~g; from the o u t p u t a linearly de-
creasing or increasing voltage, depending on the polarity of source Z, is drawn,
provided that a constant voltage is applied to the input. The slope of this volt-
age (potential scan rate) is given by the value of time constant RC, since for
the o u t p u t voltage of the integrator it holds that
dEsiJdt = --Ez/RC (4-4)
The potential scan rate can thus be controlled by varying Ez or, preferentially,
by varying R. Einit c a n be supplied from another battery through a polarity
switch and a potentiometer that determines its magnitude. To the same input
of the potentiostatic amplifier can also be applied e.g. an a.c. signal for a.c.
86

polarography. Instead of Esig taken from the integrator another t y p e of pro-

grammed voltage can be used, e.g. triangular wave for cyclic voltammetry,
rectangular wave, etc.
At the current follower output, a voltage proportional to the current passing
through the disk appears, given by
E 0 = --IDR 4 (4-5)
The CF thus converts current values into voltage and, by means of the R4
value, the magnitude of the o u t p u t signal, fed to the recorder, can be adjusted.
In order to suppress noise it is convenient to bypass this resistor using a small
capacitor (of the order of n F ) . The I R drop in the solution can be compensated
by introducing positive feedback between the CF o u t p u t and the potentiostatic
amplifier.
The ring electrode circuit contains voltage follower F1, protecting the refer-
ence electrode, inverter I, potentiostatic amplifier P2 and the ring electrode
voltage follower, F2. The potentiostat maintains the potential difference be-
tween the ring and the reference electrode at the E'sig value, independent of the
disk electrode; hence
E R -- Ere f = --Ersig (4-6)
provided that

R5 ] \ R s + (1 - - p ) Rll
and
Rio + p'R9 = Rll (4-8)
where p is the fraction of resistance R 7 in the inverter feedback and p' is the
fraction of resistance R 9 in series with R i o . The auxiliary electrode is c o m m o n
for the two indication electrodes and is connected to the o u t p u t of P1 ; hence
the algebraic sum of the disk and ring currents passes through it.
The condition expressed by equation (4-7) is met in the following way:
E'~iu is adjusted to zero and R7 is adjusted so that, on a change in Esig by +1.0 V,
the change in the ring potential against that of the reference electrode is less
than +-0.1 mV. The condition given b y equation (4-8) is met by adjusting E~ig
to zero and fraction p' is adjusted by potentiometer R9 so that the potential
difference between E'sig and the o u t p u t of follower F2 amounts to less than
+0.1 mV on a change in E'si~ of +1.0 V. Noise can again be eliminated by by-
passing resistor R12, controlling the magnitude of the o u t p u t voltage propor-
tional to the ring current, with a small capacitor.
This bipotentiostatic circuit has been described by Schwarz and Shain
[620], Tacussel [657] and Napp et al. [508]. Miller [472] described a po-
tentiostat for work with a split ring-disk eiectrode. Other operational amplifier
circuits, which are almost exclusively used in connection with RRDEs, can be
 87

f o u n d in t h e p u b l i c a t i o n s o f B r u c k e n s t e i n a n d Miller [ 1 2 7 , 1 2 8 , 4 7 6 , 4 7 7 ] a n d
of o t h e r a u t h o r s [ 1 3 4 ] ; h e r e i n s t r u m e n t s are d e s c r i b e d f o r m o n i t o r i n g n o n -
s t a t i o n a r y p h e n o m e n a , circuits are given f o r p r o g r a m m i n g v a r i a t i o n s in t h e
r o t a t i o n r a t e in t i m e , a n d so f o r t h .

5. ACKNOWLEDGEMENTS

We w o u l d like t o t h a n k P r o f e s s o r J. K o r y t a f o r v a l u a b l e discussions a n d
P r o f e s s o r V. Pleskov f o r assistance d u r i n g t h e c o n s t r u c t i o n o f t h e n o m o g r a m
given in Fig. 4.

6. LIST OF MOST COMMONLY USED ABBREVIATIONS AND SYMBOLS

A - - disk e l e c t r o a c t i v e area
AcN -- acetonitrile
a l , a 2 --integration c o n s t a n t s (see e q u a t i o n (2-37))
B - - c o n v e c t i v e - d i f f u s i o n c u r r e n t d e n s i t y c o n s t a n t , d e f i n e d b y e q u a t i o n (2-44).
B' = A. B -- convective-diffusion current constant
C - - d i m e n s i o n l e s s c o n c e n t r a t i o n value, d e f i n e d b y e q u a t i o n (3-6); c o n v e c t i v e
c o n s t a n t d e f i n e d b y e q u a t i o n (3-79)
c -- concentration
c(0) - - c o n c e n t r a t i o n at t h e e l e c t r o d e s u r f a c e
c(oo) - - c o n c e n t r a t i o n in t h e b u l k o f t h e s o l u t i o n
CM - - c o e f f i c i e n t o f t h e m o m e n t o f t h e m e d i u m resistance
D -- diffusion coefficient
DMSO -- dimethylsulphoxide
d - - d i a m e t e r o f t h e e l e c t r o a c t i v e a r e a o f t h e disk
E - - electric field i n t e n s i t y v e c t o r in s o l u t i o n
E -- electrode potential
AE* - - activation energy
e - - c h a r g e o f an e l e c t r o n
F- Faraday constant
F(7) = v r / ( r w ) - - d i m e n s i o n l e s s f u n c t i o n d e f i n e d b y e q u a t i o n (2-16)
F ( 0 ) - - f u n c t i o n o f t h e g e o m e t r i c p a r a m e t e r s of t h e R R D E (Eqn. (2-61))
f - - v e c t o r o f e x t e r n a l forces acting on t h e fluid
f-- rotation rate
G(7) = v ~ / ( r w ) - d i m e n s i o n l e s s f u n c t i o n d e f i n e d b y e q u a t i o n (2-16)
H ( 7 ) = v y / ( a ~ v ) 1/2 - - d i m e n s i o n l e s s f u n c t i o n d e f i n e d b y e q u a t i o n (2-16)
Id - - c o n v e c t i v e - d i f f u s i o n c u r r e n t
ID - - disk c u r r e n t
IR - - ring c u r r e n t
i -- current density
id - - c o n v e c t i v e - d i f f u s i o n c u r r e n t d e n s i t y
ik - - k i n e t i c c u r r e n t d e n s i t y
io - - e x c h a n g e c u r r e n t d e n s i t y
88

j - - material flux
Jd - - c o n v e c t i v e - d i f f u s i o n material flux
Jk - - kinetic material flux
K - - dimensionless kinetic p a r a m e t e r o f h e t e r o g e n e o u s reactions d e f i n e d b y
e q u a t i o n (3-6)
h - - rate c o n s t a n t o f a h e t e r o g e n e o u s r e a c t i o n
l -- characteristic d i m e n s i o n o f a solid phase i m m e r s e d in a fluid
M - - m o m e n t o f viscosity forces; the critical value o f the disk c u r r e n t (see
e q u a t i o n (3-83))
N - - c o l l e c t i o n e f f i c i e n c y d e f i n e d b y e q u a t i o n (2-54)
N ' -- e f f i c i e n c y d u r i n g titrations in the diffusion layer
N " -- e f f i c i e n c y o f an R R D E with a very thin gap and thin ring, d e f i n e d b y
e q u a t i o n (2-65)
g k - - kinetic e f f i c i e n c y
Nu --Nusselt n u m b e r (see Table 1)
n -- the n u m b e r o f electrons e x c h a n g e d
P(~/) = p / ( p v ~ ) - - dimensionless f u n c t i o n d e f i n e d b y e q u a t i o n (2-16)
P e - - Peclet n u m b e r d e f i n e d b y e q u a t i o n (2-10)
Pr - - Prandtl n u m b e r (see Table 1)
p - - pressure
Q - - v o l u m e s t r e n g t h o f a s o u r c e o f particles
R - - universal gas c o n s t a n t
RDE - - r o t a t i n g disk electrode
RRDE - r o t a t i n g ring-disk e l e c t r o d e
-

R e - - R e y n o l d s n u m b e r d e f i n e d b y e q u a t i o n (2-7)
r - - radius; the radial c o o r d i n a t e in t h e polar c o o r d i n a t e s y s t e m
ro - - radius o f the insulating m a n t l e o f a disk e l e c t r o d e
rl o - - disk radius
r20 -- inner ring radius
r30 - - o u t e r ring radius
S - shielding e f f i c i e n c y d e f i n e d b y e q u a t i o n (2-68)
S c - - S c h m i d t n u m b e r d e f i n e d b y e q u a t i o n (2-11)
S h - - S h e r w o o d n u m b e r (see Table 1)
SCE -- s a t u r a t e d c a l o m e l e l e c t r o d e
T - - absolute t e m p e r a t u r e
t - - time
U - ionic m o b i l i t y
Uv - - v o l t a g e applied t o an e l e c t r o d e
v - - fluid v e l o c i t y v e c t o r
V -- volume
v - - scalar fluid v e l o c i t y
vr - - radial c o m p o n e n t o f the fluid v e l o c i t y v e c t o r
vy - - the n o r m a l c o m p o n e n t o f t h e fluid v e l o c i t y v e c t o r
v~ - - a z i m u t h a l c o m p o n e n t o f t h e fluid v e l o c i t y v e c t o r
~ ' - - average v e l o c i t y o f t u r b u l e n t f l o w
 89

x, y, z - - c o o r d i n a t e s in t h e C a r t e s i a n c o o r d i n a t e s y s t e m
y -- normal component of the polar coordinate
z -- ionic charge
a -- charge transfer coefficient; the rate of potential change with time; dimen-
sionless g e o m e t r i c p a r a m e t e r o f t h e R R D E d e f i n e d b y e q u a t i o n ( 2 - 6 2 )
a' -- dimensionless geometric parameter of the RRDE defined by equation
(2-66)
-- dimensionless geometric parameter of the RRDE defined by equation
(2-63)
~' - - d i m e n s i o n l e s s g e o m e t r i c p a r a m e t e r o f t h e R R D E d e f i n e d b y e q u a t i o n
(2-67)
7 -- dimensionless distance defined by e q u a t i o n (2-17)
-- diffusion boundary layer thickness
~0 - - h y d r o d y n a m i c b o u n d a r y l a y e r t h i c k n e s s
~k -- reaction layer thickness
~? - - o v e r v o l t a g e
--specific conductivity; dimensionless kinetic parameter of a volume reaction
p -- dynamic viscosity coefficient; reaction order
u -- kinematic viscosity coefficient; stoichiometric coefficient
p -- density; rate constant of a volume reaction
o -- equilibrium constant
T - - t a n g e n t i a l t e n s i o n d e f i n e d b y e q u a t i o n (2-6); t h e t i m e r e q u i r e d f o r e s t a b -
lishment of a stationary state
-- azimuthal coordinate of the polar coordinate system
¢o - - a n g u l a r v e l o c i t y

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