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Electrochimica Acta 53 (2008) 35663578
A comparison of diffusion-limited currents at microelectrodes
of various geometries for EC

reactions
R. Senthamarai, L. Rajendran

SMSV Higher Secondary School, Karaikudi 630 001, Tamilnadu, India

Received 18 August 2007; received in revised form 10 December 2007; accepted 15 December 2007
Available online 24 December 2007
Abstract
The steady-state and non-steady-state diffusion-limited currents for EC

reactions for all ultramicroelectrodes (circular disc, circular ring,

elliptical disc, elliptical ring, band, hemisphere, hemicylinder, hemi-oblate and hemi-prolate electrodes) are compared. In this paper we present a
critical assessment of the inuence of geometry on the behavior of the transient current. In the research presented here, the surface area of all the
electrodes was xed. The chronoamperometric currents for all times and for all K values are given in tabular and graphical form.
2007 Elsevier Ltd. All rights reserved.
Keywords: Reaction/diffusion; Ultramicroelectrodes; Transient current; Steady-state; EC

mechanism
1. Introduction
If the geometric dimensions of a voltammetric working elec-
trode become progressively smaller, then the behavior of the
electrode begins to quit diverge from that of a large electrode,
which can be approximated by an electrode of innite dimen-
sion. These differences are caused by changing conditions of the
mass transport from the bulk of the solution towards the elec-
trode, and have several important practical implications, such as
a decreased ohmic drop of potential, IR, fast establishment of
a steady-state signal, a current increase due to enhanced mass
transport at the electrode boundary and an increased signal-to-
noise ratio [1,2]. These effects make sufciently small electrodes
advantageous in many areas of electroanalytical chemistry. The
application of small-sized electrodes (ultramicroelectrodes) has
been further enhanced by increasing demands from analyti-
cal chemistry (e.g., the need for electrodes in miniature cells
for detection for high-performance separations or in electro-
chemical sensors) and biochemistry (in situ electroanalytical
measurements in living organisms) [1,2].
However, many electrode processes at ultramicroelectrodes
are complicated; for example, the catalytic electrode process
(EC

reaction) is one of them. With the increasing interest in

these reactions, there is a need to develop methods for the deter-

Corresponding author. Tel.: +91 4565220126.

E-mail address: raj sms@rediffmail.com (L. Rajendran).
mination of the kinetics of the coupled chemical reaction and to
understand the relationship between the rate constant, K and the
limiting current density.
1.1. Previous work
Much work has been carried out to study the EC

mechanism
at ultramicroelectrodes using analytical approximations [314]
and numerical methods [1522]. Space permits us to mention
only a few of them below. Delmastro and Smith [4] solved the
mass transport equations at a dropping mercury electrode for the
pseudo-rst-order reaction. Fleischmann et al. [5] adapted this
to give an expression for a spherical electrode. Dayton et al. [6]
also derived the spherical response using Neumanns integral
theorem. Denuault et al. [7,8] derived an analytical expression
for the steady-state current at a spherical electrode due to a
second-order EC

process. Oldham [9] has derived the current

for pseudo-rst-order kinetics at microdisc electrodes using the
equivalent sphere approximation.
Bender and Stone [10] tackled the problemof nding an exact
expression for steady-state current for disc electrodes by means
of an integral equation. Zhuang and Chen [11] have derived
the current equation for the EC

reaction at spherical electrodes

for steady-state conditions using the concept of the steady-state
reaction-diffusion layer. Phillips [12] derived a pair of asymp-
totic equations for pseudo-rst-order EC

behavior at a microdisc
electrode without resorting to a spherical approximation. Most
0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.12.050
R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578 3567
recently, Galceran et al. [13] obtained the current of inlaid and
recessed microdisc electrodes using the nite element method.
Rajendran and Sangaranarayanan [14] have derived an exact
analytical expression for steady-state current for all K using
the two-point Pade approximation. Most recently Galceran et
al. [13] presented three new formulas for steady-state current,
among which they highlighted one equation with an accuracy
better than 0.27%.
The application of numerical solutions and digital sim-
ulations to electrochemical problems are discussed in Refs.
[15,16]. Numerical solutions of currents for EC

reactions
have also been obtained by Lavagnini et al. [17], employing
the hopscotch method, and by Galceran et al. [13] using the
nite element method. Numerical simulation of currents,
for disc electrodes can also be obtained from the hopscotch
method [17], the adaptive moving-grid technique [18], the ILU
(Incomplete LU factorization) preconditioned Krylov subspace
method [19] and the adaptative nite element method [20].
These involve considerable computational effort. Abercrombie
and Denuault [21] introduced apparently for the rst time in
electrochemistry, the use of gradient recovery methods for
both error estimation and accurate current calculations for all
mechanisms and electrode geometries. Gillow et al. [22] used
an hp-adaptive discontinuous Galerkin nite element algorithm
to compute the current owing at a microdisc electrode for
steady-state E and EC

reaction mechanisms.
Cope and Tallman [23] compared the transient behaviors of
disc, ring and band microelectrodes for the E reaction. Both
disc and band electrodes may be considered limiting forms
of the ring electrode, with the disc being a ring having zero
interior annulus and the band being a ring having an innite
interior annulus. The mathematical theory for electrical capac-
itance problems is analogous to diffusion problems. Recently,
Bruckenstein and Janiszewska [24] obtained the expression for
steady-state diffusion currents and local current densities of var-
ious microelectrode geometries via this analogy. More recently,
Dudko et al. [25] presented approximate analytic expressions for
the time-dependence of the current at any inlaid microelectrode
with a simply connected shape of nite area.
However, to the best of this authors knowledge, the steady-
state and transient currents for the EC

reactions of all
microelectrodes have not been compared. In this paper, we
compare the steady and non-steady-state currents for all ultrami-
croelectrodses for EC

reactions. To facilitate this comparison,

the current variable is based on electrode area without reference
to geometrical shape.
2. Mathematical formulation of the problem and
analysis (steady-state)
As a representative example of the reaction-diffusion prob-
lems considered, the standard pseudo-rst-order catalytic
reaction scheme [26]
A +e B
B +Z
k
A +products
(1)
has been chosen, with initial and boundary conditions
corresponding to the potential step method for all ultrami-
croelectrodes. Here, A is regenerated electroactive species, B
is reacting species and Z is electroinactive species. Pseudo-
rst-order kinetics is achieved when the concentration of Z is
sufciently large. The initial boundary value problemwhich has
to be solved in this case can be written in dimensionless forms
as follows [26]:

2
c(r, z) Kc(r, z) = 0 (2)
where c refers to the dimensionless concentration of the elec-
troactive species B, K denotes the dimensionless reaction rate,
i.e., K=ka
2
/D and a denotes the characteristic length asso-
ciated with the geometry under consideration (a may be
identied as the radius for the disc). The condition pertaining
to Eq. (2) is c =0 when r . Some theoretical work has also
been published for the rst-order EC

scheme at disc and hemi-

spherical electrodes. The dimensionless chronoamperometric
current for the diffusion-limited case is evaluated fromRef. [26]
i(K)
4nFDC
0
a
=

2
_
1
b/a
_
c
z
_
z=0
r dr (3)
where the sign plus corresponds to a reduction process (n =1)
while the sign minus corresponds to a oxidation process
(n =1), F is the Faraday constant and D is the diffusion coef-
cient of species A. The chronoamperometric current [27] for all
microelectrodes (except hemicylinder and band electrodes for
small K) for small and large K values is of the form
where
a
0
=
l
0
4a
, a
1
=
l
2
0
8a
2
, b
0
=
A
4a
2
and b
1
=
P
8a
(6)
where A is the area, P is the perimeter of the electrode and
l
0
is the steady-state of the diffusion-limited current for the E
reaction. The values of A, P and l
0
for various electrodes are
given in Table 1. The dimensionless steady-state current f(K)
for small and large K values for various electrodes are reported
in Table 2. For small K values, the currents for band (Eq. (B7))
and hemicylinder (Eq. (B11)) electrodes are given in Table 2. It
is of great interest to devise a simple analytical expression for
current which is accurate for all values of K. A simple function
is constructed such that the coefcients of Eqs. (4) and (5) are
reproduced. In this case, the steady-state current is given by [27],
f(K) =
i(K)
4nFDC
0
a
= A
1
+B
1

K +C
1
exp(D
1

K) (7)
When current is normalized with respect to the area of the elec-
trode, the steady-state current is dened by
I
ss
(K)=
i(K)a
4nFDC
0
A
=
a
2
A
_
A
1
+B
1

K +C
1
exp
_
D
1

K
__
(8)
3
5
6
8
R
.
S
e
n
t
h
a
m
a
r
a
i
,
L
.
R
a
j
e
n
d
r
a
n
/
E
l
e
c
t
r
o
c
h
i
m
i
c
a
A
c
t
a
5
3
(
2
0
0
8
)
3
5
6
6

3
5
7
8
Table 1
Area (A), perimeter (P) and steady-state current (l
0
/a) of various microelectrode geometries
Microelectrode shape A P l
0
/a
a
2
2a 4 (A1)
ab 2
_

0
_
a
2
cos
2
+b
2
sin
2
d
4
_

0
d/
_
cos
2
+(b/a)
2
sin
2

(A2)
(a
2
b
2
) 2(a +b)
_
l
0
a
_
exact
=

2
(1+b/a)
ln(16(1+b/a)/(1b/a))
(A3a)
_
l
0
a
_
empirical
=

2
(1+b/a)
ln[(32(b/a)/(1b/a))+exp(
2
/4)]
(A3b)
ab 2 a (active perimeter) (actual perimeter is 2(a +b))
2

a/b
ln(64(a/b)t)
When a/b = ,
2
ln[(64t)]
(quasi-steady-state) (A4)
2a
2
2 (A5)
R
.
S
e
n
t
h
a
m
a
r
a
i
,
L
.
R
a
j
e
n
d
r
a
n
/
E
l
e
c
t
r
o
c
h
i
m
i
c
a
A
c
t
a
5
3
(
2
0
0
8
)
3
5
6
6

3
5
7
8
3
5
6
9
ab
2

a/b
ln(4 e
2
(a/b)t)
When a = b,
2
ln(4 e
2
t)
(quasi-steady-state) (A6)
a
2
+
ab
2
cosh
1
(a/b)
_
a
2
b
2

2(1(b/a)
2
)
1/4
cos
1
(b/a)
(A7)
a
2
+
ab
2
cos
1
(a/b)
_
b
2
a
2

2((b/a)
2
1)
1/2
cosh
1
(b/a)
(A8)
((a +r)(b +r) ab) when a =
bn, a
2
__
1 +
r
a
___
1
n
_
+
_
r
a
__

1
n
_
(n > 0)
2a
_
_

0
_
cos
2
+
_
1
n
2
_
sin
2
d
+
_

0
_
_
1 +
r
a
_
2
cos
2
+
_
1
n
+
r
a
_
2
sin
2
d
_
4

1/3
__
1 +
r
a
___
1
n
_
+
r
a
_

_
1
n
_

_
_

0
_
cos
2
+
_
1
n
2
_
sin
2
d +
_

0
_
_
1 +
r
a
_
2
cos
2
+
__
1
n
_
+
r
a
_
2
sin
2
d
_
1/3
(A9)
A P
_
32

2
a
3
AP
_
1/3
(A10)
3
5
7
0
R
.
S
e
n
t
h
a
m
a
r
a
i
,
L
.
R
a
j
e
n
d
r
a
n
/
E
l
e
c
t
r
o
c
h
i
m
i
c
a
A
c
t
a
5
3
(
2
0
0
8
)
3
5
6
6

3
5
7
8
Table 2
Steady-state current f(K) =I/4nFDC
0
a for the EC

reactions of various geometries

Electrode f(K) =
I
4nFDC
0
a
Small K Large K
Circular disc f(K) = 1 +
_
2

_
K
1/2
+
_
4

2

1
3
_
K (B1) f(K) =

4
K
1/2
+

4
+

16
K
1/2
(B2)
Elliptical disc f(K) =
(l
0
/a)
4
+
(l
0
/a)
2
8
K
1/2
(B3) f(K) =
(b/a)
4
K
1/2
+
_
1
4
_
_

0
_
cos
2
+
_
b
a
_
2
sin
2
d (B4)
Circular ring f(K) =
(l
0
/a)
4
+
(l
0
/a)
2
8
K
1/2
(B5) f(K) =
(1 (a/b)
2
)
4
K
1/2
+
(1 +a/b)
4
(B6)
where a and b are the inner and outer radii for a circular ring electrode
Band f(K) =
K
2
_

o
_
e
Ku
ln(22739.57u)
_
du (B7) f(K) =
(b/a)
4
K
1/2
+
1
4
when a/b = , f(K) =
1
4
K
1/2
+
1
4
(B8)
where a and b are the length and width of the band electrode.
Hemisphere f(K) =

2
+

2
K
1/2
(B9) f(K) =

2
K
1/2
+

2
(B10)
Hemicylinder f(K) =
K
2
_

0
_
e
Ku
ln(1.2609u)
_
du (B11) f(K) =
(b/a)
4
K
1/2
+

8
(at a = b) f(K) =

4
K
1/2
+

8
(B12)
where w and R
0
are the length and radius of the electrode.
Hemi-oblate f(K) =
(l
0
/a)
4
+
(l
0
/a)
2
8
K
1/2
(B13) f(K) =

4
_
1 +
_
b
a
_
2
cosh
1
_
a
b
_
_
1
_
b
a
_
2
_
1/2
_
K
1/2
+

4
_
_
b
a
_
+cos
1
_
b
a
_
_
1
_
b
a
_
2
_
1/2
_
(B14)
where a and b are the lengths of the two semi-axes and
the third axis of the hemi-oblate.
Hemi-prolate f(K) =
(l
0
/a)
4
+
(l
0
/a)
2
8
K
1/2
(B15) f(K) =

4
_
1 +
_
b
a
_
2
cos
1
_
a
b
_
_
_
b
a
_
2
1
_
1/2
_
K
1/2
+

4
_
_
b
a
_
+cosh
1
_
b
a
_
_
_
b
a
_
2
1
_
1/2
_
(B16)
where a and b are the lengths of the two semi-axes and
the third axis of the hemi-prolate.
Elliptical ring f(K) =
(l
0
/a)
4
+
(l
0
/a)
2
8
K
1/2
(B17) f(K)=

4
_
_
1+
r
a
_
__
1
n
_
+
r
a
_

_
1
n
__
K
1/2
+
1
4
_
_

0
_
cos
2
+
_
1
n
2
_
sin
2
d+
_

0
_
_
1+
r
a
_
2
cos
2
+
__
1
n
_
+
_
r
a
_
_
2
sin
2
d
_
(B18)
where a, b are the inner, outer radii and r is the width of
the elliptical ring.
where b =a/n. (In Table 3 the diffusion-limited current for elliptical rings is calculated when n =2)
R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578 3571
where
A
1
= b
1
, B
1
= b
0
, C
1
= a
0
b
1
and D
1
=

(b
0
a
1
)
(a
0
b
1
)

(9)
For circular disc electrodes, the numerical values of A
1
, B
1
, C
1
and D
1
are
A
1
= 0.7854, B
1
= 0.7854, C
1
= 0.2146 and D
1
= 0.6934
(10)
For elliptical disc electrodes, the values of A
1
, B
1
, C
1
and D
1
are
A
1
=
1
4
_

0

cos
2
+
_
b
a
_
2
sin
2
d, B
1
=

4
_
b
a
_
C
1
=
l
0
4a
A
1
and D
1
=

(B
1
(l
0
/a)
2
/8)
C
1

(11)
For circular ring electrodes, the values of A
1
, B
1
, C
1
and D
1
are
A
1
=

4
_
1 +
a
b
_
, B
1
=

4
_
1
_
b
a
_
2
_
,
C
1
=
_
l
0
4a
_
A
1
and D
1
=

B
1
((l
0
/a)
2
/8)
C
1

(12)
For elliptical ring electrodes, the values of A
1
, B
1
, C
1
and D
1
becomes
A
1
=
1
4
_
_
_

0

cos
2
+
_
1
n
2
_
sin
2
d +
_

0

_
1 +
_
r
a
__
2
cos
2
+
__
1
n
_
+
_
r
a
_
_
2
sin
2
d
_
_
,
B
1
=

4
_
_
1 +
r
a
_
__
1
n
_
+
_
r
a
_
_

_
1
n
__
,
C
1
=
_
l
0
4a
_
A
1
and D
1
=

B
1

((l
0
/a)
2
/8)
C
1

(13)
For hemi-oblate electrodes the values are
A
1
=

4
_
_
_
b
a
_
+cos
1
_
b
a
_
_
1
_
b
a
_
2
_
(1/2)
_
_
B
1
=

4
_
_
1 +
_
b
a
_
2
cosh
1
_
a
b
_
_
1
_
b
a
_
2
_
(1/2)
_
_
C
1
=
_
l
0
4a
_
A
1
D
1
=

B
1

((l
0
/a)
2
/8)
C
1

(14)
For hemi-prolate electrodes the values are
A
1
=

4
_
_
_
b
a
_
+cosh
1
_
b
a
_
__
b
a
2
_
1
_
(1/2)
_
_
B
1
=

4
_
_
1 +
_
b
a
_
2
cos
1
_
a
b
_
_
_
b
a
_
2
1
_
(1/2)
_
_
C
1
=
_
l
0
4a
_
A
1
D
1
=

B
1

((l
0
/a)
2
/8)
C
1

(15)
For hemisphere electrodes the values are
A
1
=

2
, B
1
=

2
, C
1
= 0 (16)
For hemicylinder electrodes (for large K) the values are
A
1
=

8
, B
1
=

4
, C
1
= 0, D
1
= 0 (17)
For band electrodes (for large K) the values are
A
1
=
1
4
, B
1
=
1
24
, C
1
= 0, D
1
= 0 (18)
when K=0, Eq. (7) becomes the steady-state current of the
diffusion-limited E reaction. Eq. (8) represents the steady-state
current i
ss
(K) for the EC

reactions for all electrode geometries

at all values of K.
2.1. Discussion
Tables 3A3C indicates the dimensionless steady-state
chronoamperometric currents f(K) for the EC

reactions for
all ultramicroelectrodes. Fig. 1(ad) shows the comparisons
of steady-state currents f(K) at all ultramicroelectrodes using
Eq. (7) for all values of K and all values of b/a. For these
curves, current is normalized with respect to the characteris-
tic length (a) associated with the geometry under consideration,
i.e., the ordinate is f(K) =i(K)/4nFDC
0
a. From Tables 3A3C
and Fig. 1(ad), the values of the steady-state currents for large
values of K are in the following order:
band < hemicylinder < circular disc < circular ring
< elliptical disc < hemi-oblate
< hemisphere < elliptical ring < hemi-prolate (19a)
The steady-state currents f(K) for hemicylinder and circular disc
electrodes are equal (Refer Fig. 1(c)). For elliptical disc elec-
trodes, the value of the current increases when b/a increases (or
3572 R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578
Table 3A
Comparison of steady-state current f(K) for the EC

reactions for various microelectrodes

log K K Hemicylinder Circular disc Elliptical disc Hemisphere
b/a =1 disc (e =0) b/a =0.9 (e =0.44) b/a =0.5 (e =0.9) b/a =0.1 (e =0.995)
4 0.0001 0.0079 1.0064 1.0064 0.9551 0.7318 0.4261 1.5865
3 0.001 0.0614 1.0202 1.0202 0.9676 0.7391 0.4286 1.6205
2 0.01 0.4817 1.0642 1.0642 1.0072 0.7623 0.4364 1.7279
1 0.1 0.6411 1.2061 1.2061 1.1349 0.8364 0.4606 2.0675
0 1 1.1781 1.6781 1.6781 1.5587 1.0768 0.5330 3.1416
1 10 2.8764 3.2930 3.2930 3.0075 1.8772 0.7356 6.5381
2 100 8.2467 8.6396 8.6396 7.8160 4.5339 1.2920 17.2788
3 1000 25.2292 25.6219 25.6219 23.1008 13.0238 2.9904 51.2439
4 10000 78.9327 79.3254 79.3254 71.4367 39.8755 8.3580 158.6508
Table 3B
Comparison of steady-state current f(K) for the EC

reactions for various microelectrodes

log K K Hemi-oblate b/a <1 Hemi-prolate b/a >1 Band
b/a =0.01 b/a =0.5 b/a =0.99 b/a =1.5 b/a =2 b/a =10
4 0.0001 1.0157 1.4052 1.5865 1.8461 2.0930 5.3947 0.0020
3 0.001 1.0357 1.4255 1.6205 1.8919 2.1517 5.7663 0.0154
2 0.01 1.0987 1.4907 1.7279 2.0369 2.3374 6.9168 0.1028
1 0.1 1.2954 1.7064 2.0675 2.4952 2.9245 10.3497 0.2752
0 1 1.8973 2.4293 3.1416 3.9444 4.7781 19.9756 0.3296
1 10 3.6867 4.7703 6.5381 8.5248 10.6202 47.2706 0.5017
2 100 9.0913 12.1824 17.2788 22.9963 29.0116 132.0273 1.0460
3 1000 26.0830 35.6215 51.2439 68.7268 87.0688 400.0135 2.7672
4 10000 79.8138 109.7424 158.651 213.3242 270.6480 1247.4603 8.2100
eccentricity decreases). In hemi-oblate and hemi-prolate elec-
trodes, the value of current f(K) increases when b/a increases
(Refer Table 3B). In circular ring electrodes, the value of the cur-
rent decreases when b/a increases. In elliptical ring electrodes,
the value of the current increases when a/r decreases. For small
values of K, the current values tend towards the same value for
all electrodes (see the left hand side of Fig. 1(ad).
For all electrodes, the current at short times is directly depen-
dent on the area of the electrode, and therefore, there is no
electrode geometry advantage for this condition because trans-
port will be completely planar. Normalizing the current based
on the radius or the square root of the area ignores the fact
that approaches to true diffusional steady-states are depen-
dent on the characteristic lengths of the electrode in three
dimensions being small compared to the time-dependent dif-
fusion length (Dt)
1/2
. Even a cylindrical or a band electrode
with a small radius with short characteristic lengths for two
dimensions of the electrode will not obtain a true diffusional
steady-state, but will reach a quasi-steady-state (Refer Table 2).
The inuence of the catalytic mechanism that enables a steady-
state current to be observed needs to be demonstrated without
the complications introduced by an inappropriate dimensional
normalization. Efciency based on the current density has
often been used as a criterion for the comparison of differ-
ent reaction rate/time domains and geometries for electrodes.
Using the current normalization (I
ss
(K) =i(K)a/4nFDC
0
A) may
help to better generalize electrode size and shape over large
domains of time and reaction rate. Hence in Eq. (8) current
Table 3C
Comparison of steady-state current f(K) for the EC

reactions for various microelectrodes

log K K Circular ring Elliptical ring
b/a =0 disc b/a =0.25 b/a =0.5 b/a =0.9 a/r =1 a/r =10 a/r =50
4 0.0001 1.0064 0.9975 0.9621 0.8263 1.8711 0.6427 0.3628
3 0.001 1.0202 1.0116 0.9750 0.8355 1.9180 0.6483 0.3646
2 0.01 1.0642 1.0583 1.0157 0.8644 2.0655 0.6660 0.3703
1 0.1 1.2061 1.2148 1.1447 0.9524 2.5236 0.7212 0.3882
0 1 1.6781 1.7180 1.5523 1.2007 3.9214 0.8878 0.4434
1 10 3.2930 3.3101 2.8406 1.7861 8.1951 1.3505 0.6068
2 100 8.6396 8.3447 6.9085 2.9742 21.6220 2.4644 1.0314
3 1000 25.621 24.2656 19.7274 6.2104 64.0783 5.2617 1.8843
4 10000 79.3254 74.6117 60.0794 16.4123 198.337 13.8576 3.6154
R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578 3573
Fig. 1. (a) Steady-state current f(K) for the EC

reactions for various values of K for hemicylinder, circular disc, elliptical disc, hemisphere and elliptical ring
electrodes. (b) Steady-state current f(K) for the EC

reactions for various values of K for circular disc, circular ring, band, hemi-oblate and hemi-prolate electrodes.
(c) Steady-state current f(K) for the EC

reactions for various values of K for hemicylinder and circular disc electrodes. (d) Steady-state current f(K) for the EC

reactions for various values of K for circular disc, hemicylinder, elliptical ring and circular ring electrodes.
is normalized with respect to the area (A) of the electrode,
such that the vertical ordinate is I
ss
(K) =i(K)a/4nFDC
0
A.
Tables 4A4C and Fig. 2(ad) indicate dimensionless steady-
state chronoamperometric currents I
ss
(K) for the EC

reactions
for all ultramicroelectrodes for all values of K. The values
of steady-state current i
ss
(K) for large values of K are in the
following order
hemicylinder < hemi-prolate
< hemisphere < circular disc < hemi-oblate < band
< elliptical disc < circular ring < elliptical ring (19b)
Table 4A
Comparison of steady-state current I
ss
(K) for the EC

reactions for various microelectrodes

log K K Hemicylinder Circular disc Elliptical disc Hemisphere
b/a =1 disc (e =0) b/a =0.9 (e =0.44) b/a =0.5 (e =0.9) b/a =0.1 (e =0.995)
4 0.0001 0.0025 0.3204 0.3204 0.3378 0.4659 1.3565 0.2525
3 0.001 0.0195 0.3248 0.3248 0.3422 0.4705 1.3643 0.2578
2 0.01 0.1533 0.3387 0.3387 0.3562 0.4853 1.3891 0.2750
1 0.1 0.2041 0.3839 0.3839 0.4014 0.5324 1.4660 0.3290
0 1 0.3750 0.5342 0.5342 0.5513 0.6856 1.6967 0.4999
1 10 0.9156 1.0482 1.0482 1.0637 1.1951 2.3413 1.0404
2 100 2.6251 2.7502 2.7502 2.7643 2.8865 4.1124 2.7494
3 1000 8.0310 8.1560 8.1560 8.1700 8.2915 9.5185 8.1540
4 10000 25.126 25.251 25.2510 25.2649 25.3865 26.6036 25.2447
3574 R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578
Table 4B
Comparison of steady-state current I
ss
(K) for the EC

reactions for various microelectrodes

log K K Hemi-oblate b/a <1 Hemi-prolate b/a >1 Band
b/a =0.01 b/a =0.5 b/a =0.99 b/a =1.5 b/a =2 b/a =10
4 0.0001 0.3231 0.3240 0.2525 0.2182 0.1948 0.1088 0.0062
3 0.001 0.3294 0.3287 0.2578 0.2236 0.2003 0.1163 0.0484
2 0.01 0.3495 0.3437 0.2750 0.2408 0.2176 0.1395 0.3229
1 0.1 0.4121 0.3935 0.3290 0.2949 0.2722 0.2087 0.8646
0 1 0.6035 0.5602 0.4999 0.4662 0.4448 0.4028 1.0355
1 10 1.1727 1.1000 1.0404 1.0076 0.9886 0.9532 1.5763
2 100 2.8919 2.8092 2.7494 2.7181 2.7006 2.6622 3.2862
3 1000 8.2969 8.2140 8.1540 8.1234 8.1049 8.0659 8.6939
4 10000 25.3885 25.3057 25.2447 25.2146 25.1935 25.1538 25.794
Table 4C
Comparison of steady-state current I
ss
(K) for the EC

reactions for various microelectrodes

log K K Circular ring Elliptical ring
b/a =0 disc b/a =0.25 b/a =0.5 b/a =0.9 a/r =1 a/r =10 a/r =50
4 0.0001 0.3204 0.3387 0.4082 1.3843 0.2382 1.2786 3.7992
3 0.001 0.3248 0.3434 0.4137 1.3997 0.2442 1.2899 3.8179
2 0.01 0.3387 0.3594 0.4310 1.4481 0.2630 1.3252 3.8775
1 0.1 0.3839 0.4125 0.4857 1.5955 0.3213 1.4349 4.0645
0 1 0.5342 0.5833 0.6587 2.0115 0.4992 1.7664 4.6430
1 10 1.0482 1.1239 1.2054 2.9920 1.0433 2.6869 6.3535
2 100 2.7502 2.8334 2.9314 4.9824 2.7526 4.9029 10.799
3 1000 8.1560 8.2391 8.3708 10.4037 8.1576 10.4682 19.729
4 10000 25.2510 25.3336 25.493 27.4940 25.2495 27.5698 37.855
The steady-state currents for hemicylinder, hemisphere, cir-
cular disc and band electrodes are equal (Refer Fig. 2(c)).
In elliptical disc electrodes, i
ss
(K) increases when eccentric-
ity increases [24]. In hemi-oblate and hemi-prolate electrodes,
current decreases when b/a increases, whereas in elliptical ring
electrodes, steady-state current increases when a/r increases.
In all the electrodes, steady-state current increases when K
increases. The steady-state current i
ss
(K) is relatively slowvary-
ing when log K1 for all ultramicroelectrodes.
3. Mathematical formulation of the problem and
analysis (non-steady-state)
The initial boundary value problem which has to be solved
for the case of non-steady-state can be written in dimensionless
form as follows
c(r, t)
t
=
2
c(r, t) Kc(r, t) (20)
where c refers to the dimensionless concentration of the elec-
troactive species B, K denotes the dimensionless reaction rate,
i.e., K=ka
2
/D and t denotes dimensionless time. a denotes the
characteristic associated with the geometry under consideration
(a may be identied as the radius for discs and spheres). The
general analytical expression of current is given by [28]
I
T
=
i(t)a
4nFDC
0
A
= I
ss
(K) +
1
4
K
1/2
g(K, t) (21)
where A is the area of the electrode, I
ss
(K) is the steady-state
current for the EC

reaction (Eq. (8)) and

g(K, t) = (Kt)
1/2
e
Kt
erfc(Kt)
1/2
(22)
The rst term of the Eq. (21) represents the steady-state cur-
rent for the EC

reaction. The steady-state currents I

ss
(K) of
various electrodes are given in the Eq. (8). This approximation
is more accurate for large times and large K values than for
short times and small K values [28]. When t , g(K,t) 0
(Since for large t, erfc(Kt)
1/2
(Kt)
1/2
e
Kt
). Fig. 3(a) gives
graphs of K
1/2
g(K,t) for the indicated t and K values. Fig. 3(a)
and Table 5 show in more detail, the degrees of the function
K
1/2
g(K,t) to constant value (=0). When t >1 for all ultramicro-
electrodes, K
1/2
g(K,t) =0. Now, I
T

=I
ss
(K) (Refer Table 5 and
Fig. 3(a)).
Table 5
Values of K
1/2
g(K,t) for various values of K and t
log t t K
1/2
g(K,t)
K=1 K=10 K=100
3 0.001 16.8591 14.8571 9.5962
2 0.01 4.6982 3.0346 0.5025
1 0.1 0.9596 0.1589 0.0001
0 1 0.0503 0.0000 0.0000
1 10 0.0000 0.0000 0.0000
2 100 0.0000 0.0000 0.0000
3 1000 0.0000 0.0000 0.0000
R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578 3575
Fig. 2. (a) Steady-state current I
ss
(K) for the EC

reactions for various values of K for circular disc, elliptical disc, hemisphere and elliptical ring electrodes. (b)
Steady-state current I
ss
(K) for the EC

reactions for various values of K for circular disc, hemicylinder, circular ring, hemi-oblate and hemi-prolate electrodes. (c)
Steady-state current I
ss
(K) for the EC

reactions for various values of K for hemicylinder, hemisphere, circular disc and band electrodes. (d) Steady-state current
I
ss
(K) for the EC

reactions for various values of K for circular disc, elliptical ring and circular ring electrodes.
3.1. Discussion
Tables 6A6E indicates the dimensionless non-steady-state
chronoamperometric currents I
T
=i(t)a/4nFDC
0
A for the EC

reactions for all ultramicroelectrodes. From Tables 6A6E, it is

inferred that the values of non-steady-state currents are in the
following order for all times:
hemi-cylinder < hemi-prolate < hemi sphere < circular disc
< hemi-oblate < band < elliptical disc < circular ring
< elliptical ring (23)
Table 6A
Comparison of non-steady-state current I
T
for the EC

reactions for various microelectrodes

log t t Hemicylinder Circular disc Elliptical ring
K=1 K=10 K=100 K=1 K=10 K=100 a/r =1 a/r =10 a/r =50
K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100
3 0.001 4.5897 4.6298 5.0242 4.7489 4.7625 5.1510 4.7140 4.7576 5.1518 5.9801 6.4003 7.3015 8.8599 10.0698 13.1992
2 0.01 1.5496 1.6742 2.7508 1.7087 1.8069 2.8775 1.6738 1.8019 2.8782 2.9406 3.4453 5.0284 5.8183 7.1126 10.9244
1 0.1 0.6149 0.9553 2.6251 0.7741 1.0879 2.7519 0.7391 1.0830 2.7526 2.0062 2.7266 4.9029 4.8831 6.3933 10.7988
0 1 0.3876 0.9156 2.6251 0.5468 1.0482 2.7518 0.5118 1.0433 2.7526 1.7789 2.6869 4.9029 4.6557 6.3535 10.7988
1 10 0.3750 0.9156 2.6251 0.5342 1.0482 2.7518 0.4992 1.0433 2.7526 1.7664 2.6869 4.9029 4.6430 6.3535 10.7988
2 100 0.3750 0.9156 2.6251 0.5342 1.0482 2.7518 0.4992 1.0433 2.7526 1.7664 2.6869 4.9029 4.6430 6.3535 10.7988
3 1000 0.3750 0.9156 2.6251 0.5342 1.0482 2.7518 0.4992 1.0433 2.7526 1.7664 2.6869 4.9029 4.6430 6.3535 10.7988
3576 R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578
Table 6B
Comparison of non-steady-state current I
T
for the EC

reactions for various microelectrodes

log t t Elliptical disc Hemisphere
b/a =1 b/a =0.9 b/a =0.5 b/a =0.1 K=1 K=10 K=100
K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100
3 0.001 4.7489 4.7625 5.1510 4.7662 4.7782 5.1635 4.9000 4.9092 5.2854 5.9105 6.0549 6.5111 4.7146 4.7545 5.1486
2 0.01 1.7087 1.8069 2.8775 1.7259 1.8223 2.8899 1.8601 1.9537 3.0121 2.8710 3.0997 4.2380 1.6744 1.7990 2.8750
1 0.1 0.7741 1.0879 2.7519 0.7912 1.1034 2.7643 0.9254 1.2348 2.8865 1.9365 2.3811 4.1124 0.7398 1.0801 2.7495
0 1 0.5468 1.0482 2.7518 0.5638 1.0637 2.7643 0.6982 1.1951 2.8865 1.7092 2.3413 4.1124 0.5125 1.0404 2.7494
1 10 0.5342 1.0482 2.7518 0.5513 1.0637 2.7643 0.6856 1.1951 2.8865 1.6967 2.3413 4.1124 0.4999 1.0404 2.7494
2 100 0.5342 1.0482 2.7518 0.5513 1.0637 2.7643 0.6856 1.1951 2.8865 1.6967 2.3413 4.1124 0.4999 1.0404 2.7494
3 1000 0.5342 1.0482 2.7518 0.5513 1.0637 2.7643 0.6856 1.1951 2.8865 1.6967 2.3413 4.1124 0.4999 1.0404 2.7494
Table 6C
Comparison of non-steady-state current I
T
for the EC

reactions for various microelectrodes

log t t Hemi-oblate
b/a =0.01 b/a =0.5 b/a =0.9 b/a =0.99
K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100
3 0.001 4.8186 4.8873 5.2912 4.7748 4.8140 5.2082 4.7352 4.7637 5.1579 4.7263 4.7560 5.1503
2 0.01 1.7782 1.9314 3.0176 1.7347 1.8586 2.9348 1.6951 1.8082 2.8845 1.6862 1.8001 2.8767
1 0.1 0.8435 1.2124 2.8919 0.8001 1.1397 2.8092 0.7605 1.0893 2.7589 0.7516 1.0812 2.7511
0 1 0.6161 1.1727 2.8919 0.5727 1.1000 2.8092 0.5332 1.0495 2.7589 0.5243 1.0415 2.7511
1 10 0.6035 1.1727 2.8919 0.5602 1.1000 2.8092 0.5206 1.0495 2.7589 0.5117 1.0415 2.7511
2 100 0.6035 1.1727 2.8919 0.5602 1.1000 2.8092 0.5206 1.0495 2.7589 0.5117 1.0415 2.7511
3 1000 0.6035 1.1727 2.8919 0.5602 1.1000 2.8092 0.5206 1.0495 2.7589 0.5117 1.0415 2.7511
Table 6D
Comparison of non-steady-state current I
T
for the EC

reactions for various microelectrodes

log t t Hemi-prolate Band
b/a =1.5 b/a =2 b/a =10 K=1 K=10 K=100
K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100
3 0.001 4.6812 4.7221 5.1175 4.6595 4.7028 5.0997 4.6177 4.6675 5.0613 5.2489 5.2895 5.6846
2 0.01 1.6409 1.7663 2.8437 1.6193 1.7472 2.8262 1.5773 1.7118 2.7878 2.2098 2.3347 3.4119
1 0.1 0.7061 1.0474 2.7182 0.6847 1.0283 2.7006 0.6427 0.9929 2.6622 1.2753 1.6160 3.2862
0 1 0.4788 1.0076 2.7181 0.4573 0.9886 2.7006 0.4154 0.9532 2.6622 1.0481 1.5763 3.2862
1 10 0.4662 1.0076 2.7181 0.4448 0.9886 2.7006 0.4028 0.9532 2.6622 1.0355 1.5763 3.2862
2 100 0.4662 1.0076 2.7181 0.4448 0.9886 2.7006 0.4028 0.9532 2.6622 1.0355 1.5763 3.2862
3 1000 0.4662 1.0076 2.7181 0.4448 0.9886 2.7006 0.4028 0.9532 2.6622 1.0355 1.5763 3.2862
Table 6E
Comparison of non-steady-state current I
T
for the EC

reactions for various microelectrodes

log t t Circular ring
b/a =0 b/a =0.25 b/a =0.5 b/a =0.9
K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100 K=1 K=10 K=100
3 0.001 4.7489 4.7625 5.1493 4.7977 4.8379 5.2323 4.8736 4.9198 5.3306 6.2273 6.7072 7.3820
2 0.01 1.7087 1.8069 2.8758 1.7578 1.8825 2.9590 1.8333 1.9640 3.0571 3.1863 3.7509 5.1081
1 0.1 0.7741 1.0879 2.7502 0.8232 1.1637 2.8334 0.8986 1.2451 2.9314 2.2514 3.0318 4.9824
0 1 0.5468 1.0482 2.7502 0.5959 1.1239 2.8334 0.6713 1.2054 2.9314 2.0240 2.9920 4.9824
1 10 0.5342 1.0482 2.7502 0.5833 1.1239 2.8334 0.6587 1.2054 2.9314 2.0115 2.9920 4.9824
2 100 0.5342 1.0482 2.7502 0.5833 1.1239 2.8334 0.6587 1.2054 2.9314 2.0115 2.9920 4.9824
3 1000 0.5342 1.0482 2.7502 0.5833 1.1239 2.8334 0.6587 1.2054 2.9314 2.0115 2.9920 4.9824
R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578 3577
Fig. 3. (a) Plot of the function K
1/2
g(K,t) versus log t for various values K(K=1,
K=10 and K=100). (b) Plot of Kt versus g(K,t).
The non-steady-state currents I
T
for hemicylinder, hemi-
sphere and circular disc electrodes are equal (refer Table 6A).
In all electrodes, the value of the current increases when K
increases. In elliptical ring electrodes, the value of the current
increases when a/r increases (or perimeter decreases) for all
values of K. In elliptical disc electrodes, the non-steady-state
current I
T
increases when b/a decreases (or eccentricity
increases or perimeter decreases). Elliptical disc electrodes are
advantageous under potentiodynamic conditions compared to
comparable circular disc electrodes. The larger eccentricity of
an elliptical disc electrode, the greater is its analytical sensitivity
[24]. In hemi-oblate and hemi-prolate electrodes, the value of the
current decreases when b/a increases, whereas in circular ring
electrodes, the current increases when b/a increases (or perime-
ter increases). When Kt 10, the current reaches its steady-state
value (constant value) for all electrodes (since g(K,t) =0 (Refer
Fig. 3(b))).
4. Conclusions
Closed form expressions for steady and non-steady-state
diffusion-limited currents for the EC

reactions at all microelec-

trodes are given. The steady-state current for small and large
values of K, for all microelectrodes are given in Table 2. Numer-
ical tables and gures are given that allow for comparisons of
diffusion currents at all microelectrodes. Of the nine microelec-
trode geometries investigated, the elliptical ring and circular ring
microelectrodes appear to be the superior geometries for per-
forming electroanalytical measurements for both steady-state
and non-steady-state EC

reactions. Hemicylinder, hemisphere,

circular disc, hemi-prolate and band electrodes are conrmed
to be the worst geometries for analytical and electrochemical
kinetic studies. Thus, elliptical ring and circular ring electrodes
have greater analytical sensitivity than all other microelectrodes,
and hence these electrodes are recommended for investigations
of electrode kinetics. The extension of this procedure (compar-
ison of results) to other reaction mechanisms (ECE and DISP,
etc.) and other geometries, such as rotating disc (RDE) and the
rotating ring-disc (RRDE) electrodes, etc., apart from the study
of scanning electrochemical microscope (SECM) response for
different tip shapes seems possible.
Acknowledgements
The author is very thankful to the referees for their valu-
able suggestions. The authors are pleased to acknowledge the
nancial support of the Department of Science and Technology
(DST), Government of India to L. Rajendran, which has allowed
this work to be undertaken. The author also thanks Prof. A .K.
Shukla, Director, CECRI, Karaikudi, India and MR. Valliappan,
Headmaster, SMSV Higher Secondary School for their encour-
agement. Useful discussions with Prof. P. N. Bartlett, University
of Southampton, UK and Dr. C. A. Basha, Dy. Director, Pol-
lution Control, CECRI, Karaikudi and Prof. N. Palaniappan,
Department of Mathematics, Alagappa University, Karaikudi
are gratefully acknowledged.
Appendix A. Nomenclature
Symbol Meaning Usual dimension Eq./Table involved
a Characteristic length associated with the geometry under consideration cm (3)(8)
Radius for disc electrode cm (15), Table 1 1st g)
Length of semi-major axis for elliptical ring electrode cm (11), Table 1 (2nd g)
Outer radius for circular ring electrode cm (12), Table 1 (3rd g)
Length of band electrode cm Table 1 (4th g)
Radius of hemisphere electrode cm Table 1 (5th g)
Length of hemicylinder electrode cm Table 1 (6th g)
Length of equal horizontal two semi-axes for hemi-oblate and hemi-
prolate electrodes
cm Table 1 (8th and 9th g)
3578 R. Senthamarai, L. Rajendran / Electrochimica Acta 53 (2008) 35663578
Appendix A (Continued )
Symbol Meaning Usual dimension Eq./Table involved
b Length of semi-minor axis of elliptical disc electrode cm Table 1 (2nd g)
Length of inner radius of circular ring electrode cm Table 1 (3rd g)
Width of band electrode cm Table 1 (4th g)
Radius of hemicylinder cm Table 1 (6th g)
Length of third semi-axis for hemi-oblate and hemi-prolate electrodes cm Table 1 (7th and 8th g)
Length of inner semi-minor axis of elliptical ring electrode cm Table 1 (9th g)
c Dimensionless concentration none (2)
C
0
Bulk concentration mol cm
3
(3)
D Diffusion coefcient cm
2
s
1
(3)
F Faraday constant 96487 Cmol
1
(3)
K Dimensionless reaction rate none (4)(8), (21)
k Reaction rate s
1
(1)
l
0
/a Steady-state diffusion-limited current none Table 1 (4th column), (22), (24), (32), (34) and (36)
P Perimeter of the electrode cm Table 1 (3rd column)
r Dimensionless radical-co-ordinate none (2), (20)
r Width of the elliptical ring cm (23)
z Dimensionless axis co-ordinate none (2), (20)
I
ss
(K) Dimensionless steady-state current for EC

reaction none (8)

I
T
Dimensionless non-steady-state current for EC

reaction none (21)

t Dimensionless time none (21), (22)
Eulers constant ( =0.5772156. . .) none (20)
i(t) Current density A (21)
I
ss
Dimensionless steady-state current none (8)
I
T
Dimensionless non-steady-state current none (21)
a
i
coefcients in series expansion none (4)
b
i
Coefcients in series expansion none (5)
A
1
, B
1
, C
1
, D
1
Coefcients of series none (7)
u, Integration dummy variable none (26), (30), (37), (23)
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