REPOR7

Stanley Pons
Department of Chemistry
University of Utah
Salt Lake City, Utah 841 12 I
Martin Fleischmann
Department of Chemistry
University of Southampton
A
Southampton SO9 5NH
England

In the early 1970s a number of research

groups exploited the advantages of mi-
croelectrodes, which are normally de-
fined as devices with characteristic di-
mensions smaller than about 20 fim,
over conventional electrodes. Because
many of the undesirable aspects of
electrochemical and electroanalytical
techniques can he reduced or eliminat-
ed with microelectrodes, their use has
grown rapidly.
Microelectrodes are advantageous
for several reasons. First, very small
currents (rates of reaction) as low as
A, 10 e-Is, can be measured
with relative ease. Second, iR losses in
solution are reduced a t small elec-
trodes. This “error” to the applied po-
tential at the electrode-solution inter-
face prevents electrochemical experi-
ments from being performed with
“large” electrodes in all but ionically
conducting solutions. Third, capacita-
tive charging currents, the limiting fac-
tor in all transient electrochemical
techniques, are reduced to insignifi-
cant proportions at electrodes of suffi-
ciently small area. Fourth, the rate of
mass transport to and from the elec-
trodes increases as the electrode size
decreases; moreover, steady states of
mass transfer are rapidly established.
As a consequence of reduced capacita-
tive charging currents and increased
mass transport rates, microelectrodes
exhibit excellent signal-to-noise (S/N)
characteristics. Finally, as the litera-
ture indicates, microelectrode systems
are easily implemented and involve rel-
atively low costs.
The unusual properties of microelec-
Flgure 1. Designs of microelectrodes.
trodes also allow electrochemical mea-
(a) Side view 01 a microdisk electrode. (b) plane view of a micrwing eiectrcde. (c) plane vlew 01 a micro-
surements to be made on novel sys- disk-micrwing electrode, (d) side view Of a spherical mercury drop deposited on a disk, (e) side view Of a
tems-those that are not amenable to particle in a dispersion undergoing eIecnolysis by a field applied across the cell.

0003-2700187/A359- 1391IS0 1.50/0 ANALYTiCAL CHEMISTRY. VOL. 59, NO. 24, DECEMBER 15, 1987 1391 A
@ 1987 American Chemical Society
 tography. The detector in the gas phase
is especially sensitive for analytes that
have a proton loss involved in chemical
reactions following the electron trans-
fer. The increased sensitivity results
from the high mobility of the proton.
The detectors are species-sensitive be-
cause of differences in standard poten-
tials of the analytes, and they are quan-
titatively more sensitive than thermal
conductivity detectors.
The problem ol the analysis of mass
transport to finite dkks and rhgs
It is well known that closed-form sim-
ple solutions can be obtained for most
types of electrochemical experiments
PotentialIMlts vs. AglAg+ using hemispherical or spherical micro-
electrodes, provided that any coupled
reaction kinetic terms are first order or
Flgure 2. Effect of electrolyte addition to acetonitrile when using a plt ~ ~ I disk
pseudo first order. For a spherical elec-
microelectrode of radius 0.5 wn in oxidation of 1 mM ferrocene. trode of any radius r, under conditions
(a) Wimaut electrolyie. (b) with 1 mM Et,NCIO,. of constant flux Q, the concentration
distribution is
conventional electroanalysis. In this trolytes (type 2, Figure Za),
REPORTwe will review some of these low-temperature glasses and eu-
systems and comment on some of the tectics (type 3, Figure Zb), and
more interesting properties of very the gas phase (type 4).
small electrodes, their application to Measurements of the first three with a steady-state mass transfer coef-
other types of analytical and physical types have been made with convention- ficient Dlr, (compare with the mass
measurements, and solutions to the al microdisk electrodes (Figure la). transport coefficient to a large planar
problem of mass transport to certain Type 2 measurements have also been electrode, DI6c; the minimum value of
microelectrode geometries. Further in- demonstrated using the bipolar elec- 6c 5 0.001 em for marked forced con-
formation about these areas is avail- trolysis of dispersions of metal and vection). Definitions of these and other
able; see the Suggested Reading list. semiconductor particles supported in symbols used in equations throughout
Figure 1 illustrates some of the de- solvents without added support elec- this REPORTare provided in the glos-
signs of microelectrodes. The high trolyte (Figure le). It is important that sary of symbols (see box).
mass transfer rates allow electroanalyt- ions be invariably generated (or con- Unfortunately, the applicability of
ical measurements to be made a t low sumed) in electrode reactions, that is such types of microelectrodes has thus
substrate concentrations (using the
chronoamperometric or chronopoten-
+
Ox e- a Rd- far been somewhat restricted to the
electrodeposition of ensembles or sin-
tiometric responses as well as stripping or gle mercury droplets, the electrolysis of
voltammetry of preconcentrated spe-
cies, e.g., using Hg microdrops). Other
Oxf + e- F? Fkl dispersions, or the dropping mercury
microelectrode, to name a few exam-
applications include the measurement so that conditions can be chosen to in- ples. Disk and the recently introduced
of the kinetics of fast electrode reac- crease the conductance of the solution ring microelectrodes are more easily
tions (from the kinetically controlled in the vicinity of the microelectrodes. constructed, but the necessary mathe-
polarization curves) and of the kinetics Because the bulk of the resistance is in matical analysis has thus far proved to
of fast reactions in solution coupled to this region (the resistance is propor- be rather intractable.
electrode reactions (e.g., using the radi- tional to the resistivity and the inverse A related problem, the capacitance
us dependence of the limiting currents of the electrode radius), the ohmic of a disk, was investigated experimen-
that become kinetically controlled by lases are small and calculable or mea- tally by Cavendish in the mid-lll(lOs.
the reactions in solution). These appli- surable, particularly in the kinetically The mathematical difficulties of ana-
cations are dependent on three of the controlled region of the polarization lyzing problems in the cylindrical coor-
special properties because of the spher- curves. Measurements in the gas phase dinate system result from discontinui-
ical (or quasi-spherical) concentration (type 4) are now made with disk-ring ties at the edges of the electrodes where
and potential fields surrounding the electrodes (Figure IC)where the cur- the diffusion-limited flux for a revers-
microelectrode: the reduction of iR rent will usually, hut not necessarily, ible system becomes infinite. The com-
losses, decreased capacitative currents, flow over the “insulator” surface sepa- bined effects of the finite rates of the
and increased mass transport rates. rating the disk from the surrounding surface reactions and of the distribu-
The reduced iR effect is particularly ring electrode while gas-phase species tion of potential and concentration
important to other applications of mi- diffuse to the microdisk or, most likely, (i.e., the “tertiary current distribu-
croelectrodes because it allows mea- to the edges of the disk through the tion”), however, limit the electron
surements to be made on novel systems quasi-spherical diffusion field. The transfer rates at the edges for real sys-
under unusual conditions such as the conditions are therefore somewhat dif- tems.
following: ferent from those for measurements of Microdisk and microring geometries,
nonpolar solvents in the presence types 1,2, and 3. however, share the advantage of spher-
of appropriate support electrolytes We have previously demonstrated ical microelectrodes; quasi-spherical
(type 1) the utility of these devices as sensitive diffusion fields are established in rela-
polar solvents and mixtures of po- detectors in gas-phase chromatogra- tively short amounts of time. These
lar and nonpolar solvents in the ab- phy and for measurements of picogram spherical diffusion fields give high
sence of purposely added support elec- levels of DNA bases by liquid chroma- rates of mass transfer to the surfaces of

1392A * ANALYTICAL CHEMISTRY, VOL. 59. NO. 24. DECEMBER 15, 1987
the microelectrodes so that the kinetics the surface of a disk, the discontinuous i = F(km)QC"x
of fast electrode reactions and of fast
reactions in solution can be studied un-
der steady-state conditions. Compli-
integrals
[exp (s) -e xp(w)]/

+ (s)
cated transient techniques at micro-
electrodes then may not be required,
because it is now easy to build elec- r<a exp +
trodes with very small dimensions. It is
therefore always useful to examine
whether the steady-state behavior can
be predicted directly. The steady-state associated with
sin+(:), r >a
exp (-)I
behavior is described by the diffusion
equation in the cylindrical coordinate Numerical evaluation of the inte-
system grals is straightforward. Many of the
equations may be expressed in terms of
hypergeometric functions, which are
'r<a convenient as these series generally
converge rapidly and their propagation
After separating variables, we find a 0, r>a is simple and well-suited to representa-
general solution of the form tion by efficient algorithms. A com-
satisfy the boundary conditions pro- plete development of these equations,
C = C" -
lo-
j(X) exp(-hz)J,(Xr)dX vided f(X) = (2ls)AC sin(Xa). That is,
we obtain the solution
as well as expressions for several other
experiments, are found in the litera-
ture cited in the Suggested Reading
where Jo is a Bessel function of the fust
kind of order zero. The f ( X ) are sought c = C" - - (2sC " - CS) x list.
This approach can be extended to
so that the equation satisfies the ap-
propriate boundary conditions for any predict the non-steady-state behavior
particular electrode geometry. For in- of disk electrodes for a variety of elec-
stance, for a reversible reaction under trochemical experiments. Although ex-
constant concentration conditions a t with flux F = 4D(C- - C*)a and mass periments with very small electrodes
transfer coefficient (km), = 4DIsa. For will usually be carried out in the steady
the constant flux condition a t a disk, state (or under quasi-steady-state con-
the concentration distribution is ditions), the measurement of transient
responses with readily available instru-
Glossary of symbols used mentation becomes feasible for elec-
c" Bulk concentration,mol ~ r n - ~ trodes having somewhat larger dimen-
a Radius of disk, inner radius sions. For instance, the concentration
ring, om distribution at a disk for the simple
z Coordlnate normal to plane of case of chronopotentiometry is
disk, cm
&,J, bssei functions C=C"-
%1
Q Flux, mol cm-2 s-' with mass transfer coefficient (km)Q=
0 Surface wncentration, mi 3rD/8a, where we take the average sur- Jo(ar)J,(ola)erf(D112at 112) &
cmm3 face concentration to be equal to zero, OL
b Outer radius of ring. cm and where we have made use of another
r Radial coordinate, em discontinuous integral. For the ring ge-
and the chronopotentiometric re-
D Diffusion coefficient. cm2s-l ometry under the same conditions, we
sponse for simple Butler-Volmer ki-
km Mass transport coefficient, netics is
cm s-'
2FI Hypergeometric function v -

F Faraday constant, coulomb

equivalent-'
I Current, amperes
6 Exchange current density.
amperes cm-2
2' Real part, impedance
Z" imaginary part, impedance
R Gas constant. J mi-' K-' and mass transfer coefficients, with av-
CAW Average concentration,mol erage concentration a t the surface The properties of these responses, such
cm-3 equal to zero: as the transition time, are close to those
o Angular frequency, M predicted by other workers even
a Transfer coefficient (in exp) (km)Q= -Q-- though other analyses have been based
C" on the assumption of uniform surface
D(b2 - a') concentration rather than constant
flux conditions. The close agreement of
results derived using the two approach-
3s 3s es shows that the interpretation is not
n Number of electrons reactins very sensitive to the nature of the as-
T Absolute temperature, K These coefficients can then be used to sumptions.
8 Phaseangle, rad determine the form of polarization The chronoamperometric response
6c Concentration boundary layer curves. For instance, for a disk elec- a t a disk is found from determining
ihickness, cm trode and a reaction obeying Butler- what strength of sink, Q(s),in Laplace
- Volmer kinetics we have transform space gives a constant aver-

ANALYTICAL CHEMISTRY, VOL. 59. NO. 24, DECEMBER 15. 1987 - 1393,.
age surface concentration over the elec-
trode. The result is 192 850 2450 I
U I I I I I I I I I
3703 5900 7500

D%
with@=--.
,In
Inverting to the time domain, the ex-
pression yields the known limitin1
cases: At short time intervals, we ob
tain the Cottrell equation, and a t Ion&
time intervals the known steady-state
-
value 37rD(Cm c ~ , ) / 8 a .
By a similar analysis, we find that
the ac concentration a t a disk is

sin(wt - B/2)d@
I,”PI(B81
2

+
@(1 @)I” I
Figure 9. Current-time transienl for the deposition of a single droplet of mercury
for a voltage perturbation of frequency
w. For Butler-Volmer kinetics, the im-
from a solution 0.2 mM Hg2(N0& +
10 mM “ 0 s : 7 = 5 mV; 4-pm radius carbon
disk electrode.
pedances are then given by: Top scale is the radius of the drop.

2‘ = ~

RT + 2RT
X
unFioa2 m2F2D112w112a2C~ ing transitions between discrete cur- centers of the new phase (i.e., we are
rent levels. Transitions between levels dealing with the growth of ensembles of
are associated with the insertion-reori- microelectrodes). In view of the very
entation or removal-reorientation of small dimensions of the centers (which
single molecules of the peptide, which
aggregate to form pores reaching a
maximum size of P 5 molecules. In sys-
tems of this kind the generation of the
current transducing element defmes a
“microelectrode” of molecular dimen-
sions in a substrate having an area typi-
cally 1mm2.
The use of fire-polished capillaries to
Application to other areas of isolate small patches of membranes has
research in electrochemistry greatly extended the scope of such
The investigations using microelec- measurements. It should also he noted
trodes also prompt a series of questions that in systems of this kind the subse-
regarding the connections with other quent essentially deterministic trans-
meas of research in electrochemistry. membrane ion current amplifies the
Here we consider both earlier investi- random aggregation-removal of the
gations of the behavior of microelec- pore-forming molecules so that the ki-
trodes and reinterpretation of the he- netics of these processes and the ener-
havior of known systems with a small getics of the states become measurable
number of examples. a t the molecular level (see also com-
Earlier investigations. The term ments below on nucleation). The am-
“earlier” here refers to investigations plification results from the measure-
that had somewhat different objectives ment of a large flux of ions through the
from those of current research but that
actually embodied many of the con-
cepts now used. One of the hest known
examples is the use of microelectrodes
pore as the circumference of the pore
increases from 0 to 6 5 molecules,
whereas the latter parameters are in-
vestigated by measuring the temporal
I Flgure 4. Linear sweep anodic stripping
voitammogram at a mercury drop eiec-
to stimulate and monitor physiological development of the flux and its magni- trode (r = 7.0 pm) following a 10-min
processes. Examples of direct interest tude. deposition in a quiescent solution con-
t o the study of electrochemical kinetics A second large group of phenomena taining lead (8.7 X lo-* M) and cadmi-
include ion transduction processes in that depend on the formation of micro- um ions (1.6 X lO-’M)at -800 mV vs.
lipid bilayers. The application of an ap- electrodes is that of the electrocrystal- SCE.
propriate voltage difference to bilayers lization of new phases. For large elec- Scan rate was 50 mV s-‘. Reprinted from Weh-
containing the polypeptide alamethi- trodes, these processes depend on the m e w , K. R.: Wightman. R. M. Anal. Cham..
cin induces a current-time series show- nucleation and subsequent growth of 1985,57, 1989-93.

1394A - ANALYTICAL CHEMISTRY, VOL. 59, NO. 24, DECEMBER 15, 1987
may well have radii 1-10 nm), diffusion
is rapid so that the processes are con-
trolled by the kinetics of the surface
reactions and ohmic potential losses in
solution are very low. Indeed, one can
argue (see below) that the successful
operation of many electrochemical de-
vices depends on the formation of such
ensembles of microelectrodes (e.& the
oxidation of PbS04 to O-PbOl in the
lead acid battery).
When electrocrystallization pro-
ceeds via the nucleation and growth of
two-dimensional centers of monomo-
lecular height (as is observed in the va-
riety of anodic films or in the deposi-
tion of silver on perfect sin@-crystal
[loo] substrates), the processes can be
modeled as the growth of circular or
polygonized microelectrodes. The de-
posita are usually highly oriented so
that we observe electrode reactions in
defined crystallographic directions
(Le., lattice formation a t the edges of
layer planes of the lattice). In these
cases, one characteristic length scale of
the microelectrodes is of atomic dimen-
sions and consequently, the observable
rates of reaction are very high. The
steps propagate over the surface into
regions of the solution where the re-
agents have not been depleted so that,
in contrast to stationary “line” elec-
trodes, very high rates of steady-state
mass transfer can be achieved (several
hundred centimeters per second).
The modeling of mass transfer to ar-
rays of such edges (such as those gener-
I I

ated by emergent acrew dislocations on

surfaces of growing crystals) has in fact
been known for quite some time. Cata-
lytic reactions a t the edges of island
films and at “holes” have also been
studied (e&, hydrogen evolution at
ruthenium layers and the oxidation of Now the
CO adsorbed on Pt). Mass transport well-known
rates of oxygen to the edges of micro- spectroMonitoP
islands of adsorbed CO will be ex- detector series
tremely fast, because the islands are from Milton Roy
small and the reaction rate is high. includes a truly high performance,
Reinterpretation of the behavior low cost variable uvlvis detector -
of known systems. The application of THE SM3100. Signal to noise ratio is
microelectrodes also provides new op- excellent even at ,001 AUFS
portunities for simplifying and extend-
ing research into well-known systems. sensitivity. What’s more, the
For example, it becomes possible to in- SM3100 is priced well below other
vestigate the formation of single or, a t HPLC detectors of comparable quality.
most, a few growth centers.
These processes are illustrated in MILTON ROY’S
Figure 3 with the growth of a single EXPANDD SERVICE
droplet of mercury (cf. Figure I d and
analytical applications, Figure 4) and
NETWORK
of a single center of a-Pb02 (Figures 5 Now Milton Roy
and 6) on carbon microelectrodes. Fig- instrument
ure 3 shows that the reaction is kineti- service is
cally controlled in the initial stages and available in most
that i t is now feasible to make measure- major cities.
ments on such electrodes having char-
acteristic dimensions of -10 nm. This Write or call for more information;
is shown more clearly by the second P.O. BOX 10235, RlVlERA BEACH, FL 33419
example, which is a much slower reac- T E L 800-LDGHPLC in FL (305) 8446241
tion, where the time of nucleation is

ANALYTICAL CHEMISTRY, VOL. 59, NO. 24, DECEMBER 15. 1987 1395A
 ,
Plgure 5. Deposltlon of two growth centers of a-
mlcroelecVode.
The ~ l l u t w nmmposltlon: 0.1 M Pb(Ac)*

marked by the onset of the kinetically

onto an Epm diameter carbon
+ 1 M HAC; 7 = 400 mV: depDSlllon tlm, = 120 8 .
menta of the kinetic parameters of the
controlled growth even a t very high kinetic processes. The interpretation of
overpotentials. We see that in this ex- the higher moments of the reaction
ample, as in the voltage-gated trans- rates is highly diagnostic of the mecha-
membrane ion currents. the subse- nisms of the reactions; the measure-
quent essentially deterministic pro- ment and interpretation of electro-
cesses allow the observation of the chemical “noise” therefore promises to
initial stochastic events so that it be- be a further important area for the ap-
comes possible to investigate kinetics plication of microelectrodes to analyti-
Ouktandi luminance of the nucleative trigger eventa.
fmUVto R 7 Note that if the electrodes are suffi-
ciently small, it becomes possible to in-
cal and physical problems.
The application of microelectrodes
will undoubtedly lead to many novel
Hamamatsu flash mode Super-
Quiet Xenon Lamps provide a vestigate the probability distribution ways of investigating established sys-
minimum of 100 flashes! Arc of the reaction rates for ensembles of tems. For example, in addition to the
stability is 5 times higher, service experiments and hence the higher mo- investigation of low-temperatu ,-
life 10 times longer than con-
ventional lamps. Available in three
sizes for:
stroboscopes
Chromatographs

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Figure 6. Current-time ll.llol.lll

IvI udpoaitlon of a-FbOz onto an Epn mlcrc-
m~ a m - ~phomnm igea
CIRCLE 67 ON READER SERVICE CARD
I electrode.

1396 A ANALYTICAL CHEMISTRY, VOL. 59, NO. 24, DECEMBER 15, 1987
 INTRODUCING
A NEW CONCEPT IN SAMPLE PREPARATION

PREPARATION ACCESSORY
. . . .

-
- MILTON ROY
-
- LDC DlVlSlOF
At last here is a method h/ a\"-
.. . .~ purification of analy+i-l c l@Arw,m w material
regardless of the iilton oy introduce
SF!! TM - sample prepamion ac ssory. ,/
Now pure

2 Telex:35623
 Zen solvents, microelectrodes are al- I
ready being applied to the investiga-
tion of polymer-modified electrodes. Table 1. Connections between the lnvestlgatlonoi
The electrolysis of dispersion of parti- electrochemical systems using mlcroalectrodes and
cles affords new opportunities for other flelds oi research
probing and monitoring heterogeneous
catalysis and for devising new condi- Phaaea mawred wllh
tions for electrosyntheses. I t is possible mlcroolectr0dea Reievanl area8 ot resoarch
to make electrodes having a t least one

I
dimension comparable to or smaller Llquid (types 1 and 2) High field charge injection
than the Debye screening length (e.&, Scanning tunneling mlcroscopy
by using line or ring electrodes). Mea- Heterogeneous catalysis
surements with such electrodes should Charge transfer in sollds
Solid (type 3)
therefore provide a new tool for prob. Reactions in solids
ing double-layer structure. Charge Injection into insulators
Application to other areas of Ttmrmionlc emission
analytical and physical research Field emlssion microscopy
T h e investigation of novel systems Scannlng tunnellng microscopy
prompts a series of questions about the High field lonlzatlon (generation
connection between such electrochemi- of parent ions)
cal measurements and other estab- Highvacuum experiments
lished fields of analytical and physical Heterogeneous catalysis
research. Some of these connections
are evident from the advantage of mi-
croelectrode systems that have been
described. For example, Figure 4 illus- Other applications, or at least con- to studies in the liquid phase as to
trates the very high sensitivity that can nections to other applications such as those in the gas phase. We note that
be achieved using simple techniques. those listed in Table I, are perhaps not research in the “other areas” listed in
Very high S/N ratios are observed in so self-evident. The subject divisions in Table I usually has objectives (such as
stripping voltammetry experiments, Table I are naturally somewhat arbi- the imaging of surfaces, the generation
even a t the 100 nanomolar level. More- trary. For example, consideration of of parent ions for analytical mass spec-
over, these measurements can be made the conditions for field ion microscopy trometry, the charging of fuels or poly-
on very small samples. or high-field ionization are as relevant mers) that do not include the study of

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1398A ANALYTICAL CHEMISTRY, VOL. 59, NO. 24, DECEMBER 15, 1987
the interfacial charge transfer steps. mann. M. J. Phgs. Ckpm. 1985,89,3933.
However, the total description of the IOxidations at verv high positive poten-
processes must certainly include that
of the surface reactions. It should prove
possible to design many interesting
new experiments, for example, the ex-
amination of the structure of polarized
surfaces using high-vacuum techniques
such as RHEED (high vacuum rather
than ultra-high vacuum).
COnclUSiOn
In this REPORT we have pointed out Stanley Pons (left) is professor of
some of the approaches that may be chemistry at the Uniuersity of Utah.
used to predict the electrochemical re- His research interests include uibra-
sponse to finite electrode geometries, tional spectroelectrochemistry, appli-
and we have described some new direc- cotions of microelectrodes, and mech-
tions that electrochemistry is taking. anistic studies of electrochemical re-
The future value of microelectrodes actions. He has published more than
will lie in the continued application of 100 research articles in these areas.
the devices to new systems and the re-
investigation of systems with new goals Martin Fleischmann (right) is profes-
in mind. Applications in new environ- sor of chemistry at the Uniuersity of
ments will lead tosensorsand detectors Southampton. He is a Fellow of the
for practical use. ........., Royal Society and was recentlyaward-
Fleisrhmann, M.; Laaserre. F.; Robinson,J.:
Swan. D. J. Electroonal. Chem 19R4.177. ed the Palladium Medal from the
Suggesled Reading 97 EC and CE reactions at mirroeler- Electrochemical Society. He is the au-
General References and Theory trades) thor or coauthor of numerous publica-
Fleischmann, M.; Lasserre, F.; Robinson. J. tions in electrochemistry and electro-
Fleischmann. M.; Pons, S.; Rolison, J . Electroanal. Ckem. 1984, 177, 115.
D.; Schmidt, P. P. Ultromicroelectrodes; (ECE and DlSP reactions at microelec- analytical chemistry. His interests in-
Datatech Science: Morganton. N.C., July trodes) clude electrochemistry at the
1987. (Text treating fabrication of micro- Russell, A,; Repka, K.; Dibb1e.T.; Chorogh- molecular level, in situ X-ray diffrac-
electrodes. steadv- and non-steadv-state chian, J.;Smith. J.; Fleischmann, M.; Pitt. tion of electrode surfaces, a n d other in
theory at kieroeiectrades, and a ieneral C. H.; Pons, S. Anal. Ckem. 1986, 58,
review of applications) 2961. (Determination of heteroeeneous situ techniques applied to electro-
Bond, A. M.; Fleischmann, M.; Khoo, S.B.; electron transfer rates) chemistry.
Pons, S.;Robinson. J. Ind. J. Tech. 1986.
24,492. (Review on applications and the-
..-..,
Y.,,

Wightman, R. M. Anal. Ckem. 1981. 53,

1125 A. (Earlier review on microelec-
trodes)
Fleischmann, M.; Pons. S. J . Electroanol.
Chem. 1987,222,107. (A plicationofdis-
continuous integrals to &ks and rings)
Aoki, K.; Akimoto. K.; Tokuds, K.; Mat-
suds, H.; Osteryoung, J. J. Electroonol.
Chem. 1985,182,281. (Approximate solu- $ Chemical microsensors for field or lab.
tion to the chronopotentiometric re-
sponse at the disk) Sensing
Heinne. J. J. Elertroanal. Ckem. 1981, 124.
i 3 . (Simulations of the disk response)
Oldham, K. B. J. Electroanol. Chem. 1981,
122. 1. (Analysisof the disk response)
Szaho,A.;Cope,D.;Tallman,D.E.;Kovach,
P. M.; Wightman. R. M. J. Electroanal.
FREE CATALOG
Ckem. 19R7, 217. 417. (Treatment of
hemicylinder and line electrodes)
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most versatile research
available
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ANALYTICAL CHEMISTRY. VOL. 59, NO. 24, DECEMBER 15. 1987 - 1389A