Electrochimica Acta 51 (2006) 13761388

Reflections on the history of electrochemical

impedance spectroscopy
Digby D. Macdonald
Center for Electrochemical Science & Technology, Department of Materials Science and Engineering, Pennsylvania State University,
201 Steidle Building, University Park, PA 16802, USA

Received 23 June 2004; received in revised form 24 October 2004; accepted 8 February 2005
Available online 8 September 2005

Abstract

The history of electrochemical impedance spectroscopy (EIS) is briefly reviewed, starting with the foundations laid by Heaviside in the
late 19th century in the form of Linear Systems Theory (LST). Warburg apparently was the first to extend the concept of impedance to
electrochemical systems at the turn of the 19th century, when he derived the impedance function for a diffusional process that still bears
his name. Impedance spectroscopy was next employed extensively using reactive bridges to measure the capacitance of ideally polarizable
electrodes (mostly mercury), leading to the development of models for the electrified interface. However, it was the invention of the potentiostat
in the 1940s and the development of frequency response analyzers in the 1970s that led to the use of EIS in exploring electrochemical and
corrosion mechanisms, primarily because of their ability to probe electrochemical systems at very low frequencies. These inventions have led
to an explosion in the use of EIS for exploring a wide range of systems and processes, ranging from conduction in the solid and liquid states,
ionic and electronic conduction in polymers, heterogeneous reaction mechanisms, and the important phenomenon of passivity. It is evident that
the use of EIS in identifying reaction mechanisms makes use of pattern recognition, currently through inspection. It is argued that, in the future
development of EIS, reaction mechanism analysis (RMA) would be most efficiently done by using artificial neural networks operating in the
pattern recognition mode. This strategy would require the creation of libraries of reaction mechanisms for which the theoretical impedance
functions are known.
2005 Published by Elsevier Ltd.

Keywords: History; Electrochemical impedance spectroscopy; Linear Systems Theory

1. Introduction be gleaned from the system by linear electrical perturba-

Electrochemical impedance spectroscopy (EIS) is now
well established as a powerful tool for investigating the
mechanisms of electrochemical reactions, for measuring the
dielectric and transport properties of materials, for explor-
ing the properties of porous electrodes, and for investigating
passive surfaces [19]. The power of the technique arises
from: (i) it is a linear technique and hence the results are
readily interpreted in terms of Linear Systems Theory; (ii) if
measured over an infinite frequency range, the impedance
(or admittance) contains all of the information that can
E-mail address: ddm2@psu.edu.
tion/response techniques; (iii) the experimental efficiency
(amount of information transferred to the observer compared
to the amount produced by the experiment) is extraordinar-
ily high; (iv) the validity of the data is readily determined
using integral transform techniques (the KramersKronig
transforms) that are independent of the physical processes
involved.
In the authors opinion, the full potential of EIS has yet
to be realized, partly because it has been regarded as a spe-
cialty technique requiring expensive equipment, but more
importantly because the effective interpretation of EIS data
requires a level of mathematical skills that is not commonly
held by electrochemists and corrosion scientists. When the
necessary mathematical skills are present, the power of EIS is

0013-4686/$ see front matter 2005 Published by Elsevier Ltd.

doi:10.1016/j.electacta.2005.02.107
 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388
extraordinary, in that it is capable of differentiating between
closely related mechanisms. Because these skills often are not
present, EIS data are often interpreted in terms of electrical
equivalent circuits (EECs). However, EECs are analogs not
models, and hence the information that they can deliver on
the physico-electrochemical processes involved is very lim-
ited. In the authors opinion, EEC analysis, while providing a
termination point for a paper, is not the end-of-the-road; the
amount of information that is to be gleaned from a full mech-
anistic analysis far outweighs that which can be obtained by
simply fitting electrical equivalent circuits.
EIS, in its traditional form, is restricted to electrical pertur-
bation of physico-electrochemical systems, but the same prin-
ciples apply to any conjugate perturbation/response variables
in the linear regime. The concept of mechanical impedance is
well established in mechanics and acoustics. However, many
conjugate perturbation/response pairs exist and hence it is
possible to define impedances outside of the traditional are-
nas. For example, impedances have been defined for electro-
hydrodynamical systems [8], photo-electrochemical systems
[10], and many others. The photo-electrochemical impedance
data, at least, have been shown to correctly transform accord-
ing to the KramersKronig transforms, indicating that the
system satisfies the constraints of Linear Systems Theory
and, hence, that the transfer function (ratio of the complex
photo current to the complex light intensity) is, in fact, a valid
impedance [10].
This paper briefly reviews the history of electrochemical
impedance spectroscopy with the goal of identifying some
of the major transitions that have occurred in the develop-
ment of the subject. As with the development of every subject
in science and technology, the spark may have come from
the brilliant insight of one individual, but progress results
from the hard work of many people. EIS is no different.
This review is undoubtedly incomplete and almost certainly
reflects the authors prejudices and indeed may even deviate
from the views of many others who have also reflected upon
this extraordinary subject.
2. In the beginning
The foundations of EIS began in the time frame of 1880 to
about 1900 through the extraordinary work of Oliver Heav-
iside [11]. This eccentric Englishman has been described as
the most brilliant mathematician of his era, which is high
praise indeed, because his era (early period of development
of what we now know as mathematical physics) included
such luminaries as Albert Einstein, Whitehead, Schrodinger,
and many others. However, Heaviside had a very practical
problem to tackle, the development of telegraphy and elec-
trical circuit theory. He accomplished this task by making
two extraordinary

operator transformations, namely s = d/dt,
1/s = dt, where s is the Laplace frequency. These trans-
formations, which are the foundation of operational calcu-
lus, enable the conversion of integro-differential equations
1377
describing the flow of current in circuits containing resis-
tors, capacitors, and inductors into simple (simultaneous)
algebraic equations in the Laplace-transformed independent
and dependent variables (e.g., current and voltage). Once
the equations are solved for the dependent variable, inverse
transformation yields the corresponding quantities in tem-
poral space (see below). This process for solving integro-
differential equations was heavily criticized in the later part of
the 19th century and indeed was not proven mathematically
(i.e., rigorously) until the following century. Nevertheless,
the criticism was such that it caused Heaviside to quip [11]:
Shall I refuse my dinner because I do not fully understand . . .
digestion? The transformations presented above essentially
laid the foundation of the discipline of electrical engineer-
ing. As noted in Ref. [11], Heaviside is possibly best known
(outside of scientific circles) through Andrew Lloyd Webers
song in the musical Cats based on a poem by T.S. Elliot.
The song contains the lines Up, up, up past the Russell Hotel;
Up, up, up to the Heaviside Layer, . . .. The Heaviside Layer
referred to in the song is the ionosphere, which is responsi-
ble for the propagation of radio waves around the Earth, a
phenomenon that was first explained by Heaviside [11].
Returning now to Heaviside as the father of impedance
spectroscopy, we note that he defined the terms of
impedance, admittance, and reactance. In particular,
he defined the operational impedance as
V (s)
Z(s) = (1)
I(s)
where V (s) and I(s)
are the Laplace transforms of the voltage
and the current, respectively [12]. A subsequent Heaviside
transformation, s = j, transformed the Laplace domain to
the Fourier domain, as illustrated in Fig. 1.
Fig. 1 summarizes the transformations that are possible
between the three common spaces (temporal, Laplace, and
Fig. 1. Interrelationships between temporal space and the Laplace and
Fourier frequency spaces. Note that the transformation between temporal
space (TS) and Laplace space (LS) is affected by the Laplace transform
and that between TS and Fourier space (FS) by the Fourier transform. The
transform between LS and FS is affected by the Heaviside transform.
1378 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388

Fourier). For example, while we can only visualize processes Table 1

in temporal space, the equations describing those processes Impedances of common passive elements
are frequently more amenable to solution in frequency space Element Operational impedance Fourier impedance
(Laplace or Fourier). Thus, the strategy that is commonly Resistor R R
used is to transform the problem (equations) into Laplace Capacitor 1/sC 1/jC
space or into Fourier space (particularly those with peri- Inductor sL jL
odic boundary conditions), solve the equations, transform the
solutions back to real-time space, and then optimize a model transfer reaction of the type R O + ne under semi-infinite
on the experimental data. On the other hand, it is sometimes diffusion conditions, the Faradaic impedance, Zf (s), is given
more convenient to transform the data into Laplace or Fourier by [1]
space and then to derive the model parameters, rather than
determining the model parameters in temporal space. Trans- 1 1
Zf (s) = +
formation of the experimental data is readily accomplished (I/E)CO, CR FA(I/E)CO, CR
numerically,
e.g., for the transform into Laplace space one  

uses F (t) = 0 f (t) est dt, where f(t) are the data to be (I/CO )E,CR (I/CR )E,CO 1
+ (2)
transformed and the Laplace frequency is chosen via the sam- DO
1/2 1/2
DR s 1/2
pling theorem to be 2/T < s < 1/2 t, where T is the total time
of the data record and t is the reciprocal of the data acquisi- The reader will note that substituting Heavisides transform,
tion rate. A similar transformation can be made into Fourier s = j (steady-state conditions), and de Moivres Theorem,
space. Several examples of the use of these transformations which provides that j1/2 = (1 j)/21/2 , yields the series com-
for analyzing experimental data are available in the litera- bination of a charge transfer resistance and the classical
ture [1315]. At this point, it is important to recognize that Warburg impedance. Returning now to Eq. (2), it is evident
the impedance (Laplace or Fourier domains) is only defined that a plot of Zf (s) versus s1/2 yields a straight line, which
in the steady state; impedance has no basis in time depen- is comparable to the linear plots of Z () and Z () versus
dent systems, such as those undergoing pitting corrosion, for 1/2 , where is the angular frequency.
example.
It is also important to recognize that impedance (and
admittance and reactance) is only defined within Linear Sys- 3. Operational calculus
tems Theory (LST) [7,12]. LST imposes four important con-
straints on a system: (i) the response of the system must In order to adequately demonstrate Heavisides genius in
be described by linear (differential) equations and hence the developing operational calculus, it is instructional to con-
superposition principle must hold; (ii) the system must be sta- sider a specific example, that of a series/parallel combination
ble, i.e., upon removal of the perturbation the system should of resistors, capacitors, and inductors shown in Fig. 2. The
relax to its initial state; (iii) the system must be causal, that problem, then, is to calculate the currents in each loop after
is, the system must not produce a response before t = 0 (the the switch, S, is closed. Application of Kirchoffs laws and the
time at which the perturbation is applied); (iv) the impedance definitions shown in Table 1 yields the following set of simul-
must be finite (physical systems cannot contain singularities taneous integro-differential equations that must be solved for
in the evolution of their properties). The constraints imposed the loop currents, I1 , I2 , and I3 , as shown in Fig. 2 [12]:
by LST in EIS are not widely recognized, at least judging     
by the lack of effort on the part of researchers to assure d 1 d
R1 + L1 + dt I1 + L1 I2 = V0 (3)
that the constraints identified above are satisfied. As will be dt C1 dt
shown later in this paper, compliance with the constraints can
be readily tested via the KramersKronig transforms or by
demonstrating that the frequency dispersion is accounted for
by a minimum phase electrical equivalent circuit comprising
resistors, capacitors, and inductors. Care must be employed
in using this latter method, because an EEC containing a suf-
ficient number of elements in the appropriate combination
can be made to closely fit an impedance locus.
The operational impedances of common passive circuit
elements are listed in Table 1 together with their Fourier
domain counterparts. Thus, for a purely capacitive interface
(an ideally polarizable electrode), a plot of Z(s) versus 1/s
will yield a straight line of slope 1/C. Likewise, an induc-
tive interface yields a linear plot of Z(s) versus s of slope L. Fig. 2. Multi-loop electrical circuit used to illustrate the application of oper-
The impedance of a resistor is independent of s. For a charge ational calculus in analyzing transients.
 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388 1379

    
d 1 d Fourier domain (complex) impedance directly. In any event,
L1 I1 + R2 + dt + (L1 + L2 ) I2
dt C2 dt the Fourier domain impedance has become the norm in EIS.
  The Fourier domain impedance is expressed as a complex
d
+ L2 I3 = 0 (4) number
dt
Z(j) = Z jZ (9)
    
d 1 d where Z is the real component 
and Z is the imaginary com-
L2 I2 + R3 + dt + (L2 + L3 ) I3 = 0
dt C3 dt ponent. The parameter j is 1. The impedance may be
(5) expressed in an alternate form as

Sets of integro-differential equations of this type are difficult Z(j) = |Z| ej (10)
to solve, even in the age of computers, and were essentially
where |Z| is the magnitude of the impedance
impossible to solve in the late 19th century.

Using Heavisides

transformations of s = d/dt and 1/s = dt, and assuming that
the circuit is subjected to a step change in the voltage (i.e., |Z| = (Z )2 + (Z )2 (11)
closing of the switch), this set of equations can be converted and is the phase angle
into a set of simultaneous linear equations in the Laplace
transforms of the dependent and independent variables as Z
tanf = (12)
  Z
1 V0
R1 + sL1 + I1 [sL1 ] I2 = (6) Eqs. (9) and (10) form the basis of the two common meth-
sC1 s
ods of presenting impedance data, Z versus Z [Nyquist
  diagram (Eq. (9)) and log |Z| versus log() (Bode plane (Eq.
1 (10)))]. Both should be employed, because they display dif-
[sL1 ] I1 + R2 + + s(L1 + L2 ) I2 [sL2 ] I3 = 0
sC2 ferent features of the data.
(7) It would be inappropriate to end this section without com-
menting further on the extraordinary potential impact that
  Heavisides operational calculus has had upon another aspect
1 of electrochemistry. This is best illustrated by considering
[sL2 ] I2 + R3 +
+ s(L2 + L3 ) I3 = 0 (8)
sC3 the response of a quasi-reversible charge transfer reaction to
a step change in potential (i.e., under potentiostatic polariza-
These equations are readily solved (by using Cramers rule, tion) [1].
for example) to yield the Laplace transforms of the loop cur-
rents, I1 , I2 , and I3 , as a function of the Laplace frequency, O + ne R (13)
kf ,kb
s (chosen according to the sampling theorem). The currents
may then be inversely transformed into the time domain to In the time domain, the transient in the current is given by
yield the result that we seek. This simple example illustrates
the essence of operational calculus, and it is not difficult to i = nF (kf CO
b
kb CR
b
) exp(Q2 t) erfc(Qt 1/2 ) (14)
see that it revolutionized the analysis of complicated elec- where
trical circuits (and other linear systems, too) and led to the
kf kb
development of the discipline that we now know as electrical Q= 1/2
+ 1/2
(15)
engineering, as noted above. Finally, we note that the steady- DO DR
state currents in the Fourier domain are simple obtained by
and DO and DR are the diffusivities of O and R, respectively.
making the substitution, s = j.
Eq. (14) is difficult to handle and is usually done so only
Although Zf (s) is conceptually as powerful as its Fourier
by approximation [1]. However, in the Laplace frequency
space counterpart, Zf (j), and is significantly simpler math-
domain, the transient is described by
ematically, the operational impedance never became popular
in electrochemistry and corrosion science. However, work nF Q
= (16)
by Sierra-Alcazar et al. [15] and by Pilla [13,14] in the is1/2 (kf CO
b k C b ) + [1/(k C b k C b )]s1/2
b R f O b R
1970s demonstrated the great power of the technique in ana-
lyzing experimental data, but the author is of the opinion where the i(t) data are transformed into the Laplace domain
that this domain did not catch on because little commercial by
potential existed for instrument manufacturers. On the other 
hand, transformation into the Fourier domain from the time i = i(t) est dt (17)
0
domain is more difficult and it is often more efficient to use
an instrument to apply a sinusoidal perturbation of voltage Thus, a plot of the left side of Eq. (16) versus s1/2 yields a
or current directly to the system under study to obtain the straight line from which the rate constants can be obtained.
1380 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388

This is but one example of many where considerable advan-

tage accrues from working in the s-plane (Heaviside domain),
rather than in the time domain. These advantages are termed
potential, because, despite the obvious advantages (Ref. [1]
and citations therein), the method has not been extensively
used (although see the work of Pilla [13,14] and Sierra-
Alcazar et al. [15]).

4. Warburg and the diffusional impedance

In 1899, Warburg [16] published a remarkable paper on the

impedance of diffusional transport of an electroactive species
to an electrode surface. What makes this paper remarkable
is that the theory was developed before the theoretical basis
of electrode kinetics had evolved. Warburg was saved in this
respect by the boundary condition at x = 0 (electrode surface)
that sets the concentration of the electroactive species equal
to zero (complete mass transport control). Nevertheless, with Fig. 3. Electrochemical impedance in the case of the diffusion of species
respect to reaction (13), Warburg was able to solve the trans- under semi-infinite diffusion conditions (broken line) and restricted diffusion
port (diffusion) equations to yield an impedance function, in conditions (finite Nernst diffusion layer thickness), from [8] (frequency in
kilo Hertz).
its modern form, as
j 0, Z(j) Rct (kf N /DO ), but as , Z(j) Rct .
Z(j) = 1/2 (18)
1/2 The impedance is of a form that is often mistaken for a
depressed semi-circle (see below).
where is given by
(I/CO )E,CR
= 1/2 1/2
FADO 2 (I/E)CO ,CR 5. Porous electrodes

(I/CR )E,CO
+ 1/2 1/2
(19)
FADO 2 (I/E)CO ,CR
DO and DR are the diffusivities of species O and R,
respectively, and A is the electrode area. The differentials
(I/CO )E,CR , (I/CR )E,CO , and (I/E)CO ,CR are read-
ily evaluated from the stoichiometry of the reaction and the
kinetic orders with respect to CO and CR . The reader will note
that Eq. (18) is obtained directly from Eq. (2) with s = j, as
previously noted.
The impedance expressed by Eq. (18) is perhaps the most
famous in electrochemistry, partly because it is the oldest, but
more likely because it is frequently observed. However, there
are two issues related to the Warburg impedance that need to
be clearly identified. The first is that Eq. (18) applies strictly
to semi-infinite diffusion to a planar surface. If the system is
not quiescent, the impedance assumes a different form [8]
 
kf th(N j/DO ) kb th(N j/DR )
Z(j) = Rct 1 + + sion control in a semi-infinite pore yields a phase angle of
(jDO )1/2 (jDR )1/2
(20)
where Rct is the charge transfer resistance, th the hyper-
bolic tangent operator, N the ideal Nernst diffusion layer
thickness, and kf and kb are rate constants for the reac-
tion in the forward and reverse directions. A comparison
of Eqs. (18) and (20) is shown in Fig. 3. One notes that as
The theory of porous electrodes has been developed exten-
sively, primarily through the elegant work on deLevie [17]
in the 1960s. Briefly, the impedance of a semi-infinite, right
cylindrical pore embedded in an electronically conducting
phase of zero resistivity is written as
Zpore = (R |Z|)1/2 ej/2 (21)
where Z and are the impedance and the phase angle, respec-
tively, for the interfacial impedance at a (wall) plane surface
and R is the resistance per unit length down the pore. The
reader will note that the phase angle for the pore is half of
that for the planar case. Thus, a porous electrode with purely
capacitive walls (e.g., platinum black) yields a phase angle
of 45 (/4), even though a planar Pt surface yields a phase
angle of 78 for the case shown in Fig. 4 (the phase angle is
not /2, because the surface of platinum is not purely capaci-
tive). Thus, the porous system with capacitive walls is readily
mistaken for diffusion to a plane surface [Eq. (18)]. Diffu-
/8 (22.5 ).
Pore shape also has an important impact on the impedance
locus. Thus, with reference to Fig. 5, which shows calculated
impedance loci for pores of different shape having capaci-
tive walls [18], we see that, for the right circular pore (#1),
the impedance locus at high frequency displays a slope of
/4, but as the frequency is lowered the locus turns upwards
 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388
Fig. 4. (a and b) Impedance loci for planar and porous platinum electrodes
in 1 M KCl (after deLevie [17]).
towards capacitive behavior. This is due to the frequency
dependence of the penetration depth of the ac wave, as given
by: penetration depth (PD) = (Z/R)1/2 . Thus, as the frequency
is lowered, the impedance increases and hence the penetra-
tion depth also increases, so that at high frequencies where
L (pore depth)  PD, the pore appears to be semi-infinite
and a /4 phase angle is observed. At sufficiently low fre-
quency, however, PD  L and the electrode surface appears
to be quasi-planar, so that the impedance loci begin to take on
a form that is characteristic of a capacitor. Other pore shapes
give rise to more complicated impedance loci; for example,
in the case of a quasi-spherical pore (#4), the impedance loci
could easily be mistaken for that of diffusion to a plane sur-
Fig. 5. Calculated impedance for various shapes of a single pore assuming
a capacitive interface (after Kaiser et al. [18]).
1381
face under forced convection conditions, particularly if the
data were not measured to a sufficiently low frequency to
detect the upturn of the locus.
The material presented above illustrates some of the intri-
cacies of the impedance of porous systems. Not surprisingly,
porous systems are often misidentified, due to the dependence
of the phase angle on the geometry of the pores and on the
nature of the electrochemical process (diffusion, convection,
and charge transfer control) and the electrical properties of the
interface. In any event, the reader will note that the interpre-
tation of impedance data almost always begins with pattern
recognition, in which the observed locus is associated with
some mechanistic/morphological feature that has been estab-
lished by theory. This theme of pattern recognition will be
discussed in greater depth later in this paper.
6. Models and analogs
As in all branches of science, experimental data are inter-
preted in terms of models and EIS is no exception. Notwith-
standing the fact that models are simply our perception of
reality, and that our perception is never complete, and hence
that all models are eventually incomplete, the tools used to
interpret impedance data fall into two classes: (i) analogs
and (ii) physical models. Analogs, which almost always take
the form of electrical equivalent circuits, do not pretend to
describe the physico-electrochemical properties of the sys-
tem, but simply reproduce the properties. On the other hand,
physical models aim at not only reproducing the phenomenon
of interest [in this case, Z(j)], but of also accounting for
the mechanism of the processes occurring at the interface
in terms of physico-electrochemically valid concepts. In the
authors opinion, the ultimate goal of EIS is to characterize
the mechanism of the charge transfer reaction and hence the
mere development of an analog (which is now done by var-
ious computer programs) represents an incomplete analysis
of the data.
6.1. Electrical analogs
It may be argued that electrical analogs sprang from the
elegant work of Heaviside, but the earliest use of analogs
to explain electrochemical data appear to be due to Dolin
and Ershler [19] in 1940 and by Randles [20] in 1947. The
Randles equivalent circuit [Fig. 6(a)] provided a surprisingly
effective simulation of the impedance characteristics of a fast
charge transfer reaction at a planar electrode [Fig. 6(b)] and
has been used extensively since its introduction nearly six
decades ago. Because an explicit expression exists for the
Warburg impedance [Eq. (18)], it is possible, in this case, to
relate the electrical elements to chemical parameters. How-
ever, it is also important to note that the Warburg impedance
has no simple electrical analog, although a constant phase
element emulating Warburg impedance (phase angle = /4)
can be devised as an electrical transmission line.
1382 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388
Fig. 6. (a and b) Randles equivalent circuit for a charge transfer reaction at an
electrode surface. Re is the uncompensated resistance in the solution between
the electrode surface and the reference electrode, Rct is the charge transfer
resistance, and Cd is the double layer capacitance. = kf / DO + kb / DR .
As noted above, computer algorithms are now available
that will assign an electrical analog to account for almost
any impedance data provided that the locus is restricted
to the right side of the complex plane. The analogs are
almost always assigned without regard to the physics of
the system. Indeed, given enough parallel R/C/L (resis-
tive/capacitive/inductive) elements, almost any impedance
locus in the right side of the complex plane can be mod-
eled, but the reader should not mistake that accomplishment
with discerning the mechanism of the interfacial process.
Furthermore, because of the unrestricted nature of fitting
experimental impedance data with EECs, with little regard
to the physics of the system, the success of a fit cannot be
used to demonstrate compliance with Linear Systems The-
ory, as noted above, although this is often claimed to be the
case. There is also a tendency to declare the first analog that
is found to account for the impedance data to be the model
for the interface (this is also an important issue in mechanis-
tic analysis, as indicated later in this paper). In fact, within
the accuracy of the data, there may be many analogs (or
models) that represent the data equally well. The analog
(model) could only be identified using data of infinite accu-
racy measured over an infinite bandwidth. Clearly, this is not
an achievable state.
Part of the problem in assigning electrical analogs is that
the analogs generated by the algorithms are frequently unre-
stricted by the physics of the system. Thus, if it is known
a priori that a porous corrosion product film covers the sur-
face, then it might be expected that the electrical analog would
contain elements that could be identified with the pores in a
geometric sense. This is seldom, if ever, the case, and while
the analog may produce plots that are impressive in their fit
to the experimental data, they do little to advance the science.
There is one form of electrical analog that does satisfy the
need for conformity with the physics of the system, and that
is the electrical transmission line (TL). For example, in the
TL analog for a porous electrode, a transmission line is used
to closely simulate the actual physics of each pore. Indeed,
the impedance loci plotted in Fig. 5 for pores of different
shapes were derived from TL analogs. TLs originated from
Heaviside and Lord Kelvin in their work on telegraphy and in
particular in the development of the first trans-Atlantic cable.
Analysis of the properties of transmission lines became prac-
tical only as the result of Heavisides operational calculus,
and the same calculus is now used to analyze TL analogs of
electrochemical systems.
The first use of TLs in analyzing electrochemical systems
apparently occurred in 1905 in the simulation of membranes,
but it was deLevie who popularized TLs for simulating rough
and porous electrodes [17], as noted above. In more recent
times, the author and his colleagues have employed trans-
mission lines to simulate battery electrodes, corroding rebar
in concrete, electro-catalysts, the corrosion of carbon steel
in high temperature aqueous systems, and super-capacitors.
Indeed, Conway [21] has recently published a monograph
on super capacitors that is based extensively on transmission
line theory.
The method employed by deLevie [17], and that was sub-
sequently adopted by the present author and his colleagues
[22,23] to analyze the variety of systems referred to above,
was to discretize the transmission line into infinitesimally
small elements, apply Kirchoffs and Ohms laws and then
integrate along the line to obtain the impedance. An alterna-
tive method is to use Kirchoffs and Ohms laws directly
to derive equations for the loop currents in each discrete
segment. This is the approach taken by the author in develop-
ing active pore distribution spectroscopy (APDS), in which
EIS is used to ascertain evolution of the number of active
pores in a porous Ni(OH)2 /NiOOH battery electrode upon
charge/discharge cycling [23]. The pore geometry and trans-
mission line model assumed in this study are shown in the
upper diagrams of Fig. 7. The model recognizes that initia-
tion of a new phase [Ni(OH)2 upon discharging or NiOOH
upon charging] begins at the pore mouth and that the specific
impedance of the Ni(OH)2 /Ni interface is very much larger
than is that for NiOOH/Ni, as determined by experiment [23].
For this reason, it was necessary to scale the increments down
the pore as a geometric series. The electrode model was then
developed as an ensemble of parallel pores with the location
of the transition from Ni(OH)2 to NiOOH being distributed as
 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388 1383

Fig. 7. Transmission line model for a single pore in a porous Ni(OH)2 /NiOOH battery electrode. Physical model of a pore (pore geometry) (a), non-uniform
electrical transmission line representation of a pore (non-uniform, discretized transmission line) (b), and pore utilization as a function of cycle number (the
distribution in pores) (c) upon charge cycling the electrode in 31% KOH as determined by optimization of the model on experimental impedance data (adapted
from Ref. [23]).

a 2 distribution. Fitting of experimental data showed that, as
the electrode was charge cycled, more pores became active,
more deeper pores became active (Fig. 7c), and the charge
capacity of the electrode increased, at least over the first 596
cycles. This example illustrates the power of EIS, when cou-
pled with an electrical analog that reasonably describes the
physico-electrochemical properties of the system, to provide
detailed information on pore structure and dynamics.
One EEC that is of particular interest is the constant
phase element (CPE), which was briefly discussed above.
A CPE is described mathematically as ZCPE = A/(j) ,
where A and are empirical constants. The reader will note,
however, that when is 1, 0, and 1, the CPE corresponds
to a capacitor, resistor, and inductor, respectively. Notwith-
standing the fact that CPEs have been shown analytically
[24] to transform correctly according to the KramersKronig
transforms, provided their loci are restricted to the right side
of the complex plane, they are almost always used in an ad
hoc manner to cause an EEC to fit the experimental data.
In this sense, they are in conflict with Einsteins famous
admonishment against the introduction of ad hoc factors
simply to make a model or theory account for experimental
observation. For example, CPEs are often invoked to
account for depressed semi-circles (impedance loci in
which the center of the semi-circle in the Nyquist plane is
located below the real axis), following similar applications
in dielectric relaxation studies. Without viable physical
underpinnings (e.g., a distribution in relaxation time), the
use of CPEs for this purpose is non-sensical and should be
discouraged.
1384 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388

6.2. Reaction models Table 2

Summary of mechanisms considered for the electro-dissolution of aluminum
in concentrated KOH solution [25]
Since the introduction of the electronic potentiostat in the
1940s and the development of frequency response analyz- Mechanism Reaction scheme
k1
ers (FRAs) in the 1970s, it has been possible to measure (I) Irreversible coupled Al(SS) + OH Al(OH)ads + e
impedance data at frequencies to below 1 mHz, provided that dissolution/hydrogen k2
Al(OH)ads + OH Al(OH)2, ads + e
the system is sufficiently stable [1,4,8,9]. Among the pro- ion-atom evolution k3
Al(OH)2, ads + OH Al(OH)3, ads + e
cesses that have been probed are the mechanisms of many k4
Al(OH)3, ads + OH Al(OH)4
electrochemical processes and reactions, including the hydro- k5
gen electrode reaction (HER), the oxygen electrode reaction SS + H2 O + e H + OH
k6
(OER), metal dissolution, and passivity, as well as various H + H2 O + e H2 + OH + SS
coupled processes, such as corrosion. In particular, the group k1
(II) Coupled Al(SS) + OH Al(OH) + e
led by Epelboin in Paris [8] made major contributions to dissolution/H-atom k2
Al(OH) + OH Al(OH)2 + e
reaction mechanism analysis (RMA) using EIS, and their recombination k3
work still provides the standard against which that of oth- Al(OH)2 + OH Al(OH)3 + e
k4
ers is judged. Space does not permit a detailed discussion Al(OH)3 + OH Al(OH)4 + SS
k5
here of all of the contributions made by various workers in SS + H2 O + e H + OH
k6
the field; instead, I select the corrosion/electro-dissolution of H + HH2 + 2SS
aluminum in concentrated KOH as an example of RMA [25] k1
(Table 2). (III) Autocatalytic Al(SS) + OH Al(OH) + e
(I)/hydrogen k2
Briefly, each model described in Table 2 couples disso- Al(OH) + OH Al(OH) 2+e

ion-atom evolution k
Al(OH)2 + OH Al(OH)3 + e
3
lution with hydrogen evolution through the competition for
k4
sites on the surface and some of the candidate models invoke Al(OH)3 + OH Al(OH)4 + SS
autocatalysis in the aluminum dissolution reaction. In any kc
Al(OH)4 + AlAl(OH) + Al(OH)3 + e
event, impedance spectra were derived for each mechanism k5
SS + H2 O + e H + OH
with parameter values being selected by optimization of the k
H + H2 O + e H2 + OH + 2SS
6
models on the experimental data. Some of the experimental
k1
data used in this study are shown on the left side of Fig. 8. (IV) Autocatalytic Al(SS) + OH Al(OH) + e
Calculated impedance spectra for Mechanism I are shown on (I)/H-atom k2
Al(OH) + OH Al(OH)2 + e
the right side. recombination k3
Al(OH)2 + OH Al(OH)3 + e
I use this example, because it does what most studies k4
Al(OH)3 + OH Al(OH)4 + SS
of this type do not do; it considered alternate mechanisms kc
Al(OH)4 + AlAl(OH) + Al(OH)3 + e
(Table 2) and compared the results obtained from optimiza- k5
tion of all of the models on the experimental data. The results SS + H2 O + e H + OH
k6
are shown schematically in Table 3 and comparison between H + HH2 + 2SS
the experimental and model spectra indicates that Mechanism k1
(V) Autocatalytic Al(SS) + OH Al(OH) + e
I provides the best account of the data. (II)/H-atom k2
Al(OH) + OH Al(OH)2 + e
The reader will note, again, that the process of selecting recombination k3
the best mechanism is essentially one of pattern recognition, Al(OH)2 + OH Al(OH)3 + e
k4
in which the closest fit is normally selected by inspection, Al(OH)3 + OH Al(OH)4 + SS
kc
although statistical methods may be used. Nevertheless, the Al(OH)4 + AlAl(OH) + Al(OH)3 + e
k5
great weakness of mechanistic analysis is the lack of a reliable SS + H2 O + e H + OH
method of pattern recognition that takes account of features of k6
H + HH2 + 2SS
a large number of possible mechanisms. The author believes k1
that this problem is ideally suited to artificial neural network (VI) Autocatalytic Al(SS) + OH Al(OH) + e
(II)/hydrogen k2
(ANN) technology, but this will require the establishment of Al(OH) + OH Al(OH)2 + e
ion-atom evolution k3
a substantial library of reaction mechanisms. Al(OH)2 + OH Al(OH)3 + e
k4
Al(OH)3 + OH Al(OH)4 + SS
kc
Al(OH)4 + AlAl(OH) + Al(OH)3 + e
7. KramersKronig transforms k5
SS + H2 O + e H + OH
k6
H + H2 O + e H2 + OH + 2SS
One of the great advantages of EIS is that an independent
check of the validity of impedance data (that is, compliance SS represents a base surface site, i.e., Al(SS).
with the constraints of LST) is possible through the use of
the KramersKronig transforms. The KK transforms were
originally developed in the 1920s [26,27] to treat optical data,
 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388 1385

but they were not applied to electrochemical and corrosion to-real axis transformations, while Eq. (24) yields the real
problems until many years later [9,2835]. axis-to-imaginary axis transform, as depicted in Fig. 9.
The KK transforms stem from Cauchys theorem that By way of illustration, KK transforms of the impedance
provides the mathematical basis for causality, which is not data shown in Fig. 10 for an aluminum alloy (Al0.2 Ga0.1
only one of the constraints of LST but has been the mainstay In0.1 Tl) in KOH solution at two different potentials are
of scientific philosophy since the ancient Greeks. In their displayed in the same figure [32]. Clearly, the transforms fail
most popular form, the transforms are written as at low frequency for a voltage of 1404 mV (Hg/HgO), and
 this failure can be traced to the impedance locus protruding
  2 xZ (x) Z ()
Z () = Z () + dx (22) into the left side of the complex plane, signifying instability
0 x2 2 and failure of causality (note that stability and causality are

2 (/x)Z (x) Z () two of the constraints of LST). On the other hand, if only
Z () = Z (0) + dx (23) minimal intrusion occurs [right plots in Fig. 10, 1430 mV
0 x2 2
(Hg/HgO)], the transforms are successful. However, as shown
and below, analysis of the data in the impedance plane alone can
 be very misleading and may have led to the rejection of data
2 Z (x) Z ()
Z () = dx (24) unjustly.
0 x2 2
The KK transforms are clearly sensitive to the intrusion
where is the frequency of transform, x the frequency of inte- of the impedance locus into the left side (ostensibly violation
gration, and Z and Z are the real and imaginary components of causality, although see below) and it has been shown else-
of the impedance. Eqs. (22) and (23) provide imaginary axis- where that they are sensitive to drift in the system (stability)

Fig. 8. Experimental and simulated impedance spectra for Al in 4 M KOH at 25 C as a function of applied potential (after Macdonald et al. [25]). The simulated
spectra were derived for Mechanism I, Table 2.
1386 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388

Table 3
Summary of model spectra and experimental data for Al in 4 M KOH at 25 C (after Macdonald et al. [25])

[31]. They are not particularly sensitive to violation of the lin-

Fig. 9. Illustration of the process of KramersKronig transformation of
experimental impedance data.
earity condition [31]. A major question existed in the early
1990s concerning why impedance spectra that pass through
all four quadrants of the Nyquist plane can be predicted by
mechanisms that ostensibly satisfy all four constraints of
LST, and yet the KK transforms fail as soon as the locus pen-
etrates the left side of the complex plane. Noting that there is
no analog in passive circuit theory for a negative resistance,
it was originally believed that the KK transforms might be
too restrictive to judge all EIS data and hence their use should
be restricted to judging the viability of data in the right side
of the complex plane only. However, this issue was resolved
by Gabrielli et al. [35] in 1993, who, using impedance and
admittance data generated via analogs without restriction to
the signs of the elements, essentially pointed out that the anal-
ysis can be done in either the impedance or the admittance
Nyquist planes and that those systems whose loci intrude into
the left side of the impedance plane may transform correctly
in the admittance plane. The reason for this is deceptively sim-
ple; the impedance is simple a complex number that describes
the response of a linear system that satisfies the constraints
of LST and there is nothing in the KK relations that causes
one to select either the impedance or admittance plane. Thus,
 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388
Fig. 10. Impedance spectra and KK transforms for Al Alloy No. 21 in 4 M KOH at 25 C and at E = 1404 mV vs. Hg/HgO (left frames) and at 1430 mV
vs. Hg/HgO (right frames) (after Macdonald and Urquidi-Macdonald [28,29]).
the application of the KK transforms to judge the quality of
immittance data must consider the complementary plane if
the locus protrudes into the left side.
8. A glimpse into the future
At various places in this paper, it is emphasized that the
interpretation of EIS data is basically a pattern recogni-
tion problem, in which a mechanism or analog (e.g., an
EEC) is sought that reproduces the loci of the experimen-
tal data as a function of all accessible independent variables
using a single set of model parameters, as determined by
optimization of the model on the experimental data. Noting
that all experimental data are inaccurate, to one extent or
another, and that models are only our perceptions of real-
ity, and hence are incomplete, the model does not exist and,
indeed, many models may be found to represent the exper-
imental observations equally well. Additional experiments
(frequently employing non-electrochemical techniques) can
often exclude some candidates, but, nevertheless, the remain-
ing possibilities are frequently many and commonly differ
only in very subtle ways (e.g., in the case of the mecha-
1387
nisms examined in Tables 2 and 3). Thus, the challenge of
the future is to devise methods for differentiating between
candidate mechanisms that differ only in ever increasingly
subtle detail.
In the opinion of the author, the analysis of EIS data
would be greatly aided by the development of a library of
reaction mechanisms and by the development of artificial
neural network pattern recognition algorithms incorporating
fuzzy logic that could be used to scan the library and rec-
ognize the best candidate mechanisms. The ANN would be
subject to appropriate constraints, based upon the physico-
electrochemical properties of the system, as would be the
experimental data in their compliance with LST. Further-
more, all small amplitude techniques could be embodied in
the project, recognizing the agility with which transformation
between temporal space and Laplace and Fourier frequency
space may be accomplished. In a sense, this would become
electrochemistrys genome project, which would require
a long-term commitment to realize its full potential. How-
ever, in the opinion of the author, the potential return on the
investment would be enormous, given the increasing demand
of technological advancement on an understanding of reac-
tion mechanisms.
1388 D.D. Macdonald / Electrochimica Acta 51 (2006) 13761388
9. Summary and conclusions
A brief history of electrochemical impedance spec-
troscopy has been presented, starting with the foundations
laid in the latter part of the 19th century by Oliver Heaviside.
Heaviside not only defined the terms impedance, admit-
tance, and reactance, but he also invented operational
calculus and defined the operational impedance. Although
the operational impedance, which is defined in the Laplace
plane, is not used extensively in electrochemistry, it is a pow-
erful concept that is somewhat simpler to manipulate and
apply than is the more common Fourier domain (complex)
impedance.
Extension of the concept of impedance to electrochemi-
cal systems was apparently first reported by Warburg with
his celebrated derivation of the diffusional impedance. How-
ever, the most extensive use of impedance techniques in the
early part of the 20th century was the measurement of elec-
trode capacitance using reactive bridges at relatively high
frequencies (>500 Hz) in the study of the electrified inter-
face. These studies yielded a wealth of information that was
instrumental in defining the structure of the double layer, but
reactive bridges could not access the low frequency region
(sub-kilo Hertz) where relaxations involving charge transfer
reactions, particularly those that involved adsorbed interme-
diates in reactions, could be detected.
This situation changed dramatically with the inven-
tion of the electronic potentiostat in the early 1940s and
with the introduction of frequency response analyzers three
decades later. With these instruments, it has been possible
to probe electrochemical interfaces at frequencies into the
sub-milliHertz range, where relaxations involving surface
intermediates are readily detected. This low frequency capa-
bility has led to an explosion of application of EIS in the
study of electrochemical and corrosion mechanisms, to the
point that it is now the preferred technique for mechanistic
studies. However, mechanistic analysis is essentially an exer-
cise in pattern recognition, with recognition being performed
by inspection. The author argues that this function would
be better performed using artificial neural networks coupled
with extensive libraries of reaction mechanisms.
Acknowledgment
The author gratefully acknowledges the support of this
work by the US Department of Energy through Grants DE-
FG02-01ER15238 and DE-FG07-01ER62515.
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