Electrochimica Acta 56 (2011) 8005–8013

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Mechanism and equivalent circuits in electrochemical impedance spectroscopy

David A. Harrington a,∗ , P. van den Driessche b
a
Department of Chemistry, University of Victoria, Box 3065, Victoria, British Columbia V8W 3V6, Canada
b
Department of Mathematics and Statistics, University of Victoria, Victoria, British Columbia V8W 3R4, Canada

a r t i c l e i n f o a b s t r a c t

Article history: The utility and limitations of using equivalent circuits to analyse electrochemical impedance spectroscopy
Received 19 July 2010 (EIS) data for electrochemical reaction mechanisms are reviewed. The difficulty of assigning physical
Received in revised form 17 January 2011 meaning to elements is discussed. The utility of equivalent circuits as measurement models is empha-
Accepted 18 January 2011
sized, and ways to use them to find mechanistic information are discussed. The rules about which
Available online 26 January 2011
mechanisms can show inductive behavior are of interest, since this is a visually obvious feature. We
review our previous rules for mechanisms that can show inductive behavior, and show that inductive
Keywords:
behavior is more common for mechanisms with two adsorbed species. We discuss two variations of a
Equivalent circuit
Mechanism
simple cycle mechanism (A → B → C → A) in more detail.
Charge-transfer resistance The interpretation of the charge-transfer resistance and the polarization resistance has some subtleties.
Polarization resistance Transfer coefficients extracted from Tafel plots of steady-state current–potential measurments are often
Inductive used to determine where in the mechanism the rate-determining step is. We show that transfer coeffi-
Impedance cients from Tafel plots of the charge-transfer resistance do not have the same mechanistic significance.
EIS The polarization resistance is simply related to the slope of the polarization curve. We discuss the validity
of this relationship and its utility in interpreting spectra.
© 2011 Elsevier Ltd. All rights reserved.

1. Introduction squares fitting of data to circuits is likely the main reason for this.
However, the interpretation of the elements, and the utility of
Electrochemical impedance spectroscopy (EIS) is widely used equivalent circuits in deducing mechanistic information are con-
as a mechanistic tool, i.e., as a technique to deduce the constituent troversial. There appears to be a dichotomy in the field: some study
elementary reaction steps of an overall electrochemical reaction, mechanisms and do not use equivalent circuits; others use equiv-
and to extract the numerical values of the rate constants and other alent circuits but do not interpret the parameters mechanistically.
kinetic parameters characterizing those reaction steps. It is possi- There is a middle ground in which fitting to equivalent circuits
ble to proceed toward this goal without using equivalent circuits: is a first step in mechanistic analysis, and this forms the topic of
a mechanism is proposed, the impedance corresponding to this this paper. We review here some key issues about interpretation
mechanism is derived as a function of the kinetic parameters, and of equivalent circuit elements for reaction mechanisms. Many of
the data are then compared with this prediction. The way to derive these are known to the practitioners in the field, but they have not
the impedances for a given mechanism has been known from the all become well known to the average EIS user and are the cause of
earliest days of EIS, and has been reviewed, e.g., [1,2]. It has been common misconceptions. Since the focus is on interpretation, it is
generalized for arbitrary mechanistic schemes [3–6], and software outside the scope of this article to discuss the fitting process at the
has been developed for automation, e.g., CASIDIE [7], PIRoDE [8,9]. level of data manipulation; the assumption is that the reader under-
The comparison with the data may be visual, through comparison stands how to find and fit an equivalent circuit to real impedance
of plots of the derived impedance with the data, though occasion- data.
ally more rigorous least squares fitting to the data has been used, We begin by making some observations about the difficulty of
e.g., [10,11]. finding equivalent circuits that are simply related to the underlying
Despite this, the use of equivalent circuits is entrenched in EIS. mechanism, and show that except for some isolated cases, circuit
The easy availability of commercial software to automate the least- structure is not obviously related to mechanism. The related issue
of non-uniqueness is touched upon, but has been well discussed
previously [12]. We suggest that for extracting kinetic parameters,
∗ Corresponding author. Tel.: +1 250 721 7166; fax: +1 250 721 7147. the ladder circuit has benefits. Aspects of the underlying mecha-
E-mail addresses: [email protected] (D.A. Harrington), nism can be deduced from the numbers of capacitances, inductors
[email protected] (P. van den Driessche). and resistors, the presence or absence of a dc path, and the presence

0013-4686/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.01.067
8006 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013

Fig. 1. Some simple equivalent circuits. (a) For a simple redox reaction, (b) equiva-
lent form to (a), (c) Randles circuit for redox reaction with diffusion, and (d) alternate
form for (c). Fig. 2. Some equivalent circuits for a reaction mechanism. (a) A schematic
impedance spectrum, (b)–(d) can all fit this same impedance for particular element
values, and (e) is an inductive form for the same mechanism at a different poten-
or absence of inductive behavior. These aspects aid in the selection tial. The mechanism of reactions (7)–(9) is an example of a mechanism with these
of candidate mechanisms. We illustrate these ideas for a simple circuits.

cycle mechanism with two adsorbed intermediates, and derive a

criterion for inductive behavior for it. A special case of this mech- – it seems that the potential across the double layer no longer drives
anism is used to show that a circuit that is blocking to dc need not the charge transfer. An attempt to solve this by having the charge-
correspond to a mechanism with zero reaction rate. transfer resistance parallel to the double-layer capacitance (circuit
We finish with some observations on the nature of inductive 1d), leads to a new boxed “diffusion” element. This unfortunately
behavior and the meaning of the charge-transfer resistance, Rct , does not solve the problem, because the boxed element depends
and the polarization resistance, Rp . In particular, we show that the on kinetic parameters as well as diffusion parameters. This is no
Tafel plots of the charge-transfer resistance (potential vs. −log Rct ) better or worse than the fact that the Warburg element represent-
are not useful for distinguishing reaction mechanisms. ing diffusion is characterized by the parameter  which contains
both diffusion and reaction parameters:  is the product of Rct and
solution parameters. The point here is that there is rarely a sim-
2. Results and discussion
ple correspondence between circuit elements and reaction steps or
physical processes. Nonetheless, this Randles circuit is acceptable
2.1. Uses and limitations of equivalent circuits
as an equivalent circuit because we can use it to extract parameters
relating to the physical processes. As is generally true, individual
2.1.1. Correspondence between circuits and physical processes
physical parameters are not measurable, but only certain combina-
The simplest equivalent circuit, Fig. 1a (henceforth “circuit 1a”)
tions of them are measurable. Parameters from different processes
demonstrates the desirable correspondence between elements of
(kinetics and diffusion in this case) are typically mixed.
a circuit and physical processes. This circuit applies for example
for reaction (1) where mass transport of reactant A and product
2.1.2. Non-uniqueness and fitting choices
A+ maintains constant concentrations at the interface, and there is
Accepting that coupling of parameters is inevitable, can we min-
no complication due to adsorption. The potentials at points X and Y
imize the complexity of this coupling? How can equivalent circuits
represent the potentials on the metal and solution sides of the dou-
be useful? We discuss this general issue and then present a spe-
ble layer, and the potential difference between these points drives
cific mechanism to emphasize these points. We assume henceforth
the reaction modeled by the charge-transfer resistance Rct . Point
that the underlying mechanisms have fast mass transport and pos-
Z represents the potential at the reference electrode. The physical
sibly adsorption. We omit the solution resistance from circuits
significances of each of the three circuit elements are clear and gen-
and equations. This means that the circuit will be composed of
erally accepted. Their values separately characterize the interface
resistors, capacitors and inductors, and idealised Nyquist (com-
(Cdl ), the reaction (Rct ) and the solution (Rs ).
plex plane) plots of the impedance will consist of semicircular arcs
k1 above the real axis (capacitive) or below (inductive). As a practical
A(aq)  A+ (aq) + e− (1) matter, these features may not always be well resolved. Consider
k−1
an impedance spectrum showing three capacitive semicircles that
Circuit 1b can equally well fit data that fits circuit 1a, but has zero impedance at infinite frequency and is resistive at zero fre-
the parameters here are mixtures of the basic parameters of the quency (Fig. 2a). This will fit to an RC circuit with three capacitors
model, e.g., R1 = Rct + Rs mixes reaction rate parameters with solu- and three resistors and Fig. 2b–d gives three possibilities, which
tion parameters. Additionally, no point in the circuit corresponds correspond to the impedance expressions in Eqs. (2)–(4),
to the point Y just outside the double layer. This is evidently not a 1 1 1
good choice. However, one needs only add diffusion of one or both Z= + + (2)
sCa + (1/Ra ) sCb + (1/Rb ) sCc + (1/Rc )
solution species in reaction (1) to find that the relevant model, the
classical Randles circuit (circuit 1c), suffers the same problem. The 1
Z= (3)
point Y representing the solution side of the double layer is not clear sCdl + (1/(Rct + (1/(sC1 + (1/(R1 + (1/(sC2 + (1/R2 )))))))))
 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013 8007

 1 1 1
−1 and Ra ↔ Rb lead to the same impedance, and this can cause the
Z = sCdl + + + (4) fitting routine to have some convergence difficulties. The capaci-
R3 + (1/sC3 ) R4 + (1/sC4 ) R5
tors and resistors of the ladder circuit 2c are easily converted to
s2 + a1 s + a2 the coefficients a1 , a2 , b1 , b2 , b3 and thence to the kinetic param-
Z= (5)
Cdl (s3 + b1 s2 + b2 s + b3 ) eters (or its capacitors and resistors may be directly converted to
the kinetic parameters). For this reason it is preferred for mechanis-
(s − ˛1 )(s − ˛2 )
Z= (6) tic work. It might be argued that all forms are equivalent, because
Cdl (s − ˇ1 )(s − ˇ2 )(s − ˇ3 )
the parameters from one may be converted to parameters of the
where s = iω, and the other symbols represent real parameters that another by solving some simultaneous equations. Although this is
may be extracted from the data, six parameters for each form of the true for ideal data, in practice error propagation quickly degrades
impedance. Other combinations of three capacitors and three resis- the reliability of parameters, and it is best to fit directly to the most
tors will be equivalent if replacing the capacitors with open circuits relevant form.
(low frequency limit) leaves a resistance (there is a dc path), and
replacing the capacitors with short circuits (high frequency limit) 2.1.3. Matching mechanisms to circuits – an example
leaves a combination with zero impedance (equivalent to a short Consider the simple sequential reaction
circuit).1 Eqs. (2)–(4) are equivalent forms of the same impedance
k1
(same at all frequencies). They all simplify to Eq. (5), and factoring A− (aq) + M(site)  MA(ads) + e− (7)
the numerator and denominator leads to the pole–zero form, Eq. M k−1 MA
(6). Circuit theory [13] shows that ˇ1 < ˛1 < ˇ2 < ˛2 < ˇ3 < 0 (all real)
k2
and that a1 , a2 , b1 , b2 and b3 are all positive. MA(ads)  MB(ads) (8)
Confronted with some experimental data, the first question MA k−2 MB
would be to ask whether or not any of these fit the data, or are
k3
the data fitted by another form that is not equivalent, e.g., a circuit MB(ads)  M(site) + B(aq) (9)
with a different number of elements or one that blocks dc – these MB k−3 M
are not equivalent to Eq. (5). For this, success or failure of fitting
Here M(site) is a reaction site on a metal surface, MA means A
any of these measurement models establishes whether or not the
adsorbed on a surface M atom, and MB is a structurally rearranged
impedance is of this essential form. This is analogous to first asking
version of MA. We suppose mass transport is fast, so that the
whether some data fit a straight line or a quadratic; for the purposes
surface concentrations of A− (aq) and B(aq) are constant and can
of deciding this, any of the equivalent forms of a straight line will
be subsumed into the rate constants. These species are referred
do, e.g., y = mx + c or (y − y0 )/(x − x0 ) = m. The utility of equivalent
to as “external” or “static”, are omitted hereafter, and should be
circuits as measurement models, and some reasons for choosing
considered invisible in calculations of the number of independent
particular circuits or impedance expressions to fit data have been
reactions given below. Omitting them and the electrons shows the
discussed previously by Zoltowski [14,15]. The choice depends on
basic cyclic structure of this mechanism, M → MA → MB → M. We
the purpose for which the data are collected, and the tools available
assume Langmuir kinetics for the adsorbed species. The kinetics of
to the researcher. In the study of oscillating systems, the nature of
this mechanism (and other ones with the same cycle) are
the poles (ˇ1 , ˇ2 , ˇ3 ) and zeroes (˛1 , ˛2 ) relate most directly to the
stability of the system and give information about incipient oscilla- v1 = k1 M − k−1 MA (10)
tions without having to know the mechanism; in this case Eq. (6) is
the preferred form. As shown in Appendix A, the coefficients of the v2 = k2 MA − k−2 MB (11)
rational function form, Eq. (5) are most simply related to rate con- v3 = k3 MB − k−3 M (12)
stants: they are sums of products of rate constants. If determination
of rate constants is the primary objective (as we typically assume), with the rate constants k1 and k−1 potential dependent in the usual
then this is the preferred form. However, most commercial soft- way. The surface coverages obey the constraint  M +  MA +  MB = 1.
ware does not fit to forms (5) or (6), but to one of the equivalent The stoichiometric matrix (Eq. (13)) contains the stoichiometric
circuit forms (2)–(4). coefficients, e.g., column 1 reflects the fact that in step 1 one elec-
Given this restriction, which of the equivalent circuits is pre- tron is produced, one atom of MA is produced and one atom of M
ferred? Circuit 2b has the advantage that the three Ri Ci parts in is lost.
series correspond most directly to the three observed semicircles,
e.g., their diameters are Ra , Rb and Rc . This might be a good form for
selecting initial parameter estimates to feed to a non-linear fitting
routine, but from an interpretive point of view it has no advantages.
The double-layer capacitance is mixed into all the elements, e.g.,
−1
Cdl = Ca−1 + Cb−1 + Cc−1 . The parameters most easily extracted from
(13)
this circuit are the poles ˇ1 , ˇ2 , ˇ3 = − 1/Ca Ra , − 1/Cb Rb , − 1/Cc Rc .
Similarly, fits to circuit 2d easily allow the extraction of the zeroes If electrons are removed from this mechanism, then step 3 can writ-
˛1 , ˛2 = − 1/C3 R3 , − 1/C4 R4 . However, the poles and zeroes are ten as a combination of steps 1 and 2 in the sense of Hess’s law (step
the roots of polynomials and are related to the coefficients in a 1 + step 2 = −step 3):
very complicated way (with no closed form possible for quintics or
M  MA (1)
higher). Therefore circuits 2b and 2d are not suitable for mechanis-
MA  MB (2) (14)
tic work. They have an additional disadvantage that there is some
M  MB (−3)
ambiguity in defining circuit branches, e.g., the exchanges Ca ↔ Cb
That is, only two of the reactions are independent, we denote this by
I = 2. Once the electron is added back in, no reaction can be written
1
Some common sense needs to be applied to use this equivalence rule, e.g., two
as a linear combination of others, so all three reactions are indepen-
resistors in series cannot be distingluished from a single resistor and so count only dent and we write I = 3. We define a parameter X = 2(I − I ), which
as one, all pieces need to be connected to give a two-terminal circuit. may be either zero or two. Here X = 2. Chemically, X = 2 means that
8008 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013

it is possible to construct a reaction that includes both external

species and electrons: the overall reaction A− → B + e− satisfies this
criterion for this mechanism. It also means that the equivalent cir-
cuit will have a dc path; this is related to the fact that current flows
at steady state.
The significance of the quantities I , I and X in terms of the rank
of the stoichiometric matrix N is given in Appendix A. There, the
impedance is calculated from the rate equations. The kinetic infor-
mation is collected in a matrix Q and its submatrix Q(1), and the fact
that these matrices generally have the same ranks as matrices N and
N(1), respectively, means that some information about the equiva-
lent circuit is available by knowing only the stoichiometry, or N. The
circuit will contain I resistors (excluding the solution resistance) Fig. 3. Equivalent circuits for the mechanism of reactions (17)–(19). (a) Ladder form
and I + 1 − X/2 capacitors or inductors (including the double-layer of RC circuit and (b) inductive circuit when condition (15) applies.
capacitance) [6]. Here there will be 3 resistors and 3 capacitors
or inductors. Together with the fact that there is a dc path (X = 2), HA → HB. At steady state, each of the three steps proceeds at the
we conclude that the equivalent circuits in Fig. 2 are possibilities same rate, and the current density is zero. This therefore is an
and the impedance is that in Eqs. (2)–(6). As already noted, circuit interesting case, where the reaction proceeds at a finite rate but
2c is preferred for parameter extraction. Other mechanisms with the steady-state current is zero. There will be a transient current
I = 3 and X = 2 will also have these circuits. All mechanisms have that will enable the impedance to be measured. Here X = 2 (I − I  ) =
RC circuits at the equilibrium potential [6], so the observation of 2(2 − 2) = 0; from the chemical point of view X = 0 means that it is
inductive behavior at some other potentials may be a qualitative impossible to construct a reaction including the electrons and the
clue to the mechanism. Appendix A shows that this mechanism external species. The overall reaction does not work here because
will be inductive (circuit 2c) when electrons must be included. Since both HA and HB have the same
2 2 oxidation state, no acceptable reaction can be found. From the
(a2 + b2 + c 2 ) > (a − b) + (b − c) + (c − a)2 (15)
equivalent circuit point of view, X = 0 means that there is no dc
where a = k1 − k−2 , b = k2 − k−3 , c = k3 − k−1 . By inductive, we mean path: the behavior is blocking at low frequencies. With I = 2 and X = 0
that an equivalent circuit with positive elements, one or more of there are I = 2 resistors and I + 1 − X/2 = 3 capacitors or inductors, see
which is an inductor, fits the experimental data. This does not nec- Fig. 3.
essarily imply that the impedance will go below the real axis in a This example emphasizes that blocking behavior or the absence
Nyquist plot. That depends on the inductance being large enough of a dc path through the circuit implies lack of current flow and
to dominate. not necessarily a lack of reaction. Electrons play a special role in
An obvious question is whether there is a modification of this equivalent circuits, and current is not just a proxy for reaction rate.
cyclic mechanism for which X = 0, i.e., I = I. We have already seen This mechanism can show inductive behavior because it has the
that stripped of external species and electrons, there are two inde- same basic cyclic structure that gives the criterion of Eq. (15), which
pendent reactions so that I = 2. We need to add electrons back in also applies here. Note that although circuit 2c without R2 is the
such a way that there are still only two independent reactions; we correct RC circuit, circuit 2e without R7 is not blocking at dc, and
can achieve this if we retain the relationship step 1 + step 2 = −step so cannot be the correct inductive form. A detailed analysis shows
3. One way to do this is: that circuit 3b is appropriate.

M  MA + e− (1) 2.1.4. Analysis strategy

MA  MB (2) (16) The above considerations lead to the following strategy for using
M  MB + e− (−3) equivalent circuits to analyse the impedance of reaction mecha-
Adding in external species to balance the reactions we find that a nisms involving adsorption but uncomplicated by mass transport.
sensible example is the mechanism of Eqs. (17)–(19) with HA, HB The objective of the analysis is assumed to be deduction of the steps
and H+ as external species. in the mechanism and estimation of the rate constants.

k1
HA(aq) + M(site)  MA(ads) + H+ + e− (17) 1. Use any tools to fit to an equivalent circuit consisting of capac-
M k−1 A itors, inductors and resistors. If the low-frequency limit is
resistive (intercept is on the real axis), then the circuit will have
k2
MA(ads)  MB(ads) (18) a dc path; if the impedance tends to infinity at low frequency,
A k−2 B the circuit will be blocking at dc. A successful fit to any such
circuit with positive element values automatically satisfies the
k3
Kramers–Kronig relationships and validates the data. For block-
H+ + e− + MB(ads)  M(site) + HB(aq) (19)
B k−3 M ing behavior at dc, take X = 0 and for non-blocking behavior, take
X = 2. The number of resistors (not counting the solution resis-
The stoichiometric matrix is tance) gives the parameter I and the number of capacitors and
inductors is I + 1 − X/2.
2. Use the values of I and X to narrow down candidate reaction
mechanisms. The number of independent reactions including
electrons must be I and the number of independent reactions
with the electrons omitted must be I − X/2. The external species
(solution species with fast mass transport) are omitted in this
(20)
calculation. A reaction between external species and electrons is
The electron row is a linear combination of the other rows. The possible for X = 2 but not for X = 0. (Our rules here are in general
surface catalyzes the overall reaction, which is the isomerization compatible with the rule that each additional adsorbed species
 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013 8009

adds a relaxation or “loop” [1,16], because a reaction that intro-

duces a new adsorbed species must be independent of the other
reactions.) The rules (below) about which mechanisms can show
inductive behavior can assist in deciding upon candidate mech-
anisms.
3. If the ladder circuit was not fitted directly in step 1, then fit to
the ladder circuit (generalized form of circuit 2c (non-blocking)
or circuit 3a (blocking)) with the same number of resistors as
the circuit in step 1 and the same number of capacitors as the
total number of capacitors and inductors in the circuit in step 1.
For inductive behavior, it is simpler to use capacitors and allow
the circuit elements to become negative than to decide where
in the circuit the inductors should be. An exception to the rule
that the kinetic parameters are most simply related to the ladder
form occurs for mechanisms with a single adsorbed species (I = 2,
X = 2) for which an inductive form is optimum [17].
4. Fit the impedance to the ladder circuit over a wide range of
potentials to find the potential dependence of the circuit ele-
ments. Note that potentials at which the circuit has the most
elements should be used to deduce the mechanism in step 2,
because for practical reasons some features may not be resolved
under all conditions.
5. The potential dependence of the circuit elements is used to
decide between the remaining candidate mechanisms. This
requires a kinetic analysis such as that in Appendix A. Briefly,
after using the kinetic equations to find the impedance in the
rational function form, Eq. (5), a succesive division algorithm
of circuit theory is used to find the element values in terms of
the rate constants, see p. 79 in [13]. Analysis of the potential
dependence of the ladder circuit elements is simplest for those
elements closest to the double-layer capacitance, so these should
be used first in an analysis. For example, for the mechanism of
reactions (7)–(9), C1 is a simple function of rate parameters for
reaction step 1 alone (Eq. (A.19)). The double-layer capacitance Fig. 4. Resistances and time constants for some impedances with two semicircles.
is found directly, then ke from Rct , and then k1 + k−1 from C1 ; this (a) Capacitive low-frequency relaxation, (b) inductive low-frequency relaxation, and
(c) low-frequency relaxation with positive capacitance and negative resistance.
gives maximum information about step 1. Further steps in the
analysis could include fits to other forms of the impedance or
directly to a proposed kinetic scheme.
where E is the potential and jss is the steady-state current den-
sity at that potential.2 If the equivalent circuit is available, rather
2.2. Meaning of circuit elements than the impedance spectrum, then Rp is found by replacing the
capacitors with open circuits, the inductors with short circuits and
Despite the caution above that individual circuit elements rarely calculating the equivalent resistance, e.g., for circuits 2b–e it is
have direct physical significance, some observations about the Ra + Rb + Rc , Rct + R1 + R2 , R5 , and Rct + R6 , respectively. Early in the
meaning of elements are possible. The significance of Cdl is well history of impedance theory, it became “clear, whatever the com-

known, and the other capacitors are usually associated with adsorp- plexity that Z(iω → 0) is equal to ∂E/∂I [1]. That is, the polarizaton
tion. Despite being referred to as adsorption pseudocapacitances, resistance found from the impedance must equal the reciprocal of
they do not have the same significance as the steady-state pseudo the slope of the steady-state current-potential curve, Eq. (21) in
capacitance and cannot be used to simply extract coverages [17]. our notation. This equality of the impedance and steady-state defi-
An example has been given where strong coupling to mass trans- nitions of the polarization resistance was originally shown by use of
port removes capacitors and leads to only resistors and Warburg examples, including those with negative slopes in the polarization
elements even though adsorption is present (Fig. 2 in Ref. [4]). The curve [18]. In a general fomulation of the impedance, Naito et al.
charge transfer resistance, Rct , and the polarization resistance, Rp [19] derived the slope of the polarization curve under a number of
have fairly simple interpretations, though there are some subtleties stability conditions by evaluating Z(ω → 0) under these conditions,
that merit discussion. i.e., they assumed (21) was true. This relationship was later general-
ized for multiple inputs and outputs including non-electrochemical
impedances [20], but to our knowledge a proof has not been given.
In Appendix B, we show that Eq. (21) always holds, provided that
2.2.1. The polarization resistance the system is stable, though examples show that it has a wider
As determined from the impedance spectrum, the polarization validity.
resistance, Rp , is the limit of the impedance at zero frequency (first
equality in Eq. (21), see Fig. 4 for examples).
2
The polarization resistance is often defined instead as the zero-frequency inter-
 dj −1 cept minus the solution resistance. In that case, the steady-state current potential
ss
Rp = lim Z(ω) = (21) curve must be likewise corrected for ohmic drop in order for the relationship (21)
ω→0 dE to hold.
8010 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013

One practical use of Eq. (21) is to determine if there are missing Tafel plots of Rct are not diagnostic of mechanism: In the classic
relaxations at frequencies lower than those measured, as noted by Tafel analysis, the slope of a plot of the overpotential vs. the log10
Schuhmann [1]. For example, suppose the real impedance is that of of the steady-state current is used to find the transfer coefficient,
Fig. 4b, but only the high-frequency semicircle above the axis were ˛ = (RT ln 10)/(F × slope). This parameter is diagnostic of where the
measured. Measurement of the slope of steady-polarization curve rate-determining step (rds) occurs in the sequence of elementary
gives the Rp shown, and the fact that this is less than the measured reactions in the mechanism. A value close to 1/2 suggests that the
intercept (at Rct ) indicates that there is a missing relaxation (the first electron transfer is the rds, a value close to unity suggests a
inductive loop) at frequencies lower than were measured. In our chemical rds following a one-electron pre-equilibrium step, etc.
experience, this is the most useful test to decide whether or not [24]. It is common to assume that ˛R extracted in the same way
the data has been measured to low enough frequencies. from a Tafel plot of Rct , a plot of overpotential vs. −log Rct , has the
To rationalize Eq. (21), we begin by noting that the limiting low- same significance, but we show below that this is not the case.
frequency behavior must have zero phase, i.e., be resistive, because In view of the discussion above about the meaning of Rct , the
the applied potential sinusoid is slower than any of the physical state of the interface is frozen as the potential is increased, and the
processes. All of the oscillations of physical quantities, e.g., surface increase in current comes from the change in the electron transfer
concentrations are able to “keep up”; there is no phase delay, and rate of all the electron-transfer steps, regardless of whether they
the resulting current follows the potential in the same way as it are the rds or a preceding or following step. For example, dur-
would be in a measurement of a steady state polarization curve ing the mechanism of (17)–(19), there will be at any time some
using a very slow sweep. Therefore the ratio of changes in current concentrations of M, MA and MB on the surface. An increase in
to changes in potential equals the slope of the polarization curve. potential immediately increases the rate of step (17) and decreases
the rate of step (19), regardless of the fact that the three steps occur
2.2.2. The charge transfer resistance sequentially at a slower time scale. In effect the concept of the rds is
The charge transfer resistance Rct is defined as [21] not relevant at high enough frequencies that the surface condition
 −1 is frozen. The expectation is that if all the electron-transfer steps
∂jf are single-electron transfers with symmetry factors ˇ = 0.5, then
Rct = (22)
∂E these will all operate in parallel and the slope of a potential–log Rct
ci ,i
plot will yield an apparent transfer coefficient ˛R = 0.5, regardless
i.e., it measures the change in faradaic current as the potential of which step in the mechanism is rate determining. Rct is a parallel
across the double layer is changed, while keeping the composi- combination of the charge-transfer resistances of each step [4,22],
tion at the surface constant. In contrast to Rp where the potential even if these steps are not parallel steps in the mechanistic sense.
is changed slowly so that the surface condition changes during the Ref. [21] suggests that the parallel relationship only holds when the
perturbation, here the potential is changed rapidly so that the sur- mass impedances are small. However, we suppose that Rct is calcu-
face condition has no time to change. It is the limit of the faradaic lated by combining the necessary resistances from wherever in the
impedance at high frequencies [4]. Therefore, it may be found from circuit they occur, so this need not be a restriction. For a numerical
an equivalent circuit as the effective resistance in parallel with Cdl example of the significance of the Tafel plots, consider the hydrogen
after replacing inductors with open circuits and capacitors except oxidation reaction (HOR) with the following mechanism:
Cdl with short circuits, e.g., it is the parallel combination of R3 , R4
k1
and R5 in circuit 2d. It usually approximates the diameter of the
H2 + Pt(site)  PtH(ads) + H+ + e− (23)
highest frequency semicircle, as indicated in Fig. 4. 1− k−1 
In the simple picture of Fig. 1a, increasing the potential increases
the potential at X relative to the potential at Y, which promotes k2
PtH(ads)  Pt(site) + H+ + e− (24)
current to the right, i.e., an increase in positive (anodic) current.  k−2 1−
Therefore in this picture, Rct must always be positive. It was empha-
sized in Ref. [21], p. 1851, that Rct for a single reaction would go The adsorbed hydrogen has fractional coverage  and H2 and H+
negative only under extreme conditions. Negative Rct has been pro- are considered as external species. Suppose that the second step is
posed to explain the origin of some oscillating mechanisms, but a rate determining, so that the first step can be considered as a pre-
more detailed analysis by Berthier et al. [22] shows that the real equilibrium. Then the classical analysis (valid for low coverages)
Rct is positive in all cases, under a mild set of assumptions, as we says that the expected transfer coefficient deduced from the mea-
propose here. A simple resolution of these apparent inconsistencies sured Tafel slope of the steady-state current-potential relationship
is to note that if reactions are fast enough that the composition of is ˛ = 1 + ˇ2 ≈ 1.5. In contrast, we expect Rct to be unrelated to the
the interface can change on the timescale of double-layer charging position of the rds in the mechanism, and that a Tafel plot of Rct
( = Cdl Rs ), then it is impossible to measure the true Rct defined by leads to ˛R ≈ ˇ1 ≈ ˇ2 ≈ 0.5. This mechanism has the advantage that
Eq. (22). In this case Rct is so small that another resistive element is an analytical expression can be obtained for the steady state cur-
measured as an apparent charge-transfer resistance. For example, rent and the charge transfer resistance (see, e.g., [17]) and so this
if in circuit 2c R1 were negative for some reason and Rct were very expectation can be numerically tested. Fig. 5 shows Tafel plots for
small, then C1 combines in parallel with Cdl to give an apparently the steady-state current and charge-transfer resistances, for rate
large double-layer capacitance, and R1 appears as an apparent neg- constants that lead to low coverages over the whole overpotential
ative charge-transfer resistance. Other explanations for apparent range. The higher slope of the Rct plot by a factor of three reflects the
negative charge transfer resistances have been given [1,19]. three times lower apparent transfer coefficient (˛R = 0.5 vs. ˛ = 1.5).
The defining equation (22) invokes faradaic current and If the Tafel slope from the Rct plot were naively interpreted as indi-
therefore is specific to electron transfer. However, non-faradaic cating where the rds lies in the mechanism, the incorrect conclusion
adsorption or structural rearrangements of adsorbed species can would be that the first step were rate determining.
lead to a capacitance change and an induced current flow that leads Although in general Rct Tafel plots always lead to ˛R = 0.5 and
to a similar resistor in an equivalent circuit [23]. For this reason, it is have no diagnostic usefulness, there are two simple exceptions. The
better to think of Rct as representing the dissipation of energy asso- first is where there is a single semicircle, so that Rct = Rp and then the
ciated with an activation energy, rather than as being specifically two plots lead to the same correct conclusion. The second is where
associated with electron transfer. Rct indicates that ˛R = 1, indicating that there is a concerted two-
 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013 8011

the inductive case corresponds to the case where Rp < Rct . The case
with a negative time constant (Fig. 4c) also has Rp < Rct but a neg-
ative time constant is unusual, and we may therefore anticipate
inductive behavior when Rp < Rct . That is, the inductive nature is
perhaps less significant than the fact that the impedance decreases
on going to lower frequencies. The criterion Rp < Rct in some sense
means that the overall (low-frequency) rate is faster than the intrin-
sic rate of electron transfer. This seems paradoxical if there is only a
single electron-transfer step. However, two electron-transfer steps
working cooperatively to produce and then remove the intermedi-
ate (ODA + RDA) can facilitate the responsiveness of the overall rate
to the potential.
One class of mechanisms that can never show inductive behav-
ior and always have RC circuits are those with tree-graph structures
and only one electron [29]. Mechanisms that only have RC circuits
are rather rare because the circuit theory criterion for RC behav-
ior is rather restrictive: the poles and zeroes must alternate along
the negative real axis of the s plane. Given that pole–zero locations
Fig. 5. Tafel plots for HOR example. Mechanism of Eqs. (23) and (24) for rate parame- can in general be sprinkled anywhere in the left half-plane, mecha-
ters, k1 = 1, k−1 = 1 × 1018 , k2 = 1 × 10−4 , k−2 = 1 × 10−22 (all mol m−2 s−1 ), ˇ1 = ˇ2 = 0.5.
nisms that can show inductive behavior will be the rule rather than
the exception.
electron reaction. This discussion suggests that a measurement of The ODA + RDA mechanisms are inductive because the poles and
the potential dependence of Rct may be the easiest way to detect zeroes no longer alternate, but they are still real. Inductive behav-
concerted two-electron transfer steps. ior also occurs when the poles or zeroes become complex; there
must be at least two adsorbed species for this to happen. Note that
2.2.3. Inductive behavior zeroes relate to the “skeletal” structure of the mechanism in the
The significance of inductors has continued to be a topic of absence of electrons. Classification of different mechanisms with
active interest, perhaps because they seem to imply a magnetic two adsorbed species [30] as to the location of the zeroes showed
field, which is not present at the electrochemical interface. If a that a mechanism with a single cycle skeleton (of any stoichiom-
capacitor dominates the impedance, the current lags the poten- etry) could have complex zeroes. Here we have verified that the
tial and the impedance is above the real axis (Fig. 4a), but if an simplest cycle (all reactions first order) can be “dressed” with exter-
inductor dominates the impedance, the current leads the potential nal species and one electron to give a real mechanism, reactions
and the impedance is below the real axis (Fig. 4b). The fact that (7)–(9), that does show inductive behavior. This illustrates that two
kinetic equations predict that the impedance is sometimes below electrons are not required for inductive behavior; it also seems to
the axis requires that the corresponding equivalent (not real!) cir- lack the “electrons in opposition” behavior that was required for
cuit will contain an inductor; there is no implication that magnetic single-adsorbate mechanisms. Diard et al. [31] examined a mecha-
fields are present. Monte-Carlo simulations of a two step adsorp- nism with two adsorbed species and saw inductive behavior; their
tion/desorption mechanism (such as the HOR mechanism above) mechanism was a two-electron mechanism containing ODA and
have been used to emphasize the point that kinetics alone are suf- RDA steps, but they did also find inductive behavior associated with
ficient to give inductive behavior [25,26]. Inductive behavior in complex poles or zeroes.
corrosion has long been associated with inhibitors [27], but this The two mechanisms, (7)–(9) and (17)–(19), have the same
cannot be a universal explanation. A nice review of the history of skeletal stucture. Therefore, they share the same criterion, Eq. (15),
these ideas is given in [25]. for inductive behavior arising from the complex nature of the
Although the “meaning” of inductive behavior remains elusive, zeroes of the impedance. The skeletal structure of single adsorbed
it is useful to categorize adsorption mechanisms with Langmuir mechanisms is simple (connections only between the adsorbed
kinetics that may or may not show this behavior. We apply the species and sites), but recognition of common origins for inductive
adjective “inductive” to a mechanism that has an equivalent circuit behavior will be significant in better understanding inductance in
with positive element values and at least one inductor for some more complicated mechanisms. Although we have discussed the
set of rate constants at some potential. At other potentials or sets common inductive behavior arising from the zeroes for the two
of rate constants the circuit may have only resistors or capacitors, “dressed” examples, we have not attempted to explore other types
i.e., an inductive mechanism is one that may have an equivalent of inductive behavior that might arise in these mechanisms.
circuit with an inductor. In fact, since all such mechanisms have
RC circuits at equilibrium [6], there is no mechanism that is always
inductive. We previously showed [28] that for mechanisms with a 3. Conclusions
single adsorbed species, inductive behavior requires the combina-
tion of (i) a step that has the adsorbed species on the same side of the We have argued that equivalent circuits are useful in analyzing
reaction as the electrons, i.e., is oxidizing in the direction of adsorp- impedance spectra arising from reaction mechanisms. They pro-
tion (ODA), e.g., reaction (23), and (ii) a step that has the adsorbed vide a measurement model to validate the data, and the number
species on the other side of the reaction from the electrons, i.e., is and type of circuit elements can be used to screen candidate mech-
reducing in the direction of adsorption (RDA), e.g., reaction (24). anisms. There is rarely a direct physical significance of the values
In a loose sense, oxidation and reduction processes are working in of the circuit element, since parameters from different physical
opposition on an adsorbed species. The above mechanism for the processes are typically coupled in complicated ways. For reaction
HOR, reactions (23) and (24), has both ODA and RDA steps and can mechanisms with adsorbed species and fast mass transport, the
show inductive behavior. ladder circuit (e.g., circuit 2a) has elements that are more sim-
This is a mechanism with two relaxations (semicircles), and ply related to kinetic parameters than other forms, except perhaps
examination of the possiblilties for this case (Fig. 4) shows that in the case of a single adsorbed species. Analysis of the potential
8012 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013

⎡ ⎤
dependence of element values can then be used to further nar- k−1 + k2 −k−2 −k1
row down possible reaction mechanisms. This procedure is more ⎢ ⎥
Q(1) = ⎣ −k2 k3 + k−2 −k−3 ⎦ (A.5)
systematic that directly fitting data to a range of kinetic models.
Two mechanisms, each with two adsorbed species, illustrate the −k−1 −k3 k1 + k−3
above ideas. These mechanisms have the same skeletal structure
when external species and electrons are removed: that of a simple It may be explicitly verified that rank(Q) = rank(N) = 3 and
cycle in the adsorbed species (M → MA → MB → M). This common rank(Q(1)) = rank(N(1)) = 2. Expansion of the determinants in (A.1)
structure means that a common criterion for when these mecha- leads to (A.6), so that the coefficients in this equation are sums
nisms must be inductive can be given. One of these mechanisms, of products of rate constants (scaled according to  m ); the two
reactions (17)–(19), proceeds at a finite rate, but the steady-state numerator coefficients being given in (A.7) and (A.8) as examples.
current is zero. This has a circuit that is blocking at dc, indicating m (s2 + a1 s + a2 )s
that blocking behavior implies a lack of current but not necessarily Z= (A.6)
Cdl (s3 + b1 s2 + b2 s + b3 )s
a lack of reaction rate.
k1 + k−1 + k2 + k−2 + k3 + k−3
a1 = (A.7)
m
k2 k3 + k−3 k−1 + k−3 k−2 + k−3 k2 + k1 k3 + k1 k−2 + k1 k2 + k−1 k3 + k−1 k−2
a2 = (A.8)
m2
The common factors of s in the numerator and denominator of (A.6)
The significance of the polarization and charge transfer resis-
can be cancelled to give (5). If the numerator has complex roots, the
tances has been discussed. Tafel plots of Rct are not diagnostic of
equivalent circuit is inductive [13]. These roots are eigenvalues of
where the rate-determining step is in a reaction mechanism, but
the matrix −m−1 Q(1), which are −m−1 times the eigenvalues of
are sensitive to concerted two-electron transfer steps.
Q(1), which are the eigenvalues of RQ(1)R−1 where R is defined
implicitly below.
Acknowledgements   
1 0 0 k−1 + k2 −k−2 −k1
−1
RQ(1)R = 0 1 0 −k2 k3 + k−2 −k−3
We thank the Natural Sciences and Engineering Research Coun-
1 1 1 −k−1 −k3 k1 + k−3
cil of Canada and the University of Victoria for financial support of
this research. We thank Frode Seland and Dan Bizzotto for useful  
1 0 0
discussions relating to this work. × 0 1 0 (A.9)
−1 −1 1
Appendix A.
 
k1 + k−1 + k2 k1 − k−2 −k1
The impedance for a general mechanism with adsorption but −1
RQ(1)R = k−3 − k2 k−3 + k3 + k−2 −k−3 (A.10)
without mass transport is given by (A.1) 0 0 0
 −1 
−m Q(1) − sI The zero eigenvalue gives the factor s in the numerator of (A.6); the
Z=−   (A.1) other two eigenvalues of Q(1) are the eigenvalues of
Cdl −m−1 Q − sI  
 k1 + k−1 + k2 k1 − k−2
where Q = − NJ is a matrix constructed as described in [28,29], Q= (A.11)
k−3 − k2 k−3 + k3 + k−2
Q(1) is the same matrix with its first (“electron”) row and col-
umn removed, s = iω,  m is the surface concentration of M atoms This has the characteristic polynomial P(s)
(mol m−2 ) and I is the appropriately sized identity matrix. The
)s + det(Q
P(s) = s2 − trace(Q ) (A.12)
parameters I, I and X are defined as I = rank(N) I = rank(N(1)) and
X = 2(rank(N) − rank(N(1)) = 2(I − I ). For the mechanism of (7)–(9), which has complex roots if and only if the discriminant is negative
with 1 , 2 , 3 given by (10)–(12),
⎡ ⎤ ) − 4 det(Q
discrim(P) = trace2 (Q ) (A.13)
−(Fm /Cdl )(∂v1 /∂E) ∂v1 /∂MA ∂v1 /∂MB ∂v1 /∂M 2 2 2
discrim(P) = (a − b) + (b − c) + (c − a) − (a2 + b2 + c 2 ) (A.14)
⎢ ⎥
J = ⎣ −(Fm /Cdl )(∂v2 /∂E) ∂v2 /∂MA ∂v2 /∂MB ∂v2 /∂M ⎦ (A.2)
discrim(P) = u2 + v2 − w2 (A.15)
−(Fm /Cdl )(∂v3 /∂E) ∂v3 /∂MA ∂v3 /∂MB ∂v3 /∂M
⎡ ⎤ √ a = k1 − k−2 , b = k2 − k−3 , √
where c = k3 − k−1 and u = (a + b −
−ke −k−1 0 k1 2c)/ 3, v = b − a, w = (a + b + c)/ 3. That is, inductive behavior
⎢ ⎥ occurs for
J=⎣ 0 k2 −k−2 0 ⎦ (A.3)
2 2
(a2 + b2 + c 2 ) > (a − b) + (b − c) + (c − a)2 (A.16)
0 0 k3 −k−3
the inequality stated in (15), or equivalently
where ke = (F2  m /RTCdl )((1 − ˇ1 )k1 + ˇ1 k−1 ) with ˇ1 the symmetry
w2 > u2 + v2 (A.17)
factor for step 1. Multiplying by –N gives:
⎡ ⎤ Equality in (A.17) defines a pair of cones in (u, v, w) space within
ke k−1 0 −k1 which the behavior is inductive. For equality in (A.16), the shapes
⎢ ⎥ in (a, b, c) space are similar but distorted. The circuit elements for
⎢ ke k−1 + k2 −k−2 −k1 ⎥
Q=⎢
⎢
⎥
⎥ (A.4) the RC and inductive cases (circuits 2c,e and 3a,b) are given by
⎣ 0 −k2 k3 + k−2 −k−3 ⎦ m RT
Rct = = 2 (A.18)
−ke −k−1 −k3 k1 + k−3 Cdl ke F [(1 − ˇ1 )k1 + ˇ1 k−1 ]
 D.A. Harrington, P. van den Driessche / Electrochimica Acta 56 (2011) 8005–8013 8013

Cdl ke for making an impedance measurement that perturbs around this

C1 = (A.19)
k1 + k−1 steady state. However, tests show that this relationship appears to
2 hold more widely than this, for example on the unstable branches
m (k−1 + k1 ) of the current potential curve exhibited in case of the Frumkin
R1 = (A.20)
(k−3 k1 + k−1 k2 )Cdl ke isotherm [34].
(k1 k2 + k−2 k1 + k−2 k−1 + k3 k1 + k3 k−1 + k−3 k−1 )m
R6 = (A.21)
(k−2 k−3 + k−3 k2 + k3 k2 )ke Cdl
L (k1 k−3 + k2 k−1 )m
= R2 C2 = (A.22)
R7 k−2 k−3 k1 + k−1 k−2 k−3 + k2 k3 k1 + k3 k2 k−1 + k−3 k2 k1 + k−3 k2 k−1
where we have omitted the overly complicated expressions for R2 ,
C2 , R7 and L.
References

[1] D. Schuhmann, Electrochim. Acta 35 (1990) 1527.

Appendix B. [2] A. Lasia, in: B.E. Conway, J. Bockris, R. White (Eds.), Modern Aspects of Electro-
chemistry, vol. 32, Kluwer Academic/Plenum, New York, 1999, pp. 143–248.
[3] D.A. Harrington, J. Electroanal. Chem. 403 (1996) 11.
(Adapted from Ref. [32] with permisssion.) We here show that [4] D.A. Harrington, J. Electroanal. Chem. 449 (1998) 9.
limω→0 Z(ω) = (djss /dE)−1 [5] D.A. Harrington, J. Electroanal. Chem. 449 (1998) 29.
[6] D.A. Harrington, P. van den Driessche, Electrochim. Acta 44 (1999) 4321.
Assume potentiostatic regulation. The admittance is the trans- [7] J.P. Diard, B. Le Gorrec, C. Montella, J. Electroanal. Chem. 205 (1986) 77.
fer function for potentiostatic control, being the Laplace transform [8] L. Pauwels, A. Hubin, B. Van Den Bossche, L. Bortels, J. Deconinck, Electrochim.
of the output (current) over the Laplace transform of the input Acta 51 (2006) 1505.
[9] C. Dan, B. Van Den Bossche, L. Bortels, G. Nelissen, J. Deconinck, J. Electroanal.
(potential). It would seem straightforward to apply a constant Chem. 505 (2001) 12.
potential E at time t = 0 with Laplace transform E/s (where s [10] A.C.D. Angelo,.A. Lasia, J. Electrochem. Soc. 142 (1995) 3313.
is the Laplace parameter) and calculate the output current as [11] J. Vazquez-Arenas, M. Pritzker, J. Electrochem. Soc. 157 (2010) D283.
[12] S. Fletcher, J. Electrochem. Soc. 141 (1994) 1823–1826.
the inverse Laplace transform of Y(s)E/s, and this would be
[13] G.C. Temes, J.W. LaPatra, Circuit Synthesis and Design, McGraw-Hill, NY, 1977.
correct if the system were linear. However, we deal in electro- [14] P. Zoltowski, J. Electroanal. Chem. 375 (1994) 45.
chemistry with non-linear systems that are linearized around [15] P. Zoltowski, J. Electroanal. Chem. 424 (1997) 173.
the operating point. Therefore we suppose that the system is [16] C. Gabrielli, M. Keddam, Electrochim. Acta 41 (1996) 957.
[17] D.A. Harrington, B.E. Conway, Electrochim. Acta 32 (1987) 1703.
initially at steady state with applied potential E and result- [18] D. Schuhmann, J. Electroanal. Chem. 17 (1968) 45.
ing steady-state current density jss . We then make a small [19] M. Naito, N. Tanaka, H. Okamoto, J. Chem. Phys. 111 (1999) 9908.
step in potential ıE away from steady-state and wait for a [20] C. Gabrielli, B. Tribollet, J. Electrochem. Soc. 141 (1994) 1147.
[21] M. Sluyters-Rehbach, Pure Appl. Chem. 68 (1994) 1831.
new steady state. The Laplace transform of a small poten- [22] F. Berthier, J.-P. Diard, C. Montella, Electrochim. Acta 44 (1999) 2397.
tial step at time t = 0 is ıE/s. Therefore the Laplace transform [23] A.N. Frumkin, V.I. Melik-Gaikazyan, Dokl. Akad. Nauk. 77 (1951) 855.
of the current output perturbation of the linearized system is [24] J. O’M.Bockris, A.K.N. Reddy, Modern Electrochemistry, vol. 2, Plenum, NY, 1970
(Ch. 9).
the transfer function Y(s) times ıE/s. The value of the cur- [25] P. Córdoba-Torresa, M. Keddam, R.P. Nogueira, Electrochim. Acta 54 (2008) 518.
rent perturbation after a long time, ıj, can be found from the [26] P. Córdoba-Torresa, M. Keddam, R.P. Nogueira, Electrochim. Acta 54 (2009)
final value theorem: f(t → ∞)= lims→0 sF(s) [33]. The result is that 6779.
[27] I. Epelboin, M. Keddam, H. Takenouti, J. Appl. Electrochem. 2 (1972) 71.
ıj = lims→0 sY(s)ıE/s = lims→0 Y(s)ıE = ıE lims→0 Y(s). Thus the slope of [28] D.A. Harrington, P. van den Driessche, J. Electroanal. Chem. 501 (2001) 222.
the polarization curve ıj/ıE is equal to lims→0 Y(s), which is the [29] D.A. Harrington, P. van den Driessche, J. Electroanal. Chem. 567 (2004) 153.
polarization resistance determined by extrapolating the impedance [30] J.D. Campbell, D.A. Harrington, P. van den Driessche, J. Watmough, J. Math.
Chem. 32 (2002) 281.
spectrum to zero frequency.
[31] J.-P. Diard, B. Le Gorrec, C. Montella, C. Montero-Ocampo, J. Electroanal. Chem.
The proof uses the final value theorem, which requires stabil- 352 (1993) 1.
ity, i.e., the absence of poles in the closed right half plane. Thus, [32] F. Seland, Electrochemical Oxidation of Methanol and Formic Acid in Fuel
whenever we have stability, the relationship holds: it is a sufficient Cell Processes, Ph.D. thesis, Norwegian University of Science and Technology,
Trondheim, 2005.
condition. Since stability is a prerequisite for achieving a steady [33] F.F. Kuo, Network Analysis and Synthesis, 2nd ed., Wiley, NY, 1966, p. 167.
current at an imposed dc potential, it is usually also a prerequisite [34] F. Berthier, J.-P. Diard, C. Montella, I. Volovik, J. Electroanal. Chem. 402 (1996) 29.