Electrochtmrco ACIU. Vol 40, No 4. pp. 439 445.

1995

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THE AMPLITUDE ANALYSIS OF IMPEDANCE SPECTRA

KAZIMIERZ DAROWICKI
Department of Anticorrosion Protection Technology, Faculty of Chemistry, Technical University of
Gdatisk, 80-952 Gdafisk, ul. Narutowicza 1l/12, Poland

(Received 5 July 1993; in revised form 4 July 1994)

Abstract-The amplitude analysis of a non-linear model of an electric system has been carried out. The
possibility of linear and non-linear electric element differentiation has been stated on the basis of imped-
ance measurements. The simultaneous frequency and amplitude analysis of impedance spectra allowed
the determination by extrapolation of electric element values corresponding to the zero value of the
perturbation signal. The amplitude analysis of impedance spectra allows the determination of the effective
amplitude value in an accurate way. The determination of the polarization resistance dependence on the
function of the effective amplitude of the perturbation signal is the static characteristic of a tested system.

Key words: non-linear impedance, harmonic analysis

INTRODUCTION allows the determination of the fundamental-

harmonic impedance, which is the function of the
Classic impedance investigations are carried out in amplitude and frequency of the perturbation signal.
the conditions of stability, causality and linearity of The relationship between the perturbation signal
the tested electrochemical system. Electrochemical amplitude and the fundamental-harmonic impedance
systems are non-linear systems. The linearity condi- is another matter. The knowledge of this relationship
tion is realized by applying low amplitude sine per- would allow the determination by extrapolation of
turbation signals with a sequentially changing impedance parameter values, corresponding to the
frequency. As a result, the electrochemical process in zero value of the sine voltage perturbation signal
the vicinity of the point at which impedance mea- amplitude value.
surements are carried out, is described with linear The determination of the amplitude characteristics
equations. The carrying out of impedance measure- of each element of the substitute electric schematic
ments in linear conditions significantly simplifies the diagram would allow the differentiation of linear and
measurement methodology and the frequency non-linear electric elements. Additionally, the ampli-
analysis of impedance spectra. It also allows the neg- tude analysis of polarization resistance should enable
ligence of the effect of the perturbation signal on the the determination of the static characteristic of the
physicochemical state of the tested system, and thus tested electrochemical system.
ensures the stability condition. The use of high In this work I have attempted to describe the non-
amplitude sine perturbation signals causes the neces- linear impedance, determined on the basis of the fun-
sity of the taking into account of furhter harmonic damental harmonic analysis of the response signal of
components, apart from the basic component. This the investigated system. The suitability of the simul-
effect is used in the Faradaic rectification taneous frequency amplitude analysis of impedance
technique[ l-63 and the Fardaic distortion tech- spectra has been checked for the complex character-
nique. The determination of each harmonic com- ization of the tested system.
ponent of the response signal of the tested system
allows its full characteristic.
The analysis of each harmonic component has
been carried out independently by Bertocci[ lo], IMPEDANCE OF THE FUNDAMENTAL
Callow and coworkers[ll, 123, Deavy and HARMONIC
Meszaros[ 131, and Gill et a/.[ 141.
The method of non-linear impedance measure- Transmittance analyzers are generally used for
ments, proposed in his work, is different from immittance measurements of electrochemical pro-
methods discussed in the literature and is based on cesses. Two signals are generated in the transmit-
the analysis of the fundamental-harmonic com- tance analyzer[ 15, 161: the proper perturbation
ponent of the response signal of the tested system. signal, and the signal generated in parallel, shifted in
The two-channel method of impedance measure- phase by a n/2 angle, being the reference signal. In
ments applied in ttransmittance analyzers allows the the multiplying block of the first channel the
determination of the fundamental-harmonic com- response signal of the investigated system is multi-
ponent of the response signal. As a result, the appli- plied by the proper perturbation signal. In the multi-
cation of the high amplitude sine perturbation signal plying block of the second channel the response

439
440 K. DAROWICKI

signal of the investigated system is multiplied by the For a sufficiently small amplitude of the sine voltage
reference signal. perturbation signal the alternating current is approx-
In the integrating blocks the signal in the first imated by the linear part of equation (4). As a result,
channel and the signal in the second channel are the immittance of the investigated procss depends on
integrated. the amplitude of the sine voltage perturbation signal.
The multiplication and the integration of the The application of higher amplitudes of the sine
response signal by the perturbation signal and the voltage perturbation signal requires the taking into
reference signal eliminates its higher harmonics. account of higher terms than linear of the power
Only the rspose signal fundamental harmonic of the series in the description of the alternating current (4).
investigated system is analyzed, which is divided into In this work we have limited the analysis to third
a component in phase and a component shifted by a order terms. Equation (4) can be resolved in accord-
n/2 angle in relation to the perturbation signal. As a ance with trigonometry principles into the current
result, on the output of both analyzer channels, component independent of the frequency called the
quantities are obtained, proportional to the real and Faradaic rectification current[ 18-203, the fundamen-
imaginary parts of the investigated system immit- tal harmonic component and further harmonic
tance. To recapitulate, the two-channel analysis of components[18,20] :
measurement signals allows the separation of the
fundamental harmonic. The multiplying and averag-
AI(t) z i,,, + Ai + Ai(2wt) + Ai(3wt) + . . (5)
ing operations of the measurement signal in both The faradaic rectification current is equal to :
channels are equivalent to filtration operations in a
narrow-band filterC15, 163.
In classic electrochemical impedance spectrometry E, AE;.

the amplitude of the perturbation signal is so small

that the response signal of the investigated electro- Equation (6) has been derived on the basis of equa-
chemical system is proportional to the perturbation tion (4), with only third order terms taken into
signal. The immitance of the investigated system is account. The taking into account of further terms of
the proportionality coefficient, which is generally a the power series causes the necessity of using the
function of the perturbation signal frequency. The next quaternary term describing the faradaic rectifi-
linearity condition is fulfilled if the measured immit- cation current:
tance does not depend on the amplitude of the sine
perturbation signal[15, 171. AE;.
The situation is different if the amplitude of the
sine perturbation signal is so large that the investi-
The range of sine voltage amplitudes of the pertur-
gated non-linear system cannot be estimated by a
linear approximation. In this case the measured bation signal, for which equation (6) is fulfilled, is
immittance is a function of the frequency and the strictly connected with the potential region (E,
amplitude of the sine perturbation signal. - AE,, E, + AE,), for which equation (1) is fulfilled.
Let us consider the immittance of the electrode The fundamental harmonic component of the elec-
process, the stationary characteristic of which is trode process current is given by equation (7)[21]:
defined by the general equation:
Ai z $ AE,
i = i(E), (1) [( > ES
where: i = current, E = potential.
+;(-&$AE;+...]coswt. (7)
The excitation of the analyzed non-linear system
by a signal described with a relation:
The two-channel analysis of the response signal of
AE(wt) = E(t) - E, = AE, cos wt, (2) the investigated system allows the separation of the
fundamental alternate current harmonic. The
where: AE(ot) = the voltage perturbation signal, remaining harmonic components are filtered away.
E, = the bias potential, AE, = the amplitude of the As a result, the polarization resistance of the investi-
sine voltage perturbation signal, w = the angular fre- gated electrode process is determined by the
quency, t = time, causes a direct current flow: relationship :
i, = i(E,). (3)

The alternating current of the electrode process may

be presented in the form of a Taylor power series:

Equation (8) is the static characteristic of the

investigated system. The knowledge of this charac-
teristic and the frequency characteristics allow the
determination of the transmission properties of a
given process. In reference to electrochemical pro-
cesses, the knowledge of frequency and static charac-
teristics enables the unequivocal determination of
 Amplitude analysis of impedance spectra 441

the mechanism and kinetics. The impedance mea- The effective amplitude of the perturbation signal
surements of the investigated electrode process as a requires additional comment. When determining the
function of the amplitude of the sine voltage pertur- R, resistances, it has been assumed that the gener-
bation signal enable the determination of the values ated and effective amplitude of the sine voltage per-
of the first and third current derivatives in relation to turbation signal are qua]. In reality, due to the
the potential, determined for the potential E, . Addi- prsence of the R, resistance describing the electrolyte
tionally, the determination of the second current resistance, the effective and generated amplitudes
derivative in relation to the potential and the values should be differentiated. To do this, the sine voltage
of the current for potential E, are possible on the perturbation signal diagram, presented in Fig. 2,
basis of the direct current as the function of the should be analyzed. The amplitude of the generated
amplitude of the sine voltage of the perturbation sine voltage perturbation signal in the transmittance
signal. analyzer system is equal to AE,,. The amplitude of
Let us consider the non-linar model of an electric the effective sine voltage perturbation signal is deter-
system presented in Fig. 1. This system is character- mined by the relationship:
ized by two time constants. It contains one non-
linear element D, and three linear elements C,, C, AE,(wt) =
Zo’w AEo,) - R, AE

and R,. From the electrochemical point of view the Zo’w, AE,,) ”
electric system can be treated as a non-linear, simpli-
= AR;(w) + jAEb/(w) (13)
fied analogue of a substitute electric diagram of a
two-step electrode reaction with adsorption of the where: AEb(w) the real part of the effective amplitude
intermediate product. As a result, the C, capacitor of the sine voltage perturbation signal, AER(w) the
represents the capacitance of the electric double imaginary part of the amplitude of the sine voltage
layer. The R, resistor and the C, capacitor represent perturbation signal and R, the electrolyte resistance.
the adsorption process of the intermediate product.
The amplitude of the generated sine perturbation
The R, resistance represents the charge transfer
signal AE,, is a real quantity. The effective ampli-
process. The connection of a diode in the model elec-
tude of the sine perturbation signal AE,(wt) is a
tric system in the conductivity direction causes a
complex quantity. The magnitude of the effective
direct current flow, which is an exponential function
amplitude of the sine voltage perturbation signal
of the voltage:
depends on the amplitude of the generated sine
i, = i” exp(bE,) (9) voltage signal and on the relation between the
impedance of the investigated system Z(jw, AE,,)
where b = the voltage constant of the diode and and the R, electrolyte resistance. For limiting low
i” = the current constant of the diode. frequencies equation (13) takes the form :
The faradaic rectification current is equal to [7] :
R2
lim AE,(wt) = AE, = ___ AEo, (14)
(10) 0-0 &+R2

The resistance of the diode is given by the relation- where: AE, = the effective amplitude of the sine
ship : voltage perturbation signal determined for limiting
low frequencies.
1 The polarization resistance of the investigated
--ii, b+cAEi+.... (11) system is defined by the relationship:
ROW,)
Taking into account the remaining electric elements R,(AE,) = lim Z(jw, AE,,) - lim Z(jw, AE,,)
and introducing the imaginary module, the imped- w-0 w 'L

ance of the analyzed non-linear electric system is (15)

easily determined :
The polarization resistance of the non-linear elec-
1 tric system is equal to the resistance of the diode for
ZCjw, AR,,) = R, +
1 jwc, ’ the considered model.
joC, + -
R,(AE,)+ 1 +jwC, R,

(12)
where: j2 = - I and AE,, = the generated ampli-
tude of the sine voltage perturbation signal.

, , C,=2OpF

Fig. 2. The schematic presentation of the distribution of

the amplitude of the sine voltage perturbation signal.
A&o-the amplitude of the generated signal, AR,-the
Fig. 1. The investigated non-linear electric system. C,, effective sine voltage perturbation signal. Z(jo)-the imped-
C,--capacitors, R,, R,-resistors, D,4iode. ance of the investigated process.
442 K. DAROWICKI

A relatively high value of the electrolyte resistance 00~~0 14 mV

in relation to the polarization resistance affects, in a a=*** 20 mV
•~~nn42 mV
basic way, the value of the effective amplitude of the mm... 56 mV
perturbation signal. To obtain a correct static char- a*.&& 70 mv
la&AA04 mV
acteristic in the form R =f(AE,), it is essential to lOOO-
$ 8 .o 0
take into account the effect of the electrolyte resist-
ance on the value of the effective amplitude of the 19 : : ;Aa”b.p*o
perturbation signal.
500:
Nh
I a nu
. a 0 lO
: 8 .O
. :.
_ .’ .
‘i :&$
EXPERIMENTAL
0 -““‘~“‘,‘I’.III~I,,,I,,,,,,I,,,,,,,,,~
0 500 1000 1500 2000
The analysis has been carried out of the equivalent
circuit, presented in Fig. 1. The impedance measure- Re(Z)/Ohm
ments have been carried out in the lOmHz-1OkHz Fig. 4. The impedance spectra of the investigated non-
frequency range, using a measurement assembly linear electric system detrmied for E, = 0.4OOV and each
made up of the ATLAS 8511 transmittance analyzer amplitude of the sine voltage perturbation signal.
and the ATLAS 8531 potentiostat. The value of the
amplitude of the sine voltage perturbation signal was
changed in the 14-86mV range. The amplitude of dence the non-linear impedance investigations have
the sine voltage perturbation signal was controlled been carried out. In Figs 4-7, the impedance spectra
with an oscilloscope. The polarization investigations of the investigated electric system have been present-
of model electric systems were carried out using a ed, determined for various amplitudes of the sine
potential scan rate of 1 mV s- ‘. voltage perturbation signal and different E, poten-
tials. The impedance spectra are characterized by
two time constants and take the form of two capac-
RESULTS AND DISCUSSION

The polarization curve of the analyzed non-linear

electric system is presented in Fig. 3. Curve A corre-
sponds to the polarization relationship without
elimination of the ohmic drop iR,. Curve B is the
polarization characteristic of the analyzed system
after ohmic drop iR, elimination. In accordance with
expectations the real relationship of the logarithm of
the current from the potential is a straight line. The
direction coefficient of the determined relation in
i =f(E) is equal to the diode voltage coefficient.

In points A (E, = 0,400), B (E, = 0,500), C (E, =

0,600) and D (E, = 0,700) of the polarization depen- Re(Z)/Ohm
Fig. 5. The impedance spectra of the investigated non-
linear electric system determined for E, = 0.500 V and each
-4.0
1 amplitude of the sine voltage perturbation signal.

-6.0 -f

400 600 600

E/mV Re(Z)/Ohm
Fig. 3. The polarization characteristic of the investigated Fig. 6. The impedance spectra of the investigated non-
non-linear electric system. (A) with no IR, ohmic drop cor- linear electric system determined for E, = 0.600 V and each
rection. (B) with iR, ohmic drop correction. amplitude of the sine voltage perturbation signal.
 Amplitude analysis of impedance spectra 443

diode resistance, which is equal to the value of the

polarization resistance. The dependence of the
inverse of the perturbation resistance from the
square of the amplitude of the sine voltage pertur-
bation signal has been presented in Fig. 8. In accord-
ance with the derived equation (11) the obtained
relations take the form of straight lines. The direc-
tion coefficients of these straight lines and the inter-
cept values enable the determination of the diode
voltage coetlicient. The values of the diode voltage
coefficients and the values of the polarization resist-
ance have been gathered in Table 1.
20.00 21 .oo 22.00 23.00 24.00 25.00 The impedance spectra corresponding to the zero
Re(Z)/Ohm value of the sine voltage perturbation signal can be
obtained by determining, by extrapolation, the
Fig. 7. The impedance spectra of the investigated non-
linear electric system determined for E, = 0.7OOV and each
dependence of the real and imaginary part of imped-
amplitude of the sine voltage perturbation signal. ance from the amplitude of the sine voltage pertur-
bation signal for each frequency. In reference to
electrochemical systems, the spectra correspond to
itance semicircles. A decrease of the polarization the free course of electrode processes. The extrapo-
resistance is observed, together with an increase of lated impedance spectra of the model electric system
the amplitude of the sine voltage perturbation signal. are presented in Fig. 9. The extrapolated impedance
The impedance spectra determined for each ampli- corresponds to the spectral power density, which is
tude of the sine voltage perturbation signal has been
subjected to frequency analysis. The frequency
Table 1. The values of the diode voltage coefficients deter-
analysis of the impedance spectra has been carried
mined by the method of non-linear impedance spectros-
out on the basis of the EQUIVCRT.PAS
copy and the method of potentiostatic polarization
algorithm[22], proposed by Boukamp. In accord-
ance with expectations, the C,, C, and R, values, &IV 0.4 0.5 0.6 0.7
determined on the basis of frequency analysis, do not
b/5-’ NIS 19.80 19.82 20.12 20.31
depend on the amplitude of the sine voltage pertur-
Pot. P. 19.80
bation signal because they are linear elements. A
strong dependence from the amplitude of the sine NIS-Non-linear impedance spectroscopy.
voltage perturbation signal is exhibited by the R, Pot. P.-Potentiostatic polarization.

4.60

3.60 1
0.00 2.00 4.00

103A E” ‘/‘I’

D)
0.240

E
Y
i

.
cz” 0.220 y
0.200
0.00 2.00 4.00
lObE’-/V’ 103AEoa/V2
Fig. 8. The dependence of the inverse of the polarization resistance and the square of the amplitude
determined for each E, value. (A) E, = 0.4OOV, (B) E, = 0.500 V, (C) E, = 0.600 V, (D) E, = 0.700 V.
444 K. DAROWICKI

AI

~~~ Re(Z)/Ohm $_“0 Re(Z)/Ohm

D)

lim Re(Z)/Ohm lim Re(Z)/Ohm

Ar-0 AE-0

Fig. 9. The extrapolated impedance spectra determined for each E, value. (A) E, = 0.4OOV, (B) E, =
OSOOV, (C) E, = 0.6OOV, (D) E, = 0.7OOV.

determined by the electrochemical noise correspond to the free course of the electrode
technique[23]. process.
The presented considerations and measurements
concerned the non-linear model of an electric system,
SUMMARY simulating an electrode process. The stability condi-
tion of the investigated electric systems was thus ful-
The carried out non-linear impedance investiga- filled. The effect of the magnitude of the amplitude of
tions of the model electric system simulating the the perturbation signal on the physicochemical state
electrode process confirms the correctness of the of the system, and thus its stability, is a different
theoretical analysis. They also confirm the possibility matter. This matter will be discussed in the following
of using transmittance analyzers in non-linear articles on the amplitude analysis of impedance
impedance investigations. The immittance of the spectra of specific electrochemical systems.
analyzed electric system depends on the frequency
and the amplitude of the sine voltage perturbation Acknowledyements-This work was financed by the
signal. Non-linear impedance investigations enable BW93904/047 grant.
not only the frequency but also the amplitude
analysis of immittance spectra. The amplitude
analysis of immittance spectra enables the differen-
REFERENCES
tiation of linear and non-linear quantities describing
the investigated electrode process. Immittance mea-
1. L. Oldham, Trans. Faraday Sot. 53.80 ( 1957).
surements allow the facile elimination of the electro- 2. G. Barker, R. Faircloth and A. Gardner, Nature 181,
lye resistance and the determination of the effective 247 (1958).
amplitude of the sine voltage perturbation signal. 3. G. Barker, Anal. Chim. Acta 18, 118 (1958).
The dependence of the inverse of the polarization 4. P. Delahay, M. Senda and C. H. Weis, J. phys. Chem.
resistance on the square of the amplitude of the sine 64,960 (1960).
voltage perturbation signal is the static characteristic 5. I. Iami and P. Delahay, J. phys. Chem. 66, 1108 (1962).
of the investigated electrode process. The character- 6. H. H. Bauer, Australian J. Chem. 17, 715 (1964).
7. P. Delahay, New Instrumental Methods in Electrochem-
istic is determined in the potential range from E,
istry, Interscience, New York (1954).
- AE, to E, + AE, and is the differential form of
8. B. Breyer and H. H. Bauer, Akernating Current Polar-
the polarization characteristic i =j’(E). It is possible ography and Tensammetry. Interscience, New York
to determine the values of each electric element cor- (1964).
responding to the zero value of the sine voltage per- 9. D. E. Smith, Electroanalytical Chemistry, (Edited by A.
turbation signal, based on the amplitude I. Bard) Vol. 1. Marcel Dekker, New York (1966).
characteristic. The values determined in this way 10. U. Bertocci, Corrosion Sci. 35, 21 I (1979).
 Amplitude analysis of impedance spectra 445

Il. L. M. Callow, J. A. Richardson and J. L. Dawson, Brit. System (Edited by J. R. Macdonald) John Wiley, New
Corrosion J. 11, 123 (1976). York (1987).
12. L. M. Callow, J. A. Richardson and J. L. Dawson, &it. 18. P. Delahay, in Advances in Electrochemistry nnd Elec-
Corrosion J. 11, 132 (1976). trochemical Engineering (Edited by P. Delahay and C.
13. J. Deavy and L. Meszaros, Acra Chim. Acad. Sci. Hung. W. Tobias) Vol. I. Interscience, New York (1961).
104, 311 (1980). 19. M. A. V. Devanathan, Electrochim. Acta 17, 1755
14. J. S. Gill, L. M. Callow and J. D. Scantlebuery, Corro- (1972).
sion 39, 61 (1983). 20. M. A. V. Devanathan. Electrochim. Acata 17, 1683
15. C. Gabrielli, Identification of Electrochemical Processes (1972).
hy Frequency Response Anulysis, Technical Report No. 21. K. Darowicki, Ph.D. Thesis, Technical University of
4/00X3. Farnborough, Schlumberger (1981). Gdatisk, Gdatisk 1991.
16. C. Gabrielli and M. Keddam, Corrosion 48, 794 (1992). 22. B. A. Boukamp. S&d Stute lomcs 20, 31 (1986).
17. M. C. H. MacKubre and D. d. Macdonald, in impen- 23. C. Gabrielli, F. Huet and M. Keddam. Elccrrochim.
danw Spwtro.tcopy Emphasiziny Solid Materials and Acta 31, 1025 (1986).

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