EC-Lab – Application Note #15

2009

Two questions about Kramers-Kronig transformations

I – INTRODUCTION
Using the Kramers-Kronig (KK) transforms, the Z and ZKK diagrams are similar for all
real part of a transfer function can be frequencies, therefore impedance
calculated for a causal, stable, linear time measurements have been carried out for a
invariant and finite system when f → 0 and causal, stable, linear and time invariant
f → ∞ , when the change in its imaginary system.
part, as a function of the frequency, is known. -Im(Z) vs. Re(Z)
-Im (Z) vs. Re(Z)
PEIS_-0-35V_circuit3_kk.mpp

Alternatively, the imaginary part of a transfer

21.1 Hz
function can be calculated when the evolution 1

of its real part is known [1-4]. When the 0.8

impedance of an electrode reaction is

-Im(Z)/kOhm
0.6
measured, it is possible to calculate the
imaginary part using experimental values for 0.4

the real part and calculate the real part using 0.2

experimental values for the imaginary part. 0

Comparing calculated impedance Z KK with
1 2
the experimental impedance Z is a useful Re(Z)/kOhm

tool to check the validity of the impedance Figure 2: Test circuit #3. Nyquist impedance diagram
measurement with respect to the conditions measured at point a (Figure 1) using PEIS technique.
of applicability of KK transforms. EWE = -0.35 V, Va = 10 mV, fmin = 0.2 Hz, fmax = 50 kHz
CV_circuit3.m pr
(blue markers) and Nyquist diagram obtained using KK
<I> vs. Ew e
transforms (red curve).
b
1.5
The Nyquist impedance diagram shown in
Figure 3 has been measured using a large
1
value of potential amplitude (Va = 375 mV) of
<I>/mA

the sinusoidal modulation of potential EWE, i.e.

0.5
for non-linear conditions. This diagram is still
a
made of two capacitive arcs, the low
0
frequency arc being smaller than the
0 1 2
corresponding arc in the case of Figure 2.
Ewe/V vs. SCE

Figure 1: Test-box 3, test circuit #3. I vs. EWE steady- The calculated impedance ZKK using KK
state curve. transforms is shown in Figure 3. These two
impedance diagrams are different, showing
As an example, the Nyquist impedance that the impedance measurement has been
diagram shown in Figure 2 has been measured carried out for non-linear conditions.
for circuit #3 of the Bio-Logic Test-box 3 using
the PEIS technique. Test circuit #3 mainly
consists of two transistors. It is a model for
metal passivation [5, 6]. The Nyquist
impedance diagram shown in Figure 2 is made
of two capacitive arcs well separated in
frequency. The calculated impedance ZKK
using KK transforms is shown in the Fig. 2.

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 EC-Lab – Application Note #15
2009

-Im(Z) vs. Re(Z)

-Im (Z) vs. Re(Z)
PEIS_1-35V_Va=375mV_circuit3_kk.mpp
the user to check the consistency of
experimental data without using the KK
0.2 68.0 Hz relationships [7]. The theoretical impedance
shown in Figure 5 shows the validity of the
0.15
truncated experimental impedance diagram.
-Im(Z)/kOhm

0.1
3.3 kHz

0.05

-0.05
0.2 0.4
Re(Z)/kOhm

Figure 3: Test circuit #3. Nyquist impedance diagram

measured using PEIS technique. EWE = -0.35 V,
Va = 375 mV, fmin = 0.2 Hz, fmax = 50 kHz (blue markers)
and Nyquist impedance diagram obtained using KK
transforms (red curve).

II – WHAT CAN WE DO WITH

TRUNCATED IMPEDANCE?
Let us suppose that, for some reason, the
Nyquist diagram has been measured for a
limited-range frequency values (Figure 4).
-Im (Z) vs. Re(Z)
-Im(Z) vs. Re(Z) PEIStruncated_-0-35V_circuit3_kk.mpp

1 21.7 Hz

0.8
-Im(Z)/kOhm

0.6

0.4

0.2

0
0 1
Re(Z)/kOhm

Figure 4: Truncated impedance diagram obtained for

limited-range frequency values. EWE = -0.35 V,
Va = 10 mV, fmin = 10 Hz, fmax = 50 kHz (blue curve) and
Nyquist diagram obtained using KK transforms (red
curve).

Obviously Z and ZKK impedance diagrams show

a large discrepancy. What can we do to check
the validity of the experimental impedance
diagram shown in Figure 4? It is always Figure 5: Truncated impedance diagram obtained for
possible to check this validity using ZFit [6] limited-range frequency values (blue curve), ZFit
with a measurement model, i.e. a Voigt circuit window for Voigt circuit R1+C2/R2+C3/R3 and
theoretical impedance diagram (red curve).
R1+C2/R2+C3/R3. As the measurement model
is consistent with the KK relations, it allows

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 EC-Lab – Application Note #15
2009

III – WHAT CAN WE DO WITH AN (GC), whereas it could under potentiostatic

UNSTABLE SYSTEM UNDER control (PC). Gabrielli et al. [9] have
demonstrated that, in this case, it was
GALVANOSTATIC CONTROL (GC)?
possible to calculate the admittance and then
III - 1 TEST-BOX 3 CIRCUIT 3
verify the validity of the admittance using KK
The Nyquist impedance diagram shown in
transforms.
Figure 6 has been measured at point b of the
steady-state curve (Figure 1) of circuit #3 of
the Bio-Logic test-box 3 using the PEIS
technique, i.e. under potential control (PC).
The Nyquist impedance diagram shown in
Figure 6 is still made of two capacitive arcs,
Figure 7: Sketch of the study of a scalar linear system
well separated in frequency with a negative under potentiostatic control (PC).
value of the real part of the impedance in low
frequency, according to the bell-shaped This problem is due to the electrochemist’s
steady-state curve. bad habit consisting of working under
-Im(Z) vs. Re(Z)
-Im (Z) vs. Re(Z)
PEIS_1-35V_circuit3_kk.mpp potentiostatic control (PC) and plotting the
100.2 Hz impedance diagram instead of an admittance
0.2
diagram. Under PC, the transfer function H(s)
of a system is not impedance but admittance.
0.1
In fact, a transfer function is given by Figure 7:
3.2 kHz
-Im(Z)/kOhm

L output ( t ) 
-0.1 H (s) =
L input ( t )  (1)
-0.2

0 0.5 Where s is the Laplace variable and L denotes

Re(Z)/kOhm
the Laplace transform. Under PC, the transfer
Figure 6: Test circuit #3. Nyquist impedance diagram function of an electrochemical system is:
measured at point b (Figure 1) using PEIS technique.
EWE = 1.35 V, Va = 10 mV, fmin = 1 Hz, fmax = 100 kHz
(blue markers) and Nyquist impedance diagram L  ∆I ( t )  1
obtained using KK transforms (red curve). (s)
H= = = Y (s) (2)
L  ∆E ( t )  Z ( s )
The result of the KK transform (Figure 6)
shows a large discrepancy in the low Therefore, checking the consistency of the
frequency domain. It has been shown [8, 9] experimental impedance diagram shown in
that it is not possible to directly verify the Figure 6 should be made with admittance data
validity of an impedance diagram instead of impedance data. Figure 8 shows the
measurement of an « unstable » electro- good agreement between Y and YKK
chemical system, such as it would be found, admittance diagrams and the consistency of
for instance, in the case of a steady-state the measured impedance.
current density vs. electrode potential curve
exhibiting a part with a negative slope. In fact,
the KK transforms do not really fail. The bell-
shaped curve steady-state current vs.
potential curve shown in Figure 1 cannot be
entirely drawn under galvanostatic control

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 EC-Lab – Application Note #15
2009

Im(Y) vs. Re(Y)

Im (Y) vs. Re(Y)
PEIS_1-35V_admi_circuit3_kk.mpp
domain. Obviously, the Z and ZKK Nyquist
diagrams are quite different, and the
6
experimental impedance Z does not obey the
68.0 Hz
KK relationships.
Im(Y)/kOhm-1

4 -Im (Z) vs. Re(Z)

6.8 kHz -Im(Z) vs. Re(Z) fANKK10_01_kk.mpp

2
400

0 134.2 Hz
200

-Im(Z)/Ohm
-2 0.45 Hz
0
-5 0 5 10
Re(Y)/kOhm-1
-200
Figure 8: Test circuit #3. Nyquist admittance diagram
measured using PEIS technique. EWE = 1.35 V,
-400
Va = 10 mV, fmin = 1 Hz, fmax = 100 kHz (blue markers)
and Nyquist admittance diagram obtained using KK -500 0 500 1,000
Re(Z)/Ohm
transforms (red curve).
Figure 10: Ni electrode in acidic medium (H2SO4
To conclude, it is therefore possible to 1 mol.L-1, Φ = 2 mm). Nyquist impedance diagram
measured using PEIS technique. EWE = 0.9 V/ECS,
transform YKK admittance diagrams into ZKK
Va = 12.5 mV, fmin = 50 mHz, fmax = 10 kHz with 25
impedance diagrams as it is shown in Fig. 9. points per decade (blue markers) and Nyquist diagram
-Im (Z) vs. Re(Z)
PEIS_1-35V_admi_circuit3.mpr # PEIS_1-35V_admi_circuit3_kk.mpp
obtained using KK transforms (red curve).
100.2 Hz
0.2
Figure 11 shows the good agreement
0.15
between Y and YKK admittance diagrams and
the consistency of the measured impedance
-Im(Z)/kOhm

0.1 of Ni electrode in acidic medium. The shift

3.2 kHz between the admittance diagrams is due to
0.05 the measurement error of the real part of the
impedance for f → ∞ .
Im (Y) vs. Re(Y)
0 fANKK10_01.mpr # fANKK10_01_kk.mpp

0
0.05
6.9 kHz
Re(Z)/kOhm

Figure 9: Z (blue markers) and ZKK (red curve) 0.04

impedance diagrams obtained by inversing 0.03

Im(Y)/Ohm-1

admittance diagrams shown in Figure 8.

0.02

III - 2 NI ELECTRODE IN ACIDIC MEDIUM 0.01

The well-known impedance diagram obtained 0

for Ni electrode in H2SO4 medium using the 0.20 Hz
-0.01
PEIS technique is shown in Fig. 10 [10, 11]. 0 0.05 0.1

Such diagrams are obtained for anodic Re(Y)/Ohm-1

Figure 11: Ni electrode in acidic medium. Nyquist
dissolution-passivation of Ni under PC in the
admittance diagram measured using PEIS technique.
instability range of the electrode|electrolyte EWE = 0.9 V/ECS, Va = 12.5 mV, fmin = 50 mHz,
interface with respect to current control. The fmax = 10 kHz with 25 points per decade (blue markers)
impedance diagram is made of two parts, a and Nyquist admittance diagram obtained using KK
near semi-circle in the high frequency domain transforms (red curve).
and a near circle arc in the low frequency

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 EC-Lab – Application Note #15
2009

IV – CONCLUSION
In this note, we have introduced the KK
transform, available in EC-Lab® to obtain
impedance diagrams. The KK transform is a
useful tool, but in some cases, we should be
careful: if we work with truncated impedance
and little data, it is better to use ZFit. If we
work with an unstable system, we should
work with admittance diagrams and convert
them to impedance if necessary.

Data files can be found in :

C:\Users\xxx\Documents\EC-
Lab\Data\Samples\EIS\ AN15_X

REFERENCES
1) V. A. Tyagay, G. Y. Kolbasov, Elektrokhimiya,
8 (1972) 59.
2) R. L. V. Meirhaeghe, E. C. Dutoit, F. Cardon,
W. P Gomes, Electrochim. Acta, 21 (1976), 39.
3) J.-P. Diard, P. Landaud, J.-M. Le Canut, B. Le
Gorrec, C. Montella, Electrochim. Acta, 39
(1994) 2585.
4) A. Sadkowski, M. Dolata, J.-P. Diard, J.
Electrochem. Soc., 151 (1) E20-E31.
5) Application Note #9 “Linear vs non linear
systems in impedance measurements”
6) Application Note #14 “Zfit and equivalent
electrical circuits”
7) P. K. Shukla, M. E. Orazem, O . D. Crisalle,
Electrochim. Acta, 49 (2004) 2881.
8) D. D. MacDonald, Electrochim. Acta, 35
(1990) 1509.
9) C. Gabrielli, M. Keddam, H. Takenouti, Proc.
5th Electrochemical Impedance Forum,
Montrouge (1991).
10) I. Epelboin, M. Keddam, M.-C. Petit,
Electrochim. Acta, 17 (1972) 177.
11) F. Berthier, J.-P. Diard, B. Le Gorrec, C.
Montella, J. Electroanal. Chem., 572 (2004)
267.

Revised in 08/2019

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