Dielectric spectroscopy

the past few years and is now being widely employed in

a wide variety of scientic elds such as fuel cell testing,
biomolecular interaction, and microstructural characterization. Often, EIS reveals information about the reaction
mechanism of an electrochemical process: dierent reaction steps will dominate at certain frequencies, and the
frequency response shown by EIS can help identify the
rate limiting step.

='+i''

'

dipolar

''
atomic
ionic

electronic

1 Dielectric mechanisms
103

106

109

1012

1015

microwave infrared VIS UV

Frequency in Hz
A dielectric permittivity spectrum over a wide range of frequencies. The real and imaginary parts of permittivity are shown, and
various processes are depicted: ionic and dipolar relaxation, and
atomic and electronic resonances at higher energies. From the
Dielectric spectroscopy page of the research group of Dr. Kenneth A. Mauritz.

Dielectric spectroscopy (sometimes called impedance

spectroscopy), and also known as electrochemical impedance spectroscopy (EIS), measures the
dielectric properties of a medium as a function of
frequency.[1][2][3][4] It is based on the interaction of an
external eld with the electric dipole moment of the
sample, often expressed by permittivity.
It is also an experimental method of characterizing
electrochemical systems. This technique measures the
impedance of a system over a range of frequencies, and
therefore the frequency response of the system, including
the energy storage and dissipation properties, is revealed.
Often, data obtained by EIS is expressed graphically in a
Bode plot or a Nyquist plot.
Impedance is the opposition to the ow of alternating current (AC) in a complex system. A passive complex electrical system comprises both energy dissipater (resistor) CSIRO Dielectrics spectroscopy machine
and energy storage (capacitor) elements. If the system is
purely resistive, then the opposition to AC or direct cur- There are a number of dierent dielectric mechanisms,
connected to the way a studied medium reacts to the
rent (DC) is simply resistance.
applied eld (see the gure illustration). Each dielecAlmost any physico-chemical system, such as tric mechanism is centered around its characteristic freelectrochemical cells, mass-beam oscillators, and quency, which is the reciprocal of the characteristic time
even biological tissue possesses energy storage and of the process. In general, dielectric mechanisms can
dissipation properties. EIS examines them.
be divided into relaxation and resonance processes. The
This technique has grown tremendously in stature over most common, starting from high frequencies, are:
1

1.1

2 PRINCIPLES

Electronic polarization

This resonant process occurs in a neutral atom when the

electric eld displaces the electron density relative to the
nucleus it surrounds.

resonant electronic transitions or molecular vibrations,

which usually have frequencies above 1012 Hz.

2 Principles

This displacement occurs due to the equilibrium between

restoration and electric forces. Electronic polarization 2.1 Steady-state
may be understood by assuming an atom as a point nucleus surrounded by spherical electron cloud of uniform For a redox reaction R O + e, without mass-transfer
charge density.
limitation, the relationship between the current density
and the electrode overpotential is given by the ButlerVolmer equation:
1.2 Atomic polarization
jt = j0 (exp(o f ) exp(r f ))
Atomic polarization is observed when the nucleus of the
atom reorients in response to the electric eld. This is a
resonant process. Atomic polarization is intrinsic to the
nature of the atom and is a consequence of an applied
eld. Electronic polarization refers to the electron density
and is a consequence of an applied eld. Atomic polarization is usually small compared to electronic polarization.

1.3

with
= E Eeq , f = F /(R T ), o + r = 1 . j0 is the
exchange current density and o and r are the symmetry
factors.

Dipole relaxation

This originates from permanent and induced dipoles

aligning to an electric eld. Their orientation polarisation is disturbed by thermal noise (which mis-aligns the
dipole vectors from the direction of the eld), and the
time needed for dipoles to relax is determined by the local
viscosity. These two facts make dipole relaxation heavily dependent on temperature, pressure[5] and chemical
surrounding.

1.4

Ionic relaxation

Ionic relaxation comprises ionic conductivity and interfacial and space charge relaxation. Ionic conductivity predominates at low frequencies and introduces only losses to
the system. Interfacial relaxation occurs when charge carriers are trapped at interfaces of heterogeneous systems.
A related eect is Maxwell-Wagner-Sillars polarization,
where charge carriers blocked at inner dielectric boundary layers (on the mesoscopic scale) or external electrodes
(on a macroscopic scale) lead to a separation of charges.
The charges may be separated by a considerable distance
and therefore make contributions to the dielectric loss
that are orders of magnitude larger than the response due
to molecular uctuations.[1]

Fig. 1 : Steady-state current density vs. overpotential for a redox

reaction.

The curve jt vs. E is not a straight line (Fig. 1), therefore

a redox reaction is not a linear system.[6]

2.2 Dynamic behavior

2.2.1 Faradaic impedance
Main article: Faradaic impedance

1.5

Dielectric relaxation

In an electrochemical cell the faradaic impedance of an

Dielectric relaxation as a whole is the result of the move- electrolyte-electrode interface is the joint electrical resisment of dipoles (dipole relaxation) and electric charges tance and capacitance at that interface.
(ionic relaxation) due to an applied alternating eld, and Let us suppose that the Butler-Volmer relationship coris usually observed in the frequency range 102 1010 Hz. rectly describes the dynamic behavior of the redox reacRelaxation mechanisms are relatively slow compared to tion :

jt (t)
=
jt ((t))
j0 (exp(o f (t)) exp(r f (t)))

Dynamic behavior of the redox reaction is characterized

by the so-called charge transfer resistance dened by :
Rct =

1
jt /

1
f j0 (o exp(o f )+r exp(r f ))

The value of the charge transfer resistance changes with

the overpotential. For this simplest example the Faradaic
impedance is reduced to a resistance. It is worthwhile to
notice that:
Rct =

1
f j0

for = 0 .
2.2.2

Double layer capacitance

Fig. 3 : Electrochemists Nyquist diagram of a RC parallel circuit.

The arrow indicates increasing angular frequencies.

An electrode | electrolyte interface behaves like a capacitance called electrochemical double-layer capacitance Cdl is translated to the right.
. The equivalent electrical circuit for the redox reaction taking account of the double-layer capacitance is
shown in Fig. 2. Another analog circuit commonly 3 Measurement
used to model the electrochemical double-layer is called
parameters
a constant phase element.

of the impedance

Plotting the Nyquist diagram with a potentiostat[8] and

an impedance analyzer, most often included in modern
potentiostats, allows the user to determine charge transfer
resistance, double layer capacitance and ohmic resistance.
The exchange current density j0 can be easily determined
measuring the impedance of a redox reaction for = 0 .
Nyquist diagrams are made of several arcs for reactions more complex than redox reactions and with masstransfer limitations.

4 Applications
Fig. 2 : Equivalent circuit for a redox reaction without masstransfer limitation.

The electrical impedance of this circuit is easily obtained

remembering the impedance of a capacitance which is
given by :
Zdl () =

1
i Cdl

where is the angular frequency of a sinusoidal signal

(rd/s), and i= 1 . It is obtained:

Z() =

Rt
1+Rt Cdl i

Nyquist diagram of the impedance of the circuit shown

in Fig. 3 is a semicircle with a diameter Rt and an angular
frequency at the apex equal to 1/(Rt Cdc ) (Fig. 3). Others
representations, Bode or Black plans can be used.[7]
2.2.3

Ohmic resistance

The ohmic resistance R appears in series with the electrode impedance of the reaction and the Nyquist diagram

Electrochemical Impedance Spectroscopy is used in a

wide range of applications.[9]
In the paint industry it is a useful tool to investigate the
quality of coatings[10][11] and to detect the presence of
corrosion.[12][13]
It is used in many biosensor systems as a label free
technique to measure bacterial concentration[14] and
to detect dangerous pathogens such as Escherichia
Coli O157:H7[15] and Salmonella[16] as well as yeast
cells.[17][18]
Electrochemical Impedance Spectroscopy is also used
to analyze and characterize dierent food products.
Some examples are the assessment of food/package
interactions,[19] the analysis of milk composition,[20] the
characterization[21] and the determination of the freezing
end-point[22] of ice-cream mixes, the measure of meat
ageing,[23] the investigation of ripeness and quality in
fruits[24][25][26] and the determination of free acidity in
olive oil.[27][28]
In the eld of human health monitoring is better known

REFERENCES

as Bioelectrical Impedance Analysis (BIA)[29] and is used

to estimate body composition[30] as well as dierent parameters such as total body water and free fat mass.[31]

[11] Amirudin, A.; Thieny, D. (1995). Application of

electrochemical impedance spectroscopy to study the
degradation of polymer-coated metals. Progress in
Organic Coatings 26 (1): 128. doi:10.1016/03009440(95)00581-1.

[12] Bonora, P.L.; Deorian, F.; Fedrizzi, L. (1996). Electrochemical impedance spectroscopy as a tool for investigating underpaint corrosion. Electrochimica Acta 41 (7-8):
10731082. doi:10.1016/0013-4686(95)00440-8.

See also
Loss tangent
Debye relaxation
Ellipsometry
Linear response function
KramersKronig relation
GreenKubo relations
Electrochemistry
Potentiostat

References

[1] Kremer F., Schonhals A., Luck W. Broadband Dielectric

Spectroscopy. Springer-Verlag, 2002.
[2] Sidorovich A. M., Dielectric Spectrum of Water.
Ukrainian Physical Journal, 1984, vol. 29, No 8, p. 11751181 (In Russian).
[3] Hippel A. R. Dielectrics and Waves. N. Y.: John Willey
& Sons, 1954.
[4] Volkov A. A., Prokhorov A. S., Broadband Dielectric
Spectroscopy of Solids. Radiophysics and Quantum
Electronics, 2003, vol. 46, Issue 8, p. 657665.
[5] Floudas G., Paluch, M., Grzybowski A., Ngai K. L.
Molecular Dynamics of Glass-Forming Systems - Eects
of Pressure. Springer-Verlag, 2011.
[6] Linear vs. non-linear systems in impedance measurements Archived December 5, 2008, at the Wayback Machine.
[7] Potentiostat stability mystery explained (PDF). Retrieved 2011-11-08.
[8] Impedance, admittance, Nyquist, Bode, Black, etc.
Archived July 21, 2011, at the Wayback Machine.
[9] Lasia, A. Electrochemical Impedance Spectroscopy and Its
Applications. In Modern aspects of electrochemistry, volume 32. pp. 143248.
[10] McIntyre, J.M.; Pham, H.Q. (1996). Electrochemical
impedance spectroscopy; a tool for organic coatings optimizations. Progress in Organic Coatings 27 (1-4): 201
207. doi:10.1016/0300-9440(95)00532-3.

[13] Rammelt, U.; Reinhard, G. (1992). Application of electrochemical impedance spectroscopy (EIS) for characterizing the corrosion-protective performance of organic
coatings on metals. Progress in Organic Coatings 21 (23): 205226. doi:10.1016/0033-0655(92)87005-U.
[14] Maalouf, R.; Fournier-Wirth, C.; Coste, J.; Chebib, H.;
Saikali, Y.; Vittori, O.; Errachid, A.; Cloarec, J.P.;
Martelet, C.; Jarezic-Renault, N. (2007). Label-Free
Detection of Bacteria by Electrochemical Impedance
Spectroscopy: Comparison to Surface Plasmon Resonance. Analytical Chemistry 79 (13): 48794886.
doi:10.1021/ac070085n.
[15] Ruan, C.; Yang, L.; Li, Y. (2002). Immunobiosensor
Chips for Detection of Escherichia coli O157:H7 Using
Electrochemical Impedance Spectroscopy. Analytical
Chemistry 74 (18): 48144820. doi:10.1021/ac025647b.
[16] Nandakumar, V.; La Belle, J.T.; Reed, J.; Shah,
M.; Cochran, D.; Joshi, L.; Alford, T.L. (2008).
A methodology for rapid detection of Salmonella typhimurium using label-free electrochemical impedance
spectroscopy. Biosensors & Bioelectronics 24 (4): 1039
1042. doi:10.1016/j.bios.2008.06.036.
[17] Soley, A.; Lecina, M.; Gamez, X.; Cairo, J.J.; Riu,
P.; Rosell, X.; Bragos, R.; Godia, F. (2005). Online monitoring of yeast cell growth by impedance spectroscopy. Journal of Biotechnology 118 (4): 398405.
doi:10.1016/j.jbiotec.2005.05.022.
[18] Chen, H.; Heng, C.K.; Puiu, P.D.; Zhou, X.D.; Lee,
A.C.; Lim, T.M.; Tan, S.N. (2005). Detection of
Saccharomyces cerevisiae immobilized on self-assembled
monolayer (SAM) of alkanethiolate using electrochemical
impedance spectroscopy. Analytica Chimica Acta 554
(1-2): 5259. doi:10.1016/j.aca.2005.08.086.
[19] Hollaender, J. (2009).
Rapid assessment of
food/package interactions by electrochemical impedance
spectroscopy (EIS)". Food Additives & Contaminants 14
(6-7): 617626. doi:10.1080/02652039709374574.
[20] Mabrook, M.F.; Petty, M.C. (2003). Eect of composition on the electrical conductance of milk. Journal of
Food Engineering 60 (3): 321325. doi:10.1016/S02608774(03)00054-2.
[21] Grossi, M.; Lanzoni, M.; Lazzarini, R.; Ricc,
B. (2012).
Automatici ce-cream characterization by impedance measurements for optimal
machine setting.
Measurement 45: 17471754.
doi:10.1016/j.measurement.2012.04.009.

[22] Grossi, M.; Lazzarini, R.; Lanzoni, M.; Ricc, B. (2011).

A novel technique to control ice-cream freezing by electrical characteristics analysis. Journal of Food Engineering 106: 347354. doi:10.1016/j.jfoodeng.2011.05.035.
[23] Damez, J.L.; Clerion, S.; Abouelkaram, S.; Lepetit, J.
(2008). Beef meat electrical impedance spectroscopy
and anisotropy sensing for non-invasive early assessment
of meat ageing. Journal of Food Engineering 85 (1):
116122. doi:10.1016/j.jfoodeng.2007.07.026.
[24] Rehman, M.; Abu Izneid, J.A.; Abdullha, M.Z.; Arshad, M.R. (2011). Assessment of quality of fruits
using impedance spectroscopy. International Journal
of Food Science & Technology 46 (6): 13031309.
doi:10.1111/j.1365-2621.2011.02636.x.
[25] Harker, F.R.; Forbes, S.K. (1997). Ripening and development of chilling injury in persimmon fruit: An
electrical impedance study. New Zealand Journal
of Crop and Horticultural Science 25 (2): 149157.
doi:10.1080/01140671.1997.9514001.
[26] Bauchot, A.D.; Harker, F.R.; Arnold, W.M. (2000). ").
The use of electrical impedance spectroscopy to assess
the physiological condition of kiwifruit. Postharvest Biology and Technology 18 (1): 918. doi:10.1016/S09255214(99)00056-3.
[27] Grossi, M.; Di Lecce, G.; Gallina Toschi, T.; Ricc,
B. (2014).
Fast and accurate determination of
olive oil acidity by electrochemical impedance spectroscopy. IEEE Sensors Journal 14 (9): 29472954.
doi:10.1109/JSEN.2014.2321323.
[28] Grossi, M.; Di Lecce, G.; Gallina Toschi, T.; Ricc,
B. (2014). A novel electrochemical method for olive
oil acidity determination. Microelectronics Journal 45:
17011707. doi:10.1016/j.mejo.2014.07.006.
[29] Kyle, U.G.; Bosaeus, I.; De Lorenzo, A.D.; Deurenberg,
P.; Elia, M.; Gomez, J.M.; Heitmann, B.L.; Kent-Smith,
L.; Melchior, J.C.; Pirlich, M.; Scharfetter, H.; Schols, A.;
Pichard, C. (2004). Bioelectrical impedance analysis
part I: review of principles and methods. Clinical Nutrition 23 (5): 12261243. doi:10.1016/j.clnu.2004.06.004.
[30] Tengvall, M.; Ellegard, L.; Malmros, V.; Bosaeus,
N.; Lissner, L.; Bosaeus, I. (2009). Body composition in the elderly: Reference values and bioelectrical impedance spectroscopy to predict total body skeletal muscle mass. Clinical Nutrition 28 (1): 5258.
doi:10.1016/j.clnu.2008.10.005.
[31] Van Loan, M.D.; Withers, P.; Matthie, J.; Mayclin, P.L.
Use of Bioimpedance Spectroscopy to Determine Extracellular Fluid, Intracellular Fluid, Total Body Water, and FatFree Mass. Chapter in Human Body Composition, Volume
60 of the series Basic Life Sciences. pp. 6770.

Basics of Electrochemical Impedance Spectroscopy

Electrochimica Acta

7 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Text and image sources, contributors, and licenses

7.1

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Dielectric spectroscopy Source: https://en.wikipedia.org/wiki/Dielectric_spectroscopy?oldid=707707766 Contributors: XJaM, Topbanana, Altenmann, Karol Langner, M1ss1ontomars2k4, Malo, Bluemoose, Essjay, V8rik, Rjwilmsi, Mushin, Gaius Cornelius, Salsb,
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and Anonymous: 28

7.2

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