formed by air sparging a hydrogen sulfide saturated solution of 8. R. L. Martin. Materials Performance, Vol. 13, No.7, p.

19
ferrous derived sulfides.
3. Cathodic acceleration by these suspended sulfides ap-
pears due to hydrogen ion adsorption by the sulfides; hydrogen
ions are thus more available to the cathodic reaction during colli-
sions of particles with the metal surface. Hydrogen atom adsorp-
tion onto suspended sulfide particles is not ruled out but must at
least be a lower order effect.
4. Suspended sulfide particles formed by sulfidation of fer-
rous and ferric ions are more reactive than corresponding bulk
sulfides and so can be easily "overoxidized" past marcasite (or
pyrite).
5. To inhibit steel corrosion in the presence of oxidized
suspended sulfides, different compounds are required than those
effective in simple hydrogen sulfide corrosion. This is especially
true when oxidized sulfides and dissolved oxygen co-exist.
References
1. F. H. Meyer, O. H. Riggs, R. L. McGlasson, and J. D. Sud-
bury. Corrosion, Vol. 14, p. 109t (1958).
2. J. B. Sardisco, W. B. Wright, and E. C. Greco. Corrosion, Vol.
19, p. 354t (1963).
3. J. B. Sardisco and R. E. Pitts. Corrosion, Vol. 21, p. 245
(1965).
4. E. C. Greco and J. B. Sardisco. Proceedings of 3rd Inter.
Congr. on Metal. Corr. in Moscow, p. 130 (1966).
5. C. M. Hudgins, Jr. and R. L. McGlasson. The Effects of Tem-
perature (70-400 F) On the Aqueous Sulfide Stress Cracking
of an N80 Type Steel; Paper presented at 1971 Canadian
Western Regional Conference of NACE.
6. C. Milton. Corrosion, Vol. 22, p. 191 (1966).
7. R. H. Hausler, L. A. Goeller, R. P. Zimmerman, and R. H.
Rosenwald. Corrosion, Vol. 28, p. 7 (1972).
(1974).
9. G. J. Booth, L. Elford, and D. S. Wakerly. Br. Corros. J.,
Vol. 3, p. 242 (1968).
10. D. D. Mara and D. J. A. Williams. Br. Corros. J., Vol. 7, p. 94
(1972).
11. R. A. King, J. D. A. Miller, and J. S. Smith. Br. Corros. J.,
Vol. 8, p. 137 (1973).
12. J. S. Smith and J. D. A. Miller. Br. Corros. J., Vol. 10, p. 136
(1975).
13. H. G. Byars and B. R. Gallop. Materials Performance, Vol. 13,
No. 12, p. 31 (1974).
14. D. C. Bond and G. A. Marsh. Corrosion, Vol. 6, p. 22 (1950).
15. R. R. Annand. Corrosion, Vol. 22, p. 215 (1966).
16. E. S. Snavely and F. E. Blount. Corrosion, Vol. 25, p. 397
(1969).
17. M. I. Khokhar, E. G. Haney, and P. Fugassi. Corrosion, Vol.
26,p.180(1970).
18. M. I. Khokhar, P. Fugassi, and E. G. Haney. Corrosion, Vol.
27, p. 91 (1971).
19. H. Behret, H. Binder, and G. Sandstede. Echem. Acta., Vol.
20, p. 111 (1975).
20. T. Biegler, D. A. J. Rand, and R. Woods. Electroanal. Chem.
and Interfact. Echem., Vol. 60, p. 151 (1975).
21. R. L. Martin, R. R. Annand, D. Wilson, and W. E. Abraham-
son. Materials Protection and Performance, Vol. 10, No. 12,
p. 33 (1971).
22. R. R. Annand and R. L. Martin. SPE Paper 4223 presented
at SPE, Los Angeles, Oil Field Water Treating Conference
(1972).
23. B. D. Craig. Corrosion, Vol. 35, p. 137 (1979).
24. B. C. Syrett. Corrosion, Vol. 33, p. 257 (1977).

Recording and Analysis of AC Impedance

Data for Corrosion Studies *
I. Background and Methods of Analysis
FLORIAN MANSFELD *

Abstract

A brief review is given of the application of AC impedance measurements to electrochemical proc-

esses. Only very few applications for corrosion processes have been reported. The background and
various methods of analysis of AC impedance data are discussed. The parameters which char-
acterize the corrosion behavior can be determined from plots of the frequency dependence of the
impedance in the complex plane which result in semicircles for very simple cases. These
parameters can also be determined from straight line plots of the real part Z' vs wZ" or Z..k», where
Z.. is the imaginary part of the impedance and the frequency f is expressed as w = 2rl. Additional
methods of analysis include evaluation of the frequency dependenceof the series resistance R. and
series capacitance C.' the absolute value of the impedance IZ I and the phase angle o. Experimental
results obtained with a system for automatic recording and analysis of impedance data are given
for a dummy cell which represents a corroding electrode.

Introduction corrosion reactions and measuring corrosion rates in low conduc-

AC impedance techniques are finding increasing application in tivity media where traditional DC methods fail, and the fact that
corrosion research due to their promise in obtaining mechanistic polarization resistance as well as double layer capacitance data
data and due to the possibility of using the technique for corrosion can be obtained in the same measurement. Haruyama1.2 has pro-
monitoring. Some of the advantages of AC impedance techniques posed a corrosion monitoring device which measures AC im-
are the use of only very small signals which do not disturb the pedance data at two frequencies and has reported corrosion rate
electrode properties to be measured, the possibility of studying data for a large number of metal/electrolyte systems which in-
clude tap water and distilled water. It is important to note at this
*Submitted for publication April, 1980; revised October, 1980. point that the analysis of impedance data leads only to the value
"Rockwell International Science Center, Thousand Oaks, of the polarization resistance. The values of the Tafel slopes,
California. which have to be known as a function of time. electrode and elec-
0010-9312/81/000095/$3.0010
Vol. 36, No.5, May, 1981 ©1981, National Association of Corrosion Engineers 301
trolyte parameters in order to calculate the corrosion current RI)
density (c.d.) icorr or the corrosion rate, have to be obtained—if Z = Z' + jZ" = +
1 + jcoR p C
possible simultaneously—by an independent method.
Information concerning theoretical and practical aspects of R P jWCR1,
recording and analysis of AC impedance data is scattered through- Rn +
1 4. co 2c2R2 4. cd 2c2R 12 (1)
out the literature of basic electrochemical studies, 4-26 deter-
mination of battery parameters, 31-37 organic coatings where j = V-1 and the frequency f (Hz) of the AC signal is
properties, 55-59 evaluation of dissolution and passivation expressed in radians/s by w = 20. For impedance analysis,
phenomena, 38-54 and studies of electrodeposition. 6 " 1 Only very an equivalent series circuit is considered in Figure 1 where
few papers deal with the determination of the polarization resis- Z' = R $ and Z" = 1 /coC o .
tance from AC impedance data. Epelboin and co-workers have The simple model in Figure 1 does not take into account rate
discussed their impedance results and distinguished between the control by diffusion of charged species, which leads to the occur-
polarization resistance R p and the transfer resistance R s ." The rence of the so-called Warburg impedance, or the occurrence of
approach of Haruyama and co-workers has already been men- inductive loops, the significance of which is not clearly under-
tioned. 1 . 2 Haruyama has also given an analysis of the faradaic im- stood at present. The approach by Lorenz, et 81, 62 65 might lead to
'

pedance of mixed potential electrodes. 14 Dawson, et al, have a better understanding of this subject.
applied electrochemical measurements to the complicated subject The analysis of Equation (1) is best performed by considering
of corrosion of reinforcing steel in concrete. 28 Macdonald, et al, the admittance Y.
have used impedance measurements in a study of corrosion of 1
— = Y = Y' + jY"
Cu-Ni alloys in flowing sea water." Armstrong, et al, have given a
(2)
general discussion of a method for automatic impedance
measurements and analysis." Smyrl and Pohlman" have used The real (Z') and imaginary (Z") part of the impedance Z can be
digital signal analysis for the determination of the polarization calculated as a function of frequency for known values of Ro,R p
resistance. and C by Equation (4):
Since a complete survey of the possibilities of applying AC
Ro + R p + (coCRfiR p ) 2 (3a)
impedance measurements to corrosion studies is not available, a Y' =
few basic concepts are outlined here and methods of recording (Ro + R p ) 2 (COCROR p ) 2
and analysis of AC impedance data of corroding electrodes as
used in the author's laboratory are discussed in this paper. Part I coCR1,
shows how a number of different methods can be used to deter- Y" —
R p ) 2 (COCROR, (3b)
mine the characteristic parameters of a corroding electrode, and
Part II will discuss advantages and disadvantages of a number of
The real (Z') and imaginary (Z") part of the impedance Z can be
experimental arrangements for recording AC impedance data at
calculated as a function of frequency for known values of RO,R p
controlled potential or current. Examples for experimental results
and C by Equation (4):
obtained for a number of different corrosion systems will also be
Y ' Y"
given in Part II. Z' = and Z" = (4)
Y" 2
Analysis of AC Impedance Data
For the following discussion, it is assumed that the elec- Elimination of w leads to:
trochemical reactions that determine the corrosion behavior are of 1 R.
very simple nature and can be represented by the equivalent cir- [Z' — (Rn + — R p 11 2 + (Z"1 2 = 1=1 2
2 (5)
cuit shown in Figure 1. This circuit consists of the resistance, RU,
which includes the resistance of the electrolyte, surface films, cir- which is the equation of a circle with a radius of %R p , the center
cuit leads, etc. The polarization resistance, R p , is in parallel with of which lies on the Z'-axis at Zo = RU + Y2 li p as shown in Figure
the capacitance, C, which represents—in simple cases—the dou- 1, in which the negative value of jZ" is plotted vs Z'. Since only
ble layer capacitance, Cdt. For the circuit elements in Figure 1, the impedance data in the quadrant shown in Figure 1 are meaningful
impedance Z is given by: for the circuit shown, a semicircle is plotted in this complex plane
plot which sometimes is also called an Argand or a Cole-Cole 22
plot.
At the apex of the semicircle:

..n•n•ANn 1
<=>
R s2 Rs Cs W max =
CR p (6)
R
P
It is possible, therefore, to obtain all three parameters (RU, R p ,
and C) from a complex impedance plot as shown in Figure 1 pro-
vided a sufficient frequency range is investigated.
The polarization resistance, R p , could also be determined
from the maximum value of the phase angle, S mo„ and the cor-
responding value of I Z I according to (Figure 1):

.Je R p = 21Z1 tan „,.

13 (7)

N However, this method is not very accurate as will be discussed in

Part II.
Results obtained for a dummy cell are shown in Figure 2 as a
plot according to Equation (5). These data have been recorded
using an automatic system which includes a Solartron Frequency
Analyzer 1174 and a Hewlett Packard desktop computer 9825S
with a plotter 9872B. Potentiostatic or galvanostatic control
R 11 R s2 +%R P R 12 + R p
(PAR potentiostat 173 with coulometer plug-in 179) is used in
same cases; additional measurements are conducted at open cir-
FIGURE 1 — Equivalent circuit of corroding electrode and cuit by using a differential amplifier or a series measuring resistor
complex plane plot (theoretical). to determine the AC data. A computer program has been written

302 CO R R OSI ON —NACE
 10µF
• GALV. STAT. 100ft H
15.72 Hz
0 POT. STAT. O
0 100012
0
0
400 —
•

200

\t) 200 400 600 800

1000

1200
t (ohms)

FIGURE 2 — Complex plane plot for dummy cell (galvanostatic and potentiostatic data).

to perform the impedance measurements, store the data on mag-
netic tape and plot the data according to the different methods
discussed below. Details of the experimental approach and a
discussion of problems which can arise due to phase shifts from
potentiostats, etc. will be discussed in Part II of this paper. The
data presented here have been obtained under the optimum condi-
tions of the present experimental arrangement (choice of current
amplifier, sensitivity range, etc.).
The data in Figure 2 were obtained under galvanostatic and
under potentiostatic control for the same dummy cell shown over
a frequency range of 98.7 KHz to 0.3 Hz (15 points per decade).
The individual data fall on a semicircle of a diameter equal to R p =
1000 a For high frequencies, Z" 0 and Z' = Fin, while for low
frequencies Z" 0 and Z' = Rg + R p . In the high frequency re-
gion (f > 1.6 kHz), deviations occur from the ideal behavior of the
dummy cell. Under galvanostatic control (ldc = 0, lac = 1 mA),
another semicircle is found, while at potentiostatic control (E * = 0;
E8C = 10 mV), negative values of Z" are measured. These devia-
tions are considered to be due to phase shifts arising from the
potentiostat as discussed in Part II.
Since it is often difficult to determine the correct semicircle
through experimental points, especially if there is a significant
scatter in the data, linear plots have also been employed. 22 A plot
of Z' vs 02" according to:
Z' = R0 + R p — R p CcAZ"
(8)
leads to a straight line with a slope of -R p C and an intercept of R p
+ It for 6) — 0. If Z' is plotted vs Z"/...) according to:

Z"/c.) (ohms•sec)

3 6 9 12 15

1

0 0.3 0.6 0.9 1.2 1.5
we . x 10- 5 (ohms/sec)

FIGURE 3 — Determination of circuit elements according to Equations (8) and (9) for dummy cell of
Figure 2.

Vol. 36, No. 5, May, 1981 303

 1200 1.2
Z" JP 0 POT. STAT.
Z' = Rg + _ • GAIN. STAT.
wR p C (9) Rp +
.(1°Cr '.9.. c'''4 - 73C
0

cn P***6100 -
R0 can be obtained from the intercept at Z"/co = 0. co

The capacitance can be determined from the slope of the 00

straight lines according to Equations (8) or (9) or from a Z' vs wZ"

0
plot at Z' = RD, since at this point a" = 1/C. Similarly for a Z' vs 800 0.8

0
Z"/co plot at Z" = RO + R p the value of Z"/(.4 = FqC. The plots, co2" x 10-5
according to Equations (8) and (9), shown in Figure 3 illustrate the 0
(ohnu/se0
results obtained with the present experimental arrangement.
The data points in Figure 3 for the dummy cell in Figure 2 fall
exactly on the straight lines according to Equations (8) and (9) for 0

a capacitor of 9.76 AF. Smyrl, 3 ° using a digital fast Fourier 400 0.4

transfer technique, experienced much more scatter in similar plots

when measuring dummy cells, which made it necessary to use a 0

correction factor based on the theoretical impedance value for

each frequency. RE2 ..'• ............... .C1 nCLICPC.FOIID
It is often of interest to follow variations of R s and C s (Figure
1) as a function of frequency. For this purpose, Z' = R. and 02" o 0 0
2 4 6
= 1/C s can be plotted as a function of log w as shown in Figure 4 log w

(data from Figure 2). Since at high frequencies, Z' RD and at

low frequencies Z' R p + RD, both R p and RD can be determined FIGURE 4 — Frequency dependence of Z' = R, and 1 /C, =
from the horizontal parts of the Z'-log w, plot. This plot has an in- wZ" (data of Figure 2).
flection at co % = (R p C) -1 . The wZ"-log (.0 plot has an inflection at
the same point; at high frequencies, wZ" becomes independent of 4 90

frequency with wZ",,,_ 0, — 1/C.

Due to the phase shifts mentioned above, the wZ"-log CO does
not remain horizontal in the entire high frequency range. Since Z"
becomes negative for f > 10 KHz for the potentiostatic measure-
ment, wZ" becomes negative also, while wZ" increases sharply
Rp + on 3
above the theoretical value for the galvanostatic measurement. 60
Another method for evaluating the impedance data is the
anal sis of the frequency dependence of the absolute value I Z I =
Z' + Z" and the phase angle 6 (Figure 1), which is defined as: N
45 I

Z "

tan 6 = —= (wC„R s ) 1 .
(10)
Z'
2 30
From plots of log I Z I and S as a function of log CU so-called Bode
—

plots—the parameters of the circuit can be determined.

As an example, the data for the dummy cell in Figure 2 are
replotted in Figure 5. At very high and very low frequencies, I Z
becomes independent of frequency. From thes' horizontal lines
(dashed lines in Figure 5), the values of R p and RD can be deter- 0

mined. This analysis is the basis of the corrosion monitor sug-

gested by Haruyama, 1 ' 2 who determines I Z I at one frequency in
each of the horizontal parts of the Bode plot. For an intermeditae
frequency range, I Z I is inversely proportional to w and a straight FIGURE 5 — Frequency dependence of 1Z and phase angle 6
line with a slope of -1 is observed in a log I Z I -log w plot (dashed (data of Figure 2).
line in Figure 5). From an extrapolation of this straight line to 0) =
1, the capacitance can be determined as I Z I = 1/C. The break Z" cs)CR,i
points for this plot have been given by Haruyama 2 as: tan 6 = — =
Z' Ro + R p + Ro(wCR p 1 2 112)
1 1
w h — and we =
ROC + R,IC
• (11) From Equation (11) one finds that 6 = 45 °, for:
1 1
Since the phase angle changes sharply around 6 = 45 °, use (0 1,2 =
2R0C
t
2RoRpC
R — VP
— 411t) (13)
can be made of this fact to locate the break point for unknown
systems. The frequencies at which these break points occur can This result is different from (oh f in Equation (10) for the break
be calculated based on Equation (10) with Equations (3) and (4): points of a Bode plot. The reason for this discrepancy is the fact

TABLE 1 — Characteristic Parameters for Bode Plot

(R = 1000 0, C = 10 AF)

Ra (ohm) wh uy

w/ MX &max (degree)
Equation (11) Equation (13) Equation (16) Equation (15)

1 1 x 10 5 100 9.99 x 10 4 100 3164 86.4

10 10000 99 9898 102 1005 78.6
50 2000 95 1889 111 450 65.4
100 1000 91 874 126 331 56.5
200 500 83 300 200 245 45.6

304 CORROSION—NACE
 90
With increasing Ra at constant R p , both the phase angle 6,„, and
Wm, decrease. Equations (13), (15), and (16) can be used to
calculate R p , NI and C for unknown systems.
Since it is not always possible to perform measurements at
the very low frequencies which are necessary to obtain a semi-
circle for a system with very low corrosion rates and/or a high
K capacitance, a Bode plot could be used to extrapolate from high
frequency data to the break point at 6 = 45° and determine R p in
45
this manner.
For some electrode reactions, more than one reaction step
might be of importance and, consequently, more than one semi-
circle will occur in the complex plane plots. If the rate of one reac-
tion is very different from that of the other, the occurrence of this
reaction might not be detected in a complex plane plot. An exam-
ple is given in Figure 7 for the dummy cell shown. The high fre-
0 2 4
log 4)

a 5000

COMPLEX IMPEDANCE DIAGRAM

4000
DUMMY CELL

3000

25
2000
50 10

1000
— AAN-
CE 100 10K WE
REF

of
8000

10,000
2000 4000 8000
Z' (ohm.)

FIGURE 7 — Complex plane plot for dummy cell shown.

quency semicircle for the parallel combination of C 1 = 25 µ F and

R 1 = 100 0 can barely be seen in this plot. When the same data
are plotted in a Bode plot (Figure 8), it becomes obvious from the
frequency dependence of the impedance and the phase angle, 6,
log

b that two circuit elements are responsible for the measured im-
pedance spectrum. In several studies of organic coatings, 57-59 im-
FIGURE 6 — Effect of increasing R( on frequency de-
pedance data have been displayed as Bode plots. It has been
pendence of I Z I (Figure 6a) and phase angle 8 (Figure
observed that the impedance spectrum contains contributions
6b) (data of Figure 2, potentiostatic).
from the corrosion reaction in pores and defects of the coatings
that a straight line with a slope of -1 is observed only for R p Ro, and from the coating/electrolyte interface which leads to im-
in which case Equation (11) is a good approximation. The pedance data such as those in Figure 8. From the changes of the
theoretical values for wk, p and w 1 , 2 are indicated in Figure 5, the
solid line connects the break points at ce i and co 2 .
90
The break points in a Bode plot have been calculated for a COMPLEX IMPEDANCE DIAGRAM

theoretical case (dummy cell of Figure 2) in Table 1 according to DUMMY CELL

Equations (11) and (13) for increasing values of Ro. According to 4

Equation (11), cob and we both decrease with increasing RU while
Equation (13) shows that co l decreases but 412 increases with in-
creasing R0 and the two break points approach the value: 3

co — 1 (14a)
for 2R(C
2

Rp
—
2 + 2 V2 (14b)

at which point S = 45 °.
The experimental data in Figure 6 for the parameters in Table
1 confirm Equation (13), for Rg = 200 0 the break points are
2 12 2 3 4 5
almost equal (Figure 6b). These results suggest that it will be dif- log

ficult to analyze experimental impedance data on the basis of a

Bode plot in cases where R p and R0 are of similar magnitude. FIGURE 8 — Bode plot for dummy cell in Figure 7 show-
For a complete analysis of the system, one can also calculate ing contributions from the two parallel resistor-
the maximum of the phase angle S m ..: capacitor combinations.
RI)
tan O m . — high frequency semicircle, conclusions concerning the corrosion
2Rc2(1
rn l Rp ) - (15)
reaction occurring under the coating can be made.
and the corresponding frequency w The Bode plot could also be used for a more accurate deter-
— max:
a 1
1 41 Rp
mination of R according to Equation (7) than from the semicircle
4) max = plot. The maximum of band the corresponding value of I Z I can be
1161
CR p Ro determined from plots such as shown in Figures 5 and 6.

Vol. 36, No. 5, May, 1981 305

 Additional information is available from Bode plots concerning
the selection of a suitable sweep rate s for determination of R p in
potentiodynamic experiments as shown in the ASTM Recom-
mended Practice G59. The sweep rate has to be low enough that
the corresponding frequency s/AE, where AE is the amplitude of
the AC signal, falls into the low frequency range where I Z1 is in-
dependent of frequency. If s is chosen too high, the measured R p
will be too low as can be seen clearly from the Bode plot. 64
Deviations from Ideal Behavior
Experimentally, it has been observed that deviations from the
results expected for simple equivalent circuits such as shown in
Figures 1 and 2 occur for real, corroding systems. While the
results for iron and steel in acid media containing inhibitors 66,67
and other systems will be discussed in detail in Part II of this
paper, a few comments will be made here concerning analysis of
the experimental impedance data. Results for iron (Johnson-
Matthey) in aerated 1N H 2 SO 4 and 1N HCI are shown in Figure 9.
The solid lines represents semicircles which have their centers on
the Z'-axis. These circles were constructed to fit the experimental
data at the high and low frequency limit. The dashed lines are
semicircles which were constructed to fit the experimental data
as much as possible with the exception of the inductive loop. In
this case, the center of the semicircles does not lie on the Z'-axis,
but is shifted to negative Z"-values. This method of analysis is
based on the assumption of frequency or time constant dispersion
according to Cole-Cole. 22 Epelboin, et a/, 27 among others, have
used this type of analysis of experimental impedance diagrams.
The occurrence of the inductive loop, which becomes more
pronounced in the presence of inhibitors, has created the addi-
tional problem concerning the significance of the inductive loop
The analysis of experimental impedance curves has been
discussed recently by Lorenz and Mansfeld" who pointed out
that an analysis such as shown in Figure 9 for R t and RI could lead
to erroneous results. The experimental data in Figure 9 can be
simulated by the equivalent circuit in Figure 10a. If a semicircle is
drawn through the experimental data at high frequencies, FL and
RI can be determined as indicated. However, these values do not
correspond to the numerical values of the elements in the
equivalent circuit.
Another method of analysis is shown in Figure 1013" which
corresponds to the occurrence of a second time constant in the
capacitive loop. After separation of the double layer capacitance
Cdt the contribution of the faradaic impedance Zf remains. In this
case, Fi t really is found as the limit of the impedance at w— 00, ac-
cording to Equation (18), while R p corresponds to w-0. This
discussion shows that the definition of Rt by Epelboin, et ed, 27 and
the evaluation of the experimental data by the same group are not
consistant.
Summary
A review of methods for analysis of AC impedance data has
been given. In addition to the plot in the impedance plane which
results in a semicircle for simple electrode reactions, the deter-
mination of electrode parameters from the frequency dependence
of the series resistance, R 8 , and series capacitance, C 8 , and from
the absolute value of the impedance I Z I and the phase angle s5
have been discussed.
400 I
Cdl
SEMICIRCLE WITH
-- DIAMETER R1 + R2 +113 r --- 4--- 1
-

132 113
and its relationship to the polarization resistance R p , which is I
SEMICIRCLE ACCORDING 1 R1 -1=3- -4=1- I
defined as: — TO COLE-COLE •-i-1=1- _ _L.
--II.- -rer,
Rp = lim Re Zt}. Eco,T — EXPERIMENTAL DATA
C I
o (17) 200 •I

where Re iZt denotes the real part of the complex faradiac im-
pedance. Epelboin, et a/, 27 based on experimental results for iron E %(131 + R2 + R3)
0
in sulfuric acid containing propargyl alcohol and a nonuniform cor-
N I
rosion model found it necessary to define the change transfer
resistance 13,
R t = lira Re Zf E con.
0
%R•
t
Rp
n Rt

— co (18) ••••••...

RT
Experimentally, a better agreement of weight loss data with R t (a)
than with R was claimed. 27 The values of R R t , and RI which
corresponds to the diameter of the semicircle with the center - 200
0 200 400 600
a
below the Z'-axis, are indicated in Figure 9.
Z' (ohm)
40
300

200

20

E
E O

100 • • • ...
N
Zf
N •
••
R t Rp
0
0

(b)

- 100

0 100 200 300 400 500

20 b Z' (ohm)

FIGURE 10 — Analysis of data for equivalent circuit shown

in Figure 10a. C dl = 25 g, C = 50 AF, R 1 = 1000, R2 =
FIGURE 9 — Experimental impedance diagram for iron 2000, R3 = 1000, L = 100H. (a) Analysis assuming fre-
(Johnson-Matthey) in aerated 1N H 2 SO 4 and 1N HCI after quency dispersion. (b) Analysis assuming occurrence of
7 hours. more than one time constants in capacitive loop.

306 COR ROSION—NACE
 Acknowledgment
The author acknowledges the assistance of Cameron Ogden,
Rockwell International Electronic Research Center, who wrote the
computer program for recording and analysis of AC impedance
data, and many helpful discussions with David K. Roe, Portland
State University. Sue Tsai collected the experimental data. This
work was funded by the Science Center IR&D Project "Corrosion
and Environmental Effect."
References
1. T. Tsuru and S. Haruyama. Boshoku Gijustu, (Corr. Eng.) Vol.
27, p. 573 (1978).
2. S. Haruyama and T. Tsuru. ASTM STP, Progress in Elec-
trochemical Corrosion Testing, to be published.
3. F. Mansfeld. Corrosion, Vol. 29, p. 397 (1973).
4. H. Gerischer. Z. Elektrochem., Vol. 58, p. 9 (1954).
5. R. H. Cole. J. Chem. Phys., Vol. 23, p. 493 (1955).
6. W. Lorenz. Z. Elektrochem., Vol. 62, p. 192 (1958).
7. J. H. Sluyters. Rec. Trans. Chem., Vol. 79, p. 1092 (1960).
8. J. H. Sluyters and J. J. C. Oomen. Rec. Trans. Chem., Vol.
79, p. 1001 (1960).
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