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aqueous reaction to form the hydrated fluorides which are tion studies, to B. A. LaMont and co-workers for the
subsequently dehydrated at elevated temperatures in an chemical analyses, and to C. Lentz and associates for the
atmosphere of H F gas. Extensive studies were made of the spectrographic analyses.
conditions for the preparation of high-purity ZrF4, and
pilot plant equipment is described which was used to pre- Manuscript received February 23, 1956. Contribution
No. 480. Work was performed in the Ames Laboratory of
pare 100 lb batches of the fluorides.
the A.E.C.
The reduction step was investigated thoroughly, par- Any discussion of this paper will appear in a Discussion
ticularly for Zr, and those factors which affect metal Section to be published in the December 1957 JOURNAL.
quality and yield were determined. Reduction yields of
96 % were obtained with both Zr and Hf. After are-melting, REFERENCES
the sponge Zr had a hardness of 40-45 Rockwell A and 1. K. A. WALSrI, U. S. A.E.C. Report No. AECD-3640,
was readily cold-rolled into sheet. Zr metal thus prepared (1950).
had a purity of about 99.8%. 2. D. PETERSON AND H. A. WILI-IEL?r Unpublished work,
Hf metal, similarly prepared, had a hardness of 69 Ames Laboratory, Iowa State College, (1950).
3. F. J. LAMBERT, P. J. HAGELSTON, AND R. O. HUTClrlI-
Rockwell A and was hot-rolled but was too brittle to be 9SON, Oak Ridge National Lab. Report No. Y-595,
easily cold worked. The Hf was low in metallic impurities, (1950).
but contained considerable amounts of C, N, and oxygen. 4. J. L. WILLIAMS AND B. WEAVER, U. S. A.E.C. Report
No. AECD-3329, (1950).
ACXNOWLI~DGMENTS 5. M. U. ConEs, Rev. Sei. Instr., 6, 68, (1936).
6. R. M. TRECO, J. Metals, 5, 344, (1953).
The authors are especially grateful to J. W. Starbuek 7. R. A. F o o s AND H. A. WILtIELM, V. S. A.E.C. Report
for his valuable contribution in the experimental redue- ISC-693, (1956).
Electrochemical Polarization
I. A Theoretical Analysis of t h e Shape of Polarization Curves
Metals Research Laboratory, Electro Metallurgical Company, A Division of Union Carbide and Carbon Corporation,
Niagara Falls, New York
ABSTRACT
At low overvoltage values, deviations from Tafel behavior for a noncorroding elec-
trode are due primarily to the reverse reaction of the oxidation-reduction system, and
at high overvoltages to concentration and/or resistance polarization. It is
shown further that the practice of placing straight lines through a few experimental
points is extremely hazardous, while the indiscriminate introduction of "breaks" is
contrary to the electrode kinetics described.
Further complexities arising from a corroding electrode are described. In this in-
stance, the forward and reverse reactions of both of the oxidation-reduction systems
forming the corrosion couple must be considered. This representation of the local
polarization diagram of a corroding metal is more fundamental than that used pre-
viously in the literature, and thus provides a clearer picture of the various factors
which affect the corrosion rate and the shape of polarization curves.
A region of linear dependence of potential on applied current is described for a
corroding electrode by treating it in a manner analogous to that for a noncorroding
electrode. An equation is derived relating the slope of this linear region to the corrosion
rate and Tafel slopes. This relation provides an important new experimental approach
to the study of the electrochemistry of corroding metals since, in some instances, in-
terfering reactions prevent determination of T~fel slopes at higher current densities.
Polarization measurements are an important research data and the correct interpretation of "breaks" in polariza-
tool in investigations of a variety of electrochemical phe- tion curves. Abrupt changes in slope of overvoltage vs.
nomena. Such measurements pernfit studies of the reac- log current have been given considerable significance in the
tion mechanism and the kinetics of corrosion phenomena past few years. Logan (1) examined various methods of
and metal deposition. I n spite of their wide applicability plotting cathodic polarization measurements to evaluate
and extensive use, considerable uncertainty in the inter- the correspondence between current required for complete
pretation of polarization measurements still exists. Some cathodic protection of a system and current flow at the
of the uncertainties include the proper method of plotting potential break. He reported that the potential break
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Vol. 104, No. 1 ELECTROCHEMICAL POLARIZATION 57
method indicated a different current requirement than * o . Z ~ o B t . ' E ..... i ........ J ........ , ','~;,,
that indicated by other criteria9 I n addition, breaks could N /
be obtained regardless of whether the potential was plot-
ted as a linear or logarithmic function of applied current.
However, examination of the data presented indicates that
;qxr176
there is no real experimental evidence pointing toward
existence of breaks. I n most cases, the plots would best
have been considered smooth curves rather than a series
~ Oi(:] EOUlUBRIUM POTENTIAL
of straight lines. Schwerdtfeger and McDorman (2) pre-
sented a theory which permitted calculation of the corro-
sion rate of a metal from its polarization characteristics.
The calculation was based on plotting both anodie and
cathodic polarization as linear functions of current and
using currents at the potential "breaks" in a formula de-
rived essentially from trigonometric consideratior/si Again,
however, experimental evidence for the existence of breaks
was not clear-cut. Still another discussion of potential
"breaks" was presented recently by Johnson and Babb (3)
who used irreversible thermodynamics to derive Pearson's
-0.2,
.01
Z .I
....... I
I
,
CURRENT(MICROAMPERES)
FIG. 1. Relationship between overvoltage and current
,
I0 I00
(4) equation for the relation between the corrosion cur- for the anodic and cathodic reactions of a single electrode
system.
rent and potential breaks. Data presented by these in-
vestigators for the corrosion of Fe in KC1 solutions indi-
of Z is equal to the rate of reduction of Z+(Z+ + e ~ Z).
eate that a great deal of imagination must be used when
The reaction rate and current flow are directly related ae-
drawing the curves in order to obtain "breaks" 9
cording to F a r a d a y s Law. If {, is defined as the current in
Changes in slope rather than a sharp break can be ob-
the forward (reduction) direction (Z+ + e -~ Z) and
tained in H activation overvoltage measurements as a
g~ as the current in the reverse (oxidation) direction
result of the H being discharged by two different rate-
(Z --* Z+ + e), the electrode equilibrium may be expressed
determining reactions. Parsons (5) discussed a dual mecha-
in the form
nism of H discharge and from energy considerations
calculated the potential ranges where more than one rate- ~z = ~ = io,z (I)
determining step might be expected. However, he did not
where io,, is commonly called the exchange current9 When
imply that a "break" should be found. Bockris and Con-
the reaction rate is controlled by a slow step requiring an
way (6) found the cathodic overvoltage vs. log i plots for
activation energy, the dependence of current on over-
Ag in 0.1-7.0N HC1 solutions showed a marked change in
slope at current densities which depended on acid concen- voltage may be expressed as 2
tration. They attribute the change in slope to a change in
symmetry of the energy barrier at the electrode interface
rather than to a dual discharge mechanism. Here again a
sharp break was not found, the two linear portions of the ~ = /o,~exp + ~ ,~, ) (III)
plot being connected by a curve over a short range of
overvoltage values.
where the overvoltage, 7, is the difference between the
The purpose of this discussion is to analyze the shape
potential of the working electrode and the equilibrium po-
of polarization curves in terms of modern concepts of elec-
tential of the reaction being studied, and/3'~ and fl~ are
trochemistry. I t is shown that many of the reported breaks
constants. For a system with a symmetrical energy barrier
in polarization curves are not real, and result either from 9 t
at the electrode interface, fl~ is equal to fl~P. Therefore, Eq.
attempts tc~.apply activation overvoltage theory to data
(II) and (III) may be written as
obtained under conditions where other types of overvolt-
age are included in the measurements, or from a combina-
~7 = -fl~ log 7 - 9 (IV)
tion of insufficient data and an erroneous assumption that ~o,z
a break must exist. I n such a presentation, it is convenient
to consider first the shapes of polarization curves for a r/ = ~
q-fl~ log -=- (v)
noncorroding electrode, then to extertd the analysis to in- Zo,z
clude further complexities which arise from local action
where r = 2.3 fl~ = 2.3 fl~'.
currents.
To aid in visualizing the relations given by Eqs. (IV)
i ~ONCORRODING ELECTRODE SYSTEM and (V), they have been plotted on Fig. 1 by arbitrarily
Consider a substance Z in a solution containing its ions giving fl~ a value of 0.100 v and io.~ a value of 1.0 #a. These
Z+2 I n such a system at equilibrium, the rate of oxidation Other investigators have expressed these equations in
This might be Cu in equilibrium with Cu +. The same more fundamental terms. They are simplified here in order
analysis also applies to an inert electrode in an oxidation- not to detract from the main purpose of the discussion.
reduction system such as Pt in a ferrous-ferric solution or Excellent literature reviews and discussions on the subject
in a reducing acid solution saturated with H gas. are presented by Bockris (7, 8) and Vetter (9).
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58 JOURNAL OF THE ELECTROCHEMICAL SOCIETY J a n u a r y 1957
( i i t 4Tl~
are of the same order of magnitude commonly found by
NOBLE7%"~.Xo,,X'~rz
experiment; exchange current values generally vary from
I0-~ to 100/aa and ~ values from 0.03 to 0.30 v.
Fig. 1 illustrates the relationship between the oxidation ~ -OI
~
>8
and reduction rates and the exchange current at the equi- o\
librium potential and the effect of overvoltage on these rates.
When the electrode equilibrium is disturbed by external tl.I
polarization, the reaction rates change in accord with the ~.J -'O2
curves in Fig. 1. Experimentally, however, the individual O
>
Bz= moo %o
(E Io,z = I.O.laAMP \o\
oxidation or reduction rates cannot be measured. The ex- hi
>
\
ternal current used for polarization actually is a measure o_0.5
of the difference between the two rates. For example, if \
the electrode under discussion (Fig. 1) is cathodically po-
larized from its equilibrium potential to an overvoltage ~CTIVE
-O.~ 84~, . . . . . . . . i , , ,,H,,I . . . . . . . . I , , , ,,,,,I ,
\o + ..... N
I hOBLE~oQ~+~-I z
- ~, = g~ (VI) I / 0%
I /<rz %,
then ~ is the external cathodic current when the electrode
is polarized to some overvoltage value, ~7.I t is evident that
-m|
\
$~ approaches $~ at overvoltage values sufficiently removed ~
from the reversible potential. I t is important to emphasize
again that experimentally the only factors measured direc- -0.2 oN
tly are y and ~ or ~ . The individual rate of oxidation or =
reduction cannot be measured. Although theory shows (.9
n =-~,mg : (VII)
$o,z
-aft ]
Using the same arbitrary values for the constants ~ ~,CTIVE
, , ..... i .... ,,,
and io,.. as indicated previously, and knowing the relation 0. I
, , ,,J,,,i
1.0
,
I0
,,,,i
I00
, i LI ',,,I
1,000
, if
I0,000
between ~ and L (Eq. V), a plot of the variation of y with
APPLIED CATHODIC CURRENT,~x(MICROAMPERES}
log ~ may be constructed. This is shown in Fig. 2. 3 Note
that deviation from a Tafel slope exists at the low values FIG. 3. Effect of concentration polarization on the re-
lationship between overvoltage and applied cathodic
of applied current. Only when the reverse (oxidation) cur- current for a single electrode system.
rent, L , becomes insignificant in comparison to the for-
ward or reduction current can a true Tafel relation be ex- The measurement of activation overvoltage may be
pected. Further, Tafel slopes cannot be obtained until complicated by two interfering phenomena--concentra-
applied currents reach magnitudes of several times io,~. tion polarization and resistance drop effects--when the
If it is assumed that experimental verification of a linear value of the exchange current is large. Concentration po-
relationship between ~ and log ~ requires linearity over a larization occurs when the reaction rate or the applied
range of about two logarithmic cycles of current, reliable external current is so large that the species being oxidized
estimates of the Tafel constants ~ and io.~4 require meas- or reduced cannot reach the surface at a sufficiently rapid
urements in the region of 1000 times i .... rate. The solution adjacent to the electrode surface be-
s Points shown on this figure and all subsequent figures comes depleted of the reacting ions, and the rate then is
are not experimental. They are calculated from the de- controlled by the rate at which the reacting species can
rived equations and are included to illustrate the need for diffuse to the surface. The electrode potential changes
considerable data to define accurately the shape of a po- sharply in this region until a potential is reached where a
larization curve. It is quite evident, on inspection of
several of the figures, that insufficient data might lead to new reaction proceeds. The change in potential caused by
a series of straight lines. ment of the slope of ,1 vs. log i~ in the Tafel region, while
4 These constants are derived experimentally from data io,= is found by extrapolation of the Tafel region to the
obtained in the Tafel region, f~= is obtained by measure- reversible potential.
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Vol. 10~, No. 1 ELECTROCHEMICAL POLARIZATION 59
NOBLE// ~162 z
plest form ~ as
RT iL - ~ // Iz %..
~?..... = 2.3 ~ - log iL (VIII) -O.I "x\o\
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60 JOURNAL OF THE ELECTROCHEMICAL SOCIETY January 1957
~ = G- + ~m) - G + ~ ) (XlV)
*t = - 3 ~ log -:---
~o,~ = -0.100 log 1-~ (X) ,,z \\
-J B Z = 0.100 \o
Z Oxidation Io~z * 1.0= AMPS
No
Metal Reduction
L
= +3z log __ = +0.I00 log - -
'~o,~
~z
1.0
(XI) > -o~ \
,\
aCTIVE %,
-04' , , , ,,,,,I ..... ,,,I , ~ ...... I , , , ,,,,,I , , ,,,,
o.I I.O Io Ioo LOO0 IO000
n = -0.160 - fl~ log ~~'~ = -0.160 - ~'~
0.060 log b-~ (XlI)
APPLIED CATHODIC CURRENT, ~ (MICROAMPERES)
current ordinate starting at zero are not strictly valid. ACTIVE ~ ~'x
....... d I I Illllll I i ,,i,,,l , , i1,iiii i ill,'
Although the diagram in Fig. 5 is more in accord with ol I.O I0 IOO 1,000
'
I~0O0
modern electrochemical principles, its greatest value lies
APPLJED CATHODIC CURRENT. T, (MICROAMPERES)
in the ease with which it perufits an understanding of the
FIG. 7. Effect of concentration polarization and re-
shape and nature of experimental polarization curves. An sistance polarization on the relationship between over-
expression describing the shape of the experimental ca- voltage and applied cathodic current for a corroding elec-
thodic polarization curve of a corroding electrode may be trode system.
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Vol. 10~, N o . 1 ELECTROCHEMICAL POLARIZATION 61
I t
Since the variations of ~ and i ~ with 7 are known [Eq. i
(XI), (XII), and (XIII)], Eq. (XVIt) permits a calcula- ~. Ot '~ d)~\ Bz .
tion of the potential change as a function of applied ca-
o\
thodic current. A similar equation m a y be derived for
anodic polarization and would be of the form:
~.o~o~- o~
7 = --0.160 + fl,, log ~ + i~ + $,, (XVIII)
io.m
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62 JOURNAL OF THE ELECTROCHEMICAL SOCIETY January 1957
"x.x
0 I--DI C
~g ~z Bm "
z>_
~ -o'- 2.3 i r z + ,~m )" ,0004(
:Sw
j j " -.02 (
.J
zz 9
o o
a.a. ~'. -0..'
,
",',-)o.
-.050 Z "~ 4 5 6 7 8 9 I0 II 12 13 14 15 ~ -O.I
FIG. 10
applied current values higher than the corrosion current.
As stated previously, Tafel behavior would not be indi- served in a potential range where two or more reduction
cated until applied current values approximately ten reactions occur at similar rates.
times i .... are reached. A further extension of the concepts presented here shows
In the data reported by Straumanis (25, 26) for the that an improvement in the efficiency of reducing M + at
linear dependence of H overvoltage on applied current for any given potential may be achieved by increasing flz,
Ti in H F , the region where Tafel behavior would be ex- decreasing /~,~, increasing i . . . . decreasing i . . . . or by
pected to appear had not been reached experimentally be- reducing the difference between the reversible potentials
cause of the high corrosion current under the conditions of the two oxidation reduction systems. Thus, the analysis
of test. For example, the corrosion rate of Ti in 1N H F presented here is important in the study of metal plating
has been reported as equivalent to 85 m a / c m 2 (28), while efficiency as well as corrosion phenomena.
the overvoltage measurements were not carried farther
than 50 ma/cm 2. DISCUSSION
Eq. (XXIV) is valuable from both a theoretical and an The picture of a mixed electrode presented above could
experimental point of view, since it relates the corrosion be made more extensive by including even a third oxida-
rate and the Tafcl slopes to polarization measurements tion reduction system2 I t is doubtful whether a detailed
close to thc corrosion potential. Thus, low current po- discussion of such a system would be of benefit at the
larization measurements combined with corrosion rate present, but it will be included in a future publication.
data permit a calculation of one of the Tafel slopes if the I t is worth noting in passing, however, that the polariza-
other is known. This is of great value when concentration tion curves would be even more complex than those dis-
polarization or I R drop effects interfere with measure- cussed here.
ments at the higher currents. In addition, measurements This analysis has illustrated several important concepts
are made close to the corrosion potential, thus eliminating which arc worth listing for emphasis.
any surface changes which may result from high current 1. The representation of a corroding metal by polariza-
polarization. tion diagrams should be extended to include the reverse
reactions of the various oxidation reduction systems which
i~-.DDITIONAL CAUSES FOR TAFEL DEVIATION are operative.
The Tafel constants for Fig. 5 have been picked con- 2. Deviations from Tafel behavior may be caused by
veniently to yield a single Tafel relation at the currents local action currents, concentration polarization, and I R
illustrated in Fig. 6. Inspection of Fig. 5, however, reveals drop effects, and by a change in the predominant electrode
that ~,~ Lecomes significant in respect to $~ at very high reaction.
current values. I n this current region, the Tafel slope of 3. An experimental polarization curve may show a linear
Fig. 6 will gradually change from ~ to f ~ . When ~ >> $~, dependence of potential on applied current for small
a new Tafel slope exists with a value of fl~. A pl0t of the amounts of polarization.
overvoltage curve for this situation is presented in Fig. 10. 4. An equation has been derived which relates the slope
Obviously, a different choice o f / ~ , fl,~, i . . . . and i .... could of the linear region of a polarization measurement to the
create this shift in Tafel slope at lower currents and smaller corrosion rate and the Tafel slopes. This equation will
values of overvoltage. I t is important to note that the prove valuable when interfering reactions prevcnt the de-
change in slope takes place gradually and results in a curve termination of the Tafel constants at higher currents.
which is only "Tafel-like" in nature over a considerable 5. The shape of an experimental electrochemical po-
range of current. I t would be a simple matter, although larization curve, either cathodic or anodic, can be analyzed
incorrect, to draw several Tafel lines through this curve. 9 An example of this would be Fe corroding in acid with
Thus, it is evident that real Tafel behavior will not be ob- a depolarizer such as oxygen or ferric ion.
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Vol. 10~, No. 1 ELECTROCHEMICAL POLARIZATION 63
if sufficient d a t a are obtained to permit an accurate de- K, = Resistance factor for calculating the IR drop
scription of the curve. Placing straight lines through four included in polarization measurements.
or five experimental points is hazardous, while the indis- This factor includes the solution conduc-
criminate introduction of " b r e a k s " is contrary to modern t i v i t y and the system geometry.
= The difference between the potential polarized
electrochemical concepts. Sufficient information concern-
by applied current and the corrosion poten-
ing the system should be available to estimate whether
tial.
concentration polarization or resistance drop effects h a v e k
been included in the measurements. d~) = The slope of the overvoltage vs. current curve for
Although this analysis contains only calculated polar- small overvoltage values.
ization curves, a subsequent discussion will illustrate how
experimental measurements comply with the electrode = The slope of the ~ vs. current curve for small
d~ ~-~o
kinetics described. vahles of e.
The picture of a corroding metal presented here is con-
sistent with the concept or theory of mixed potentials REFERENCES
originally treated by Wagner and T r a u d (29) and subse- 1. K. H. LOGAN, Corrosion, 10, 206 (1954).
quently discussed by Petrocelli (30). The concept of dis- 2. W. J. SCttWERDTFEGER AND 0 . N. McDoRMAN, This
crete anodie and cathodic areas in electrochemical corro-
Journal, 99, 407 (1952).
3. P. A. JOHNSON AND A. L. BABB, Ind. Eng. Chem., 46,
sion m a y be considered a special case of this theory. 518 (1954).
4. J. M. PEARSON, Trans. Electrochem. Soc., 81,483 (1942).
Manuscript received Feb. 24, 1956. 5. R. PARSONS, J. Chim. Phys., 49, C 82 (1952).
Any discussion of this paper will appear in a Discussion 6. J. O'M. BOCKRIS AND B. E. CONWAY, Trans. Faraday
Section to be published in the December 1957 JOURNAL. Soc., 48, 724 (1952).
7. J. O'M. BocKRIS AND E. C. POTTER, This Journal, 99,
L I S T OF SYMBOLS U S E D
169 (1952).
~ = Cathodic or reduction current of Z oxidation 8. J. O'M. Boc~ms, "Modern Aspects of Electrochemis-
reduction system. t r y , " Academic Press Inc., New York (1954).
~,~ = Cathodic or reduction current of M oxidation 9. K. J. VETTER, Z. Elektrochem., 50, 435 (1955).
reduction system. 10. C. W. TOBIAS, M. EISENBERG, AND C. R. WILXE, This
Journal, 99, 395C (1952).
~ = Anodic or oxidation current of Z oxidation 11. C. R. WlLKE, M. EISENBERG, AND C. W. TOBIAS, ibid.,
reduction system. 100, 513 (1953).
~,,~ = Anodic or oxidation current of M oxidation 12. J. V. PETROCELLI, ibid., 98, 187 (1951).
reduction system. 13. M. STERN, ibid., 102, 609, 663 (1955).
io.~ = The exchange current of the Z reaction. This 14. M. STERN, ibid., 102, 356 (1955).
is equal to the oxidation or reduction cur- 15. C. V. KING, ibid., 102, 193 (1955).
rent at equilibrium 16. S. SCHULDIN~R, ibid., 101, 426 (1954).
io.m = The exchange current of the M reaction. This 17. J. P. HOARE AND S. SCHULDINER, ibid., 109., 485 (1955).
is equal to the oxidation or reduction cur- 18. F. P. BOWDEN, Trans. Faraday Soc., 24, 473 (1928).
19. F. P. BOWDEN,Proc. Roy. Soc., 126A, 107 (1930).
rent at equilibrium
20. S. BARNARTT, This Journal, 99, 549 (1952).
dn 21. J. N. AGAR AND F. P. BOWDEN, Proc. Roy. Soc., 169A,
~ = The Tafel slope or ~ for the Z oxidation
206 (1938).
reduction system. 22. J. ELZE AND H. FISHER, This Journal, 99, 259 (1952)
dn 23. U. R. EVANS, "Metallic Corrosion, Passivity, and
t~,~ = The Tafel slope or d ~ o g i for the M oxidation Protection," p. 350, Longmans Green and Co., New
York (1948).
reduction system. 24. H. H. UnLIG, ed., "Corrosion Handbook," p. 436, J.
~ = The external applied cathodic current. Wiley & Sons, Inc., New York (1948).
~ = The external applied anodic current. 25. M. E. STRAUMANIS, S. T. SHIH, AND A. W. SCHLECH-
n = Overvoltage or difference in potential between TEN, J. Phys. Chem., 59, 317 (1955).
a polarized electrode and an electrode at 26. M. E. STBAUMANIS, S. T. SHIH, AND A. W. SCHLECH-
equilibrium for the same reaction. TEN, This Journal, 102, 573 (1955).
27. ft. A. V. BUTLER AND G. ARMSTRONG, J. Chem. Soc.,
~/.... = Concentration overvoltage.
1934, 743.
~s = Resistance overvottage. 28. M. E. STRAUMANIS AND P. C. CHEN, This Journal, 98,
iL = Limiting diffusion current. 234 (1951).
i~ = Local action current. 29. C. WAGNER AND W. TRAUD, Z. Elektrochem., 44, 391
Qo~ = Corrosion current or the local action current (1938).
at the corrosion potential. 30. J. V. PETROCELLI, This Journal, 97, 10 (1950).
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