ASM Handbook, Volume 13A: Corrosion: Fundamentals, Testing, and Protection
S.D. Cramer, B.S. Covino, Jr., editors, p42-51
DOI: 10.1361/asmhba0003583
Kinetics of Aqueous Corrosion
D.W. Shoesmith, University of Western Ontario
THIS ARTICLE gives a general introduction
to the kinetics of aqueous corrosion, with an em-
phasis on electrochemical principles. The con-
cept of a corrosion process as a combination of
electrochemical reactions is important, because,
for aqueous corrosion processes, electrochemical
techniques are the predominant methods used in
their study to measure rates as well as in the
development of on-line sensors. The primary
goal of this article is to introduce the electro-
chemical concepts. Readers interested in more
fundamental details of electrochemistry, electro-
chemical methods, and their application to cor-
rosion processes will find Ref 1 to 4 useful.
Basis of Corrosion Reactions
Aqueous corrosion is an electrochemical pro-
cess occurring at the interface between a material
(commonly, but not exclusively, a metal) and an
aqueous solution. For corrosion to occur, an ox-
idation reaction (generally, metal dissolution
and/or metal oxide formation) and a reduction
reaction (commonly, proton, water, or dissolved
oxygen reduction) must occur simultaneously. In
electrochemical terms, an anodic (oxidation, or
Ox) reaction:
M r MnⳭ Ⳮ neⳮ (Eq 1)
where M denotes a metal and MnⳭ a dissolved
metal cation, is coupled to a cathodic (reduction,
or R) reaction:
Ox Ⳮ neⳮ r Red (Eq 2)
where Ox denotes a soluble oxidant and Red the
reduced form of the oxidant that may or may not
be a soluble species. An example of a cathodic
reagent that produces a soluble product is oxy-
gen reduction:
O2 Ⳮ 2H2O Ⳮ 4eⳮ r 4OHⳮ (Eq 3)
An example of a cathodic reaction producing
a gaseous product is proton reduction:
Ⳮ ⳮ
2H Ⳮ 2e r H2 (Eq 4)
The sum of two electrochemical half-reac-
tions, one anodic (such as Eq 1) and one cathodic
(such as Eq 2), is the overall corrosion reaction:
M Ⳮ Ox r MnⳭ Ⳮ Red
An example is the dissolution of iron in an
aerated solution:
2Fe Ⳮ O2 Ⳮ 2H2O r 2Fe2Ⳮ Ⳮ 4OHⳮ
Thus, corrosion is the coupling together of
two electrochemical reactions on the same sur-
face. This coupling occurs at a single potential,
known as the corrosion potential (Ecorr). This po-
tential will depend on the relative rates of the
coupled anodic and cathodic reactions (see sub-
sequent information), and the oxidation state of
the dissolved metal cation may change as Ecorr
changes. Thus, an oxidant capable of driving the
corrosion potential to a more positive value
could produce a higher oxidation state of the
metal (e.g., Fe3Ⳮ rather than Fe2Ⳮ). The corrod-
ing material-solution combination can be consid-
ered a short-circuited galvanic cell in which the
energy is dissipated by the consumption of cath-
odic reagent (oxidant). This situation is illus-
trated schematically in Fig. 1(a).
To maintain a balance, the amount of cathodic
reagent (Ox) consumed must be equal to the
Fig. 1 Galvanic cells. (a) Schematic illustrating the short-circuit galvanic cell that exists during corrosion. (b) The
coupling of an anodic reaction with two distinct cathodic reactions. The relative anodic (Aa) and cathodic (Ac)
areas of the corroding surface are also illustrated.
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amount of corrosion product (MnⳭ) formed. Be-
cause electrons are liberated by the anodic re-
action and consumed by the cathodic reaction,
corrosion can be expressed in terms of an elec-
(Eq 5) trochemical current (I). Furthermore, the require-
ment for mass balance requires that the current
flowing into the cathodic reaction must be equal
to the current flowing out of the anodic reaction.
Clearly, by inspection of Fig. 1(a), these currents
(Eq 6)
are opposite in sign.
By definition, under open-circuit or freely cor-
roding conditions:
Ia ⳱ |Ic| ⳱ Icorr (Eq 7)
where Ia is the anodic current, Ic is the cathodic
current, and Icorr is the corrosion current. The
short-circuited nature of the overall corrosion
process means that Icorr cannot be directly mea-
sured on open circuit. Techniques for its mea-
surement are discussed elsewhere in this Vol-
ume. The value of Icorr is a measure of the rate
of the corrosion process and therefore of the rate
of material degradation. The current and the
amount of material corroded are related by Far-
aday’s law:
nFw
I corr t =
M (Eq 8)
where Icorr is expressed in amps; t is the time of
exposure to the corrosive environment (sec-

onds); nF is the number of coulombs (C) re-
quired to convert 1 mol of material to corrosion
product; n is the number of electrons transferred
or liberated in the oxidation reaction; F is the
Faraday constant (96,480 C/mol); M is the mo-
lecular weight of the material in grams (g); and
w is the mass of corroded material (g).
It is possible for the anodic reaction to be sup-
ported by more than one cathodic reaction (Fig.
1b). For example, in oxygenated acidic solu-
tions, the generic corrosion reaction (Eq 1) could
be driven by both proton reduction (Eq 4) and
oxygen reduction (Eq 3). When complex alloys
are involved, the anodic corrosion reaction may
also be the sum of more than one dissolution
reaction; that is, the congruent dissolution of a
Ni-Cr-Mo alloy would involve the dissolution of
each alloy component with partial anodic cur-
rents proportional to the atomic fraction of each
component in the alloy. The corrosion current
(Icorr) then equals the sum of the component par-
tial currents:
Icorr ⳱
Ia ⳱ ⳮ
Ic (Eq 9)
Additionally, the area and location of the an-
odic and cathodic sites (Aa and Ac, Fig. 1b) may
be different. As a consequence, although the to-
tal anodic and cathodic currents must be equal,
the respective current densities need not be:
Ia ⳱ ⳮIc; Aa ⬆ Ac (Eq 10)
And, therefore:
Ia I
≠− c
Aa Ac (Eq 11)
The term I/A is a current density and will be
designated i.
This inequality in current densities can have
serious implications. For a smooth, single-com-
ponent metal surface, the anodic and cathodic
sites will be separated, at any one instant, by
only a few nanometers. In general terms, the an-
odic and cathodic sites will shift with time, so
that the surface reacts evenly as it undergoes
general corrosion. At the atomic scale, however,
the surface is not necessarily smooth and is usu-
ally considered to comprise surface terraces,
ledges, and kinks, as illustrated in Fig. 2. Also,
surface defects such as ad-atoms, vacancies, and
Fig. 2 A metal surface on the atomic scale showing the
existence of kinks, ledges, and terraces
emergent defects may also exist. Because the co-
ordination number (N) of atoms in these various
locations differs, that is:
Nterrace  Nledge  Nkink (Eq 12)
there will be a difference in strength of surface
bonding, and atoms will be preferentially re-
moved in the order kink, then ledge, then terrace;
that is, surface defects represent potential anodic
sites.
The separation of anodes and cathodes in-
duced by these atomic defects is, however, minor
compared to the separations induced by other
surface features, such as surface asperity, alloy
phases, grain boundaries, impurity inclusions,
residual stresses due to processes such as cold
working, and high-resistance surface oxide
films. These features can often lead to the sta-
bilization of discrete anodic and cathodic sites.
The specific combination of a small anode area
and a large cathode area can lead to large dis-
crepancies in anodic and cathodic current den-
sities, that is, to large anodic current densities at
a small number of discrete sites. Such a situation
is particularly dangerous when the majority of a
metal surface is oxide covered (acting as a cath-
ode) and only a small number of bare metal sites
(acting as anodes) are exposed to the solution
environment. Such a situation exists during pit-
ting, crevice corrosion, and stress-corrosion
cracking, as illustrated for pitting in Fig. 3.
Thus, it is clear that aqueous corrosion is a
complicated process that can occur in a wide va-
riety of forms and is affected by many chemical,
electrochemical, and metallurgical variables, in-
cluding:
● The composition and metallurgical properties
of the metal or alloy
● The chemical composition and physical prop-
erties of the environment, such as temperature
and conductivity
● The presence or absence of surface films
● The properties of the surface films, such as
resistivity, thickness, nature of defects, and
coherence
Fig. 3 A small anode/large cathode situation that can exist at a local corrosion site. Aa and Ac are the available anode
and cathode areas; MnⳭ is the corrosion product
Kinetics of Aqueous Corrosion / 43
Thermodynamic Basis for Corrosion
The thermodynamic feasibility of a particular
corrosion reaction is determined by the relative
values of the equilibrium potentials, Ee, of the
electrochemical reactions involved. These po-
tentials can be determined from the Nernst equa-
tion, which, for the two half-reactions, Eq 1 and
Eq 2, can be written:
( Ee )M Mn+ = ( E 0 )M Mn+ + 2.303 nF log {aMn+ }
RT
(Eq 13)
where the activity of the solid, M, is taken as 1,
and:
a 
( Ee )Ox Red = ( E 0 )Ox Red − 2.303 nF log  aRed 
RT
 Ox  (Eq 14)
to yield for the overall corrosion reaction:
2.303 RT log  aMn+ aRed 
Ee = ∆E 0 −  
nF  aOx aM  (Eq 15)
where DE 0 is the difference in standard poten-
tials for the anodic (Eq 1) and cathodic (Eq 2)
reactions (available from a table of standard po-
tentials), R is the gas constant equal to 8.314 J/
mol • K, T is absolute temperature, n and F are
as defined in Eq 8, and ai represents the activities
of the various species involved. Because the ac-
tivity of a solid is 1, aM is eliminated from Eq
15, and it is more common to write the equation
in terms of concentration (c):
RT log  cMn+ cRed 
Ee = ∆E 0 − 2.303  
nF  cOx  (Eq 16)
The thermodynamics of a particular metal-
aqueous system can be summarized in a poten-
tial-pH, or Pourbaix diagram, as described else-
where in this Volume. The key feature in
determining whether or not a particular corrosion
reaction can proceed is the difference in equilib-
rium potentials (Ee) for the two component elec-
44 / Fundamentals of Corrosion
trochemical half-reactions, as illustrated in Fig.
4. That is:
( Ee )M Mn+ < ( Ee )Ox Red (Eq 17)
Thus, the thermodynamic driving force (DEtherm)
for corrosion is given by:
∆Etherm = ( Ee )Ox Red − ( Ee )M Mn+
(Eq 18)
It is possible that this driving force could in-
crease or decrease with time if either the con-
centration of available oxidant, cOx, or the con-
centration of soluble corrosion product, cMn+,
change with time, as illustrated in Fig. 4 and dis-
(c ) > (c )
cernible by inspection of Eq 16. However, the
most important questions for the corrosion en-
gineer are: How fast does the corrosion reaction
occur, and can it be prevented or at least slowed
to an acceptable rate? To answer these questions
and to determine a course of action, it is essential
to have some knowledge of the steps involved
in the overall corrosion process.
Kinetics of Aqueous
Corrosion Processes
The overall process can be controlled by any
one or combination of several reactions depicted
in Fig. 5. The interfacial kinetics of either the
anodic (step 1) or cathodic (step 2) reactions
could be rate controlling. Alternatively, if these
reactions are fast and the concentration of cath-
Fig. 4 The thermodynamic driving force for corrosion across a metal/aqueous solution interface in the presence of a
soluble oxidant, Ox. The values of the equilibrium potentials are shown schematically.
odic reagent (cOx) is low, then the rate of trans-
port of the oxidant (Ox) to the cathodic site (step
3 r 2) could be rate limiting. This situation is
quite common for corrosion driven by dissolved
oxygen that has limited solubility. If the metal
dissolution reaction (step 1) is reversible, that is,
the reverse metal deposition (MnⳭ Ⳮ neⳮ r M)
can also occur, then the rate of transport of MnⳭ
away from the anodic site (step 4) could be rate
determining.
The presence of corrosion films can add many
additional complications. If the anodic reaction
(step 1) is fast and the transport step (step 4) is
slow, then local supersaturation with dissolved
corrosion product at the corroding surface:
Mn+ Mn + sat (Eq 19)
could lead to the deposition of corrosion product
deposits such as oxides, hydroxides, or metal
salts. These deposition processes could be ac-
celerated or prevented by local pH changes due
to the cathodic reaction (Eq 3) or metal cation
hydrolysis equilibria:
( n − y )−
M n + + yOH − ↔ M (OH )y + 2 yH +
(Eq 20)
The local situation at the corroding surface be-
comes complicated, and the primary parameter
governing whether or not corrosion product de-
posits form, aside from the balance between in-
terfacial kinetics and solution transport, is the
deposit solubility and how it varies with pH (Fig.
6). As shown, the solubility tends to be at a min-
imum at approximately neutral pH and to in-
crease at high and, especially, low pH. At high
pH, solubility is increased by the stabilization of
hydrolyzed metal cations (i.e., the equilibrium
the reaction in Eq 20 is pushed to the right),
whereas in acidic solutions, the oxide/hydroxide
is destabilized by the increased proton concen-
tration (i.e., the equilibrium in Eq 20 is pushed
to the left). This is a very simplified description
of oxide/hydroxide solubility, and the reader is
referred to Ref. 5 for a more detailed discussion.
Precipitation reactions of this type are likely
to produce porous deposits, and corrosion could
then become controlled by the transport of MnⳭ
or Ox (step 6 in Fig. 5) through these porous
deposits. By contrast, when coherent, nonporous
oxide films (passive films) form spontaneously
on the metal surface by solid state as opposed to
precipitation reactions, then ionic or defect trans-
port processes through the oxide (step 7 in Fig.
5) would ensure extremely low corrosion rates.
This represents the condition of passivity. The
presence of defects in the passive film in the
form of pores, grain boundaries, or fractures can
lead to localized corrosion. Finally, it is possible
for the corrosion process to be controlled by the
electronic conductivity of passive films (step 8
in Fig. 5) when the cathodic reaction occurs on
the surface of the film. Using this range of pos-
Fig. 5 Various possible reaction steps on a corroding
metal surface. Reactions 1 to 8 are defined
in the text.
Fig. 6 Solubility of a metal cation as a function of so-
lution pH

sibilities, the remainder of this article discusses
some of these processes and the laws that govern
them.
Activation Control of Corrosion
Activation control is the term used to describe
control of the corrosion process by the electro-
chemical half-reactions (Eq 1, 2) and step 1 and
2 in Fig. 5 The overall anodic reaction is the
transfer of a metal atom from the metal surface
to the aqueous solution as the +cation MnⳭ or as
some hydrolyzed+ (M(OH)(yn − y) ) or anion-com-
plexed (MA (yn − yx ) ) form, where complexation is
with the anion Axⳮ:
+ n+ n+
Msurface → Msurface → Msurface → Msolution (Eq 21)
As indicated in Eq 21, various surface inter-
mediates may be involved in the overall anodic
dissolution process, although these intermediates
may only be detectable in a detailed electro-
chemical investigation. Thus, the simplest pro-
posed mechanism for the anodic dissolution of
iron under acidic conditions proceeds via the fol-
lowing steps:
Fe Ⳮ H2O } Fe(OH)ads Ⳮ HⳭ Ⳮ e (Eq 22)
Fe(OH)ads } FeOHⳭ Ⳮ eⳮ (Eq 23)
FeOHⳭ Ⳮ HⳭ } Fe2Ⳮ Ⳮ H2O (Eq 24)
Similarly, the cathodic reaction, for example,
O2 reduction, proceeds via a sequence of reac-
tion steps involving intermediates such as hy-
drogen peroxide:
O2 Ⳮ 2HⳭ Ⳮ 2eⳮ r H2O2 (Eq 25)
H2O2 Ⳮ 2HⳭ Ⳮ 2eⳮ r 2H2O (Eq 26)
Either the anodic or cathodic reaction can con-
trol the overall rate of the corrosion reaction.
Electrochemical methods (Ref 6) can be used to
disturb these reactions from their equilibrium
potentials and hence to determine the relation-
ship between current and potential. An example
of the form of this relationship, demonstrating a
metal dissolution/deposition reaction, is shown
in Fig. 7. This curve follows the Butler-Volmer
equation:
  αF  F 
I = I 0 exp  η − exp (1 − α ) η
  RT  RT  (Eq 27)
where I is the current; I0 is the exchange current;
F is the Faraday constant; R is the gas constant;
T the absolute temperature; and ␣ is the transfer
or symmetry coefficient, generally taken to be
0.5. The term g is the overpotential, defined by:
η = E − ( E e )M Mn+
(Eq 28)
where E is the experimentally applied potential,
and Ee is given by the Nernst equation (Eq 16),
with DE0 ⳱ E M 0
Mn+
. The overpotential is a mea-
sure of how far the reaction is from equilibrium.
At equilibrium (g ⳱ 0; E ⳱ Ee), no measur-
able current flows, but the equilibrium is dy-
namic, with the rate of metal dissolution (M r
MnⳭ Ⳮ neⳮ) (Ia) equal to the rate of metal cation
deposition (MnⳭ Ⳮ neⳮ r M) (ⳮIc):
Ia ⳱ ⳮIc ⳱ Io (Eq 29)
where Io is termed the exchange current for this
electrochemical reaction. The exchange current
is the equivalent of an electrochemical rate con-
stant and is therefore a direct measure of the ki-
netics of the reaction. The dynamic nature of the
reaction at E ⳱ Ee can be appreciated by con-
sideration of the partial anodic and cathodic cur-
rents, plotted as dashed lines in Fig. 7. If the
potential is made more positive than the equilib-
rium potential, then Ia  |Ic| (i.e., the first ex-
ponential term in Eq 27 increases in value, and
the second one decreases), and the metal disso-
lution reaction will proceed. Similarly, if E is
made more negative than the equilibrium poten-
tial, Ia  |Ic|, then metal cation deposition pro-
ceeds. Over a short potential range, the two re-
actions oppose each other, but for sufficiently
large overpotentials (ga, anodic; or gc, cathodic),
one reaction occurs at a negligible rate; that is,
one or the other of the exponential terms in the
Butler-Volmer equation (Eq 27) becomes negli-
gible. In this condition, the overpotential is in
the Tafel region (as indicated by point 1 in Fig.
7), and for this positive polarization, the metal
dissolution current is given by:
Fig. 7 Current-potential (Butler-Volmer) relationship for a metal dissolution/deposition reaction. The solid line shows
the measurable current; the dashed lines (Ia, Ic) show the partial dissolution/deposition currents; Io is the ex-
change current at Ee; (ga) is the anodic overpotential that would exist if the potential were held at point 1.
Kinetics of Aqueous Corrosion / 45
 αF 
I a = I o exp  ηa 
 RT  (Eq 30)
or
αF
log I a = log I o + 2.303 ηa
RT (Eq 31)
and a plot of log Ia versus ga will yield an inter-
cept from which Io can be obtained and will have
a slope with a Tafel coefficient, ba, given by:
RT
βa = 2.303
αF (Eq 32)
A similar procedure could be applied for a suf-
ficiently large cathodic overpotential (gc) to
yield an equal value of Io as well as a value for
the cathodic Tafel coefficient, bc. The values of
ba and bc contain much information on the mech-
anism of the dissolution/deposition reaction
steps but are commonly used as empirical coef-
ficients in corrosion engineering studies. A simi-
lar analysis could be performed for a potential
cathodic reaction (Eq 2), and Fig. 8 shows the
two current-potential curves on the same plot.
The establishment of a corrosion reaction in-
volves the coupling together of the anodic half
of one reaction to the cathodic half of another.
Which reaction provides which half is deter-
mined by the relative values of the equilibrium
potentials, that is, condition (Eq 17), as illus-
trated in Fig. 4. This coupling of half-reactions
produces an equation relating the measured cur-
rent to the corrosion current, which is similar in
form to the Butler-Volmer equation (Eq 27):
  α F η  −α F η 
i = icorr exp  a  − exp  c  
  RT   RT   (Eq 33)
46 / Fundamentals of Corrosion
where i and icorr represent current densities (cur-
rent/surface area), ␣a ⬆ ␣c, and there is no reason
why ␣a Ⳮ ␣c ⳱ 1, as was the case with the
Butler-Volmer equation. Note: From this point
on, current densities (i) rather than currents (I)
will be used.
Because this coupling of half-reactions pro-
duces a short-circuited corrosion reaction on the
surface of the metal, the anodic current due to
metal dissolution must be equal and opposite in
sign to the cathodic current due to oxidant re-
duction:
ia ⳱ ⳮic ⳱ icorr (Eq 34)
where ia is given by the first term in Eq 33 and
ic by the second. This coupling together to pro-
duce equal anodic and cathodic currents can only
occur at a single potential, designated the cor-
rosion potential, Ecorr, which must lie between
the two equilibrium potentials (Fig. 8), thus sat-
isfying the condition in Eq 15:
(Ee)a  Ecorr  (Ee)c (Eq 35)
where (Ee)a is equivalent to ( Ee )M/Mn+ and (Ee)c
to (Ee)Ox/Red.
The metal dissolution (anodic) reaction is
driven by an anodic activation overpotential:
ηaA = Ecorr − ( Ee )a (Eq 36)
and the oxidant reduction (cathodic) reaction by
a cathodic activation overpotential:
ηcA = Ecorr − ( Ee )c (Eq 37)
Obviously, from Eq 18:
∆E = ηaA + | ηcA | (Eq 38)
Two additional observations can be made with
regard to Fig. 8. First, DE is sufficiently large
that Ecorr is in the Tafel regions for both the an-
odic and cathodic half-reaction. This is not nec-
essarily always the case, as discussed subse-
quently. Second, the two current-potential curves
are not necessarily symmetrical and seldom have
an identical shape. The shape and symmetry of
the curves are determined by the differences in
io for the coupled anodic and cathodic reactions
and the values of the Tafel coefficients, ba and
bc. In Fig. 8, the metal dissolution/deposition re-
action is shown to have a larger io than the oxi-
dant/reductant reaction, and the anodic and cath-
odic branches are shown close to symmetrical
(i.e., ba  bc). The consequence of the large io
is that the current-potential curve is steep, and
only small values of gA a are required to achieve
large currents. By contrast, the current-potential
relationship for the cathodic reaction is shallow,
because io is small, and the anodic and cathodic
branches are not symmetrical (i.e., ba ⬆ bc).
Because both reactions are occurring on dif-
ferent sites on the same surface,Fig. 1, icorr can-
not be measured by coupling the metal to an am-
meter. However, Ecorr can be measured against a
suitable reference electrode by using a voltmeter
with an input impedance high enough to draw
insignificant current in the measuring circuit.
Figure 8 shows that the value of Ecorr is deter-
mined by the shape of the current-potential re-
lationships for the two reactions; that is, it is a
parameter with kinetic but not thermodynamic
significance. Because its value is determined by
the properties of more than one reaction, the cor-
rosion potential is often termed a mixed poten-
tial.
In the literature, diagrams such as the one in
Fig. 8 are often plotted in the form log i versus
E, and the algebraic sign of the cathodic current
is neglected, so that the anodic and cathodic cur-
rents can be plotted in the same quadrant (Fig.
9). Such diagrams are termed Evans diagrams.
The two linear portions in an Evans diagram are
the Tafel regions, with slopes given by Eq 30
and the equivalent plot for the cathodic reaction.
Sometimes, the nonlinearity close to the equilib-
rium potentials is ignored, and the curves are
plotted as totally linear. This approximation ac-
knowledges that, commonly, the two io values
are orders of magnitude lower than icorr and
therefore have a negligible effect on the scale of
the Evans diagram. It should be noted that the
currents plotted in an Evans diagram are the par-
tial currents for the anodic and cathodic reac-
tions, and that the measurable current is the sum
of these two partial currents (taking into account
that they are opposite in sign). The value of such
diagrams is in their use to illustrate the influence
of various parameters on the corrosion process.
Figure 10(a) shows an Evans diagram for the
same anodic dissolution process coupled to two
different cathodic reactions. Recalling the defi-
nition of DEtherm from Eq 18, the following can
be written:
Fig. 8 Current-potential relationships for a metal dis-
solution/deposition process (M } MnⳭ Ⳮ eⳮ)
and an oxidant/reductant reaction (O Ⳮ neⳮ } R) showing
the coupling together of the anodic component of one re-
action to the cathodic component of the other to yield a
corrosion reaction proceeding at the corrosion potential,
Ecorr
′ < ∆Etherm
∆Etherm ″ (Eq 39)
leading to:
′ < icorr
icorr ″ (Eq 40)
that is, the bigger the difference in equilibrium
potentials, the larger the corrosion current. The
anodic activation overpotential for the first re-
a ⳱ Ecorr ⳮ(Ee)a) is less than that for
action (gA
the second:
(η ) ″ > (η ) ′
A
a
A
a (Eq 41)
The value of DEtherm is not the only parameter
controlling the corrosion rate. Figure 10(b)
shows the same situation as in Fig. 10(a) , except
that the two cathodic reactions possess very dif-
ferent polarization characteristics (i.e., relation-
ships between current and potential). Despite the
fact that ( Ee )c″ > ( Ee )′c, the activation overpoten-
tial ( ηaA )″ < ( ηaA )′, and the corrosion couple with
the largest thermodynamic driving force pro-
duces the lowest corrosion current. Inspection of
Fig. 10(b) shows this can be attributed to the
differences in exchange currents, io, and slopes,
hence different Tafel coefficients, bc, for the two
cathodic reactions. This situation is common for
active metals in acidic or neutral aerated solu-
tions. Even though the thermodynamic driving
force for corrosion is greater in neutral solutions
containing dissolved oxygen, corrosion proceeds
more rapidly in deaerated acidic solutions. This
is due to the slowness of the kinetics for oxygen
reduction and can be appreciated by comparing
the kinetic characteristics for the two processes
on iron. Thus, (io )H+ H2 ⳱ 10ⳮ3 to 10ⳮ2 A/m2,
and (βc )H+ H2 艑 120 mV/decade. By comparison,
(io )O2 H2 O 艑 10ⳮ10 A/m2, and (βc )O2 H2 O  120
mV/decade.
Rate Control by the Anodic or Cathodic
Reaction. The overall rate of corrosion will be
controlled by the kinetically slowest reaction,
that is, the one with the smallest exchange cur-
Fig. 9 The current-potential relationships of Fig. 8 plot-
ted in the form of an Evans diagram. Note: The
solid lines are partial anodic and cathodic currents, not
measurable currents.

Fig. 10 Evans diagram for one anodic dissolution reaction coupled (separately) to one of two different oxidant reduction reactions. (a) The two oxidant reduction reactions have
similar kinetic characteristics (i.e., similar current-potential shapes). (b) The two oxidant reduction reactions have very different kinetic characteristics (i.e., very different
current-potential shapes). (c) An anodic dissolution reaction with a large (icorr)a coupled to an oxidant reduction reaction with a small (icorr)c. The currents labeled C1 and C2 show the
effect on log (icorr) and Ecorr of changing the concentration of available oxidant.
rent and/or largest Tafel coefficient. This can be
appreciated from Fig. 10(c) in which (io)a  (io)c
and ba  bc. This leads to a large difference in
activation overpotentials, with:
ηaA
ηaC (Eq 42)
This means the cathodic reaction is strongly
polarized and must be driven significantly to
achieve the corrosion current. By contrast, the
anodic reaction remains close to equilibrium, re-
quiring only a small overpotential (anodic) to
achieve the same corrosion current.
Under these conditions, the corrosion poten-
tial, Ecorr, lies close to the equilibrium potential
for the kinetically fastest reaction. If the cathodic
reaction was the fastest, then Ecorr r (Ee)C, and
the anodic metal dissolution reaction would be
rate controlling. If the kinetics of the two half-
reactions were similar (i.e., (io)a 艑 (io)c and ba
艑 bc), then Ecorr would be approximately equi-
distant between the two equilibrium potentials,
and the corrosion reaction would be under mixed
anodic/cathodic control. This is the situation il-
lustrated in Fig. 9. The corrosion of iron in aer-
ated neutral solution can be used to illustrate the
point. For the metal dissolution reaction, (io )Fe Fe2+
艑 10ⳮ4 to 10ⳮ5 A/m2 and (βa )Fe Fe2+ 艑 50 to 80
mV/decade, whereas for O2 reduction, (io )O2 H2 O
艑 10ⳮ10 A/m2 and (βc )O2 H2 O  120 mV/decade.
Consequently, O2 reduction should be rate con-
trolling, and Ecorr would lie close to the equilib-
rium potential for iron dissolution.
Figure 10(c) also shows the effects of chang-
ing the kinetics of the two reactions. Such
changes could be caused by increasing the avail-
able concentration of cathodic reagent or by in-
creasing the surface area of available metal.
Changing the reagent concentration would also
lead to a change in (Ee)c, but this is ignored in
Fig. 10(c) for the sake of clarity. Changes in the
kinetics of the fast anodic reaction are reflected
in changes in the value of Ecorr (D(Ecorr)a large)
but have little effect on icorr (Dlog(icorr)a small).
However, changes in the kinetics of the slow
Kinetics of Aqueous Corrosion / 47
cathodic reaction have little effect on Ecorr at the corroding site (x ⳱ 0), where D is the
(D(Ecorr)c small) but a significant influence on diffusion coefficient, and cO is the reagent con-
icorr (Dlog(icorr)c large). Thus, in this example, the centration at point x. Diffusion gradients evolve
cathodic reaction is the rate-controlling reaction, with time, according to Fick’s second law:
and the anodic reaction is said to be potential
determining. Such changes in Ecorr can some- ∂cO  ∂2c 
= D 2 
times be used as diagnostic tests for ascertaining ∂t  ∂x  x , t (Eq 44)
the rate-determining step, and the maximum
benefit in slowing corrosion can be gained by
and, for non-steady-state conditions (i.e., c/x
attending to the rate-determining step. Addition-
at x varies with time), conditions are compli-
ally, a measurement of Ecorr and its evolution
cated.
with time provides a simple but only qualitative
General corrosion processes, however, gener-
way of tracking the evolution of a corrosion pro-
ally occur under steady-state conditions, because
cess with time.
convective flow of the environment occurs (e.g.,
flow down a pipe). For this situation, a simple
analysis can be achieved by linearizing the con-
Mass Transport Control centration-distance profile according to the
Nernst diffusion layer treatment (Fig. 11). This
The relationships between current and poten- linearization yields a demarcation line at a dis-
tial described previously are valid when the tance, d, from the surface such that, for x  d,
overall corrosion process is under activation
control, that is, controlled by the interfacial rate
of one or the other of the half-reactions (step 1
or 2 in Fig. 5). However, if the cathodic reagent
at the corrosion site is in short supply, then mass
transport of this reagent could become rate con-
trolling (Eq 3, Fig. 5). Under these conditions,
the cathodic charge-transfer process is fast
enough to reduce the concentration of the cath-
odic reagent at the corrosion site to a value less
than that in the bulk solution. Because the rate
of the cathodic reaction is proportional to the
surface concentration of reagent, the reaction
rate will be limited (polarized) by this drop in
concentration. For a sufficiently fast charge
transfer, the surface concentration will fall to 0,
and the corrosion process will be totally con-
trolled by flux of oxidant to the corroding sur-
face. In the case of one-dimensional transport,
this flux (J) can be calculated from the solution Fig. 11 Illustration showing the concentration-distance
of Fick’s first law: profile for oxidant O involved in a corrosion
process with a metal in which the overall process is par-
tially controlled by convective-diffusive transport of the ox-
idant to the corroding surface. The dashed-dotted lines
 ∂c 
J = − D  Ox  show the concentration profile assumed in the Nernst dif-
 ∂x  x = 0 (Eq 43) fusion layer treatment.
48 / Fundamentals of Corrosion
the bulk concentration is maintained by convec-
tion. For x  d, the oxidant is assumed to be
transported to the surface by diffusion only. This
solution layer is termed the diffusion layer, and
its thickness is determined by the local geometry
at the site and the solution velocity (degree of
convection). Of course, this is an approximation,
because the transition from convective flow to
diffusive transport is more gradual and not so
strictly demarcated.
Using this simplified treatment, Eq 43 can be
written:
J=−
D s
δ
(
cOx − cOx
b
) (Eq 45)
where csOx is the oxidant concentration at the cor-
roding surface (x ⳱ 0), and cbO is the concentra-
tion for x ⱖ d. For steady-state conditions, all
the oxidant transported down the concentration
gradient to the corroding surface must react elec-
trochemically. If it did not, then the concentra-
tion at the corroding surface would adjust until
it did.
This condition of mass balance means that the
cathodic current (expressed in A/cm2) must be
directly proportional to the flux (expressed in
mol/cm2/s). The proportionality constant is
given by Faraday’s law (Eq 8) and can be writ-
ten:
icorr = ic = −
nFDO s
δ
(
cOx − cOx
b
) (Eq 46)
The corrosion current is equal to the cathodic
current, because the overall corrosion reaction is
controlled by the transport of oxidant to the sur-
face; that is, corrosion can only progress at the
rate that oxidant becomes available. Under lim-
iting conditions, csO r 0, and a maximum trans-
port-controlled corrosion current is obtained:
nFDOx b
(ic )lim = (icorr )max = cOx
δ (Eq 47)
When corrosion is occurring at this limiting rate,
the rate can only be increased or decreased by
varying either the bulk concentration of oxidant,
cbOx, or the thickness of the diffusion layer, d.
This limitation on corrosion rate is termed
concentration polarization and is illustrated in
the Evans diagram in Fig. 12. For a small shift
of the potential away from the equilibrium po-
tential (point 1), csOx ⳱ cbOx, and there is no lim-
itation on reagent supply. The current remains in
the Tafel region; that is, charge transfer is still
rate controlling, and the overpotential is purely
an activation overpotential (gA c ). For a larger
shift of potential from (Ee)c, csOx  cOxb
(point 2),
and the current is less than expected on the basis
of activation control; that is, the current follows
the solid line as opposed to the dashed-dotted
line. Under these conditions, the current is partly
activation and partly transport controlled, and
the total overpotential (gT) is the sum of an ac-
tivation (gA) and a concentration (gC) overpo-
tential:
gT ⳱ g Ⳮ gA C
(Eq 48)
For a sufficiently large polarization from equi-
librium, csOx r 0, the current becomes indepen-
dent of potential, and the cathodic current is now
at the maximum given by Eq 47.
The effect of a number of corrosion parame-
ters for a corrosion process proceeding under
various degrees of activation/mass transport con-
trol can be assessed using an Evans diagram, as
shown in Fig. 13. Three situations are consid-
ered. For cathodic curve 1, corrosion occurs with
the anodic reaction totally activation controlled
(gTa ⳱ gA a ) and the cathodic reaction totally mass
transport controlled (gTc ⳱ gCc ), that is, cOx
s
⳱ 0.
If the solution is now made to flow, the thickness
of the diffusion layer (d) will decrease, (ic)lim (Eq
47) will increase and hence so will the corrosion
current. The figure shows that Ecorr shifts to a
more positive value, and:
ηcT = ( Ee )c − Ecorr = ηcA + ηCc (Eq 49)
decreases due to a decrease in gCc . For more vig-
orous stirring, gCc reaches 0, because the flux of
oxidant to the corroding surface is now suffi-
ciently large to maintain cOxs
⳱ cOxb
. Again, Ecorr
shifts to a more positive value to reflect this de-
crease in gTc because gcC ⳱ 0. The cathodic re-
action is now fully activation controlled (gTc ⳱
gA
c ), and further increases in fluid velocity will
not affect the corrosion rate. Such changes in
Ecorr and icorr with the degree of convection can
be used to indicate whether mass transport con-
trol is operative. If the anodic, as opposed to the
cathodic, reaction was mass transport controlled,
then a similar analysis would apply, but Ecorr
would shift to more negative values with increas-
ing degree of convection.
More generally, the term DO/d is termed the
mass transport coefficient (mc), and Eq 46 is
written in the form:
icorr
nF
(
= mc cOx
b
− cOx
s
) (Eq 50)
An equation for the corrosion rate under ac-
tivation control can also be written in the sim-
plified form:
Fig. 12 Partial Evans diagram (i.e., showing only the
partial current for the oxidant reduction reac-
tion) for mixed activation-concentration polarization
icorr
= kc cOx
s
nF (Eq 51)
where kc can be considered a potential-depen-
dent rate constant for the cathodic reaction.
Equation 51 could be considered a restatement
of the Butler-Volmer equation, and the reader is
referred to standard electrochemical text books
for more detailed descriptions (Ref 6). Combin-
ing Eq 50 and 51 and eliminating csOx yields:
 
b  mc kc
icorr = nFcOx  
 ( mc + kc ) 
(Eq 52)
where kc can be considered the activation control
parameter and mc the mass transport control pa-
rameter.
Whether activation or mass transport kinetics
determine the corrosion rate is straight forwardly
appreciated by considering the relative values of
mc and kc in Eq 52. For mc k kc, the bracketed
term reduces to kc, and the corrosion current is
activation controlled. For mc K kc, the term re-
duces to mc, and corrosion would be mass trans-
port controlled.
While Eq 52 may define the relative impor-
tance of activation and mass transport control, it
does not contain any information on the factors
that control mass transport and hence determine
the value of mc. The dependence of mc on solu-
tion flow rate can be determined experimentally,
and its form varies, depending on the geometry
of the system. In general, this dependence takes
the form:
icorr  f n (Eq 53)
where f is the flow rate, and n is a constant that
depends primarily on the geometry of the sys-
tem. For flow over a flat plate, n is 0.33 for lam-
inar flow (smooth, Re  2200), where Re is the
Reynold’s number (defined subsequently).
The variation of mc depends not only on flow
rate but also on properties such as the kinematic
viscosity of the fluid (m), the diffusion coefficient
of the species (D), as well as the geometry of the
system. These effects can be specified using di-
Fig. 13 Evans diagram showing the influence on Ecorr
and log (icorr) of changing the transport rate of
oxidant O to the corroding surface

mensionless parameters such as the Reynold’s;
Re; and Schmidt, Sc, numbers given by:
L to build up at the corroding surface, supersatu-
Re = f
ν (Eq 54)
ν 5). These corrosion product deposits will form
Sc =
D (Eq 55)
The Reynolds number is a measure of the ratio
of convective to viscous forces in the fluid, and,
for laminar flow down a pipe, L is a character-
istic length. The Schmidt number quantifies the
relationship between hydrodynamic and diffu-
sion boundary layers at the corroding surface.
Thus, it can be shown that for flow over a
smooth, flat, corroding surface:
(icorr )max = 0.62nFDOcOb ( Re)α (Sc )β (Eq 56)
where ␣ and b are numerical constants that de-
pend on the geometry of the system and the con-
vective flow conditions.
Smooth, laminar flow can only be achieved up
to a certain Reynold’s number or flow rate, f, if
L and m are constant, beyond which the flow be-
comes turbulent, and the dependence of icorr on
flow rate increases. For still higher rates, acti-
vation control can be achieved (mc k kc), and
the corrosion rate becomes independent of flow
rate. This behavior is illustrated in Fig. 14. The
solid line shows the effect of flow rate when the
corrosion reaction is fast (kc large), and a large
flow rate is required to achieve activation control
(mc k kc). The dotted line shows the behavior
expected for a slow corrosion reaction (kc small),
when only a small flow rate is required to
achieve activation control.
Influence of
Corrosion Product Deposits
Thus far in the discussion of transport effects,
only the transport of the cathodic reagent (step
3 in Fig. 5) has been considered. The transport
Fig. 14 The influence of solution flow rate on the cor-
rosion rate (expressed as a current) showing the
response in different flow regimes
of the anodic (metal) dissolution product (step 4
in Fig. 5) also affects the corrosion rate but in a
different way. If dissolved metal ions are allowed
ration of solid oxides/hydroxides can occur,
leading to film formation reactions (step 5 in Fig.
at a rate determined by the rate of the corrosion
process and the solubility of the metal cations in
the particular exposure environment. Determin-
ing their influence on the corrosion rate is not
simple. A key feature is the porosity of the de-
posit (e), because this determines the area of
metal left exposed and also reduces the diffusion
coefficient of both the anodic dissolution product
and the cathodic reagent by a factor directly pro-
portional to the porosity. The pores are also
likely to be nonlinear, and their effective length
will be greater than the thickness of the deposit.
The diffusion coefficient will, therefore, also be
attenuated by a tortuosity (s) factor. The effec-
tive diffusion coefficient (Deff) will be given by:
Deff ⳱ esDOx (Eq 57)
This situation is illustrated schematically in Fig.
15, and Eq 45 for the corrosion rate could be
rewritten to yield:
nF ετDOx s
icorr =
l
(cOx − cOx
b
) (Eq 58)
where corrosion is only occurring on a fraction
(eA) of the original exposed metal area, A, and l
is the thickness of the corrosion product deposit.
It should be noted that this represents a very sim-
plified discussion of what could be a much more
complicated process.
Fig. 15 Schematic illustrating how the presence of a
corrosion product deposit influences the cor-
rosion of an underlying metal by limiting both the area of
exposed metal and the diffusion of oxidant to the corroding
surface. D, diffusion coefficient; e, porosity; s, tortuosity
factor; A, area
Kinetics of Aqueous Corrosion / 49
Kinetics of
Corrosion of Passive Metals
The formation of a passive film (step 7 in Fig.
5) can have a large influence on the corrosion
rate. Passivation becomes thermodynamically
possible when the corrosion potential exceeds
(becomes more positive than) the potential cor-
responding to the equilibrium between the metal
and one of its oxides/hydroxides:
Ecorr  (Ee)M/MO (Eq 59)
Inspection of the Pourbaix diagram for the metal/
metal oxide/aqueous solution system shows that
this condition moves Ecorr into the oxide stability
region, as illustrated in Fig. 16 for the iron/iron
oxide/water system. For point 1, Ecorr 
(Ee)M/MO, and corrosion of the bare metal is ex-
pected, while, for point 2, Ecorr  (Ee)M/MO, and
the metal should be oxide covered and passive.
It should be noted that experimentally measured
primary passive potentials inevitably do not cor-
respond directly with these thermodynamically
determined potentials, because kinetic as well as
thermodynamic effects are involved in oxide
film formation.
The current-potential or polarization curve for
the anodic process is shown in Fig. 17 and can
be divided into a number of regions. In region
AB, the active region, metal dissolution is un-
impeded, because no passive film is present. Be-
cause such polarization curves are usually re-
corded under activation control conditions, local
supersaturation leading to the deposition of cor-
rosion products (discussed previously) is gener-
ally assumed not to influence the active disso-
lution of the metal. However, for real corrosion
conditions, and especially for reactive metals
such as iron, the current in this region could be
suppressed by corrosion product deposits, as dis-
cussed previously. For the purposes of the pres-
ent discussion, it is assumed that this does not
occur. For active dissolution, therefore, the cur-
Fig. 16 Simplified Pourbaix (equilibrium potential-pH)
diagram for the iron-water system. The upper
dashed line shows the potential for H2O in equilibrium
with O2.
50 / Fundamentals of Corrosion

rent should conform to the Tafel relationship (Eq
30), and its extrapolation back to (Ee)a would
yield a value of (io)a.
At a potential B, shown in Fig. 17 to coincide
with (Ee)M/MO (although, as noted previously,
this is rarely the case experimentally), there is a
departure from the Tafel relationship, leading
eventually to a decrease in current to a low value.
The electrode is said to have undergone an ac-
tive-to-passive transition and, by point C, has be-
come passive. The potential at point B may or
may not correspond to the potential (Ee)M/MO.
Thermodynamics demands only that the condi-
tion in Eq 59 be satisfied. The maximum current
achieved immediately before the transition is
termed the critical passivating current (icrit). The
potential at which the current falls to the passive
value is called the passivation potential (Epass),
and it corresponds to the onset of full passivity.
For gold, silver, and platinum, the passivation
potential is close to (Ee)M/MO, but for most other
metals, it is much more positive than this equi-
librium value.
For E  Epass, the metal is said to be in the
passive state, and the current is very low. A com-
parison of critical currents to passive currents
puts the industrial importance of passivity into
perspective. Critical passivating currents (ex-
pressed as current densities) can be as high as
tens of mA/cm2, while passive currents can be
as low as nA/cm2. Consequently, from the in-
dustrial corrosion perspective, the establishment
of passivity is an important feature.
A detailed discussion of the properties of pas-
sive films is beyond the scope of this article (see
the article “Passivity” in this Volume). A number
of theories exist to explain the growth kinetics
and properties of oxide films, but the discussion
of one of them, the point defect model (Ref 7),
serves to illustrate the critical features of the cur-
rent-potential behavior in the passive region. The
essential features of this model are shown sche-
matically in Fig. 18. The film is assumed to be
composed of an inner barrier layer, whose insu-
lating properties provide the essential corrosion
protection, and an outer recrystallized layer that
confers little extra corrosion protection and is
composed of hydrated metal species. This outer
layer may not exist in acidic solutions in which
the metal cations are highly soluble (Fig. 6).
Considerable experimental evidence exists to
support this structure.
Oxide growth is assumed to occur by the
transport of defects through the film under the
influence of the electric field that exists within
the oxide. The nature of the defect depends on
the metal/alloy and the nature of the growing
oxide. However, the key vacancies are anion va-
cancies (Vo⋅⋅ ) created at the metal-oxide inter-
face, cation vacancies (Vm) created at the oxide-
solution interface, and cation interstitials created
at the metal-oxide interface. The general obser-
vation that the current in the passive region is
independent of potential can be interpreted in
terms of this model. As the potential is increased
through the passive region, a progressive thick-
ening of the oxide occurs, such that the electric
field within the oxide remains constant. Thus,
Metal Barrier layer
(1)
(8) Cation vacancy transport
M Mm
Creation of lattice cation
(2)
Mm
M
Vo··
(9) Anion vacancy transport
Lattice cation creates
anion vacancy (Vo··)
the steady-state current at each potential is a bal-
ance between oxide formation at the metal-oxide
interface and dissolution/recrystallization (to the
outer hydrated layer) at the oxide-solution inter-
face. Reference 7 provides more extensive dis-
cussions.
For high anodic potentials, the observed be-
havior depends on the nature of the metal and
the properties of the oxide film. For metals that
form insulating oxides (e.g., aluminum, tita-
nium, zirconium), the films continue to thicken
with increasing potential, and low passive cur-
rents are maintained. For other metals, for ex-
ample, iron, chromium, nickel, and materials
such as stainless steels and nickel-chromium al-
loys, oxygen evolution can occur on the outside
of the passive film once the potential exceeds
point E (Fig. 17):
2H2O r O2 Ⳮ4HⳭ Ⳮ 4eⳮ (Eq 60)
For this reaction to occur, the film must be elec-
tronically conducting. This is possible because
Outer
layer/solution
Mm
(4) M(x+y)+
Vm
Oxidative dissolution
(5)
Vo·· O2– H2O
2H+

Elimination of
oxygen vacancy

(3)
M xi + (6)
M M xi + M(x+y)+

Cation interstitial creation

Oxidative dissolution

MOx/2 Mx+ + H2O

(7)
xH +

Chemical dissolution

Fig. 17 Polarization curve for a metal that undergoes

active-to-passive and passive-to-transpassive
transitions Fig. 18 Schematic description of the point defect model for the growth of a passive oxide film

the passive films formed are thin (nanometers)
and possess semiconducting properties. The
dashed-dotted line in Fig. 17, in the potential re-
gion D to E, corresponds to the phenomenon of
transpassivity. In this region, the oxide film be-
gins to dissolve oxidatively, generally as a hy-
drolyzed cation in a higher oxidation state than
that which exists in the film. An example would
be the dissolution of chromium, present in the
passive film on stainless steels as CrIII, as CrVI
in the form of CrO2ⳮ 4 . While transpassive dis-
solution, starting at point D, and O2 evolution,
starting at point E, are shown as clearly separated
in Fig. 17, they often occur together, and a dis-
tinct transpassive region cannot be observed.
When coupled to a cathodic reaction in a cor-
rosion process, a number of criteria must be sat-
isfied if the metal is to be in the passive region
Fig. 19 Effect of various cathodic reactions on the cor-
rosion current and potential for a metal capa-
ble of undergoing an active-passive transition
and, on normal industrial time scales, free of cor-
rosion:
● The equilibrium potential for the cathodic re-
action ((Ee)c) must be greater than the passi-
vation potential (Epass).
● The cathodic reaction must be capable of
driving the anodic reaction to a current in ex-
cess of the critical passivation current, icrit, in
Fig. 17.
Three possible situations are shown in the
Evans diagram in Fig. 19. The solid line shows
the anodic polarization curve, and lines 1, 2, and
3 show the cathodic polarization curves for three
different cathodic half-reactions (On Ⳮ neⳮ r
Rn).
For cathodic reaction 1 (Fig. 19), (Ee)c1 
Epass. Because the corrosion potential must lie
between (Ee)a and (Ee)c1 for the two reactions to
form a corrosion couple, the required condition
for passivation, Ecorr  Epass, cannot be achieved.
Therefore, Ecorr remains in the active region, and
the metal will actively corrode.
For cathodic reaction 2 (Fig. 19), the condition
(Ee)c2  Epass is met, but the two polarization
curves intersect at an anodic current icrit.
Again, Ecorr  Epass, and the metal corrodes in
the active region at an even higher current than
for cathodic reaction 1.
For cathodic reaction 3 (Fig. 19), the condi-
tions (Ee)c3  Epass and i  icrit are both met. As
a consequence, Ecorr  Epass, and the metal pas-
sivates, with the corrosion current equal to the
passive dissolution current.
It is clear from this discussion that mild oxi-
dizing agents (DEtherm ⳱ (Ee)c ⳮ (Ee)a small)
could leave the material susceptible to corrosion,
and strong oxidizing agents (DEtherm large) are
required to ensure the metal will be in the passive
Kinetics of Aqueous Corrosion / 51
region. However, in the presence of extremely
strong oxidizing agents, it is possible for Ecorr to
become sufficiently positive that physical insta-
bilities in the oxide become feasible. These mi-
nor film breakdown events can lead to many
forms of localized corrosion if allowed to sta-
bilize. A discussion of these processes is beyond
the scope of this article, but the danger in frac-
turing the passive film can be appreciated from
a consideration of the extrapolation of the anodic
active region, shown by the dashed-dotted line
in Fig. 19. If the oxide did not form, then this
extrapolation shows that currents at positive po-
tentials would be very large. Thus, breakdown
of the passive film at a local site within the pas-
sive region would lead to an extremely high local
current density and the possibility of deep local-
ized corrosion of the metal.
REFERENCES
1. J.H. West, Electrodeposition and Corrosion
Processes, Van Nostrand Reinhold, 1971
2. D. Jones, Principles and Prevention of Cor-
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3. L.L. Shreir, R.A. Jarman, and G.T. Burstein,
Ed., Metal/Environment Interactions, Corro-
sion, Vol 1, 3rd ed., Butterworth/Heinemann,
1994
4. L.L. Shreir, R.A. Jarman, and G.T. Burstein,
Ed., Corrosion Control, Corrosion, Vol 2, 3rd
ed., Butterworth/Heinemann, 1994
5. C.F. Baes and R.E. Mesmer, The Hydrolysis
of Cations, John Wiley and Sons, 1976.
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