Determination of electrochemical parameters

and corrosion rate for carbon steel in

un-buered sodium chloride solutions
using a superposition model
Luis Caceres
a,
*
, Tomas Vargas
b
, Leandro Herrera
b
a
Chemical Engineering Department, Universidad de Antofagasta, Av. Angamos 601 Antofagasta, Chile
b
Chemical Engineering Department, Universidad de Chile, Beauchef 861, Santiago, Chile
Received 3 October 2005; accepted 27 March 2007
Available online 19 April 2007
Abstract
Corrosion of carbon steel in un-buered NaCl solutions was studied applying linear potential
sweep technique to a rotating disk electrode. Currentpotential curves were obtained from linear
potential sweep at a rate of 1 mV s
1
in solution with concentrations in the range 0.021 M NaCl
and rotation rates in the range 170370 rad s
1
, at 22 C. Potential sweeps, which were conducted
in the potential range 700 to 100 mV/SHE, were started from the cathodic limit in order to
approach the measurement of corrosion under rust-free conditions. Polarization curves were analyzed
with a superimposition model developed ad hoc and implemented in a computer program, which
enabled determining the corrosion rate and kinetics parameters of the underlying anodic and cathodic
sub-processes. The anodic sub-process, dissolution of iron, was well described in terms of a pure
charge transfer controlled reaction, while the cathodic sub-process, oxygen reduction on iron, was
well described in terms of mixed mass transfer and charge transfer control. Increase of electrode rota-
tion rate increases the limiting current of oxygen reduction, which results in an enhanced corrosion
rate of carbon steel. Increase of NaCl concentration has a dual eect: the limiting current of oxygen
reduction decreases as a result of the inuence of NaCl concentration on solution viscosity and the
anodic dissolution of iron increases due to the inuence of NaCl on pitting formation. However, this
last mechanism predominates and a net increase in carbon steel corrosion rate is observed in this case.
2007 Elsevier Ltd. All rights reserved.
0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2007.03.003
*
Corresponding author. Tel.: +56 55 637342; fax: +56 55 240152.
E-mail address: lcaceres@uantof.cl (L. Caceres).
Corrosion Science 49 (2007) 31683184
www.elsevier.com/locate/corsci
Keywords: A. Mild steel; B. Modelling studies; B. Polarization; C. Kinetic parameters
1. Introduction
Studying corrosion of iron or carbon steels in NaCl containing solutions is relevant for
understanding the behaviour of these materials in marine conditions [1] and other indus-
trial conditions where normally chloride ions are present [2,3]. Oxidation of carbon steels
in NaCl solutions is also the base of galvanocoagulation methods aimed at producing
reagents such as ferrous and ferric ions intended for industrial treatment of wastes [4].
Linear potential sweep technique is one of the various methods that can be used for
determining corrosion rates of these materials. However, the advantage of the linear
potential technique is that the analysis of the obtained currentpotential curves also
enables the determination of the kinetics parameters of the anodic and cathodic sub-
processes. This information is very relevant in the present case if one wants to understand
in depth the mechanismof corrosion of iron and carbon steels in NaCl containing solutions.
For instance, the linear potential sweep technique has been used to determine the
kinetic parameters for oxygen reduction on iron in un-buered chloride solutions assum-
ing mixed charge transfer and mass transfer control [5,6]. Similarly, the kinetic parameters
for iron oxidation under pure charge transfer control in acid electrolytes have been also
calculated [7]. The approach used in those cases has been based on the analysis of the
respective single branch of the polarization curve, either anodic or cathodic. However,
it has been recognized that the determination of the kinetics parameters with this simpli-
ed approach are subject to some uncertainty. In fact, for the experimental current to be
associated only to one single sub-process, either anodic or cathodic, current needs to be
measured at potentials suciently distant from the corrosion potential, where undesirable
reactions which interfere with the determinations can be activated [8,9]. As an alternative
method several superimposition models have been proposed to determine kinetic param-
eters by deconvoluting the polarization curve in potential ranges closer to the corrosion
potential [1014]. This approach enables more accurate determinations of corrosion rates
and kinetic parameters from linear potential sweep data.
In the present study, the kinetics parameters for carbon steel corrosion in aerated NaCl
solutions were determined from experimental polarization curves by developing a super-
position model for oxygen reduction and iron oxidation which was implemented in a com-
puter program. The application of this model permitted a more accurate characterization
of the kinetic parameters of oxygen reduction and iron oxidation than the one obtained by
the single analysis of the cathodic and anodic branches. It also enabled to explicitly under-
stand how these sub-processes aect the rate of corrosion of carbon steel in the chloride
solutions.
2. Experimental
A BAS/100 electrochemical interface with a BAS/RDE-1 rotating electrode system was
employed for voltammetry measurements. A conventional three electrode cell was used:
a rotating working electrode made of carbon steel (WE), a platinum wire as a counter
electrode and an Ag/AgCl 1 M KCl cell as a reference electrode. The WE was a 4 mm
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3169
diameter 5 mm cylinder made of carbon steel SAE 1010 with chemical content wt% 98.5
Fe, 0.2 C, 0.6 Mn and traces of P, S, Si, Sn, Cu, Ni, Cr and Mo. An 8 mm diame-
ter 20 mm polyamide plastic rod was drilled along its axis to insert the specimen in
one end and adapt a rotating shaft in the other. The specimen was inserted in the plastic
rod applying resin adhesive in order to minimize a crevice formation between the exposed
circular surface of the steel and the plastic rod. The cell was immersed in a thermostatic
bath operating at 22 C.
Measurements were conducted in electrolytes prepared by dissolving laboratory grade
NaCl in distilled water. In each run, once the cell was lled with electrolyte, air was bub-
bled for about 15 min until a saturated concentration of oxygen was reached. Oxygen con-
centration in the electrolyte was measured using a WTW model 340 oxygen meter. Just
before each measurement, the WE was abraded in a rotating plate with wet SiC paper (ini-
tially with 400 grade and thereafter with 1200 grade), then degreased by immersion in ace-
tone, cleaned in an ultrasound bath for 2 min rinsed with distilled water and immediately
inserted in the cell.
Currentpotential polarization curves were obtained from linear potential sweep at a
rate of 1 mV s
1
, a sweep rate reported to guarantee obtaining steady-state currentpoten-
tial curves [5]. Potential sweeps were conducted in the potential range 700 to 100 mV/
SHE and started from the cathodic limit, 700 mV/SHE, in order to minimize the inu-
ence of surface rust formation on the measurements. Measurements were conducted in
electrolytes with 0.02, 0.1, 0.5 and 1 M NaCl with the working electrode rotating in the
range 10370 rad s
1
. Several measurements were conducted at each experimental condi-
tion after successive polishing of the carbon steel electrode, until reproducible polarization
curves were obtained. However, reproducible polarization curves could only be obtained
at rotation rates of 170 rad s
1
or larger. At rotation rates below 170 rad s
1
there was
presence of air bubbles which remained attached on the electrode surface and could not
be removed at these low rotation rates, which interfered with the measurements.
3. Results and discussion
3.1. Polarization curves
Curves obtained at various rotation rates at the lowest and highest NaCl concentrations
used, 0.02 and 1 M, are shown in Figs. 1 and 2. An interesting feature in those results is
that the currents in the anodic branch of the curve decrease with an increase in the rotation
rate of the electrode. This clearly shows that the anodic branch, which in neutral solutions
is known to be solely related to charge transfer controlled iron dissolution [15] is distorted
by the inuence of the mass transfer controlled cathodic process. From this observation it
is evident that in this system it is not correct to determine the iron dissolution kinetic
parameters directly from a single analysis of the experimentally obtained anodic branch,
even though at potential ranges where a pseudo Tafel region is achieved. With a sym-
metric reasoning, one can also assume that the cathodic curves are correspondingly dis-
torted by the inuence of the anodic process. Therefore, it does not seem accurate to
determine oxygen reduction parameters directly from a single analysis of the respective
cathodic curve branch. This is why in the present system to determine the kinetic para-
meters of the anodic and cathodic sub-processes and the corrosion rate it is necessary
3170 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
to analyze the complete polarization curves with a superposition model which considers
simultaneously both sub-processes.
3.2. The model and kinetic parameters determination
Several models have been proposed as a basis for analysing linear potential sweep data
by a curve tting procedure. Some authors have applied a model which is restricted to sys-
tems which are completely under charge transfer control which are not adequate for the
-30.0
-20.0
-10.0
0.0
10.0
20.0
-700 -500 -300
E (mV/SHE)
I

(
A
/
m
2
)
170 rad s
-1
210
260
310
370
Fig. 1. Experimental currentpotential curves for dierent electrode rotation rates in 1 M NaCl solution.
-15.0
-10.0
-5.0
0.0
5.0
10.0
15.0
20.0
-700 -500 -300 -100
E (mV/SHE)
I

(
A
/
m
2
)
170 rad s
-1
210
260
310
370
Fig. 2. Experimental currentpotential curves for dierent electrode rotation rates in 0.02 M NaCl solution.
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3171
present case [9]. A modied model based on a cathodic process with mixed charge trans-
fermass transfer controlled and an anodic process with charge transfer control has been
later proposed [12]. This equation could be applied to obtain electrochemical parameters
for steel corrosion in near neutral solutions. Later a more complex model which includes
cathodic and anodic processes with combined diusion, pitting and passivation pheno-
mena have been presented and implemented as a computer program [13]. In this model
oxygen reduction on metal surfaces is assumed to be a rst order reaction with respect
to oxygen concentration in the electrolyte. This approximation is not directly applicable
to the present system, where a 0.5 order dependence on oxygen concentration has been
reported [5].
The model developed in the present work assumes that the anodic reaction is under
pure charge transfer controlled and the cathodic reaction is under mixed charge trans-
fermass transfer control [15]. As a dierent feature, the order of the reaction with respect
to oxygen concentration was left as another parameter to be determined during the tting
process. The expression for the total current is:
i i
O
2
i
Fe
1
where i
O
2
is the current associated to oxygen reduction, the predominant cathodic reac-
tion, and i
Fe
is the current associated to iron oxidation. The kinetic expression for oxygen
reduction was assumed to be [5,6]:
i
O
2
i
0O
2
1
i
O
2
i
lO
2
_ _
m
f
c
exp 2:3
g
O
2
t
c
_ _
2
The kinetic expression for i
Fe
is [5,6]:
i
Fe
i
0Fe
f
a
exp 2:3
g
Fe
t
a
_ _
3
The dimensionless f factors [5] for sodium chloride solution are expressed as
f
a
a
s
Cl

_ _
j
1
a
s
OH

_ _
j
2
4
f
c
a
s
Cl

_ _
j
3
a
s
OH

_ _
j
4
5
where a
s
Cl
, a
s
OH
are the activity values of Cl and OH

ions on the electrode surface,

respectively, j
1
, j
2
, j
3
, j
4
are dimensionless parameters, i
O
2
(A m
2
) and i
Fe
(A m
2
) the par-
tial current densities for oxygen reduction and iron oxidation, respectively, i
lO
2
(A m
2
)
the limiting current density for oxygen reduction, i
0O
2
(A m
2
) and i
0Fe
(A m
2
) the ex-
change current densities for oxygen reduction and iron oxidation, respectively,
g
O
2
E E
eqO
2
mV, g
Fe
= E E
eqFe
(mV), the oxygen reduction and iron oxidation
overpotential, respectively, E (mV) applied potential, E
eqO
2
; E
eqFe
mV the equilibrium
potential for oxygen reduction and iron oxidation and t
a
, t
c
the anodic and cathodic Tafel
slope expressed as mV dec
1
, respectively.
In order to facilitate manipulation Eqs. (2) and (3) were expressed as follows:
i
O
2
a 1
i
O
2
c
_ _
m
expbE 6
i
Fe
d expeE 7
3172 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
where a f
c
i
0O
2
Am
2
; b = 2.3/t
c
(mV
1
); c i
lO
2
Am
2
; d = f
a
i
0Fe
(A m
2
);
e = 2.3/t
a
(mV
1
).
From the tted parameters the values of exchange current densities, limiting current,
and Tafel slopes, were calculated as follows:
i
0O
2
a exp bE
eq
O
2
_ _
8
i
0Fe
d exp eE
eq
Fe
9
i
l
c 10
t
c

2:3
b
11
t
a

2:3
d
12
A conventional software routine based in the simplex method [16,17] was used to nd
parameters a, b, c, d and e using experimental polarization data. A maximum of 600 cur-
rentpotential values were available from each polarization experiment. The calculating
procedure is further explained in Appendix A.
A ferrous iron concentration value of 1 10
6
M was arbitrarily assumed for E
eq
Fe
cal-
culation following the suggestion given by Bockris et al. [18]. The corrosion potential E
corr
and current i
corr
were calculated from the zero total current density value of the theoretical
expressions (1) and (9).
3.3. Fitted parameters and model application
Values of parameters a, b, c, d and e obtained using the model from experimental polar-
ization curves obtained at each NaCl concentration and electrode rotation rate, are given
in Table A1, Appendix A. Electrochemical kinetic parameters calculated from parameters
in Table A1 according to Eqs. (8)(12) are listed in Table 1.
With the determined kinetic parameters it is now possible to represent and analyze the
currentvoltage curves simulated by the model for the global current and for each of the
associated anodic and cathodic sub-processes involved in carbon steel corrosion in NaCl
solutions. Fig. 3 shows a comparison of the experimental polarization curve (continuous
line) obtained for the case of corrosion of a carbon steel electrode in 0.5 M NaCl solutions
at 260 rad s
1
with the curve calculated with the model using the respective tted param-
eters (dotted line). The degree of adjustment observed between the calculated curve and
the experimental one for this particular case is representative of those obtained in all
the other experimental cases.
Curves in Fig. 3 show that there is a wide potential range, between point A (550 mV/
SHE) and point C (180 mV/SHE), where the theoretical curve coincides perfectly with
the experimental one. It is then possible to say that in this potential range carbon steel cor-
rosion in NaCl solutions is well described simply in terms of one anodic sub-process, the
anodic dissolution of iron under charge transfer control, and a single cathodic reaction,
oxygen reduction under with mixed charge transfermass transfer control.
At potentials more cathodic than point A, the experimental cathodic current becomes
larger than the theoretical current. This deviation, which increases with the increase of
potential, indicates the onset of the reduction of protons involving formation of gaseous
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3173
hydrogen on the carbon steel [15]. This result shows that this reaction is only relevant at
this high cathodic potential range and should have little importance in the vicinity of the
corrosion potential. Therefore, it should not have major inuence on the corrosion rate of
carbon steel and it does not need to be considered in the model.
At potentials more anodic than point C the experimental anodic current becomes larger
than the theoretical current. The potential at point C, 180 mV/SHE, is in the potential
range where pitting formation has been observed in corrosion of iron in NaCl solutions
[19]. Therefore, one can assume that the observed increase in anodic current with respect
to the simple charge transfer mechanism can be related here to the distorting eect intro-
duced by pitting formation. From this deviation it becomes clear that an attempt to draw a
Tafel line based on the anodic branch in a log(i)E plot will give an underestimated Tafel
slope (calculated as mV dec
1
) with respect to that obtained from Eq. (1). For instance,
using methods such as graphical extrapolation in a log (i)E plot or numerical calculation
based on mixed charge transfer reaction (i.e. four-point method [20]) will produce under-
estimated absolute anodic Tafel values. For various polarization curves this underestima-
tion were found to be between 5% and 40% with respect to tted values using Eq. (1). It is
very interesting to note that the lowest underestimations were observed at 1 M NaCl.
Probably at this concentration a faster pit development will generate faster inhibition
through rust coverage giving rise to an apparent Tafel-like behaviour. The evidence of
Table 1
Kinetics parameters calculated from the model
NaCl
(M)
X
(rad s
1
)
i
0Fe
(A m
2
)
t
a
(mV dec
1
)
i
0O
2
10
4
(A m
2
)
t
c
(mV dec
1
)
i
l
(A m
2
)
E
corr
(mV)
i
corr
(A m
2
)
002 170 0.07 245 1.9 228 10.9 234 2.6
210 0.11 291 1.4 215 12.2 214 2.5
260 0.08 267 1.6 207 13.3 221 2.5
310 0.09 274 0.8 205 14.4 216 2.5
370 0.10 291 1.0 200 15.1 206 2.5
Average 0.09 274 1.3 211
0.1 170 0.06 215 2.4 237 8.9 242 3.2
210 0.07 228 2.2 232 10.5 234 3.4
260 0.12 247 3.2 235 11.3 234 4.3
310 0.06 211 1.3 221 12.7 236 3.6
370 0.11 245 1.6 217 12.9 223 4.5
Average 0.08 229 2.1 228
0.5 170 0.20 202 0.8 200 8.5 303 6.9
210 0.11 184 1.9 225 9.3 295 5.6
260 0.12 192 3.3 237 10.2 291 5.8
310 0.08 185 1.6 225 10.3 286 5
370 0.16 200 6.7 247 10.6 289 6.9
Average 0.13 193 2.9 227
1 170 0.02 123 0.2 204 7.7 332 3.7
210 0.06 149 6.1 261 8.8 328 5.3
260 0.13 163 1.6 207 10.5 323 8.3
310 0.05 142 1.9 237 10.7 326 5.3
370 0.08 158 1.1 223 12.2 323 5.7
Average 0.07 147 2.2 226
3174 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
the pit activity comes from the proximity between corrosion and pitting potentials. In fact,
based on experimental data reported in a former investigation [19], pitting potentials val-
ues are between 37 and 66 mV more positive than corrosion potentials (Table 1) for iron in
NaCl concentrations from 0.02 to 1 M. However, experimental density current deviations
from Tafel behaviour are signicant only at potentials 100 mV more positive than corro-
sion potential. This can be interpreted as evidence of a previous metastable stage in the
onset of the pitting process [21].
Fig. 4 shows the same polarization curve shown in Fig. 3, but nowin Ei coordinates and
together with the respective calculated curves for the anodic and cathodic sub-processes. As
expected from corrosion theory, the experimental curve approaches the currents of the sin-
gle the sub-processes only at potentials far from the corrosion potential. For instance, the
experimental curve represents well the intrinsic cathodic current reaction only at potential
cathodic to 500 mV/SHE. This is clear evidence that in this system the experimental
cathodic current cannot be directly used to obtain the kinetic parameters associated to
the single cathodic sub-process. In fact, values of t
c
and i
0O
2
calculated from directly tting
the experimental cathodic current to the equation log(i(1 i/i
l
)
0.5
) vs. E following the pro-
cedure used in [5], dier up to 60% with respect to values calculated here with the superim-
position model. This broad variation is a the result of combined uncertainty in the
determination of the limiting current and the slope of the curve log(i(1 i/i
l
)
0.5
) vs. E.
3.4. Cathodic limiting current
As the potential sweep started from the cathodic side an important part of the cathodic
curve was obtained before the onset of surface iron oxide formation, and corresponds
to oxygen reduction on a practically rust-free carbon steel surface. A high correlation
-2
-1
0
1
2
-700 -600 -500 -400 -300 -200 -100
E (mV/SHE)
A
B
C
O
L
o
g

(
i
/
(
A
/
m
2
)
)
Fitted total current curve
Experimental curve
C'
Fig. 3. Experimental polarization curve (continuous line) for carbon steel electrode rotating at 260 rad/s
1
in
aerated 0.5 M NaCl solution. Fitted curve (dotted line) and Tafel slope, both calculated from the model, are
superimposed.
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3175
coecient value between i
l
and X
0.5
was obtained at every NaCl concentration, as can be
seen in Fig. 5. These results conrm validity of the Levich relationship [22]:
i
l
0:62nFD
2=3
O
2
m
1=6
C
O
2
X
1=2
13
where C
O
2
mol m
3
is the oxygen concentration of the bulk in, D
O
2
m s
2
the oxygen
diusion coecient, F (96,485 coulomb mol
1
) the Faraday constant, n the number of
electrons transferred, m (m s
2
) the kinematic viscosity and X (rad s
1
) the rotation rate
of the iron steel electrode. The Levich slope values indicated as S in Fig. 5 are in agreement
0.1 M S = 0.70
R
2
= 0.99
0.02 M S = 0.82
R
2
= 0.99
1 M S = 0.60
R
2
= 0.98
0.5 M S = 0.7
R
2
= 0.96
5
9
13
17
12 14 16 18 20
(rad/s)

0.5
i
l


A
/
m
2
1 M
0.5 M
0.1 M
0.02 M
Fig. 5. Linear dependency of the limiting current density from X
0.5
at dierent NaCl solution concentrations.
Fig. 4. Total and partial current densities tted using the model from experimental data in Fig. 3.
3176 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
with those reported in other investigations [23]. Assuming that S is solely dependent on
NaCl concentration at a xed temperature, an overall analytical expression for i
l
data
shown in Fig. 5 is as follows:
i
l
0:6144 0:2261e
9:7942C
NaCl

X
0:5
for 0:02 < C
NaCl
< 1M
and 170 < X < 370 rad s
1
14
The n values associated with the reduction of dissolved oxygen were calculated by using
Eq. (13) using physical data from dierent sources [2426]. These values are between
2.4 and 4. Possibly, oxygen reduction on carbon steel could take place simultaneously
by both, a 2 and 4 electron transfer process as reported for bare and passive iron, respec-
tively [5,23].
3.5. Inuence of electrode rotation rate on anodic and cathodic sub-processes
Fig. 6 shows currentpotential curves calculated with the model for the anodic and
cathodic sub-processes at two extreme NaCl concentrations, 0.02 M and 1 M NaCl, at
eight dierent electrode rotating rates. The trend observed in the cathodic current curves
in that gure shows that the electrode rotation rate has a clear inuence on the kinetics of
oxygen reduction on carbon steel. This reaction, therefore, is clearly inuenced by mass
transfer phenomena which is itself dependent on uidodynamic conditions at the electrode
surface. As values of t
C
and i
0O
2
seem to vary randomly with variations of electrode rota-
tion rate (see Table 1) one can conclude that the increase in the cathodic currents with
rotation rate is due to variations in the limiting current, i
l
, which consistently increases
with the increase of rotating rate (see previous section).
On the other hand, Fig. 6 shows that anodic current curves vary randomly with the
increase of rotation rate. This behaviour conrms that the anodic parameters t
a
and i
0Fe
calculated with the model are in fact independent of mass transfer inuence and truly rep-
resent the intrinsic kinetic parameters associated to a pure charge transfer control. Ran-
dom variation of anodic parameters is related to the statistical nature of the pitting
process mainly originated from its early metastable stage. This eect has been reported
as current uctuations in corrosion of mild steel in NaNO
2
NaCl solutions using a sta-
tionary electrode [21].
3.6. Eect of NaCl concentration on anodic and cathodic sub-processes
Fig. 7 shows iE curves for the anodic and cathodic sub-processes at two rotation rates,
310 and 370 rad s
1
, for each of the four NaCl concentrations used, 0.02, 0.1, 0.5 and 1 M.
Results in that gure show that the anodic current curves clearly rises with an increase in
NaCl either at low or high rotation rates. As data in Table 1 shows that i
0Fe
varies ran-
domly with variations of NaCl concentration, variations in the anodic current curves
can be mainly attributed to variations of t
a
, which systematically decreases as NaCl con-
centration increases (see Table 1). This tendency shows that the increase in NaCl concen-
tration enhances the rate of pitting formation occurring on the surface of carbon steel.
The trend observed in the cathodic curves in this Fig. 7 shows that the concentration of
NaCl has also an inuence on the kinetics of oxygen reduction on carbon iron oxidation.
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3177
The cathodic current decreases with a NaCl concentration increase, behaviour which is
determined by the decrease in the cathodic limiting current. This tendency can be related
to the increase in solution viscosity which accompanies the increase of NaCl concentration
which, subsequently, reduces the cathodic limiting current as shown by the Levich rela-
tionship [22]. The eect of NaCl concentration increase is more marked at high rotation
rates. On the other hand, variations of kinetics parameters associated to the mechanism
of charge transfer control in oxygen reduction, i
0O
2
and t
c
, showed only a random varia-
tion with the increase in NaCl concentration.
0.0
5.0
10.0
15.0
-700 -500 -300 -100
E (mV/SHE)
I

(
A
/
m
2
)
I

(
A
/
m
2
)
170 rad/s
210
260
310
370
0.0
5.0
10.0
15.0
-700 -500 -300
E (mV/SHE)
170 rad/s
210
310
370
260
Fig. 6. Partial anodic and cathodic curves for carbon steel disk rotating at dierent angular velocities: (a) 0.02 M
NaCl solutions; (b) 1 M NaCl solutions. Corrosion currents at each curves interception are highlighted with a
dot.
3178 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
3.7. Kinetics expressions
After analyzing the inuence of electrode rotation rate and NaCl concentration on the
anodic and cathodic sub-processes it is possible to write explicit expressions for the kinet-
ics of each of these sub-processes. In the case of the anodic sub-process as i
0Fe
and t
a
varied
randomly with rotation rates average values of these parameters were calculated for each
0.0
5.0
10.0
15.0
-700 -500 -300 -100
E (mV/EHE)
E (mV/EHE)
I

(
A
/
m
2
)
I

(
A
/
m
2
)
1 M
1 M
0.5 M
0.5 M
0.1 M
0.1 M
0.02 M
0.02 M
0.0
5.0
10.0
15.0
-700 -500 -300 -100
1 M
0.5 M
0.1 M
0.02 M
0.02 M
0.1 M
0.5 M
1 M
Fig. 7. Partial anodic and cathodic curves for carbon steel disk at dierent NaCl concentrations: (a) 310 rad/s;
(b) 170 rad/s. Corrosion currents at each curves interception are highlighted with a dot.
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3179
NaCl concentration, which are shown in Table 1. Then, the dependence of these average
values on NaCl concentration was analyzed and found to be:
i
0Fe
0:096 0:008C
NaCl
15
t
a
257 115C
NaCl
16
From these results the rate of the anodic dissolution of carbon steel could be nally ex-
pressed as:
i
Fe
0:096 0:008C
NaCl
exp
E
591 265C
NaCl
_ _
17
In the case of the cathodic sub-process the inuence of rotation rate and NaCl concentra-
tion is summarized in its eect on mass transfer, which inuences the limiting current,
which are summarized in Eq. (14). On the other hand, as i
0O
2
and t
c
varied randomly with
rotation rates average values of these parameters were calculated at each NaCl concentra-
tion, which are presented in Table 1. From these results the rate of the cathodic oxygen
reduction on carbon steel can be nally expressed as:
i
O
2
2:1 10
4
1
i
O
2
0:6144 0:2261e
9:7942C
NaCl

X
0:5
_ _
0:5
exp0:0103E 18
3.8. Corrosion rate
Fig. 8 summarizes the dependence of corrosion current on the electrode rotating rate
and NaCl concentrations. The trends observed in that gure can be now well understood
in terms of the behaviour of the cathodic and anodic sub-processes described in Figs. 6 and 7.
0
2
4
6
8
10
150 250 350 450
rad s
-1
I

(
A
/
m
-
2
)
1 M
0.5 M
0.1 M
0.02 M
Fig. 8. Corrosion current density vs. electrode rotation rate.
3180 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
In those gures values of corrosion currents are dened at the crossing of the respective
anodic and anodic curves and are graphically represented as lled circles.
Fig. 8 shows that in solutions with 0.02, 0.1 and 0.5 M NaCl, the inuence of rotation
rate on the corrosion current does not show a clear trend, but at 1.0 M NaCl corrosion
rate, on average, increases with rotation rate increase. The behaviour observed at 0.02,
0.1 and 0.5 M can be explained in terms of the trend observed in anodic and cathodic
curves in Fig. 6a, drawn for 0.02 M NaCl. At this low NaCl concentration the anodic
curve crosses the respective cathodic curve in a potential region where the cathodic process
is mainly controlled by charge transfer and is, therefore, independent of mass transfer. On
the other hand, the behaviour observed at 1.0 M can be explained with respect to Fig. 6b,
which shows that the situation changes at 1 M NaCl: at this high NaCl concentration the
kinetics of the anodic process is much faster and the anodic curve now crosses the cathodic
curve at a much higher potential, where the cathodic process is strongly inuenced by mass
transfer.
Fig. 8 shows that the corrosion current increases with an increase in NaCl concentra-
tion. This behaviour can be explained in terms of Fig. 7 which shows that even though
the cathodic limiting current decreases with a NaCl concentration increase, the strong
inuence of NaCl concentration on the anodic current predominates and the result in a
net increase of the corrosion current.
4. Conclusions
Currentpotential curves for carbon steel corrosion in NaCl solutions were obtained
from linear potential sweep at a rate of 1 mV s
1
in solution with concentrations in the
range 0.021 M NaCl and rotation rates in the range 170370 rad s
1
.
The observed inuence of rotation rate on the obtained polarization curves gave evi-
dence that the cathodic and anodic current branches are interdependent on both the ano-
dic and cathodic sub-processes and can not be independently used to characterize carbon
steel corrosion.
Application of a superimposition model developed ad hoc and implemented in a com-
puter program enabled determining the corrosion rate of carbon steel and the kinetics
parameters of the underlying anodic and cathodic sub-processes.
The anodic sub-process, dissolution of iron, is well described in terms of a pure charge
transfer controlled kinetics in which the Tafel slope decreases with a NaCl concentration
increase.
The cathodic sub-process, oxygen reduction on iron, is well described in terms of a
mixed mass transfer and charge transfer controlled kinetics where the limiting current
increases with the rotation rate increases but decreases with NaCl concentration increase.
The inuence of NaCl concentration and electrode rotation rate on carbon steel corro-
sion rate can be well explained in terms of their specic inuence on the anodic and catho-
dic sub-processes.
Acknowledgments
The nancial support from projects MECESUP ANTO102 and MEL 2004 developed
in the Faculty of Engineering at the Universidad de Antofagasta, Antofagasta, Chile, is
greatly appreciated.
L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184 3181
Appendix A. Unconstrained optimization method for parameter determination
The unknowns parameters a, b, c, d, e were determined by minimization of the total
sum of the squared values as follows:
SSV

n
1

i
exp
j
i
j

2
_
20
where n is the number of current, potential data, i
exp
j
is a steady-state current density mea-
surement taken at a given applied potential E
j
in the iron steel/NaCl solution cell, and i
j
the theoretical expression for current density at the same potential
Table A1
Fitted parameters for experimental currentpotential values according to Eq. (18)
NaCl conc. X
(rad s
1
)
a
(A m
2
)
b
(m V
1
)
c
(A m
2
)
d
(A m
2
)
e
(mV
1
)
E
corr
(mV
SHE)
i
corr
(A m
2
)
1 M NaCl 10 0.047 0.014 3.7 935.4 0.016 369 3.0
42 0.277 0.009 4.0 1315.5 0.017 357 3.1
84 0.281 0.011 5.2 999.0 0.016 348 4.4
168 0.121 0.011 7.7 1823.8 0.019 332 3.7
209 0.498 0.009 8.8 808.3 0.015 328 5.3
262 0.763 0.011 10.5 776.1 0.014 323 8.3
314 0.310 0.010 10.7 1047.7 0.016 326 5.3
367 0.276 0.010 12.2 618.2 0.015 323 5.7
Av. 0.322 0.011 935.4 0.016
0.5 M NaCl 10 0.005 0.021 2.4 329.3 0.015 341 2.2
42 0.046 0.016 4.7 301.9 0.014 321 3.6
84 0.079 0.016 6.7 239.6 0.013 307 4.8
168 0.489 0.012 8.5 217.8 0.011 303 6.9
209 0.451 0.010 9.3 226.8 0.013 295 5.6
262 0.540 0.010 10.2 190.8 0.012 291 5.8
314 0.385 0.010 10.3 170.9 0.012 286 5.0
367 0.797 0.009 10.6 189.9 0.012 289 6.9
Av. 0.349 0.013 233.4 0.013
0.1 M NaCl 10 0.062 0.014 2.7 55.2 0.017 232 1.1
42 0.220 0.012 5.0 43.8 0.011 253 3.0
84 0.213 0.011 6.2 34.8 0.012 233 2.3
168 0.383 0.010 8.9 42.0 0.011 242 3.2
209 0.410 0.010 10.5 35.8 0.010 234 3.4
262 0.555 0.010 11.3 38.3 0.009 234 4.3
314 0.360 0.010 12.7 47.9 0.011 236 3.6
367 0.527 0.011 12.9 36.6 0.009 223 4.5
Av. 0.341 0.011 41.8 0.011
0.02 M
NaCl
10 0.020 0.008 2.7 23.0 0.010 306 1.3
42 0.128 0.009 5.0 23.1 0.010 257 1.6
84 0.156 0.010 7.4 16.4 0.009 243 1.7
168 0.416 0.010 10.9 22.7 0.009 234 2.6
209 0.485 0.011 12.2 13.6 0.008 214 2.5
262 0.729 0.011 13.3 16.5 0.009 221 2.5
314 0.426 0.011 14.4 14.9 0.008 216 2.5
367 0.636 0.012 15.1 13.1 0.008 206 2.5
Av. 0.374 0.010 17.9 0.009
Av., Average value.
3182 L. Ca ceres et al. / Corrosion Science 49 (2007) 31683184
i
j
a 1
i
O
2
c
_ _
m
exp bE
j
_ _
d expeE
j
21
To ensure convergence in the optimization process the procedure to handle expression (21)
was as follows:
(a) The independent variable E was normalized in terms of its median and standard
deviation values.
E
0

E E
m
E
d
22
where E
m
and E
d
are the arithmetic average and the standard deviation of potential
values considered for minimization, respectively.
(b) Due to diculties experienced with the implicit i
O
2
variable of Eq. (6), the corre-
sponding m value was previously estimated by linear regression from a ln(i) vs.
ln(1 i/i
l
) plot at dierent X values and 500 mV [5].
Thus using m = 0.5, Eq. (1) is expressed as
i
j

a
2c
expbE
j
a expbE
j

a
2
exp2bE
j
4c
2
_
d expeE
j
23
For this equation, the rst term of the right hand side is the explicit form of the
cathodic partial current density and the second term the anodic partial current
density.
(c) The quality of the t for a given potential interval was evaluated using the root mean
squared error dened as
RMSE

n
j1
i
exp
j
i
j
_ _
2
n r

24
where, r is the number of independent variables.
(d) Initial estimates of a, b, c, d, e parameters for optimization was done in a sequential
order. First, c equals to the experimental current value at 500 mV (EHE), b equal
to the minimum-squared slope of the experimental values log(i(1 i/c)
0.5
) vs. E, in
a selected potential cathodic range, a equals to i exp(bE)(1 i/c)
0,5
, e equals to
the minimum-squared slope of the experimental values log(i) vs. E, in a selected
potential anodic range, and d equals to i exp(eE).
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