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_ _
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
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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