Corrosion Science 133 (2018) 417–422

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Discussion on “Electrochemistry of CO2 corrosion of mild steel: Effect of CO2 T

on iron dissolution reaction” by A. Kahyarian, B. Brown, S. Nesic, [Corros.
Sci. 129 (2017) 146–151]
⁎
T.C. Almeida , M.C.E. Bandeira, R.M. Moreira, O.R. Mattos
Laboratorio de Ensaios Não Destrutivos, Corrosão e Soldagem – LNDC, COPPE Universidade Federal do Rio de Janeiro – UFRJ, Cx. Postal 68505, CEP 21945-970, Rio de
Janeiro, RJ, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: This discussion presents an analysis of the recent paper by Kahyarian, Brown and Nesic published in this Journal
CO2 corrosion Kahyarian et al. (2017). Indeed, the paper claims an anodic participation of CO2 in the iron dissolution me-
Iron dissolution chanism, not detected by our work also published in this same journal Almeida et al. (2017). The anodic role
Mechanism was, however, only limited to the analysis of Tafel slopes behaviour. This is what was typically done in the early
Polarization
works of iron dissolution in acid media during the 1960′s, so that a discussion about this methodology based on
EIS
the progress of the electrochemistry that has been developed since the 1980′s is absolutely necessary.

1. Positioning the problem
An overview of corrosion issues in the oil and gas industry has
shown that a better understanding of the CO2 corrosion mechanism
plays a relevant role in more accurate steel corrosion predictions. It
means, on the one hand, reducing project costs by avoiding over-
estimation of the corrosion rate and, on the other hand, minimizing
risks of accidents in the case of underestimation of the corrosion rates,
which may result in failures. In this regard, much research on this
subject has been developed over, at least, more than 40 years [1–12].
In order to explain results obtained from steady-state techniques,
Nesic, Thevenot and Crolet [9], in 1996, proposed a direct reaction of
CO2 on the free iron surface. Recently, Kahyarian, Brown and Nesic [1],
also by means of steady-state techniques, sustained the participation of
the carbonate species in the iron dissolution. Otherwise, Almeida,
Bandeira, Moreira and Mattos [2] conducting an investigation by means
of transient techniques, in this case, electrochemical impedance, did not
observe any direct action of CO2 on the free iron surface in the studied
conditions. In the paper of Almeida et al. [2] the impedances were
measured only at the open circuit potential since the authors used a
high resistive solution free of chloride saturated with CO2.
Although the mechanism of iron dissolution has been the subject of
several papers [13–22], the one under discussion focuses its analysis on
the works from the early 1960′s about the iron dissolution mechanism.
In this period, the discussion was limited to two mechanisms based on
the slope of the steady-state polarisation curves, or simply, Tafel slope.
Only 10 mV of Tafel slope separated one mechanism from the other.
Indeed, during many years, iron dissolution was analysed around
two main mechanisms; one proposed by Heusler [15] and the other by
Bockris et al. [16,17]. In the first, the dissolution of iron was taking
place in two steps, coupled by monovalent adsorbed iron playing a
catalytic role. In the second, the reaction model involving two con-
secutive steps.
Heusler [15] mechanism:
Fe (s) + OH(−aq) ⇌ (FeOH )ads + e− (1-a)
Fe (s) + (FeOH )ads + OH(−aq) → (FeOH )ads + FeOH(+aq) + 2e− (1-b)
Bockris et al. [16,17] mechanism:
Fe (s) + OH(−aq) ⇌ (FeOH )ads + e− (pseudo − equilibrium) (2-a)
slow
(FeOH )ads ⎯⎯⎯→ FeOH(+aq) + e− (2-b)
Both mechanisms were proposed in the attempt to take into account
their steady-state results, in which Heusler [15] obtained a Tafel slope
of 30 mV/decade and Bockris et al. [16,17], 40 mV/decade. Moreover,
the two mechanisms considered the transfer coefficient (α), which is a
measure of the symmetry of the energy barrier related to the fraction of
energy supplied by the electric field in electrochemical reaction, to be
constant for all steps and equal to 0.5. Although it is often referred to as
a theoretical value, even in the paper under discussion [1], the choice of
a transfer coefficient a priori equal to 0.5 is completely arbitrary. First

⁎
Corresponding author.
E-mail addresses: tatianadaschagas@gmail.com, talmeida@metalmat.ufrj.br (T.C. Almeida).

https://doi.org/10.1016/j.corsci.2018.02.004
Received 4 December 2017; Received in revised form 23 January 2018; Accepted 1 February 2018
Available online 05 February 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.
T.C. Almeida et al.
of all, it is important to emphasise that, there is absolutely no theory
that establishes a fixed value of 0.5 for all steps of a mechanism. The
transfer coefficient can range from zero to one, depending on the shape
of the intersection region of the activation free energy curves for oxi-
dation and reduction, which change during the faradaic process [23].
Secondly, if arbitrarily all coefficients were 0.5, it would not be possible
to simulate the experimental results for the mathematically calculated
electrochemical impedance, as it was highlighted by Epelboin and
Keddam [18] and corroborated later by Keddam et al. [13,22]. This
limitation was evidenced even by groups that traditionally considered
the transfer coefficient to be always 0.5, since, when working with
impedance [24], they were forced to consider 0.4 < α < 0.6 to si-
mulate partially the impedance Diagrams [25]. Therefore, to assume
α = 0.5 for all elementary steps of a mechanism to explain a Tafel slope
can leads to strongly inaccurate approaches and sometimes to mis-
interpretations. As shown in 1981 by Keddam et al. [13,22], using this
approach, the impedance would always be limited to a single capacitive
loop related to a double layer in parallel with the charge transfer re-
sistance. It occurs because, frequently, in the mathematical develop-
ment of impedance it appears the expression(α1 − α2)(dθ / dE ), and if
α1 = α2 = 0.5, θ, the fraction of the electrode surface filled by inter-
mediate species, is not seen and there will not be faradaic impedance,
only the double layer relaxation.
Specifically in the mechanism proposed by Bockris et al. [16,17], a
deeply relevant further analysis is related to the inference of a Tafel
slope equal to 40 mV assuming a very restrictive hypothesis of a
pseudo-equilibrium for the first step. The occurrence of a pseudo-
equilibrium reaction involves an electrode potential close to its ther-
modynamic equilibrium potential and its reaction rate very fast com-
pared to that of step (2-b) [22]. With regard to the impedance simu-
lation, it means that even if the transfer coefficient is different from 0.5,
there will always be a capacitive loop coupled with the double layer,
and this would be the calculated impedance in any range of potential
where this restrictive hypothesis was imposed, and this is not what is
observed experimentally for iron and iron alloys in acid medium
[13,22].
2. The role of CO2 in the anodic dissolution mechanism of iron
Kahyarian et al. [1] found that in the presence of CO2, the Tafel
slope at the active dissolution range decreased from ∼28 mV to
∼22 mV. In this case, the difference used to propose that CO2 has a
direct role in the iron dissolution mechanism is 6 mV. Considering the
deviations, (28 ± σ) mV/decade and (22 ± σ)/decade, what would be
the real difference used to define CO2 participation in the anodic me-
chanism? In other words, 6 mV of difference means that, from a statistic
point of view, a standard deviation only of 3 mV/decade applied to the
different curves could make that difference to vanish. From a more
physical point of view, even if we consider the 6 mV as unmovable, this
would indicate an extremely sensitive electrochemical system in which,
only 6 mV through an entire current decade would be related to two
different mechanisms, since one in the absence and the other in the
presence of CO2. This mechanistic conclusion based on the single
steady-stated Tafel slope analysis relying on a so small difference thus
seems yet quite fragile.
This is so much important as the reliable determination of such a
small difference (6 mV) on the Tafel slope is not an easy task and under
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Corrosion Science 133 (2018) 417–422
or over corrections of 3 mV can be easily done. Another point is that
even if the correction of the ohmic drop was not overestimated (or
under), a mechanism with a Tafel slope as small as 22 mV was never
proposed in the literature. Therefore, when the current changes, for
example, from 0.1 mA to 1 mA or 1 mA to 10 mA, or from 10 mA to
100 mA, the interface is so active that it is polarised only by 22 mV.
Even in very concentrated acid, such as sulphuric acid or chloride acid,
at pH = 0, such active behaviour has never be seen. Indeed, as shown
by Epelboin et al. [26], in the potential range near the corrosion po-
tential, as done by the paper under discussion, high values of Tafel
slope can be associated with the dissolution process coupled with the
oxidation of hydrogen adsorbed at the electrode surface (H ⇌
H+ + e−).
Despite all this, suppose now that it is experimentally possible to
differentiate these two values, which would mean that 6 mV has a real
physical meaning. Nevertheless, the Tafel slope is not able to define a
reaction mechanism. This issue was exhaustively discussed analytically
in 1981 [13,22]. The same Tafel slope may be associated to different
mechanisms and different Tafel slopes may be associated to a unique
mechanism. Thus, even if 28 mV/dec and 22 mV/dec have a real phy-
sical meaning, they may be associated to a single mechanism and
cannot be used to claim a CO2 role in one case and not in another one.
The analytical discussion presented in 1981 [13,22] can still be
easily revisited but, for the sake of clarity, this issue will be commented
now by means of electrical circuit the situation above outlined. How-
ever, it is important to emphasise that the impedance we are dealing
with in electrochemical science is, a fortiori, an electrochemical prop-
erty of the interface and not a single electrical quantity, an aspect not
always remembered by the users of the technique.
Fig. 1 presents two equivalent circuits that represent two largely
different mechanisms, although providing the same Tafel slope, as it
immediately appears in the Figures through the identical low frequency
limit values that, by definition, represent the polarisation resistance,
Rp, the most widely used parameter to the estimation of the corrosion
current density, and which is the reciprocal of the Tafel slopes at the
polarisation point. Indeed, suppose that both proposed equivalent cir-
cuits perfectly simulated the experimental results shown in Fig. 2 for a
current equal to 10 mA, area of 1 cm2, and furthermore, that the current
for all range of the polarisation curve under discussion follows a simple
relation (Eq. (3)), as proposed in the paper under discussion [1].
E − Ecorr ⎞
I = Icorr exp ⎛
⎜ ⎟
⎝ ba ⎠ (3).
Its derivative provides:
dI 1 1
= =I
dE Rp ba (4)
In which ba is the slope of the curves in the anodic range (Tafel
slope), Rp is the polarisation resistance, I is the current and E is the
potential. Thus, the equivalent circuits presented in Fig. 1A and B, with
the parameters specified in Table 1, provide for both, a polarisation
dI 1
resistance equal to 4 ohm. Therefore, dE = 4 and for I = 10 mA,
ba = 40 mV for the two equivalent circuits, that represent two com-
pletely distinct models (Fig. 2A and B). Therefore, the same Tafel slope
can be provided by different mechanisms.
Another situation is presented in Figs. 3 and 4. Here, the opposite of
the first illustration (Figs. 1 and 2) can be seen.
Fig. 1. Equivalent electrical circuits used to represent
two electrochemical processes; A) Electrochemical
process 1, B) Electrochemical process 2.
T.C. Almeida et al. Corrosion Science 133 (2018) 417–422

Fig. 2. Simulated impedances for equivalent electrical circuits proposed in Fig. 1 for; A) Electrochemical process 1, B) Electrochemical process 2.

Table 1
Parameters of the electrical circuits presented in Fig. 1 used to simulate the impedances in
Fig. 2.

Circuit A Circuit B
Parameters Valores Valores

R1 (Ω) 1.5 2.5

R2 (Ω) 1.0 1.5 Fig. 3. The same equivalent electrical circuit used to represent two different electro-
R3 (Ω) 1.0 – chemical processes.
R4 (Ω) 2.0 –
C1 (F) 6.369E-05 6.369E-05
C2 (F) 7.962E-02 1.062E-01

419
T.C. Almeida et al. Corrosion Science 133 (2018) 417–422

Table 2 The parameters used to simulate the equivalent circuit in Fig. 3 are
Parameters of the electrical circuits presented in Fig. 3 used to simulate the impedances in shown in Table 2
Fig. 4.
Considering the same I = 10 mA, in Fig. 4A and B there are two
Circuit A Circuit B identical mechanisms with only one time constant concerning the far-
Parameters Valores Valores adaic capacitive process. The polarisation resistances are different. For
the mechanism in Fig. 4A, 2.8 ohm, while for the mechanism in Fig. 4B,
R1′ (Ω) 1.5 1.5
2.2 ohm. These resistances give rise to two distinct Tafel slopes, 28 mV
R2′ (Ω) 1.3 0.70
C1′ (F) 1.060E-04 1.060E-04 per decade and 22 mV per decade, respectively. This shows that the fact
C2′ (F) 1.225E-01 2.227E-01 of obtaining two distinct Tafel slopes does not assure distinct me-
chanisms as claimed in the paper under discussion by Kahyarian et al.
[1]. The same could be said for 30–40 mV previously presented. This
discussion requires transient measures.
Concerning the understanding of the CO2 corrosion mechanism, a

Fig. 4. Simulated impedances for the equivalent electrical circuit proposed in Fig. 3; A) Electrochemical process with Rp equal to 28 mV/dec, B) Electrochemical process with Rp equal to
22 mV/dec.

420
T.C. Almeida et al.
good way to investigate a reaction mechanism is doing the same that
was done in 1981 by Keddam et al. [13,22] for the iron dissolution in
acid media. On that occasion, steady-state polarisation curves and
electrochemical impedances were measured during the dissolution of
iron in a Na2SO4 solution acidified by the addition of H2SO4 and the
experiments were performed over a very wide pH (0–5) and current
density (up to 0.1 A cm2) ranges. The whole set of experimental results
were interpreted quantitatively by a reaction model. This model was
able to simulate suitably all the polarisation curves and the impedance
diagrams, even the steady-state polarisation curve that showed two
current maximums, as was reproduced by Kahyarian et al. [1] in Fig. 1
of their paper. This curve, as was well discussed in the study performed
by Bessone et al. [27], is due to a simple change in the dissolution path
in the reaction mechanism and not necessarily due to a prepassivation.
In addition, later on, the mechanism proposed in 1981 [13,22] was
used to explain the experimental impedance for the dissolution-passi-
vation process of iron-chromium alloy, in which Fe was considered to
be perturbed by the addition of Cr. Finally, the chloride and sulphate
anions effect was explained by this same mechanism [28], illustrating
its robustness.
From what has been mentioned above, this model could probably be
extended to CO2-rich systems, but to conduct an investigation such as
this presents some experimental limitations. In the real world of the oil
and gas industry, the solutions come with chloride ions, an active anion
also present in the paper under discussion (NaCl 0.1 M) [1]. NaCl is not
a supporting electrolyte, since it can actively participate in the elec-
trode process [28]. Even perchlorate, a less active anion, cannot be
considered as a supporting electrolyte in apparently non-aggressive
media such as ethanol [29]. Thus, to perform this kind of investigation,
it is important to work only with CO2, eliminating any other anions
present in the aqueous solution. Nevertheless, the electrochemical
medium containing only water and CO2 has a highly resistive solution,
which complicates this study. In this context, based on a two-electrode
cell, a new device, specific for autoclave, was developed to work only
with CO2, in the absence of chloride, at high pressure of CO2 [2]. The
use of a two-electrode cell with a large surface area and a small distance
between the electrodes decreases the solution resistance and makes
impedance measurements possible, in this case at high pressure of CO2.
This experimental set up is useful to eliminate any chloride effect, but
prevents work outside the corrosion potential as done by Keddam et al.
[13,22]. A tentative of using a small reference electrode in between the
two plates could be envisaged for future works.
Despite the limitations, this was the first time that CO2-water was
studied free of the presence of chloride under high pressure [2]. In this
work, it was shown that, on the corrosion potential, it is not correct to
affirm that CO2 acts on free iron surface as proposed by Nesic et al.
[1,9]. On iron surface, the first dissolution step is always the formation
of FeOHads, a water specie relaxation, as shown by Epelboin and
Keddam [18]. Chloride and sulphate anions only participate in the
dissolution process in other steps of the mechanism formed from FeO-
Hads [28]. Like chloride and sulphate, would CO2 be capable of playing
a role in iron dissolution? Yes, it could be, but never direct acting over
the free iron surface. As seen, like chloride and sulphate, eventually, if
exist, its role will occur over the species Fe(OH)ads. Certainly, a parti-
cular role of CO2 could exist at the experimental condition in which
siderite is supposed to be formed at the electrode surface. The favour-
able conditions include high temperature, high pressure and a propi-
tious pH range. The formation of iron carbonate is a very different
matter from the issue discussed here. It is important to emphasise that
siderite can also be formed by direct chemical precipitation due to the
saturation of Fe2+ and CO32− at the surface. In this case, one kinetic
role of CO2 is not necessary, but this is an open question.
To confirm the hypothesis of a CO2 role in the anodic mechanism,
the system would need to be polarised, and this is only possible, until
this moment, with an addition of anions. With the addition of chlorides,
a possible effect of CO2 would be difficult to observe. It would be
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Corrosion Science 133 (2018) 417–422
necessary to develop an experimental protocol to polarise the system,
with chloride, in the presence and absence of CO2. Many experimental
measures would be necessary to show any systematic change of fre-
quency in the second capacitive loop that would indicate the CO2
participation, since it is competing with chloride over FeOHads, but not
directly on free iron surface as previously proposed [1]. Certainly, it
must be done by means of transient technique, in the case of our group,
electrochemical impedance. New techniques as proposed by Keddam
et al. [30] could also be useful to detect an eventual anodic role of CO2.
Concerning the mass transport role, if it occurs, new setups were re-
cently developed [31].
3. Final remarks
The understanding of the reaction processes is relevant from the
applied and fundamental point of view. In this context, steady-state
techniques and transient techniques can be used additionally to propose
reaction mechanism. Kinetics studies, different from thermodynamics,
necessarily involve time (frequency). Tafel slope is obtained in the
steady-state condition, so time is equal to infinite (zero frequency). A
mechanism, proposed from a research to infer an anion participation
must be done in a large domain of time (spectre of frequency) and not
only limited to a steady-state. It is necessary to insist that only Tafel
slope cannot be used to certify a specific mechanism or anion partici-
pation, even though it has physical meaning and statistical reproduci-
bility. Insisting on this path is to go back to the 1960′s and ignore the
progress of electrochemistry in the field of modelling since the 1980′s.
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