Corrosion Mechanisms of Iron and Pipeline Steels in Bicarbonate and

Carbonate Solutions – A Review

Faysal Fayez Eliyan and Akram Alfantazi

Corrosion group, Department of Materials Engineering, The University of British
Columbia, Vancouver, BC, Canada, V6T 1Z4.

Summary
This paper presents a mechanistic review on the corrosion reactions of iron and pipeline
steels in bicarbonate and carbonate solutions. It consolidates key details about the
corrosion reactions, from the early steps of dissolution till complete passivation, from a
large scatter of electrochemical studies. It reviews some of the early and modern
research in which voltammetric and polarization techniques are employed. It begins with
discussing the controversial role(s) of bicarbonate with the dissolution reactions as
being an impeder of film formation or as being a direct anodic catalyzer. It presents the
steps and the rate-determining steps of formation of Fe(OH)2 and its interrelation with
that of FeCO3. It describes the roles of bicarbonate and carbon-carrying adsorbents with
the precipitation of FeCO3 as an independent outer-layer over Fe(OH)2. Depending on
bicarbonate, carbonate, oxygen, hydroxyl, temperature and applied potential, FeCO 3
transforms by oxidation or electro-oxidation to iron oxides, such as Fe2O3 and Fe3O4, in
many paths, which are discussed. Finally, the paper outlines the governing reactions in
carbonate solutions of dissolution and FeCO3-based passivation, and the possible
transformations it undergoes.

1. Bicarbonate and Dissolution Steps

For pure iron immersed in an aqueous solution:
Fe + H2O Fe.H2Oads (1)
Bicarbonate was reported uninvolved with its first oxidation step. In solutions of pH
higher than 7, it is expressed as [1]:
- -
(2)
- -
(3)
Rather, it impedes the FeOHads monolayer surface-covering process, as bicarbonate
reacts with it, in a second oxidation step to produce the complex species as
[2]:
- - -
(4)
As a result, a linear anodic Tafel region in a scratching constant-potential test, carried
out in [2], extended to a higher bare-surface current density than that in a borate (inert
species) solution. The Tafel slope in both solutions was the same, of nearly 112
mV/decade, to indicate that bicarbonate does not involve with, or accelerate the first
oxidation step. Reaction (4) was considered a competitive process with that of film
formation. Simard et al., on contrary, regarded as a product that results from
the involvement (not the non-involvement [2]) of bicarbonate with the dissolution steps
of a rotating 1024 mild steel electrode, during 5 mV/s voltammogram scans, as [3]:
- -
(5)
That was associated to the increase of the critical currents, of the first anodic peaks at -
0.65 V vs. SCE, with increased bicarbonate concentration in solutions of pH of nearly 9.
The linear relationship of their reciprocals with the (rotation speed)-0.5 in 0.1 M NaHCO3
solutions was an evidence for a diffusion-limited role of bicarbonate in driving the
dissolution reactions. They mentioned that FeCO3 precipitation, with greater tendency
with higher bicarbonate concentration, is governed by the increasing localized
concentrations of , with relevant mechanisms proposed.

2. Formation of Fe(OH)2 and FeCO3

Castro et al. suggested that Fe(OH)2 in the beginning forms (Eq.6), before FeCO3, at
the first anodic peak at nearly -0.6 V vs. NHE (-0.844 V vs. SCE), which was
independent from the rotation speed [4].
-
(6)
Their voltammogram scans were made at 25 mV/s, in solutions containing trace 0.05 M
K2CO3 amounts. The second anodic peaks of locations, and sizes to increase with
bicarbonate concentration, similar to those reported by Simard et al., were attributed to
the partial removal of Fe(OH)2, not to the formation of FeCO3 as:
- - -
(7)
Niu et al. reported the instability of Fe(OH)2 in deoxygenated, dilute bicarbonate
solutions with the same mechanism (Eq.7), and in the presence of oxygen they
suggested that FeCO3 precipitates, after Fe(OH)2 pre-passivation, to decelerate the
anodic currents of API-X70 steel in near-neutral pH solutions [5]. Valentini et al., more
precisely, affirmed the formation of Fe(OH)2 being the onset of passivation, during a
temperature-independent, multi-step charge-transfer process, for iron in bicarbonate-
carbonate solutions [6] as:
-
(8)
-
(9)
-
(10)
In few studies, Fe(OH)2 was considered to form as an inner layer under FeCO 3,
together, to be a multilayered passivation growing as the applied potentials are higher
[7, 8]. Similar to another proposition, by Rangel et al., that is at a first anodic peak, the
passive film grows to become a mixture (not a multilayer) of FeCO3 and Fe(OH)2 [9].
The precipitation of FeCO3, as a result of direct oxidation (Eq. 11 [10]) remained, in
some studies, as a valid hypothesis to describe also the dissolution of ferrite in
bicarbonate solutions during specific ranges of anodic polarization.
- -
(11)
Referring again to , Castro et al. reported two mechanisms in [11,4], to explain
FeCO3 formation, along with the roles of bicarbonate and carbonate, during which
Fe(HCO3)2 can also form, as:
-
(12)
 -
(13)
and
-

-
(14)
-
Alternatively, Lu et al. suggested that another intermediate agent, in aerated
bicarbonate solutions, is involved in the adsorption steps of the anodic dissolution to
result in FeCO3 (which can further react with bicarbonate to result in new carbon-
carrying intermediates) as [12]:
- -
(15)
- -
(16)
- -
(17)
(18)
(19)

3. Formation of Fe2O3, Fe3O4 and F(III) oxides

Most of the mechanistic bicarbonate studies suggested that Fe(OH)2 and FeCO3
oxidize, or electro-oxidize, to form Fe2O3, Fe3O4, and/or Fe3+oxides when a test steel is
polarized within a specific range of passivation potentials. Sherar et al. reported a role
-
of bicarbonate [13], and so did Lu et al. [12] for in transforming Fe(OH)2 to Fe(OH)3
and Fe2O3 as:
- -
(20)
And
- -
(21)
(22)
Castro et al., also suggested that FeCO3 oxidizes to FeOOH and Fe(OH)3, correlating
that to a third anodic voltammetric peak, at nearly -0.2 V vs. NHE (-0.444 V vs. SCE), in
0.75 M KHCO3 + 0.05 M K2CO3 solutions as [7]:
- -
- - (23)
- -
(24)
Transformation of FeCO3 to Fe2O3 and/or Fe3O4, in association to an applied potential,
pH, and bicarbonate and carbonate concentrations and temperature, was represented
-
with many mechanisms in literature. The roles of bicarbonate and were
represented in electro-oxidation reactions of FeCO3 to result in Fe3O4 and Fe2O3 as
[12]:
- - -
(25)
- - -
(26)
Parkins et al. [14] and Castro et al. [11] reported that the FeCO3/ electro-oxidation
proceeds as:
- -
- (27)
and
- -
- (28)
In aerated bicarbonate-carbonate solutions, Zhang et al. [15] and Fu et al. [16],
attributed the FeCO3 oxidation to the dissolved oxygen as:
-
(29)
-
(30)

4. Reactions in Carbonate Solutions

In carbonate solutions, Thomas et al., in an early work, linked the first anodic peaks, of
10 mV/min (0.167 mV/s) potentiodynamic scans, which increased in size with the
carbonate concentration, to the formation of FeCO3 as [17]:
- -
(31)
That was inferred for pure iron in aerated solutions of pH of nearly 11, in comparison to
NaOH solutions of the same pH. At that first anodic peak, at -0.58 V vs. NHE (-0.824 V
vs. SCE), they suggested that FeCO3 formation interfere with that of Fe3O4. They
observed a color change of the passive film during up to a second peak at -0.22 V vs.
NHE (-0.466 V vs. SCE) to report that FeCO3 electro-oxidizes to Fe2O3 as:
- -
(32)
In deoxygenated 0.2 mol/L NaHCO3 + Na2CO3 solutions, Lee et al. reported the
influence of the green rust on stabilizing the corrosion rates, unlike with the more
concentrated 1 mol/L solutions in which carbonate complexes Fe 2+ to make the
FeCO3.H2O films increasingly more porous, accelerating, in turn, the corrosion rates
[18]. Detecting Fe3O4 in solutions of pH of nearly 9, they suggested that the green rust
acts as an intermediate product between Fe(OH)2 -FeOOH or Fe3O4 in a slow
conversion process as:
- -
(33)
-
(34)

5. References

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- -
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