Materials and Corrosion 2007, 58, No. 7
200604038 1
Effect of turbulent flow on the anodic
and cathodic kinetics of API X52 steel corrosion
in H2S containing solutions. A rotating cylinder
electrode study
This work presents the electrochemical kinetics results measured
during the corrosion of API X52 pipeline steel immersed in
aqueous environments, containing dissolved hydrogen sulfide
(H2S) under turbulent flow conditions. In order to control the
turbulent flow con-
ditions, a rotating cylinder electrode (RCE) was used. Five different
1 Introduction
In the oil industry, hydrogen sulfide (H 2S) has been asso-
ciated to damage by corrosion and stress corrosion cracking
(SCC) induced by sulfides or hydrogen [1]. H 2S gas can dis-
solve in aqueous solutions turning them in corrosive
solutions, known as „sour“ [2, 3]. The increment of
temperature and/or pressure can increase the aggressiveness
of H2S solution to carbon steel. Corrosion of steel in H 2S
containing solutions can be represented according to [4–6]:
Fe þ H2Saq ! FeS þ H2
The majority of studies on the corrosion of steels in envir-
onments containing dissolved H 2S, have been carried out un-
der static conditions [7]. The main objective of these studies
is the determination of the resistance of different alloys to
com- bined conditions of corrosion and mechanical stresses.
In many real situations, H2S corrosion occurs under flowing
con- ditions, for example, in transport of hydrocarbons in
pipelines
* J. Genesca
Dpto. Ingenier´ıa Metalu´rgica, Facultad Qu´ımica,
Universidad Nacional Auto´noma Me´xico, UNAM
Ciudad Universitaria, 04510 Me´xico D.F (Me
´xico) E-mail: genesca@servidor.unam.mx
R. Galvan-Martinez
Grupo Anticorrosio´n-Instituto de Ingenier´ıa,
Universidad Veracruzana
SS. Juan Pablo II s/n, Zona Universitaria, CP
91919 Boca del Rio, Veracruz (Me´xico)
J. Mendoza-Flores, R. Duran-Romero
Instituto Mexicano del Petro´leo, Direccio´n Ejecutiva de
Exploracio´n y Produccio´n, Corrosio´n Eje Central L. Ca
´rdenas 152. Me´xico DF 07730 (Me´xico)
# 40502 / WILEY-VCH / W+K / Artikel W
4038
DOI: 10.1002/maco.
R. Galvan-Martinez, J. Mendoza-Flores,
R. Duran-Romero, and J. Genesca*
rotation rates were studied: 0 (or static conditions), 1000, 3000,
5000 and 7000 rpm. It was found that the turbulent flow increases
the corrosion rate and the corrosion mechanism for X52 steel ex-
hibits a significant dependence on mass transfer on the cathodic
kinetics.
[7]. Therefore, the influence of flow on the corrosion pro-
cesses is an important issue to be considered in the design
and operation of industrial equipment.
The most common type of flow conditions found in indus-
trial processes is turbulent; however, few corrosion studies
in controlled turbulent flow conditions are available. With
the increasing necessity to describe the corrosion of metals
in tur- bulent flow conditions some laboratory hydrodynamic
sys- tems have been used with different degrees of success
[8–10]. Among these hydrodynamic systems, rotating cylin-
ð1Þ der electrodes (RCEs), pipe segments, concentric pipe seg-
ments, submerged impinging jets and close-circuit loops
have been used and have been important in the improvement
of the understanding of the corrosion process taking place in
turbulent flow conditions [10–17]. The use of the rotating
cy- linder electrode (RCE), as a laboratory hydrodynamic
test sys- tem, has been gaining popularity in corrosion
studies [18, 19]. This popularity is due to its characteristics,
such as, its ope- ration mainly in turbulent flow conditions,
its well-defined hy- drodynamics, ease of assembly and
disassembly, smaller vo- lume of fluid used, and easier flow
and temperature control [20, 21].
It has been found that for a RCE enclosed in a concentric
cell, the transition between the laminar and turbulent flow
oc- curs at values of Reynolds number of 200 approximately
[8, 9, 21]. The RCE in corrosion laboratory studies is a
useful tool for the understanding of mass transfer processes,
effects of surface films, inhibition phenomena, etc. [2, 3, 22]
taking place in turbulent flow conditions. However, the use
of the RCE has been questioned by some researchers [23],
due to the differences found between the values of corrosion
rates measured on pipe flow electrodes and on the RCE. The
rea- sons for this difference are still not well understood.
However, some works have provided ideas on the
explanation of this apparent difference [24–26].
Dimensionless analysis using mass transfer concepts
showed that the corrosion when controlled by diffusion of
one of the species between the bulk fluid and the surface
could be modeled completely by the rate of mass transfer of
the rate
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 2 Galvan-Martinez, Mendoza-Flores, Duran-Romero, and Genesca
limiting species and the Reynolds (Re) and Schmidt
numbers (Sc) [27–29]. In general, the effect of flow can be
used to de- termine if corrosion is under activation, diffusion
or mixed control.
2 Experimental
2.1 Test environment
All experiments were carried out at 20 ○C and at the atmo-
spheric pressure of Mexico City (0.7 bar). One aqueous solu-
tions was used, a NACE brine specification 1D196 [30].
This test environment was selected due to the fact that most
of the H2S corrosion laboratory testing is carried out in this
solution.
In order to remove oxygen (O2) from the solution, nitrogen
(N2) gas (99.99%) was bubbled into the test solution for a
per- iod of 30 min. The measured dissolved O 2 content was
lower to 10 ppb. After oxygen removal, H 2S gas (99.99%)
was bubbled into the test solution until saturation was
reached.
The measured saturation pH was 4.2 for the NACE brine so-
lution.
In order to determine the purging time needed to remove
all O2 from the solution, a rotating cylindrical platinum
electrode was cathodically polarized in a 1 M sodium sulfate
solution, at
room temperature and at different rotation rates. It was
estab- lished that the region associated to the mass transfer
reduction of oxygen, on the cathodic polarization curve,
disappeared af-
ter 30 min of purging time.
2.2 Experimental set-up
An air-tight three-electrode electrochemical glass cell was
used. Cylindrical working electrodes were used in all experi-
ments. These cylinders were made of API X52 steel [31].
The working electrode (WE) was machined from the parent
ma- terial API X-52 and had a diameter of 1.2 cm. The
total ex-
posed area of the working electrodes was 5.68 cm2 and
3.4 cm2 for static and dynamic conditions respectively. As ref-
erence electrode a saturated calomel electrode (SCE) was
used. A sintered graphite rod was used as auxiliary electrode.
Prior to each experiment, the steel working electrode was po-
lished up to 600 grit SiC paper, cleaned in deionised water
and degreased with acetone. All electrochemical tests were
carried out on clean samples and in freshly prepared test
solutions. Hydrodynamic conditions were controlled using a
Perking- Elmer EG&G Model 636 Rotating Cylinder
Electrode (RCE) system. In dynamic conditions, the rotation
speeds tested were
1000, 3000, 5000 and 7000 rpm.
2.3 Electrochemical measurements
A SolartronTM SI 1280B Potentiostat / Galvanostat was
used in all the electrochemical tests. Potentiodynamic polar-
ization curves were recorded at a sweep rate of 1 mV s —1,
starting the potential sweep at the rest potential or corrosion
potential (Ecorr) towards more cathodic potentials.
Laboratory tests indicated that, slower scan rates produced
no significant change on the measured current.
In order to minimize the effect of the solution resistance a
Lugging capillary was used. All the experiments were
carried out by triplicate in order to check the reproducibility
of the results. A plot of three representative measured plots
is pre-
Materials and Corrosion 2007, 58, No. 7
sented, this is due to the fact that it was found that the experi-
mental variations of the measurements was negligible.
3 Experimental results and discussion
Previous work on these systems has shown that the corro-
sion mechanism for carbon steel exhibits a significant
depend- ence on mass transfer. This has led various workers
to suggest the use of dimensionless analysis as a means of
relating la- boratory-scale experiments to plant-scale
corrosion behav- iour.
For an accurate study of the influence of flow velocity
upon the corrosion rate of fluids in motion, the
hydrodynamic con- ditions must be well- defined. The
Reynolds number (Re), a dimensionless number dependent
on the fluid velocity or the electrode rotation rate, as the case
may be, density and visc- osity of the fluid, and a
characteristic dimension is used to define the type of flow.
At low velocities, i.e. at low Re, a stable or laminar flow
is encountered. Assuming the fluids under consideration to
be Newtonian and incompressible in nature, the shear stress
(sw) at any point in a laminar flow is given by
du
sw ¼ l ð2Þ
dy
If the velocity is increased, at a critical Reynolds number
(Recrit), the flow becomes turbulent and an additional
mechan- ism of momentum mass transfer appears, which is
caused by rapid and random fluctuations of velocity about its
average value. The Recrit for the transition between laminar
and turbu- lent flow will vary depending on the geometry
and Recrit for pipe flow has been experimentally found to be
around 2100. The Reynolds number for the RCE (ReRCE) is
given by the expression:
uRCEdRCE uRCEdRCEq ð3Þ
Re ¼ ¼
RCE
m l
where uRCE is the peripheral velocity of the RCE, dRCE is
the RCE diameter, m is the kinematic viscosity of the
environment, l is the viscosity of×the environment (1
×—3 kg m—1 s—1)
10
and q is the density of the environment (1.024 103 kg m—1).
Fig. 1 shows the measured values of corrosion potential
(Ecorr) as a function of Reynolds number. Ecorr was obtained
on the API X52 steel cylindrical samples immersed in
NACE
brine saturated with hydrogen sulfide (H 2S) at different rota-
tion rates (0, 1000, 3000, 5000 and 7000 rpm) and 20 ○C.
This figure shows that the measured values of the Ecorr are
affected by the increment of the rotation rate. In the NACE
brine solu- tion, as the ReRCE (and therefore the rotation rate)
increases, the Ecorr also increases. The measured Ecorr
increased—from a value of 0.750 (at 0 rpm) to a value of
0.695¼V (at Re- 4
× RCE 5.34 10 , equivalent to 7000 rpm)
approximately. By plotting Ecorr versus Re number, if mass
transfer controls the corrosion rate, E corr is sometimes found
to have linear re- lationship when plotted in this manner and
a system is under complete mass transfer control.
In order to obtain an estimation of the corrosion current
densities (icorr), an extrapolation of the cathodic and anodic
branches of the polarization curves was made, in a region
of T 0.150 V of overpotential, approximately, with respect
to the corresponding value of Ecorr.
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Materials and Corrosion 2007, 58, No. 7
Fig. 2 shows the estimated values of i corr for NACE brine
Re0:7 . This figure
solution, as a function of the calculated RC
de- monstrates that there is a clear influence
E of flow on the
mea-
sured corrosion rate. If the corrosion current is controlled by
mass transfer, then a plot of the corrosion current versus RC
Re0:7 E
Fig. 1. Corrosion potential (Ecorr) as a function of the different ro-
tation rates of the cylindrical electrode in NACE solution at 20 ○C
and 0.7 bar
Fig. 2. Measured values of icorr as a function of Re0:7
RCE
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Effect of turbulent flow on API X52 steel corrosion 3
should result in a straight line with a slope between about
0.65 and 0.75 depending on surface roughness and surface
films. Any deviation from that slope means other effects are
occur- ring, as for example oxygen contamination leading to
a 3-di- mensional oxide that interferes with complete mass
transfer control.
Fig. 3 shows the cathodic polarization curves obtained on
API X52 steel cylindrical electrodes, in the NACE brine sa-
turated with H2S at 20 ○ C and at 0.7 bar, as a function of the
rotation rate. In this figure it is possible to see that all cathodic
polarization curves (at all rotation rates) have a region where
a diffusion process is influencing the overall cathodic
current. It is clear that the measured cathodic current is
affected by the rotation rate of the electrode. At a constant
value of E, as the rotation rate of the electrode increases the
measured values of current density also increase. It is
important to note that these features can suggest that a
diffusion process is taking place on the surface of the
cylindrical electrode.
If Hþ ions are considered to be the main diffusing species
in the environment, it is possible to calculate the cathodic
current density due to Hþ reduction (ilim,Hþ). In order to do
this, the
expression proposed by Eisenberg et al. [32] was used:
ilim;Hþ ¼ 0:0791nFCHþ d—0:3
RC m
—0:344 0:644 0:7
DHþ uRC ð4Þ
E E
where: n ¼number of electrons; F Faraday constant; CHþ
bulk ¼ concentration of H ; þdRCE RCE diameter; m
¼
kinematic viscosity; DHþ ¼
diffusion coefficient and uR- CE
RCE¼ peripheral velocity. This expression indicates a di- rect
relationship of the calculated limiting current density (ilim,Hþ)
to the peripheral velocity of the RCE (uRCE), to a po- wer of
0.7.
Fig. 4 compares the different measured and calculated cur-
rent densities as a function of uRCE to a power of 0.7 in
NACE brine. The values of cathodic current densities (ic)
were taken from the corresponding cathodic polarization
—
curves in Fig. 3, at a constant potential of 0.860 V (SCE).
The estimated va- lues of corrosion current densities (icorr)
correspond to NACE
Fig. 3. Cathodic polarization curves as
a function of different rotation rates. Cy-
lindrical API X52 steel electrode im-
mersed in NACE brine saturated with
H2S at 20 ○C and 0.7 bar
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4 Galvan-Martinez, Mendoza-Flores, Duran-Romero, and Genesca
Fig. 4. API X52 steel immersed in NACE brine saturated with H2S
at 20 ○C and 0.7 bar. Cathodic current densities (ic) read at 0.860
—V (SCE) on the cathodic polarization curves in Fig. 3; cal- culated
limiting current density [32] for the diffusion of Hþ (ilim,Hþ) and
corrosion current density (icorr), as a function of the RCE per-
ipheral velocity (uRCE), to a power of 0.7. Hþ diffusion
coefficient
—3
¼ 1.04 × 10—8 m2 s—1, H concentration ¼ 0.0794 mol
þ
m
6
; RCE diameter ¼ 0.012 m; kinematic viscosity ¼ 1 × 10—
m2s—1
brine shown in Fig. 2. The values of cathodic limiting densi-
ties (ilim) for Hþ diffusion were calculated with equation (4).
This analysis demonstrates that the measured cathodic cur-
rent is affected by flow and this current can be associated to
the diffusion of Hþ ions from the bulk of the solution to the
surface of the electrode, where they are reduced to H 2 gas. It
also demonstrates that the flow dependency of the i corr can be
associated to this diffusion process.
The analysis of this Fig. 4 confirms the influence of flow
on the cathodic kinetics. As the rotation rate of the electrode
in-
creases the measured cathodic current also increases. It is
also
possible to suggest that the measured cathodic current can be
associated to the diffusion and reduction of Hþ ions. It is also
demonstrated that the flow dependency of the i corr can be as-
sociated to this diffusion process.
3.1 Analysis of cathodic reaction
In an H2S containing solution and in the absence of dis-
solved oxygen, the cathodic reaction of carbon steel, respon-
sible for the corrosion of iron, may be attributed to hydrogen
evolution produced by the reduction of hydrogen ions, where
the hydrogen ions are supplied by dissociation of H2S, as
fol- lows:
2Hþ þ 2e— ! H2 ð5Þ
In the present testing solution, the source of Hþ, which
pro- motes the above hydrogen evolution, may be H2S or
H2O.
Bolmer [33] showed that hydrogen evolution, in the pre-
sence of H2S, might be represented by the overall reaction:
2H2S þ 2e— ! H2 þ 2HS—
ð6Þ
This reaction is limited by diffusion of H2S to the
electrode surface when the overpotential is far removed from
Materials and Corrosion 2007, 58, No. 7
Fig. 5. Mass transfer coefficient, kH vs.þ Reynold number, Re0.7. API
X52 steel immersed in NACE brine saturated with H 2S at 20 ○C
and 0.7 bar
have been proposed [33, 35] as the main cathodic reactions
in H 2S containing solutions in absence of oxygen.
a) 2 Hþ þ 2 e— ! H2
b) 2 H2S þ 2 e— ! H2 2 HS—
c) 2 HS— þ 2 e— þ ! H2 2 S2—
d) H2S þ 2 e— ! þ H2 2 S2—
þ
According to different authors [33, 34, 36] reactions (a) and
(b) seem to be the more probable.
As it was proposed by Eisenberg et al. [32], for the RCE,
it is possible to calculate the contribution to the limiting
catho- dic current for a species „i“, using equation (4).
If the above expression for the RCE proposed by
Eisenberg et al. [32] is considered and the values of limiting
current den- sities, ilim are taken from Fig. 3 at each rotation
rate, then plotted versus the rotation rate of the electrode
to a powerRCE
of 0.7, u0:7 , Fig. 5 (for Hþ) is obtained. In this figure the ro-
tation rate of the electrode is expressed as peripheral velocity,
uRCE.
This analysis shows that the measured ilim is affected by
the rotation rate of the electrode and a linear relationship
with u0.7 clearly exists between both parameters, as
predicted for the
RCE equation proposed by Eisenberg et al. [32], equation
(4), which can be expressed in a simplified form by equation
(7):
i ¼ A u0:7 ð7Þ
lim;i i RCE
the Ecorr [33, 34].
The measured experimental cathodic current should be a
consequence of all the possible reduction reactions that can
occur in the NaCl-H2S system. The following reactions
 where Ai is a constant. Concerning the flow dependent
component in Fig. 3 and if the concentration of dissolved
O2 is considered as negligible, then the species in solution
cap- able of being reduced are: H 2S and Hþ. As the
concentration
of H2O can be considered constant and the reduction rate of
Hþ and H2S slow and influenced by the diffusion of
reactants, then it is possible to assume that in H2S
solution, both the Hþ ions and H2S are reduced at the
surface. Then, at a given flow rate, the total diffusion-
limited current, ilim,diff for a H2S solu- tion could be
described by the addition of two components:
ilim;diff ¼ ilim;Hþ þ ilim;H2S ð8Þ
where ilim,Hþ and ilim,H2S are the limiting current densities in
turbulent flow conditions for H þ ions and H2S molecules re-
spectively.
These components can be defined, in turbulent flow
condi- tions, in an analogous way as Schmitt and Rothmann
[37] did for laminar flow conditions on the rotating disk
electrode, but
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Materials and Corrosion 2007, 58, No. 7
using the relationship proposed by Eisenberg et al. [32] for
the mass transfer on the RCE, equation (4).
Schmitt and Rothmann [37] and Mendoza [25] proposed
þ
that the theoretical ilim for H2S and H reduction calculated
by equation (4) could be compared with the experimentally
measured ilim, in order to obtain information about the predo-
minant cathodic reaction (kinetics).
To determine the theoretical relationship between i lim and
u
0:7 for either H S or Hþ, the values of density and
RCE
kinematic 2
viscosity were calculated according to the analysis proposed
by Mendoza [25]. The other parameters, like the H þ and H2S
diffusion coefficients, were taken from reference [38].
Substi- tuting these parameters, the theoretical relationship
for Hþ re- duction reaction can be obtained, as shown in
Fig. 4.
From this figure it is possible to note the linear
relationship between the experimental limiting current
density and the per- ipheral velocity of the RCE. The H þ
reduction shows a linear relationship with the rotation rate of
the electrode, to a power of 0.7, and although its values does
not adjust exactly to the
theoretical current, a good correlation can be observed, as it
can be seen in Fig. 4. According to this analysis, one conclu-
sion can be obtained, that the dominant cathodic reaction is
the
reduction of hydrogen ions, Hþ.
As a first approximation to the possible cathodic reaction
mechanism prevailing under the experimental conditions stu-
died, it is proposed, as a first step
H2SðgÞ $ H2SðaqÞ;
K ¼ 0:1023 mol:l—1:atm—1; pK ¼ 0:99 ð9Þ
In aqueous solutions H2S is a weak acid. At 20 ○C [39]
H2SðaqÞ $ — increases. Based on this study, the Re number dependence
þ HS ðaqÞ pKa1 ¼ 6:88 T 0:02 ð10Þ
ðaq
Hþ Þ
HS— Hþ
ðaqÞ ðaqÞ þ S2—ÞpKa2 ¼ 14:15 T 0:05 ð11Þ
$ ðaq
As predicted by reaction (10) it is possible to get in
solution H2S, Hþ and HS—. Under turbulent flow conditions,
and as it has been experimentally demonstrated, the
diffusion-limited reaction is a consequence of H þ diffusion.
Mass transfer and surface shear effects may have a pro-
found effect on the rate of material degradation, either by
modifying the rate of transport of chemical species to or
from the surface or by shear-stripping protective films from
the metal/solution interface. As a result, an accurate simula-
tion of corrosion phenomena that occur in pipelines can be
made in the laboratory only if the hydrodynamic effects are
taken into account. Then, parameters such as the mass
transfer coefficient, ki, shear stress at the wall, s, and the
Sherwood
number, Sh, can be derived from these results.
Values of limiting current density were used to estimate
the mass transfer coefficients, k, for the whole range of Re.
Ex- perimental correlations of k (or Sh) with Sc are not
necessarily simple. This is because changing Sc by
temperature leads to change many physical properties that
have a direct influence on k (or Sh). These physical
Effect of turbulent flow on API X52 steel corrosion 5
ilim;i
ki ¼ ð12Þ
nFACb;i
¼
in which¼ilim,i mass transfer limited current (A) for spe-
cies „i“, F Faradayy¨ s contant, n number of electrons in-
volved in the reaction, A area of the working electrode
(cm2), and Cb,i bulk concentration
¼ of the diffusing species
„i“. It is evident from Fig. 5 that, there is a linear
relationship
between and the Re number. As Silverman pointed out
kH þ
[40] the measured mass-transfer coefficient could be con-
verted to the Sherwood number and plotted as a function
of the Reynolds number. The resulting plot is in good agree-
ment with the theoretical values calculated with the equation
proposed by Eisenberg for turbulent flow conditions.
The Sh number is a dimensionless number that expresses
mass transport under forced convective flow conditions.
The Sh number and the mass transfer coefficient, ki, are re-
lated by the equation:
kidRCE dRCE
Shi ¼ ð13Þ
D i ¼ dN
where ki mass transport coefficient of species „i“,
¼ diameter of the the rotating cylinder (char-
dRCE the outside
¼ length), D diffusion coefficient of species „i“, it
acteristic i
is the diffusivity of ¼ H
þ
in the NaCl-H 2S system, dN Nernst
diffusion layer thickness. The Sh number expresses¼the size
of
the characteristic length in comparison to the Nernst diffusion
layer.
Fig. 6 shows the calculated Sherwood numbers as a func-
tion of the calculated Re number. From this figure it is
evident that the Sherwood number, Sh, increases as the Re
number
with the Sh number, appears to be proportional to a 0.7th
power law. The coefficient of 0.7, which is the flow
dependence of
the Sh number, almost corresponds to the coefficients of the
Re number, as indicated by the Eisenberg relationship [32] and
properties are mainly the hydrogen diffusivity, DHþ,
bulk concentration, Cb and kinematic viscosity,
t. Fig. 5 shows the variation of the calculated mass transfer
coefficient, kHþ, with Re as obtained from the ilim in
Fig. 3. Mass transfer studies of electrochemical reactions are
normally carried out under mass transfer limited current
conditions. When limiting conditions prevail, the mass transfer
coefficient for a given species „i“, ki, can be expressed as:
Chilton and Coburn analogy [41]. Eisenberg et al [32]
showed that in the range of 103 < Re > 105 equation (5) is
a straight- line approximation over a more-limited Re
number range.
In the case of a predominating forced convection, the
mass transfer correlation can be written in the form:

Sh ¼ aRebScc

ð14Þ

The values of a, b and c depend upon both electrode

geo- metry and flow conditions [42]. For example, the Re
expo- nent, b, tends to be greater in turbulent flow than in Fig. 6. Variation of dimensionless corrosion rate, expressed as the
laminar flow. It is common to consider the Schmidt, Sc, Sh number as a function of Re number. API X52 steel immersed in
exponent, c, to NACE brine saturated with H2S at 20C and 0.7 bar

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6 Galvan-Martinez, Mendoza-Flores, Duran-Romero, and Genesca
have a value of 1/3, in accordance to known hydrodynamic
theory [42].
The case of a smooth RCE was first extensively studied
by Eisenberg et al. [32] who achieved the following
empirical correlation.
Sh ¼ 0:079Re0:70Sc0:356 ð15Þ
while Gabe and Walsh [21] have proposed expressions of
the type
Sh ¼ 0:079Re0:74Sc0:356 ð16Þ
for the case of metal deposition.
Silverman [40] compiled various Sh number vs Re number
relationships for a hydrodynamically smooth rotating cylin-
der, similar to, but not equal to equation (15).
Concerning the effect of corrosion products formed on the
RCE on its mass transport properties, Walsh [42], among
others researchers, stated that, the enhancement of the mass
transport towards the surface of a RCE, with a metal powder
deposit, depends upon the increased surface area and en-
hanced micro-turbulence, at the RCE surface. It may be ex-
pressed relative to a smooth cylinder as a predicted enhance-
ment factor, b, which depends of the peripheral velocity for
a RCE. Although we have experimental evidence of
mackina- wite formation [3] on the RCE surface, under the
experimental conditions prevailing in this study, no attempt
was made to take into account the possible enhancement in
mass transport to an RCE by the effect of the sulfide film
formed.
Under the experimental conditions used in this study, the
measured cathodic current showed a linear dependence
with the derived parameters, Sh number (Fig. 6) and mass
transfer coefficient, k (Fig. 5). This behaviour indicates that
the cathodic current is controlled by the mass transfer rate.
Fig. 7 shows the measured anodic polarization curves ob-
tained on API X52 steel cylindrical electrodes immersed in
the NACE brine, saturated with H2S at 20 ○C and 0.7 bar,
Materials and Corrosion 2007, 58, No. 7
for different rotation rates. In this figure, it is possible to ob-
serve that the anodic Tafel slopes (ba) are relatively high.
This fact indicates a passivation process, taking place on the
sur- face of the electrode. It is important to note that the
anodic
polarization curves measured from 3000 to 7000 rpm are not
as influenced by rotation rate of the electrode.
Fig. 8 shows the estimated anodic Tafel slopes (ba) as a
function of ReRCE, on cylindrical API X52 steel electrodes
im- mersed in NACE brine and 3.5% NaCl solution,
saturated with H2S at 20 ○ C and 0.7 bar. The slopes were
calculated on each anodic polarization curve, in the region
from
þ 0.150 V of overpotential, to the corresponding E corr. All
the estimations of the Tafel slopes, in the NACE brine,
were higher than 0.180 V/decade.
4 Conclusions
1. In NACE brine solution the cathodic polarization curves
show a region that is influenced by a diffusion process,
at all rotation rates.
2. All cathodic polarization curves are affected by the
rotation rate of the cylindrical electrode, in general, when
the rota- tion rate of the cylindrical electrode increases,
the measured cathodic current density also increases.
3. The cathodic process taking place on the surface of the
elec- trode can be associated to the diffusion of Hþ ions,
from the bulk of the solution towards the surface of the
electrode, and their reduction to H2 gas at the surface.
4. In NACE brine solution the measured cathodic current den-
sity values (at a constant E), are in good correlation with
the theoretical limiting current density values, calculated
by the Eisenberg et al. [32] expression for Hþ ions
(ilim,Hþ).
5. All the anodic polarization curves show a high anodic Tafel
slope (ba). This fact can be associated to a passivation pro-
cess, taking place on the surface of the cylindrical elec-
trode.
Fig. 7. Anodic polarization curves as
a function of different rotation rates.
Cylindrical API X52 steel electrode
immersed in NACE brine saturated
with H2S at 20 ○C and 0.7 bar
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Materials and Corrosion 2007, 58, No. 7
6. The anodic polarization curves corresponding to 3000,
5000 and 7000 rpm obtained in NACE brine are not af-
fected by the rotation rate.
7. The mass transfer coefficient (kHþ and ShHþ) is flow depen-
dent, because it increases as the rotation rate also
increases.
5 Acknowledgements
The authors would like to thank the Mexican National
Council of Science and Technology (CONACYT) for the
grant awarded to Mr. Galvan-Martinez, required to develop
this work and to Mexican Petroleum Institute, IMP, for
finan- cial support (FIES).
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(Received: September 29, 2006) W 4038
8 Galvan-Martinez, Mendoza-Flores, Duran-Romero, and Genesca Materials and Corrosion 2007, 58, No. 7

Schlagworte:
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Key words:
API X52 steel
flow
hydrogen sulfide
mass transfer
RCE (rotating cylinder electrode)

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