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In situ monitoring the effects of a magnetic

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Article in Corrosion Science February 2008

DOI: 10.1016/j.corsci.2007.07.009

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Corrosion Science 50 (2008) 510522

www.elsevier.com/locate/corsci

In situ monitoring the eects of a magnetic eld on the

open-circuit corrosion states of iron in acidic and neutral solutions
Zhanpeng Lu *, Wu Yang
Shanghai Research Institute of Materials, 99 Handan Road, Shanghai 200437, PR China

Received 12 June 2007; accepted 27 July 2007

Available online 24 August 2007

Abstract

The eects of a 0.4 T horizontal magnetic eld (HMF) on the open-circuit corrosion states of iron in static aqueous solutions are
studied by in situ monitoring the responses of two electrochemical parameters to the applied magnetic eld, i.e. the open-circuit potential
(OCP) and the current under potentiostatic polarization. The applied magnetic eld makes the OCP shift in the noble direction. With-
drawing the magnetic eld causes a negative shift of the OCP in acidic solutions, but it does not cause any signicant change of OCP in
neutral solutions. Imposing a magnetic eld induces a cathodic current for iron that was previously potentiostatically polarized at the
OCP without magnetic eld. Withdrawing the magnetic eld induces an anodic current for iron that was previously potentiostatically
polarized at the OCP with the magnetic eld. The magnetic eld eect is more signicant in the acid solutions than in the salt solutions.
The magnetic eld eects on the oxygen reduction and on the activation-controlled iron dissolution reaction are found to be insignicant.
The magnetic eld eect on the hydrogen reduction reaction on iron in acidic solutions is demonstrated. Results show the possibility that
a magnetic eld would aect the hydrogen evolution by enhancing the electron-transfer process that has been categorized in the classical
electrochemistry kinetics to be the rate-determining process. The memory eect of the magnetic eld on the electrochemical reaction is
identied and discussed.
2007 Elsevier Ltd. All rights reserved.

Keywords: A. Magnetic eld; A. Iron; C. Corrosion; C. Hydrogen ion reduction; C. Electron transfer step

1. Introduction electron-transfer process [1218]. Kelly [12] has studied the

The eects of magnetic elds on electrochemical behav-
ior of metallic materials in aqueous solutions have been
studied [125]. Magnetohydrodynamic (MHD) theory is
generally used to formulate the eect of magnetic elds
on mass transport rates, which has been reviewed in Refs.
[13]. In comparison with the large number of reports on
the magnetic eld eect on the mass transport behavior
for metallic materials in aqueous solutions [111], relatively
few reports are available on the magnetic eld eect on the
*
Corresponding author. Present address: Fracture and Reliability
Research Institute, Tohoku University, Aramaki Aoba 6-6-01, Aoba-ku,
Sendai, 980-8579, Japan. Fax: +86 21 654 20554.
E-mail addresses: zhanpeng_lu@yahoo.com, zhanpeng@rift.mech.
tohoku.ac.jp (Z. Lu), wyang@srim.com.cn (W. Yang).
eect of magnetic eld on the electrochemical behavior of
Ti in owing sulfuric acid. Changes of the open-circuit
potential (OCP or Ecorr) dierence between two Ti elec-
trodes were found to increase with increasing applied mag-
netic ux density in the range of 02.1 T, which could be
more than 240 mV at B = 2.0 T. The potential dierence
induced by a magnetic eld was dened by Kelly in the
ButtlerVolmer equation to account for the eect of the
magnetic eld on activation-controlled or electron-trans-
fer-controlled electrochemical reactions. These results were
obtained in owing solution, which could be strongly
dependent on the hydrodynamics. However, the results
can be dierent from that in static solutions. Yamanaka
et al. [13] analyzed the magnetic eld eect on the electro-
chemical reduction of cuprous ions using a new method
with magnetohydrodynamic (MHD) electrode. They found

0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2007.07.009
 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522
that there was no change of the Tafel slopes but a drastic
decrease of the current density under the external magnetic
eld up to 13 T. Aogaki et al. [14] examined the hysteresis
eect of the magnetic eld on the electron-transfer process
in the copper deposition in an acidic CuSO4 solution. Lee
et al. [15] studied the inuence of a uniform external mag-
netic eld on faradic reactions using Au and Pt microdisk
electrodes of 6.4, 12.5, and 25 lm radii. The microelectrode
was oriented vertically in the cell and the surface of the
electrode was parallel to the magnetic eld. In low ionic
strength solutions, the external magnetic eld reduced the
electrostatic driving force for electron-transfer. This mag-
netic eld eld-induced reaction overpotential was shown
to result from a steady state displacement of charge-balanc-
ing counterions at the electrode/solution interface, analo-
gous to that recently observed for a rotating microdisk
electrode [15]. White and his coworkers have [16,17] pro-
posed that two sources of magnetic eld force have a signif-
icant eect on the rate of electrochemical reactions. Devos
et al. [5] reported that a homogeneous magnetic eld paral-
lel to the electrode surface and varying up to 1 T did not
practically aect the charge-transfer coecient for dierent
redox systems that are controlled by mass transport, by
kinetics, or by mixed mass transport/kinetics. Koehler
et al. [6] reported that magnetic elds up to 1 T did
not aect the rate of electron-transfer reactions for the
redox couples [IrCl6]2/[IrCl6]3, [Fe(CN)6]3/[Fe(CN)6]4,
[Fe(H2O)6]3+/[Fe(H2O)6]2+ redox systems.
The eects of applied magnetic elds on electrochemical
behavior of corrodible metals in aqueous solutions have
been reported [711,1825]. Lots of works were on the cor-
rosion of metals in solutions containing a certain amount
of oxidants, where mass transport processes were involved
in determining the reaction rate and a positive shift of
open-circuit potential was observed [711,21,24]. The elec-
trochemical aspects of the eects of magnetic eld on
purely activation-controlled electrochemical reactions on
corrodible metals in stagnant solutions are rarely discussed.
One of the authors has reported [18,19] the magnetic eld
eect on the cathodic polarization behavior of iron in
hydrochloric acid solutions. An overpotential for hydrogen
evolution was observed, whereas the Tafel slopes were
quite similar in the presence and absence of the magnetic
eld. The memory eect of the magnetic eld on the hydro-
gen reduction reaction on iron electrode was revealed by
polarization curve measurements [19].
Hydrogen depolarization and oxygen reduction are two
most important cathodic reactions for the corrosion of
metallic materials in natural and industrial environments.
One of the main objectives for the present research is to
provide more convincing evidence for the magnetic eld
eect on hydrogen evolution. At the same time, the mem-
ory eect of magnetic eld is also studied. The magnetic
eld eects on the open-circuit corrosion of iron in neutral
and acidic solutions are studied using carefully designed
in situ monitoring methods that have been used in previous
studies [19,23,24]. The change of open-circuit potential
511
(rest potential or corrosion potential) with imposing or
withdrawing of the magnetic eld is monitored. The
response of the current density under potentiostatic polar-
ization to the applied magnetic eld is measured, which can
give more convincing and sensitive evidences for the mag-
netic eld eect on the open-circuit corrosion. Such
in situ methods are proved to be crucial in identifying the
eect of magnetic led if the eect is relatively weak.
2. Experimental methods
The experimental setup is similar to that described in a
previous publication [23]. The electrochemical cell was an
H-type pipe with an inner diameter of 30 mm. A three-elec-
trode system was used for studying the behavior of iron.
The pure iron working electrode was 5 mm in diameter
with an exposed surface area of approximately 0.2 cm2,
sealed within an epoxy resin insulator. The electrode sur-
face was polished to 1000 grit nish then rinsed in ethanol
and in acetone prior to polarization measurements. The
counter electrode was a platinum plate and the reference
electrode a saturated calomel electrode (SCE). All the
potentials were measured and quoted against SCE. A dou-
ble-salt-bridge was used between the electrochemical cell
and the reference electrode in order to prevent the contam-
ination of chloride from the reference electrode. A mag-
netic eld (B) with magnetic ux density of 0.4 T was
generated using an electromagnet with a DC galvanostatic
power source. The magnetic eld ux density refers to
0.4 T if not specially mentioned. The conguration of the
working electrode is the same as that described previously
[23]. The magnetic eld was only imposed on the working
electrode side of the H-type pipe electrochemical cell. The
working electrode surface was placed vertically. The direc-
tion of the magnetic eld was horizontal and parallel to the
surface of the working electrode. The methods for in situ
monitoring the OCP and the current density under poten-
tiostatic polarization were similar to those used in a previ-
ous work for iron in sulfuric acid solutions with high
concentrations of dichromate [24]. The experimental proce-
dures are schematically shown in Fig. 1.
Open-circuit potentials for iron in test solutions with or
without a 0.4 T magnetic eld were recorded. Ecorr became
stable after a period time of immersion in the test solution.
The steady values of Ecorr are used to characterize the mag-
netic eld eect. Sometimes it may be argued that the dif-
ference of Ecorr measured in dierent tests with or
without a magnetic eld would be aected by the potential
uctuation during separate measurements. In situ experi-
ments were designed and conducted to get more convinc-
ingly supporting results. The electrode was placed
between the two poles of the electromagnet. After Ecorr
reached a steady value without a magnetic eld, a magnetic
eld was imposed quickly and the change of Ecorr due to
the magnetic eld was observed and recorded. A similar
method was also applied to record the change of Ecorr after
withdrawing the magnetic eld.
512 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522

Immersing the electrode in the
solution and monitoring the
open-circuit potential until a
stable value (Ecorr,0T) is
reached in the absence of a
magnetic field (step T1).
Imposing a 0.4T magnetic field
and monitoring the change of
the open-circuit potential until a
stable value (Ecorr,0.4T) is reached
in the presence of the magnetic
field (step T1-A).
from 0T to 0.4T
Immersing the electrode in the
solution and monitoring the
open-circuit potential until a
stable value (Ecorr,0.4T) is
reached in the presence of a
0.4T magnetic field (step T2).
Removing the magnetic field
and monitoring the change of
the open-circuit potential until a
stable value is reached in the
presence of the magnetic field
(step T2-A).
from 0.4T to 0.4T
Polarizing the system at Ecorr,0T
and adjusting the applied
potential to make the measured
current to be 0 or very close to 0
(step T1-B1).
Imposing a 0.4T magnetic field
and monitoring the change of the
measured current until a stable
value is reached in the presence of
the magnetic field (step T1-B2)
Polarizing the system at Ecorr,0.4T
and adjusting the applied
potential to make the measured
current to be 0 or very close to 0
(step T2-B1).
Removing the magnetic field and
monitoring the change of the
measured current until a stable
value is reached in the absence of
the magnetic field (step T2-B2)
systems Fe/0.05 mol L1 HCl, Fe/0.5 mol L1 HCl, Fe/
0.5 mol L1NaCl, Fe/0.5 mol L1 H2SO4, and Fe/0.5
mol L1 Na2SO4 are summarized. The changes of the cur-
rent density for these electrode systems under potentiostat-
ic polarization with imposing or withdrawing a 0.4 T
magnetic eld are also summarized. The time-transient
behavior after imposing or withdrawing the magnetic eld
can be seen from the recorded Ecorr vs. time or i vs. time
curves. In the gures, positive current represents cathodic
current and negative current represents anodic current.
However, in the equations both the anodic and cathodic
current densities take their absolute values.
3.1. Fe/0.05 mol L1 HCl
In the absence of a magnetic eld, Ecorr of iron became
stable after a period of immersion in 0.05 mol L1 HCl
solution, Fig. 2a. The variation of Ecorr in the steady state
was less than 1 mV. It has noted that the values of Ecorr
measured in dierent tests can show relatively large varia-
tions thus the in situ monitoring on a single specimen with
or without a magnetic eld is crucial for detecting the mag-
+

Fig. 1. Schematic showing of the experimental procedures.

-1
Electrode potential, E
2mV

Fe in 0.05mol L HCl
A special technique, measurement of current change 0T-0.4T
induced by a magnetic eld, was used to study the magnetic
eld eect on the open-circuit corrosion. The procedures
were as follows: after a electrode in a solution reached a
steady state without magnetic eld, the stable Ecorr was tE,0-0.4T
recorded and the electrode was potentiostatically polarized
0T 0.4T
at this measured Ecorr. The measured current density was
nearly zero. Then a magnetic eld was imposed quickly
Time
and the current caused by the magnetic eld (imag) was 10s
recorded. A similar method was also applied to monitor 0T to 0.4T
the current change under potentiostatic polarization after
withdrawing the magnetic eld.
Five iron/solution systems, i.e. Fe/0.05 mol L1 HCl + 0.4T 0T
(system S1), Fe/0.5 mol L1 HCl (system S2), Fe/
0.5 mol L1 NaCl (system S3), Fe/0.5 mol L1 H2SO4 (sys-
tem S4), and Fe/0.5 mol L1 Na2SO4 (system S5) were
Electrode potential, E

studied. Tests were performed at room temperature of

2mV

around 20 C. Test solutions were naturally aerated, static,

and without agitation or gas bubbling. Each set of data
with and without a magnetic eld was obtained at a similar tE,0.4-0T
temperature in order to show unambiguously the magnetic
eld eect. Tests were repeated at least three times and -1
Fe in 0.05mol L HCl
showed satisfactory reproducibility. 0.4T-0T

Time
3. Experimental results 10s
0.4T to 0T
The responses of open-corrosion potential to the impos- Fig. 2. Changes of Ecorr for Fe/0.05 mol L1 Cl system after imposing or
ing and withdrawing a 0.4 T magnetic eld for electrode withdrawing a 0.4 T magnetic eld: (a) 00.4 T and (b) 0.4 0 T.
 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522 513

netic eld eect. Ecorr moved in the noble direction by
about 8 mV in a short time (10 s) after imposing a
0.4 T magnetic eld, slightly changed with time and then
reached a steady value (Ecorr or Ecorr,0.4 T) that was about
6 mV higher than Ecorr,0 T. In the presence of a 0.4 T mag-
netic eld, Ecorr of iron became stable after a period of
immersion in 0.05 mol L1 HCl solution, Fig. 2b. Ecorr
moved in the negative direction after withdrawing the mag-
netic eld and reached a stable value that was lower than
Ecorr,0.4 T by about 5 mV after about 30 s.
Before applying the magnetic eld, the measured current
at Ecorr,0 T for Fe/ 0.05 mol L1 HCl was generally less
than 1 lA/cm2 (baseline uctuation), which was due to
the small uctuation of the open-circuit potential during
the immersion, Fig. 3a. A maximum cathodic current of
0.022 mA/cm2 appeared at 13 s after imposing a 0.4 T
magnetic eld. After a certain decaying period, the steady
current density was about 0.016 mA/cm2, which was much
higher than the baseline uctuation before applying the
magnetic eld. By this way, the possible eect due to fac-
tors other than the magnetic eld during experiments can
be excluded. Fig. 3b shows that the current density at
Ecorr under a 0.4 T magnetic eld is nearly zero with uctu-
ation less than 1 lA/cm2. A stable anodic current of
0.012 mA/cm2 was recorded at about 46 s after with-
drawing the magnetic eld. The magnitude of current
induced by imposing the magnetic eld was close to (actu-
ally a little bit higher than) that induced by withdrawing
the magnetic eld, but with opposite polarity. These results
are consistent with the previous monitoring results on cor-
rosion potential, Fig. 2. Clearly, the response time for the
potential or current to imposing a magnetic eld is signi-
cantly faster than that to withdrawing a magnetic eld,
Figs. 2 and 3, showing the time-relaxation phenomenon
of the magnetic eld eect.
3.2. Fe/0.5 mol L1 HCl
The magnetic eld eect on the corrosion potential for
Fe/0.5 mol L1 HCl system is similar to that for Fe/
0.05 mol L1 HCl system. The noble shift of Ecorr reached
6 mV at about 7 s after imposing the magnetic eld,
Fig. 4a. Ecorr moved in the negative direction by about
4 mV at about 40 s after withdrawing the magnetic eld,
Fig. 4b. The response of the current to imposing or with-
drawing the magnetic eld for Fe/0.5 mol L1 HCl system

0.025 -1
Fe in 0.05mol L HCl +
0T-0.4T
0.020
-1
-2

0.015 Fe in 0.5mol L HCl

Electrode potential, E
i, mA.cm

0T-0.4T
2mV

0.010

0.005

0.000 tE,0-0.4T

0T 0.4T 0T 0.4T
-0.005
10s Time Time
10s
0.005
0T 0.4T + 0.4T 0T
-1 -1
0.000 Fe in 0.05mol L HCl Fe in 0.5mol L HCl
0.4T-0T 0.4T-0T
Electrode potential, E
-2
i/mAcm

-0.005
2mV

-0.010

tE,0.4-0T

-0.015
Time
20s
Time
20s
Fig. 3. Current density induced by magnetic eld perturbations for Fe/
0.05 mol L1 HCl system: (a) 00.4 T, polarized at Ecorr,0 T and (b) 0.4 Fig. 4. Changes of Ecorr for Fe/0.5 mol L1 HCl system after imposing or
0 T, polarized at Ecorr,0.4 T. withdrawing a 0.4 T magnetic eld: (a) 00.4 T and (b) 0.40 T.
514 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522

is also similar to that for Fe/0.05 mol L1 HCl system, 0.010
-1
while the values of the induced current are higher for Fe/ Fe in 0.5mol L NaCl
0.5 mol L1 HCl system, Fig. 5. 0.008 0T-0.4T

0.006
3.3. Fe/0.5 mol L1 NaCl

-2
i/mAcm
0.004
After imposing a 0.4 T magnetic eld, the noble shift of
the corrosion potential for Fe/0.5 mol L1 NaCl system 0.002
was rather small (close to 1 mV), which was close to the
sensitivity limit of the potential monitoring. For such a sys- 0.000
tem, current measurement is more sensitive in detecting the 0T 0.4T
magnetic eld eect. For Fe/0.5 mol L1 NaCl system, the -0.002
background current density during the polarization at Ecorr 20s Time
was 60.001 mA/cm2. A cathodic current of about 0.008
mA/cm2 was observed at about 17 s after imposing the Fig. 6. Current density induced by imposing a 0.4 magnetic eld for
magnetic eld, which decayed with time then reached a sta- Fe/0.5 mol L1 NaCl system polarized at Ecorr,0 T.
ble value of about 0.006 mA/cm2, Fig. 6. Such an in situ
current measurement conrmed the magnetic eld eect 3.4. Fe/0.5 mol L1 H2SO4
on the open-circuit state. The responses of open-circuit
potential and current to the withdrawing of the magnetic The noble shift of Ecorr for Fe/0.5 mol L1 H2SO4 sys-
eld were insignicant, showing possibly the weak mag- tem reached 4 mV at about 10 s after imposing the mag-
netic eld eect as well as the time-relaxation process. netic eld, Fig. 7a. Ecorr moved in the negative direction

-1
+ Fe in 0.5mol L H2SO4
0.06 0T-0.4T

-1
Electrode potential, E
1mV

Fe in 0.5mol L HCl
0.04
0T-0.4T
-2
i/mAcm

0.02

0.00 0T 0.4T
0T 0.4T
Time
10s Time 5s

0.02
0.4T 0T + 0.4T
0T
-1
Fe in 0.5molL HCl -1
0.00 0.4T-0T Fe in 0.5mol L H2SO4
0.4T-0T
Electrode potential, E
-2
i/mAcm

1mV

-0.02

-0.04

-0.06
40s Time
Time
10s
Fig. 5. Current density induced by magnetic eld perturbations for Fe/
0.5 mol L1 HCl system: (a) 00.4 T, polarized at Ecorr,0 T and (b) 0.40 T, Fig. 7. Changes of Ecorr for Fe/0.5 mol L1 H2SO4 system after imposing
polarized at Ecorr,0.4 T. or withdrawing a 0.4 T magnetic eld: (a) 00.4 T and (b) 0.40 T.
 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522 515

by about 3 mV at about 30 s after withdrawing the mag- 0.010 -1

netic eld, Fig. 7b. A maximum cathodic current of Fe in 0.5mol L Na2SO4
0.043 mA/cm2 appeared at 14 s after imposing a 0.4 T mag- 0.008 0T-0.4T
netic eld, Fig. 8a. After a certain decaying period for
about 48 s, the steady current density was about 0.006
0.024 mA/cm2, Fig. 8b. The time periods required for the

-2
i/mA.cm
responses of potential and current to the imposing of 0.004
the magnetic eld are shorter than those required for the
responses to the withdrawing of the magnetic eld. A 0.002
time-relaxation phenomenon was observed, which has been
observed for Fe in HCl solutions. 0.000

0T 0.4T
3.5. Fe/0.5 mol L1 Na2SO4 -0.002
Time
50s
After imposing a 0.4 T magnetic eld, the noble shift of
the corrosion potential for Fe/0.5 mol L1 Na2SO4 system Fig. 9. The current density induced by imposing a 0.4 T magnetic eld for
was close to 1 mV, which was close to the sensitivity limit Fe/0.5 mol L1 Na2SO4 system polarized at Ecorr,0 T: (a) 00.4 T.
of the potential monitoring. Similar to Fe/0.5 mol L1
NaCl system, current measurement is more sensitive for
detecting the magnetic eld eect. For Fe/0.5 mol L1 Na2SO4 system, the background current density during
the polarization at Ecorr was 60.001 mA/cm2. A cathodic
current of about 0.008 mA/cm2 was observed at about
0.05 20 s after imposing the magnetic eld, which decayed with
-1
Fe in 0.5mol L H2SO4 time then reached a quasi-stable value of about 0.006 mA/
0.04 0T-0.4T cm2, Fig. 9. The eects of the magnetic eld on the
open-circuit states of Fe/0.5 mol L1 Na2SO4 and Fe/
0.5 mol L1 systems are quite similar.
0.03
-2
i/mA.cm

4. Discussions
0.02
4.1. Electrochemical reactions occurring at open-circuit
0.01 potential

0.00
For a corrodible metal immersed in an aqueous solu-
0T 0.4T tion, the total (or measured) current density at a potential
of E, i(E), can be expressed by Eq. (1),
50s Time X X
iE ic;m E  ia;n E 1
0.02 m n

where ic,m(E) and ia,n(E) are the true cathodic and true ano-
0.01 0.4T 0T dic current densities at a potential of E, respectively. All
current densities used in the equations take their absolute
0.00 values. Symbols m and n are the number of cathodic and
-2
i/mA.cm

anodic reactions taking place on the electrode at a potential

-0.01
of E, respectively.
For the electrode systems used in the present study, the
-0.02
main cathodic reactions can be one or some of the follow-
-0.03
ing reactions: the reduction of oxygen (represented by iox),
-1
Fe in 0.5mol.L H2SO4 the reduction of hydrogen ion (represented by iH), and the
-0.04 0.4T-0T
reduction of water (represented by iH2O). The main anodic
reaction is the active dissolution of iron, assuming that the
protective role of the corrosion product is not signicant
Time
20s during the short period of the immersion at Ecorr.
Fig. 8. The current density induced by imposing or withdrawing a iE ic E  ia E
magnetic eld for Fe/0.5 mol L1 H2SO4 system: (a) 00.4 T, polarized at
Ecorr,0 T and (b) 0.40 T, polarized at Ecorr,0.4 T. iox E iH E iH2 O E  ia E 2
516 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522

At corrosion potential Ecorr, where iH(E) is the cathodic current at a potential E, iH,0 is
the exchange current density, Ee,H is the equilibrium poten-
iEcorr iox Ecorr iH Ecorr iH2 O Ecorr  ia Ecorr 3
tial, Hads is the adsorpted atomic hydrogen on the electrode
For the electrode systems in the present research, the values surface, and bH is the Tafel slop in natural logarithmic
of Ecorr are far away from the equilibrium potentials of scale for the reduction of hydrogen ion.
both the anodic and cathodic reactions, thus the backward According to the detailed description of the hydrogen
reactions for both the cathodic and anodic reactions can be evolution reaction by Gajek et al. [31]
neglected in the electrochemical kinetics equations.  
E
bH
iH E zFk H C H ;surf 1  hH e
4.1.1. Reduction of H+  
EEe;H
Hydrogen ions are in the hydrated form in the aqueous bH
zFk H;0 C H ;surf 1  hH e 10
solution, (H2O)nH+ [26,27], n can be equal to or higher
than one. To simplify the discussion in the electrochemical where z is the number of electrons involved in an electrode
kinetics equations, the hydrated hydrogen ion is written as reaction, F is the Faradays constant, C H ;surf is the concen-
H3O+, a hydronium cation, or simply as H+. tration of H+ on the electrode surface, kH is the heteroge-
neous rate constant for the reduction of H+, kH,0 is the
H + n(H2 O) = (H2 O)n H 4
standard heterogeneous rate constant for the reduction of

H + H2 O = H3 O
5 H+, and hH represents the coverage fraction of the adsorp-
ted atomic hydrogen on the electrode surface.
The main element processes for the hydrogen reduction on If hH is very small, then
a metal electrode have been described in the classical elec-  
EEe;H
trochemical theory [2830], which are schematically shown bH
in Fig. 10. Normally the diusion rate of H+ in the solution iH E zFk H;0 C H ;surf e 11
is high and the transporting rate of H2 from the electrode RT
surface to the solution is also high. Generally step H-II bH 12
aH zF
(electron-transfer step) and/or step III (IIIa or IIIb) deter-
mines the reaction rate. where aH is the transfer coecient for the reduction reac-
The rate of discharge of H+((H2O)nH+ or H3O+), iH(E), tion of hydrogen ion.
can be expressed by In acidic solutions,
C H
(H2 O)n H + e = Hads + n(H2 O) 6 C H ;surf   13
EEe;H
bH
(H2 O)H + e = Hads + (H2 O) 7 1  k  k H;0 e

or simply dd
k 14
FDH

H + e = Hads 8
  where, C H is the H+ concentration in the bulk solution,
EEe;H
bH
DH is the aqueous diusion coecient of H+, dd is the
iH E iH;0 e 9 thickness of the diusion layer.

4.1.2. Cathodic reduction of O2

Transport of
The cathodic reduction of oxygen can be expressed as
H3O+(Aq.) to the
M-S interface (H-I)
follows [28,31]:
O2 + 2H2 O + 4e = 4OH 15
Discharge of H3O+ EEe;ox  EEe;ox 
Volmer reaction (H-II) iox E zFk ox e b ox zFk ox;0 C ox;surf e box 16
H3O+ + e Had + H2O
where iox(E) is the cathodic current at a potential E for the
O2 reduction, kox is the the heterogeneous rate constant for
Chemical desorption Electrochemical desorption
the reduction of oxygen, kox,0 is the standard heteroge-
(Tafel reaction) (H-IIIa) (Heyrowsky reaction) (H-IIIb)
2Had H H2 H+ + Had + e H2
neous rate constant for the reduction of oxygen, Cox,surf
is the concentration of oxygen on the electrode surface,
Ee,ox is the equilibrium potential for the H+ reduction reac-
Leaving of H2 from the M-S tion, box is the Tafel slope in natural logarithmic scale for
interface to the Aqueous the oxygen reduction.
solution (H-IV)
Generally the aqueous mass transport of oxygen parti-
Fig. 10. Schematic showing of the element processes of hydrogen cipates in limiting the oxygen reduction rate on iron
reduction on an iron electrode. immersed in naturally aerated and static solution, then
 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522 517

iox;0 eEe;ox E=box  ic E iox E iH E iH2 O E  iH E 24

iox E iox;0 17
1 iox;L
eEe;ox E=box  +
For Fe/neutral solution systems with low H concentra-
tion, such as Fe/0.5 mol L1 NaCl (system S3) and Fe/
where iox,0 is the exchange current density for the oxygen
0.5 mol L1 Na2SO4 (system S5) systems, the cathodic
reduction, iox,L is the limiting current density for the reduc-
reaction is mainly contributed by the oxygen depolariza-
tion of oxygen.
tion that is controlled by the oxygen diusion at the
If iox,0  iox,L, then
metal/solution boundary.
iox iox;L 18
ic E iox E iH E iH2 O E  iox E 25
The limiting cathodic current density, iox,L, is described by,
Eqs. (24) and (25) show both the complex and simplied
C ox;b forms, which would be used to simply the discussion on
iL zFDox 19
dd the magnetic eld eect.
where Dox and Cox,b are the diusion coecient of O2 and If both the anodic reaction and the cathodic reaction are
the concentration of O2 in the bulk solution, respectively. controlled by the electron-transfer step, the corrosion
potential can be expressed by
4.1.3. Reduction of water  
bc Ee;a ba Ee;c ba bc i0;c
The reduction rate of water, iH2 O E, can be expressed Ecorr ln 26
ba bc ba bc i0;a
by [28,31]
If the anodic reaction is controlled by the electron-transfer
H2 O e Hads OH 20
  step and the cathodic reaction is controlled by the aqueous
EEe;H O
bH O
2 mass transport step, the corrosion potential can be ex-
iH2 O E zFk H2 O e 2
pressed by
   
EEe;H O
bH O
2
iL
zFk H2 O;0 1  hH2 O e 2 21 Ecorr Ee;a ba ln 27
i0;a
where iH2 O E is the cathodic current at a potential E for
the O2 reduction, iH2 O is the heterogeneous rate constant If the anodic reaction is controlled by the electron-transfer
for the reduction of water, k H2 O;0 is the standard heteroge- step, and the cathodic reaction is controlled by both the
neous rate constant for the reduction of oxygen, Ee;H2 O is electron-transfer step and the mass transport step, the ana-
the equilibrium potential for the water reduction reaction, lytical expression for corrosion potential is complex and
bH2 O is the Tafel slope in natural logarithmic scale for the will be discussed later along with the magnetic eld eect.
water reduction.
4.2. Eects of a magnetic eld on open-circuit corrosion
4.1.4. Anodic dissolution of iron
If there is no protective interfacial barrier lm, the rate- Similar to that in the absence of a magnetic eld, the
determining step for the active anodic dissolution reaction measured current density at potential E in the presence of
of iron at Ecorr is the electron-transfer step, a magnetic eld, i*(E), can be expressed by
X X
ia E i0;a eEEe;a =ba  zFk a  eEEe;a =ba  22 i E ic;m E  ia;n E 28
m n
where ia(E) is the anodic current at a potential E, ka is the
heterogeneous rate constant for the anodic dissolution of where superscript * represent the parameter under a mag-
iron, kox,a is the standard heterogeneous rate constant for netic eld.
the anodic dissolution of iron, Ee,a is the equilibrium poten- If polarized at Ecorr in the absence of a magnetic eld,
X X
tial for the H+ reduction reaction, ba is the Tafel slope in iEcorr ic;m Ecorr  ia;n Ecorr 0 29
natural logarithmic scale for the anodic dissolution. m n
Since all the test solutions are naturally aerated, the oxy-
If polarized at Ecorr in the presence of a magnetic eld,
gen reduction reaction participates in the cathodic reac- X X
tions. The contribution of oxygen on cathodic reactions i Ecorr ic;m Ecorr  ia;n Ecorr 30
diers from system to system. m n

ic E iox E iH E iH2 O E 23 If polarized at Ecorr in the presence of a magnetic eld,

+ X X
For Fe/acidic solution systems with high H concentration i Ecorr ic;m Ecorr  ia;n Ecorr 0 31
that is much higher than the dissolved oxygen concentra- m n
tion, such as Fe/0.05 mol L1 HCl (system S1), Fe/
If polarized at Ecorrin the absence of a magnetic eld,
0.5 mol L1 HCl (system S2), and Fe/0.5 mol L1 H2SO4 X X
(system S4) systems, the cathodic reaction is mainly con- iEcorr ic;m Ecorr  ia;n Ecorr 32
tributed by the reduction of hydrogen ion. m n
518
For the present systems studied, possible cathodic reactions
are the reduction of oxygen, hydrogen ion and water, and
the anodic reaction is the dissolution of iron. According to
above kinetic equations, then
i E iox E iH E iH2 O E  ia E
i Ecorr iox Ecorr iH Ecorr iH2 O Ecorr  ia Ecorr
iEcorr iox Ecorr iH Ecorr iH2 O Ecorr
4.2.1. Neutral or near neutral solutions
The dierence between Ecorr and Ecorr for iron in neutral
solutions is small. After imposing a 0.4 T magnetic eld,
there was only a small positive change of the open-circuit
potential. After removing the magnetic eld, the change
of the open-circuit potential is quite small. In this case,
measuring the current under potentiostatic polarization is
a more sensitive way for detecting the eect of magnetic
eld than measuring the corrosion potential. For Fe/
0.5 mol L1 NaCl (system S3, corrosion potential is Ecorr,
1
S3) and Fe/0.5 mol L Na2SO4 (system S5, corrosion
potential is Ecorr,S5) systems, [H+] is rather low, thus oxy-
gen depolarization is the main cathodic reaction and the
diusion rate of oxygen plays a predominant role as the
rate-determining step.
iS3 Ecorr;S3 iox;S3 Ecorr;S3 iH;S3 Ecorr;S3
iH2 O;S3 Ecorr;S3  ia;S3 Ecorr;S3
 iox;S3 Ecorr;S3  ia;S3 Ecorr;S3
Similarly
iS5 Ecorr;S5  iox;S5 Ecorr;S5  ia;S5 Ecorr;S5
The value of iS3 Ecorr;S3 is about 0.006 mA/cm2, which is
quite similar to iS5 Ecorr;S5 , Figs. 6 and 9. Such a small cur-
rent induced by imposing the magnetic eld for iron in neu-
tral solutions could be caused by the weak eect of the
magnetic eld on oxygen reduction as well as the reduction
reactions of hydrogen ions and water. The fact that mag-
netic eld has little eect on the corrosion potential and in-
duces a small cathodic current for iron in aerated neutral
solutions implies several things. Firstly, the eect of the
magnetic eld on the oxygen depolarization could be small.
It has been reported that the cathodic limiting current for
Fe in naturally aerated 0.5 mol L1 NaCl + 0.005 mol L1
Na2CO3 + 0.005 mol L1 NaHCO3 solution is about
0.36 mA cm2 [32]. It is expected that the cathodic limiting
current densities for iron in 0.5 mol L1 NaCl and
0.5 mol L1 Na2SO4 solutions with similar dissolved oxy-
gen contents be at this order of magnitude. In this case,
if the magnetic eld would increase the cathodic limiting
current density by 5%, the increase of current density could
reach 0.018 mA cm2. Rather low currents induced by the
magnetic eld for Fe/0.5 mol L1 NaCl and Fe/Na2SO4
Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522
systems show that the eect of the magnetic eld on oxygen
diusion rate is small. Secondly, the results also show that
the magnetic eld eect on the true anodic active dissolu-
tion rate of iron can be rather weak. A much high current
33 is expected if the magnetic eld had a signicant eect on
the true anodic polarization curve near the corrosion po-
tential. It has been observed that a 0.4 T magnetic eld
34 does not show signicant eect on the anodic dissolution
of iron in several aqueous solutions in the potential range
 ia Ecorr where the anodic dissolution is controlled by the elec-
35 tron-transfer step [2325]. The main results in the neutral
solution are expressed by Eqs. (38) and (39).
iox Ecorr  iox Ecorr 38
ia Ecorr  ia Ecorr 39
Nevertheless, previous results show that a magnetic eld
signicantly increases the diusion rate of ionic cathodic
depolarisers and signicantly enhances the anodic dissolu-
tion rate that is controlled the mass transport processes,
which have been analyzed in a previous paper based on
the fundamental electrochemical kinetics [18]. Most exper-
imental results show that the magnetic eld does not have
any obvious eect on the electron-transfer step for macro-
sized metal electrodes in static aqueous solutions [2325].
However, it is reported that the cathodic polarization
behavior for iron in acid solutions is aected by an applied
magnetic eld [18], showing the possible magnetic eld ef-
fect on the hydrogen ion reduction reaction that is de-
scribed to be controlled by the electron-transfer step
[28,29].
36 4.2.2. Acidic solutions
In aerated acid solutions, the oxygen reduction still con-
tributes to the cathodic reaction rate. However, the contri-
37 bution from the reduction of oxygen is much less than that
from the reduction of hydrogen ion. The reduction of
hydrogen ion is the main cathodic reaction for Fe/
0.05 mol L1 HCl (system S1), Fe/0.5 mol L1 HCl (system
S2), and Fe/0.5 mol L1 H2SO4 (system S4) systems.
iS2 Ecorr;S2 iH;S2 Ecorr;S2 iox;S2 Ecorr;S2  ia;S2 Ecorr;S2
40
iS2 Ecorr;S2 iH;S2 Ecorr;S2 iox;S2 Ecorr;S2  ia;S2 Ecorr;S2
41
Comparing Figs. 3a, 5a, and 6 shows that the values of
i*(Ecorr) for Fe/0.05 mol L1 HCl and Fe/0.5 mol L1
HCl systems are signicantly higher than that for Fe/
0.5 mol L1 NaCl system. Similarly, i*(Ecorr) for Fe/
0.5 mol L1 H2SO4 system is many times higher than that
for Fe/0.5 mol L1 Na2SO4 system, Figs. 8a and 9. Since
the dissolved oxygen content in 0.5 mol L1 HCl solution
is similar to that in 0.5 mol L1 NaCl solution, the cathodic
oxygen depolarization limiting current can be assumed to
be similar for the two systems. As mentioned before, the ef-
fect of the magnetic eld on the oxygen depolarization
 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522
reaction could be rather weak, then i*(Ecorr) for Fe/
0.5 mol L1 HCl system could be mainly caused by the
accelerating eect of the magnetic eld on the cathodic
hydrogen depolarization.
iS2 Ecorr;S2 iH;S2 Ecorr;S2  iH;S2 Ecorr;S2 
iox;S2 Ecorr;S2  iox;S2 Ecorr;S2 
 ia;S2 Ecorr;S2  ia;S2 Ecorr;S2 
 iH;S2 Ecorr;S2  iH;S2 Ecorr;S2
iS2 Ecorr;S2  iH;S2 Ecorr;S2  iH;S2 Ecorr;S2
Similarly
iS4 Ecorr;S4  iH;S4 Ecorr;S4  iH;S4 Ecorr;S4
iS4 Ecorr;S4  iH;S4 Ecorr;S4  iH;S4 Ecorr;S4
The eect of an applied magnetic eld on the hydrogen
reduction rate can be characterized by a coecient dH,mag
dened in Eq. (46) or by a magnetic eld-induced overpo-
tential gmag dened by Eq. (47).
iH E dmag E  iH E
gmag
dmag e bc
The experimental results show that there are corr) > 0
and iEcorr < 0 for iron in acid solutions S1, S2, and S4,
showing that iH E is higher than iH(E). There is dH,mag > 1
for the cathodic reduction of hydrogen ions on iron in
acidic solutions, which corresponds to a positive gmag that
has been observed in the cathodic polarization curves for
iron in hydrochloric acid solutions [18]. The general point
of view drawn from the present tests is that an applied
magnetic eld would enhance the hydrogen ion reduction
thus result in the shift of the open-circuit potential and
the generation of the magnetic eld-induced current under
potentiostatic polarization.
The eects of magnetic elds on electrochemical reac-
tions have been reviewed by Fahidy [1,4] and by Tacken
et al. [3]. There are mainly two working mechanisms for
the magnetic eld eect on electrochemical reactions
[1,10,16]. The rst mechanism is related to the so-called
magnetohydrodynamics (MHD) phenomenoa. MHD phe-
nomena arise form the interaction of the velocity elds with
magnetic elds. The total force on a charged particle mov-
ing in an electromagnetic eld is:
F FE FMHD
FE qE
FMHD J B
where E is the sum of the electric and electrostatic elds
El + Es, FMHD(N/m3) is the Lorentz force acting on the
chargingcarrying ions, B is the ux density of the applied
magnetic eld, J is the ux of ions (coulombs/(cm2 s)). The
changes of mass transport rates due to MHD ow in the
presence of applied magnetic elds have been documented
in many published papers, for example, Refs. [111]. Previ-
ous works [710,19,21,24] have shown the eects of mag-
519
netic eld on the corrosion potentials of metals in
solutions containing ionic oxidants. An applied magnetic
eld increases the cathodic limiting current via magnetohy-
drodynamics thus moves the corrosion potential in the po-
sitive direction or induces an imposed cathodic current.
The eect of magnetic eld on corrosion potential and elec-
trochemical behavior has been formulated based on the
fundamental electrochemistry kinetics [24]. There is a dif-
ferent interpretation [11] of the proposed analysis of the
42 magnetic eld eect on open-circuit potential [24]. As
43 shown clearly in the Evans polarization diagram with
polarization curves with and without a magnetic eld
[24], a signicant eect of a magnetic eld on corrosion po-
44 tential is expected for a cathodic reaction that is partly or
fully controlled by the mass transport processes of charged
45 reactive species. That is to say, magnetic eld can aect the
open-circuit potential without changing the type of
the rate-controlling mode. These results are based on the
assumption that the anodic reaction is purely controlled
by the charge-transfer step. If the anodic polarization
46 exhibits the activepassive transition behavior in the poten-
tial range studied, the eect of a magnetic eld on the open-
47 circuit potential would be more complex. It has been found
that the eect of magnetic eld on open-circuit potential is
i*(E
strongly dependent on the original electrochemical state of
the corrosion system [21].
The second mechanism for the magnetic eld eect on
electrochemical reactions is related to the gradient force,
F$B [11,16,33]. F$B reects the ability of diamagnetic and
paramagnetic species to move away from and toward
regions of higher magnetic eld strength, respectively,
which operates only in a nonuniform eld.
FrB v=lB  r 51
where l is the magnetic permeability.
An applied magnetic eld may aect other properties
of electrochemical systems thus changes the reaction rates
[13]. The results in the present research show that the
eect of magnetic eld on the diusion process of neutral
oxygen molecules would be rather weak, probably due to
the electric neutrality of O2 molecule whose moving rate
would not be directly aected by the applied magnetic eld.
Since the cathodic reaction rate for iron in pure acid is gen-
erally thought to be controlled by the electron-transfer step
(ETS) [2830], the mechanism for the magnetic eld eect
48 on the electrochemical behavior of iron in pure acid solu-
49 tions can be dierent from those for the systems with the
diusion process as the rate-determining step.
50
There are many ways of changing the reaction rates, such
as changing the quantity (concentration) of reactive species
at the reaction site or changing the reactivity of the reactive
species. According to Eq. (10), the reduction rate of hydro-
gen ions depends on the reaction rate constant, kH, the sur-
face concentration, the surface coverage fraction of
hydrogen, the Tafel slope (in ln form), bH, and the electrode
potential, E. Several possibilities are proposed to account
for the magnetic eld eect on the open-circuit potentials
520 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522
of iron in acidic solutions. According to the classical elec-
trochemical theory, the cathodic reaction rate of hydrogen
evolution on iron in pure acid solutions [2830] is purely
controlled by the electron-transfer step, i.e. the surface con-
centration of hydrated hydrogen ion is equal to its bulk con-
centration, consequently the magnetic eld could aect the
open-circuit state via inuencing the electron-transfer pro-
cess. The second possibility is that, if assuming that mass
transport process is one of the rate-limiting factors for the
reduction of hydrated hydrogen ion, magnetic eld may
change the surface concentration of hydrogen ions or the
surface coverage fraction of adsorpted hydrogen atoms or
other mass transport related parameter(s) and the resultant
hydrogen reduction reaction rate.
Relying on the classic electrochemical mechanism for
the reduction of hydrogen ions, it is tentatively proposed
here that the change of the reaction constant of hydrogen
reduction reaction be a main reason for the magnetic eld
eect on the open-circuit states for iron in acid solutions.
Such a magnetic eld eect could be related to the special
properties of hydrogen ions or hydrated hydrogen ions in
aqueous solutions. Most reported experimental results with
macro-sized electrodes for the reduction of charged ions
other than hydrogen ions tend to conclude that the mag-
netic eld eect on an electron-transfer process is rather
weak or negligible [5,6]. Hydrogen ions exist in aqueous
solutions as protonated water clusters (H2O)nH+, which
can be identied by experimental methods such as infrared
spectroscopy [34] or neutral diraction [35], and can be
investigated by computer simulation based on empirical
valence bond [36] and other methods. The electrochemical
reactivity of hydrogen ion can be related to the structure of
the protonated water cluster. The hydration state of hydro-
gen ions in aqueous solutions and at the electrode interface
can be aected by an applied magnetic eld, as the results
of the magnetic eld eect on water properties such as
hydrogen-bond development, water adsorption and
desorption [37,38]. These changes in the thermodynamic
and interfacial properties caused by the applied magnetic
eld may aect the cathodic reduction rate of hydrated
hydrogen ions. Even though there is still a possibility that
a magnetic eld would aect the mass transport process
of hydrated hydrogen ions or the interfacial concentration
of other intermediate reactive species, the increasing of the
reaction rate constant by an applied magnetic eld is taken
as the predominant factor for the magnetic eld eect on
hydrogen evolution reaction, i.e. k H > k H .
The magnetic eld eects on the open-circuit potentials
and the magnetic eld-induced current under potentiostatic
polarization for iron in acidic solutions are illustrated in
Fig. 11. To simplify the discussion, only the reduction of
hydrogen ions is considered as the cathodic reaction in
the schematic gure, and it is not necessary that the Tafel
slope for the true cathodic polarization curve under 0 T
be the same as that under a magnetic eld.
If both the anodic and cathodic reactions are controlled
by electron-transfer processes, the corrosion potential is
+ True cathodic(0T)
Ee,c
True cathodic(MF)
Electrode potential, E
Ecorr, M F
Ecorr,0T
True anodic(0T&MF)
Ee,a
icorr(Ecorr,MF)
icorr(Ecorr,MF)
icorr(Ecorr,0T)
icorr(Ecorr,0T)
Current density,i
(in logarithic scale)
*
*
Fig. 11. Schematic showing of the magnetic eld eect on the open-circuit
state that is controlled by electron-transfer steps for both the anodic and
the cathodic reactions.
determined by several parameters such as the equilibrium
potentials, the exchange current densities, and the Tafel
slopes for the anodic and cathodic reactions, Eq. (26). If
the real cathodic current increases while the real anodic dis-
solution rate remains unchanged after imposing a magnetic
eld, the corrosion potential, i.e. the intersection point of
the real cathodic polarization curve and the real anodic
polarization curve, will move in the noble direction. When
polarized at Ecorr, imposing a magnetic eld increases the
cathodic current at this potential thus produces an appar-
ent (or measured) cathodic current. When polarized at
Ecorr , withdrawing the magnetic eld decreases the cathodic
current thus produces a measured anodic current. The
measured anodic current after withdrawing the magnetic
eld is due to the decreasing of the cathodic current rather
than the increasing of the anodic current. The present
results from the in situ monitoring of corrosion potential
are consistent with those from the in situ monitoring of
the current under potentiostatic polarization. It is found
that the measurement of current is more sensitive and
can be used to acquire more denite evidence on the mag-
netic eld eect, especially for rather a weak eect that
cannot be easily identied by conventional ex situ measure-
ment techniques.
It is assumed that a 0.4 T magnetic eld is not strong
enough to aect the Tafel slopes for the true anodic and
the cathodic polarization curves [18], then
 
 1  ba bc i0;H
Ecorr  Ecorr E  Ee;H ln 52
bH e;H ba bc i0;H
There is Ecorr  Ecorr > 0 if Ee;H is close to Ee,H and i0;H is
higher than i0,H. For iron in acidic solutions, there are
i0 T!0:4 T;S4 Ecorr  iH Ecorr  iH;S4 Ecorr > 0 53
i0:4 T!0 T Ecorr  iH Ecorr  iH Ecorr < 0 54
 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522
where positive and negative values of current represent
apparent (measured) cathodic and anodic currents,
respectively.
The shift of the open-circuit potential and the observed
polarization current after imposing or removing a magnetic
eld are modeled based on the magnetic eld eect on the
reduction reaction rate of hydrogen ions on the iron elec-
trode. The eect of the magnetic eld is stronger in
0.5 mol L1 HCl solution than in 0.05 mol L1 HCl solu-
tion, which supports the mechanism of magnetic eld on
the reduction of hydrogen ions. The eect of magnetic eld
is stronger in 0.5 mol L1 HCl solution than in 0.5 mol L1
H2SO4 solution, which could be arisen from the dierent
thermodynamic properties of HCl and H2SO4 solutions
and the resultant dierent interface structures between
Fe/HCl and Fe/H2SO4 systems. One example of such a dif-
ference is shown in a recent paper that halide ions such as
chloride can decrease the double layer capacitance value
for iron in 0.5 mol L H2SO4 solutions thus inhibit the cor-
rosion [39].
4.2.3. Time-relaxation phenomena related to the eect
of a magnetic eld
Results in Figs. 29 show that a certain time is required
for an electrode system to reach the steady state after
imposing or removing a magnetic eld. Fig. 12 summarizes
the time constants for these transition periods. A relatively
shorter time is required for the imposed magnetic eld to
take eect than that for returning to the original 0 T
condition after removing the magnetic eld. There are
tE,0-0.4 T > tE,0.4-0 T and ti,0-0.4 T > ti,0.4-0 T. The time-relaxa-
tion eects (or called memory eects) of the magnetic eld
on the open-circuit potential and on the magnetic eld-
induced current are identied. Results in Fig. 12 show a
tendency that the time relaxation phenomenon is more sig-
nicant for the current response than that for the potential
response, probably due to the more sensitive detectability
by current measurements than that by potential measure-
ments. According to previous results by polarization curve
measurements [19], the time-relaxation phenomenon for
120
100
80
Time, t(s)
60
40
20
0 for iron in acid solutions than that for iron in neutral
1A0.05M HCl 1B0.5M HCl 1C0.5M NaCl 1D0.5M H2SO4
Systems
Fig. 12. Values of the transition time for the eect of magnetic eld on the
open-circuit corrosion parameters.
521
the eect of magnetic eld is signicant for the systems that
are possibly controlled by electron-transfer steps but not
signicant for the systems that are controlled by mass
transport steps, which support the present experimental
observations. Most reported results show that there is no
detectible eect of magnetic eld on the electron-transfer
reaction on macro-sized electrodes. However, the present
results show that the hydrogen reduction reaction on iron
could be an exception for which magnetic eld would have
a signicant eect on the electron-transfer step. The mem-
ory eect for the iron/acidic solution systems also reveals
that the related mechanism might be dierent from the
classic MHD phenomenon that has been used to account
for the magnetic eld eect on the mass transport. The
memory eects of magnetic elds on water properties have
been reported extensively, such as in Refs. [38,40,41]. It is
postulated that properties of hydrated hydrogen ions in
aqueous solutions are inuenced by the applied magnetic
eld and a time-relaxation period is necessary for these
magnetized hydrated hydrogen ions to recover their ori-
ginal properties after removing the magnetic eld. More
direct evidences are highly required to determine if such a
time-relaxation eect works for the bulk solution proper-
ties, for the interfacial properties or for both. The time-
relaxation period obtained by polarization curve measure-
ment is about several hours [19], which is longer than the
present observation by in situ electrochemical measure-
ments. Longer time-relaxation periods for the magnetic
eld eect on water properties have also been observed
[38,40,41]. The detailed mechanism(s) for the magnetic eld
eect on the thermodynamic and kinetics of solid/solution
systems remains to be a great challenge.
5. Conclusions
1. Imposing a 0.4 T magnetic eld causes a positive change
of the open-circuit potential for iron in static aerated
neutral and acidic solutions. The noble shifts of the
open-circuit potential for iron in acid solutions are lar-
ger than those for iron in neutral salt solutions. With-
drawing the magnetic eld causes a negative shift of
the open-circuit potential in acidic solutions. However,
tE,0-0.4T it does not cause any signicant change of the open-
tE,0.4-0T circuit potential in neutral solutions.
ti,0-0.4T
2. Imposing a magnetic eld induces a measured cathodic
current for iron that was previously potentiostatically
ti,0.4-0T
polarized at the open-circuit potential without magnetic
eld. Withdrawing the magnetic eld induces a mea-
sured anodic current for iron that was previously poten-
tiostatically polarized at the open-circuit potential with
the magnetic eld. The magnitude of the current induced
by imposing or withdrawing the magnetic eld is higher
1E0.5M Na2SO4
solutions.
3. Results of open-circuit potential and induced current
show that a relatively shorter time is required for the
magnetic eld to take eect than that for returning to
522 Z. Lu, W. Yang / Corrosion Science 50 (2008) 510522
the original 0 T condition after removing the magnetic
eld. The memory eect of the magnetic eld on the
electrode reaction is identied, which could be related
to the magnetic eld eect on hydrated hydrogen ions
in aqueous solutions.
4. Comparing the results in acidic and neutral solutions
shows that an applied magnetic eld has a strong eect
on the reduction of hydrogen ions while it has little eect
on oxygen reduction. The positive or negative shift of
the open-circuit potential and the current induced by
applying or withdrawing the magnetic eld is attributed
to the shift of the true cathodic polarization curve.
There are two implications of the present results. One
implication is that a magnetic eld may aect the elec-
tron-transfer rate of the reduction of hydrogen ions,
which relies on the classical corrosion-electrochemistry
mechanism. Another implication is that one or more ele-
ment steps in the reduction reaction of hydrogen ions
could be related to the rate of mass transport, which
needs further evidence. The classical electrochemical
mechanism on the hydrogen reduction seems to support
the rst implication.
Acknowledgements
This work was jointly supported by the Natural Science
Foundation of China (No.59871018) and the Special
Funds for the Major State Basic research Project (No.
G19990650). The help from Mr. D.L. Huang for the exper-
iments is acknowledged.
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