Corrosion Science, Vol. 37, No. 12. pp.

1919-1929, 1995
Elsevier Science Ltd
Printed in Great Britain
0010-938x/95 $9.50 + 0.00

0010-938X(95)00074-7

THE INHIBITION OF Ni CORROSION IN H2S04 SOLUTIONS

CONTAINING SIMPLE NON-SATURATED SUBSTANCES

C.F. ZINOLA* and A.M. CASTRO LUNA

Instituto de Investigaciones Fisicoquimicas Tebricas y Aplicadas (INIFTA), Universidad National de La

Plata, Sucursal4, Casilla de Correo 16 (1900)La Plata, Argentina
* Laboratorio de Electroquimica, Facultad de Quimica. Facultad de Ciencias, Universidad Mayor de la
Republica, Avda. Gral. Flores 2124, Casilla de Correo 1157 Montevideo, Uruguay

Abstract-The inhibition of Ni electrodissolution in HaSO solutions containing carbon monoxide, ethylene

or acetylene was investigated after adsorption equilibrium at room temperature. The interaction of these
molecules with Ni was followed by the anodic stripping of adsorbed residues. The Ni electrodissolution
inhibitory effect caused by the different adsorbates increases in the following order:
ethylene < carbon monoxide < acetylene. Anodic stripping curves were simulated by applying a numerical
method, such as Rung+Kutta’s. and the different voltammetric contributions calculated by numeric
deconvolution. These analyses provide a further insight into the mechanism of the Ni electrodissolution in
acid containing carbon monoxide, ethylene or acetylene.

INTRODUCTION

Ni electrodes are important materials for electrochemical technology and energy

conversion devices. In aqueous environments, Ni electrodes are usually covered by
electrochemically active Ni(OH)2 layers, although in acid solution Ni corrosion and
passivation take place.’ The mechanism of Ni corrosion and passivation in aqueous
solution is already reasonably well-established.2
The study of the interaction of Ni with substances exhibiting corrosion inhibitory
properties offers the possibility for modifying the characteristics of the Ni surface and
making it more resistant to an aggresive environment. It is known that the presence of
CO in aqueous solutions inhibits the corrosion of Ni over a certain potential range.3,4
The inhibition of Ni electrodissolution was explained by CO-adsorption on Ni active
surface sites.5
The interaction of some non-saturated molecules with solid electrode surfaces is
the result of adsorption and/or electro-adsorption processes. This has been recently
observed for Pt and Au electrodes immersed in acid solutions containing adsorbable
organic substances.69
This work is devoted to study the inhibition of Ni electrodissolution in acid
solution in the presence of CO, ethylene (ET) and acetylene (AC).
A mechanistic advance based on kinetic data obtained from anodic stripping
voltammetry and its mathematical simulation is presented to explain the inhibition of
Ni electrode corrosion in sulfuric solutions.

Manuscript received 21 December 1994.

1919
1920 CF. Zinola and A.M. Castro Luna

EXPERIMENTAL

Electrochemical experiments were carried out in a conventional flowing solution

electrochemical cell at room temperature, using a Ni wire (0.30 cm2 in geometric area)
as working electrode. The electrochemical set-up was completed using a Pt plate as
counter electrode and a reversible hydrogen electrode (RHE) as reference.
N2-saturated 0.5 M aqueous H2S04 was employed as plain electrolyte and
inhibitor-containing electrolytes were obtained by saturating the plain electrolyte
with CO, ET and AC (Matheson ultra high purity), i.e. 0.45 x 10-j M for CO,
5 x lop3 M for ET and 4.4 x lop2 M for AC at 25”C.i”
Rest potentials, Eresr, of Ni immersed in plain and inhibitor-containing, 0.5 M
H2S04 were determined at room temperature.
Ni working electrodes were subjected to conventional voltammetry combined with
preset potential steps as described elsewhere.4 Potential sweeps were made between
-0.2 and 1.O V at 0.1 V s-i. Occasionally, the potential was stepped to the adsorption
potential, Ead, within a range - 0.2sE,dsO.6 V, and afterwards the plain electrolyte
was changed by either CO-, ET-or AC-containing 0.5 M H2SO4. After an adsorption
time, t,d = 5 min, the solution was replaced by plain electrolyte and the anodic
stripping voltammogram of the adsorbed residues was run. The value of qox, the
anodic stripping voltammetric charge density, was then determined.
The amount of Ni dissolved in plain and inhibitor-containing electrolytes at
Ead =0.25, 0.50 and 0.8OV for 15 min was determined by conventional atomic
absorption spectroscopy (AAS).

RESULTS

Rest potentials.
Values of E,,,, for Ni at 25°C for different solutions are assembled in Table 1. In all
cases, the foreign substance shifts the value of Erest positively; the greatest
displacement is produced by AC-adsorption.

Voltammetric electrodissolution of Ni in plain electrolyte

Previously reported data,‘,’ showed that the voltammogram of Ni in H2SO4
depends on the applied potential routine, solution composition and electrode history.
Then, all variables were kept constant for data comparison.
The electrodissolution of Ni in aqueous 0.5 M HIS04 under a linear potential
sweep of 0.1 V s- ’ displays a large current peak (peak I) at 0.24 V, a hump (peak II) at

Table 1. Values of Erert for Ni in

0.5 M H2S04 and inhibitor-containing
0.5 M HISO at 25°C

System &es, 0’)

NQ0.5 M HzS04 -0.038

NW%,.) H$Q 0.018
Ni/(ET,,, ) HzS04 0.018
Ni/(AC,,,) H&XI 0.288
 Ni corrosion in H$304 solutions 1921

IJ I I 1 I I II
-a? 0 a! oh a6 0.8 Lo
E/V(RHE)
Fig. 1. Repetitive cyclic voltammogram for Ni in 02-free 0.5 M HzS04 run at 0.1 V s-‘;
T= 25°C.

- 0.4 V and a passivation current extending from 0.7 V upwards. The reverse potential
scan shows a small cathodic current peak at - 0.1 V (Fig. 1). Holding the potential at
Ead=O V for 5 min a considerable enhancement of peak I is produced in the
voltammogram run afterwards. The qoX value involved in this experiment is
210 mC cmP2.

Electrodissolution of Ni in (CO sat) aqueous 0.5 M H2S04

A negligible current transient for Ni in aqueous 0.5 M HzS04 after CO saturation
either at Ead = -0.038 V or at Ead = 0.018 V (see Table 1) is observed. It appears that
the interaction between Ni and CO in the aqueous enviroment implies no charge
transfer at these potentials.
The anodic stripping voltammogram in aqueous 0.5 M H2S04 for CO adsorbates
accumulated for 5 min at Ead=O V shows a remarkable decrease of peak I but it
exhibits a large and sharp current peak at 0.50 V (Fig. 2). A residual anodic current is
also recorded from 0.8 V upwards. qox remains constant (68 mCcmP2) in the
-0.2OsE,&O.4 V range, whereas for Ead > 0.4 V, lower qox values are attained.
When a CO-covered Ni electrode is potential cycled at 0.1 V s- ’ between - 0.2 and
1.0 V, the voltammogram gradually changes in the direction expected for a
reactivation of Ni electrodissolution and after 10 cycles the blank voltammetric
features are approached. Thus, the height of peak I grows until the voltammogram
recovers the shape of the blank, i.e., peak I becomes much higher than peak II.

Electrodissolution of Ni in (ET sat) aqueous 0.5 A4 H2S04

The same type of experiments were run in ET-saturated aqueous 0.5 M H2S04.
Current transients measured either at Ead = -0.038VoratE,d=O.O18V(seeTable 1)
showed negligible charges.
The first voltammogram runs after ET-adsorption from Ead = 0 V upwards shows
a decreasing peak I, and a rather broad and symmetric anodic peak at potentials near
to peak II in the blank (Fig. 3). A constant value of qox (48 mC cmP2) is also attained
in the - 0.2z&de0.018 V range but abruptly diminishes for Ead > 0.018 V.
1922 C.F. Zinola and A.M. Castro Luna

I I 1 I
Q
E
.
160 - I

120 -

80-

-a2 0 a2 085 06 a8 lo
EMRHE)
Fig. 2. Anodic stripping voltammogram for the CO-residue adsorbed at 0 V for 5 min from
CO-saturated 0.5 M HzSOJ solution; V = 0.1 V s-‘. 7’= 25°C.

1 1 I

a
E
.
- 12.0 -

r
a0-

1 1 I

a0 Ok 0.8
E/V(RHE)
Fig. 3. Anodic stripping voltammogram for the ET-residue adsorbed at 0 V for 5 min from
ET-saturated 0.5 M HlS04 solution; V = 0.1 V s-‘: T= 25°C.

Electrodissolution of Ni in (AC sut) aqueous 0.5 M HzS04

Current transients measured
in AC-saturated aqueous 0.5 M HISO at
Ead= -0.038 V show a negligible cathodic current as compared to the blank.
Current transient measured at Ead = 0.288 V (see Table 1) produces a remarkable
 Ni corrosion in HzS04 solutions 1923

ENRHEI
Fig. 4. Anodic stripping voltammogram for the AC-residue adsorbed at 0 V during 5 min
from AC-saturated 0.5 M HISO,; V = 0.1 V s-‘. T= 25°C.

drop of the Ni electrodissolution current to practically zero, showing a strong

inhibition due to AC-adsorption.
The anodic stripping voltammogram of AC-adsorbates on Ni formed at OV is
depicted in Fig. 4. In this case, non-zero currents appear at ca0.4 V and the anodic
stripping profile displays a wide and asymmetric peak at 0.74 V. Likewise, it results
q,,=42mCcm-2 a value considerably lower than that obtained at the blank. The
value of qox remains nearly constant in the -0.2~.&iO.288 V range, but it
diminishes for higher potentials.
The reactivation of Ni in aqueous 0.5 M H2S04is progressively achieved through a
relatively large number of cyclovoltammograms run between - 0.2 and 1.OV.

Chemical analysis data

After holding Ni electrodes at different potentials for 15 min in either plain or
inhibitor-containing electrolyte the amount of soluble Ni produced was determined by
AAS. Experimental data are assembled in Table 2. It is clear that under the chosen
experimental conditions the amount of soluble Ni decreases in the order
ET>CO>AC.

Table 2. Soluble Ni concentrations resulting after holding a Ni electrode at

different Ead for 15 min, in either plain or inhibitor-containing solution

CNi2 + CNi2+ CNi2 +

(mg dme3) (mg dme3) (mg dmm3)

System E=0.25 V E=O.SOV E=0.80 v

Ni/O.S M H2S04 26 1 1
Ni/(ET,,,) 0.5 M HrS04 23 1 1
Ni/(CO,,,) 0.5 M H2S04 1 2 1
Ni/(AC,,,) 0.5 M HzS04 1 2 1
1924 C.F. Zinola and A.M. Castro Luna

ANALYSIS OF THE ANODIC STRIPPING VOLTAMMOGRAMS

Since the anodic stripping voltammograms show multiple peaks related to Ni

electrodissolution, oxide phase formation and organic species electrodesorption, a
deconvolution of the complex contours was attempted for data analysis.
Based on the earlier proposed mechanism for Ni electrodissolution” and
references therein and Temkin adsorption conditions for the electrosorption of
different organic residues,4,9713,14 the corresponding rate equations in the differential
form were solved by the Runge-Kutta procedure.‘* The mathematical simulated
complex voltammetric contours were deconvoluted for obtaining each anodic
stripping peak.
The voltammogram simulations for Ni anodic stripping data in the different
systems are depicted in Figs 5(a)-(d). Values of k,“’ (formal electrochemical rate
constant for each voltammetric peak) together with the simulated peak potential and
current are assembled in Table 3.

15

1c

“E
3
z 5
::
:

15

10

0
0.0 0.4 0.8 1 2 0.0 0.4 0.8 1.2
Potential/V

Fig. 5. Simulation and deconvolution of the anodic stripping voltammograms for the
systems: (a) Ni/H$SO.,; (b) Ni/(CO,,,) HzS04; (c) Ni/(ET,,,) H$Od; (d) Ni/(AC,,,) HzSO+
Full lines represent the global voltammetric profile and dotted lines the single voltammetric
profiles.
 Ni corrosion in HzS04 solutions 1925

Table 3. Parameters used for the simulation of the anodic

stripping voltammograms

Peak I k,“’
Denomination (x IO’A) (cm s-‘)

A = Ni/H$Od
Peak A, 0.22 9.72 5.7 x to-2
Peak A> 0.43 1.30 1.2 x 10-4

B =Ni/(CO,,,) HsS04
Peak Br 0.27 0.38 5.0 x 10-s
Peak B2 0.51 14.30 8.3 x 10.’
Peak B3 0.58 0.73 3.1 x 10-s

C =Ni/(ET,,J HsS04
Peak Cr 0.25 9.06 4.5 x 10-s
Peak Cl 0.38 1.26 7.0 x 10-7
Peak C3 0.49 4.66 1.4 x 10-7

D za Ni/(AC,,,) H$?.04
Peak Dr 0.75 3.22 1.o x lo-‘0
Peak D2 0.76 2.72 2.9 x lo-”

DISCUSSION

An outline for the adsorption processes

Let us examine the possible processes associated with the adsorption of new M-
species from solution on the Ni surface, which has been firstly modified by an
adsorbed L-residue, being M the inhibitor adsorbate and L an OH or Hz0 species.
Then, Ni(L)Bd and Ni(M),d can coexist on the Ni surface.
For such a situation, two different main cases can be considered.
(i) The interaction between Ni(L),d and M involves the total displacement of (L),d
by M, by an adsorption reaction such as:

.v_Nn_(L)ad + XMM * XdNiYrdMhd + XLL (1)

where: xL and xM are the number of adsorbate ensembles for [Ni(L),d and [Ni(M),J
and ye and yM are the coordination numbers to the metal for L and M, respectively,
being XL,JJL= XMVI~M.
A complete displacement in reaction (1) to form [NiyM(M),d] implies that the
adsorption free energy of [NiYL(L)ad] is much smaller than that of [NiyM(M)ad],
leading in the limiting situation to a single [NiYM(M)ad] domain on the electrode
surface. In this case, only lateral interactions among [NiyM (M)ad ] would be
significant.
(ii) the electro-adsorption and interaction energies of both [NiYL(L)J and
[NiyM(M)ad] are not substantially different, a partial chemical displacement of (L)ad
by M occurs;

n_NYdLLdl + XMM * x~[WdLM + m[NiYdM),~l + (XL - X& (2)

where: x’~ is the number of residual patches for L-adsorbates and xoL =x’~
ye + XMVI~M, being x’L < XL. Accordingly, different adsorbates can co-exist on the Ni
1926 C.F. Zinola and A.M. Castro Luna

surface. As a limiting situation, when (L)ad and (M)ad are homogeneously distributed
on the electrode surface, the characteristics of each constituent can be maintained,
except the overall charge transferred in the electrochemical desorption reaction. Then,
the anodic stripping voltammogram would involve a complexity of current peaks with
a distortion in the shape arising from dilution effects and changes in lateral interaction
parameters.

Comparison of the preceding analysis with experimental results

The NijO.5 M HJSO~ system. In the absence of inhibition, Ni anodic processes in
aqueous 0.5 M H2S04 have been described in terms of three main contributions within
the potential range of the active to passive transition; namely, the electrodissolution of
Ni yielding soluble species, Ni(OH)2 formation, which constitutes the precursor of the
anodic layer, and the chemical dissolution of itself.15-19
The voltammetric profile of the Ni/H$04 interface is deconvoluted in two peaks,
namely Ai and AZ (Fig. 5(a)).
Ai can be put forward as follows:‘9

[Ni(H20)J + [Ni(OH),,] + I-I+ + e; (3)

[Ni(OH),J + [Ni(OH&] + e; (4)

[Ni(OH&] + H+ + Ni2+ + H20; (5)

[Ni(OH)LJ + Hz0 =+ Ni(OH), + H+; (6)

Ni(OH), + 2H+ j Ni2+ + 2H20; (7)

and A2 as:

WOH), + Hz0 =+ Ni(OH), . H20; (8)

Ni(OH),.HzO =+- 3[Ni(OH),,] + H+ + e; (9)

3[Ni(OH),,] =$ [2Ni(OH&] + e; (10)

[2Ni(OH),, Ni(OH)zJ + H+ + Ni(OH), + Ni2+ + H20. (11)

The preceding reactions justify the detection of soluble Ni by AAS.
Ni(OH)2 species causes the early stages of the overall pasivation process associated
to an almost constant current observed after 0.6 V beyond 1.O V. The latter process
competes with the chemical dissolution of Ni(OH)z, also yielding soluble Ni.
The presence of foreign substances on the metal surface produces a remarkable
effect on the Ni electrodissolution rate. The influence of those substances can be
formally treated by the multiple adsorption interaction model already described in the
section above.

Adsorption ofC0
The first step in the bonding of the CO molecule with a Ni surface atom proceeds
 Ni corrosion in HIS04 solutions 1927

by donation of the lone pair of electrons from the carbon atom into vacant d-orbitals
of the metal. The electrodonation power of CO is small and a back-donation of
electrons from filled d-orbitals of the metal into vacant n*-antibonding-orbitals on CO
is envisaged. ’ 3p15
According to our results (Fig. 2) the abrupt decrease in the height of peak I
indicates that Ni electrodissolution is inhibited by the presence of CO-adsorbates. The
amount of soluble Ni species determined by AAS decreases in the presence of CO
(Table 2). These results confirm the inhibiting effects of CO on Ni in aqueous
0.5 M HzS04, previously deduced from anodic stripping voltammetric data. The
shape of the CO-adsorbate electro-oxidation peak becomes almost independent on
Ead, and qOx also becomes potential-independent below the Erest of the Ni/(CO,,,)
H2S04 system. CO adsorption on Ni electrodes approaches the conditions discussed
above. The whole CO-adsorption process would firstly imply the interaction of CO
with [Ni(HZO)J as follows:
CO + 2[Ni(H#)J + [Ni(CO),,I + [Ni(I%O),J + H20. (12)
The [Ni(H20)J domains can be further electro-oxidized as shown in equations
(4)-(11) and the stripping for CO-adsorbates would be according to:4
[Ni(CO),,] + 2H20 + CO + Ni(OH), + 2H+ + 2e. (13)
In this case, the simulation of the anodic CO-stripping voltammogram (Fig. 5(b))
comprises three current contributions. The first one, denoted as B1 in Table 2, exhibits
a peak potential and kt”’ value (5 x lop2 cm s-‘) similar to Al in the Ni/H2S04 system.
Since peak A1 is related to the simultaneous Ni electrodissolution and Ni hydroxy-
species formation, B1 can be also identified with these processes. This fact confirms
that CO-adsorption on Ni, under saturation conditions, leaves some [Ni(H20).J
domains on the surface.4
On the other hand, B2 changes its potential and current peak values with CO
coverage, therefore, Bz could be assigned to the CO electrodesorption process. B3 is
related to the Ni(OH)2 formation and dissolution represented by A2 for the Ni/H2S04
system, though lateral interactions between the adsorbed species modified the
potential peak and klo’ values.

Adsorption of ET
Ethylene firstly interacts with the Ni surface through a n-orbital bond, which
involves a charge donation from an ethylene molecule to Ni d-orbitals and sometimes
a charge back-donation into the ethylene n*-orbitals.20
Considering that ethylene adsorbs molecularly on Ni and in agreement with
potentiostatic current transients, it can be assumed that ethylene electro-adsorption at
Ni electrodes also involves a non-disruptive process. Then, it is quite likely that ET-
adsorbates would approach a close packed arrangement of undissociated ethylene
molecules.
ET-adsorption on Ni reveals low inhibitory effects, since there are small changes in
the voltammetric Ni profiles with respect to that in plain electrolyte (Fig. 3).
The deconvolution of the anodic ET-stripping voltammogram (Fig. 5(c)) shows
three primary current peaks: namely C1, C2 and C3. C1 has a peak potential value of
0.25V(Table3)andk;‘is4.5~ 10-2cms-‘, very close to that of Al. Then, C1 can be
1928 CF. Zinola and A.M. Castro Luna

related to the Ni electrodissolution and Ni(OH)I formation. On the other hand, CZ

should be related to the Ni(OH)2 electrodissolution and NiO formation, though there
is a shift in k,” due to lateral interactions between adsorbed species, which make
difficult the electrochemical desorption process. Peak Cs at ca 0.5 V is attributed to an
organic residue oxidation derived from the ET-adsorption, as its peak parameters are
strongly modified by changes in ET concentration.
The ET-residue adsorption and Ni electro-oxidation can be tentatively put
forward as follows:

C2H4 + 4[Ni(HKVadl+ [NW2HdaJ + 2tWWh,~l + 2J-W (14)

and equations (3~( 11) for Ni electro-oxidation.

The ET-adsorbate electro-oxidation on metal surfaces different to Pt*’ yields
incomplete oxidated products, as could be the case on Ni electrodes.
The voltammetric characteristics of the Ni/(ET sat.) H2SO4 system are consistent
with the assumption that the structure of the composed adsorbate involves at least two
different domains, i.e., [Ni(HZO)ad] and [Ni2(C2H4),d].
A greater number of patches free of inhibitor results from ET-adsorption than
from CO-adsorption, indicating a larger inhibitory effect for CO-adsorption. This
effect can be observed in the anodic voltammetric profiles.
The ET-adsorption process on Ni electrodes is another example of the partial
displacement adsorption mechanism proposed above.

Adsorption of AC
There are many plausible structures for metal-alkynes complexes, some of them
consistent with the Dewar-Chatt-Duncanson scheme of bonding.
The low qOx value found for AC-electrodesorption reveals a strong inhibitory effect
caused by AC-residues. This effect produces a remarkable anodic shift in the Erest of
the Ni/(AC sat.) H2S04 system and small amounts of Ni soluble species. Then there is
an agreement between these data and the conclusions derived from gas phase
studies.22,23
The simulation of the anodic stripping AC-voltammetric profile shows two main
current peaks (D, and D2) at ca 0.75 V, that can be assigned to the AC-residue electro-
oxidation (Di) and Ni(OH)2 formation and electrodissolution (Dz). It should be
noted, however, that as Ni AC-free domains are produced at larger potentials than in
plain electrolyte, DZ is positively shifted.
For the AC-adsorbates a total replacement of [Ni(HZO)J by [Ni2(AC),,J can be
envisaged (case i). At the begining of the anodic stripping sweep a single [Ni2(AC),J
domain exists, yielding a strong inhibition of the Ni electrodissolution reaction. The
corresponding AC-adsorption would be:

2WiU-b0),~1+Cd32 =+N2(Cd-&l+ 2I-N (15)

and the stripping of AC-adsorbate would yield either partial or total oxidated
products.
The Ni organic free adsorbate sites from the adsorption of CO, ET and AC that
suffer an electro-oxidation process, agree with the experimental inhibition order found
according to the Ni2+ amount determined by AAS.
 Ni corrosion in HaSO solutions 1929

CONCLUSIONS
1. The Ni electrodissolution and passivation processes can be substantially
changed by the adsorption of carbon monoxide, ethylene or acetylene in acid
solutions.
2. The greatest inhibition of the Ni electrodissolution process in acid media is
caused by acetylene.
3. The simulation and deconvolution of the anodic stripping voltammograms were
useful to envisage the likely adsorption processes for the organic species.

AcknoIl,kngements-This work was financially supported by the Consejo National de Investigaciones

Cientificas y Tecnicas (CONICET) of Argentina. A.M.C.L. is a member of the research career at the
Comision de Investigaciones Cientificas de la Provincia de Bs. As. (CIC).
C.F.Z thanks CONICET and the Programa de Desarrollo de Ciencias Basicas y Aplicadas
(PEDECIBA). The authors are indebted to Mr A. Iasi of Cidepint for the AAS analysis.

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