Corrosion Science 50 (2008) 34873493

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

Kinetics study of iron dissolution in highly concentrated acidic media using Hammett acidity function
A. Kriaa a,*, N. Hamdi b, K. Jbali b, M. Tzinmann c
a

Ecole Suprieure des Sciences et Techniques de Tunis, 5 Avenue Taha Hussein, 1008 Moneury, Tunis, Tunisia Technopole Borj Cedria, Hammam lif Tunis, BP, Tunisia c Ecole Nationale Suprieure de Chimie de Paris, 11 rue Pierre et Marie Curie, 750005 Paris Cedex, France
b

a r t i c l e

i n f o

a b s t r a c t
This study aimed at establishing a mechanism of iron corrosion, in highly HCl concentrated medium, using Hammett acidity functions instead of conventional pH measurements. Linear relationships between the rate of Armco iron corrosion and the acidity of aqueous HCl media expressed in the form of Hammett acidity H00 , were obtained. At high ionic strength, it was shown by electrochemical analysis, that chloride ions were adsorbed at the metal surface and decreased the corrosion process of iron. A detailed mechanism of iron corrosion involving activity of protons H+ as promoter of the iron dissolution, the inhibiting effect of chloride activity, and activity of water as a kinetics variable parameter. It reveals that this competitive mechanism on the anodic sites, agrees well with experimental kinetic parameters obtained in this study. 2008 Elsevier Ltd. All rights reserved.

Article history: Received 28 May 2008 Accepted 5 September 2008 Available online 13 September 2008 Keywords: B. Hammett acidity functions H00 A. Iron E. Concentrated HCl media D. Mechanism C. Kinetic parameters

1. Introduction As pointed out by different authors [14], a great need of knowledge is required concerning physico-chemical properties of highly acidic aqueous solutions. In these media, where most results have been established, better understanding of the corrosion phenomena should be obtained by characterization of the acid strength of the proton in pure aqueous solution. In highly concentrated acid solutions, where conventional pH determinations are not relevant whatever the solvent is, kinetics and mechanism of iron dissolution using Hammett acidity functions has not been established. In order to relate the present work to previous kinetic studies, it will be useful to briey outline prior work which bears on the present problem. It is generally recognised that there are two main types of dissolution mechanisms for active iron, depending on the nature of the anions. According to some authors [5,6], in the absence of chloride ions and in relative weak acidic solution, the dissolution process is catalysed by OH ions. On the other hand, in presence of chloride ions, there is competitive adsorption between chloride and hydroxyl ions, the chloride will tend to prevail at high chloride activity and low pH [5]. In highly concentrated aqueous solutions, the proton act as promoter for iron dissolution [5,6], giving a positive value of electrochemical reaction order with respect to hydrogen activity
* Corresponding author. Tel./fax: +216 98509983. E-mail address: kriaa1993@yahoo.fr (A. Kriaa). 0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2008.09.004

log ia 1; 2). A positive value of nH+ ensues for synergistic (nH dd log aH adsorption of hydrogen ions on the halide ion covered surface. However, in these concentrated media, the role of Cl ions seems to be different for the anodic dissolution of iron. They can play either the role of accelerators [5,6] or inhibitors [1,7] of the corrosion process. We must emphasis that reaction mechanisms described in the literature have been presented. However, kinetic studies have not been widely studied in more concentrated acidic chloride solution using Hammett acidity function. It is therefore of interest to examine this situation and to determine a mechanism for iron dissolution in agreement with experimental results.

2. Experimental Armco iron species of 1 cm2 area were machined in a chemically inert Kel-F resin and polished with 600 and 1000 grade abrasive papers and then degreased with alcohol and cleaned in an ultrasonic water batch. Potentiostatic polarization was performed using a Tacussel potentiostat, model 352/252, equipped with a Corrosion Analysis Software. Polarization curves were obtained by a potentiodynamic method at 25 C using the saturated calomel electrode (SCE) as the reference electrode. Recording of the current densities started after 30 min of immersion of the samples in oxygen-free acidic solutions to allow stabilization of the corrosion potential, Ecorr. Stirring of the solutions was performed during immersion and during the recording of the polarization curves in order to minimize diffusion effects.

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No pitting corrosion was observed after each run and it is assumed that uniform corrosion is the only process. Electrochemical impedance spectroscopy (EIS) measurements were carried out in order to correct polarization curves for ohmic drop by evaluating the resistance of electrolyte solution, Re. These measurements were made by using a Solartron 1186 Electrochemical Interface and a Solartron 1172 Frequency Response Analyser. The tests were performed at the free corrosion potential of the Armco iron electrodes. The sinusoidal potential perturbation was 5 mV in amplitude with frequencies ranging from 100 kHz to 0.1 Hz. Solutions were prepared from analytical reagent grade HCl and NaCl and doubly distilled water. Two types of solutions were employed in this study: (i) HCl solutions at different ionic strength, having concentrations of 0.5 M up to 9 M and (ii) acidic solutions where the acidity was varied while both the total ionic strength and the chloride ion concentration were held constant. The Cl concentration was xed to 4.8 M by adding NaCl. Based on the protonation equilibrium of neutral bases B in HCl, the H00 scales using anilines as indicator can be dened as follows:

B H <> BH H00 pK BH log

  BH fB log aH B fBH

Fig. 2. polarization curves on iron in deaerated aqueous/HCl solutions.

where fB and fBH+ are the activity coefcients of the corresponding species and aH+ the activity of the proton. 3. Results and discussion The Hammett acidity functions results, obtained spectrophotometrically for HCl concentrated solutions are presented in Fig. 1. For the sake of comparison, we have plotted H00 values, derived from literature [8] for the main mineral acids encountered (HClO4 and H2SO4).The analysis of experimental curves shows that for a given acid concentration, the acidity decreases according to the following order: HClO4 $ H2SO4 > HCl. Polarization curves on iron in water containing HCl up to 9 mol/ l are shown in Fig. 2. Corrosion currents icorr have been obtained from two different methods. Determinations from a nonlinear regression method using a microcomputer [9] are in good agreement with those obtained by classical extrapolation of the cathodic and anodic linear Tafel segments. For the sake of comparison, weight loss experiments were undertaken in 1 N and 3 N HCl aqueous solutions. Assuming at two- electron transfer, calculated values of icorr were respectively, 312 and 552 lA/cm2, which is in rather good agreement with tabulated values in Table 1. 3.1. Analysis of IE curves at different ionic strength of hydrochloric acid solution The resistance of electrolyte, Re was evaluated by electrochemical impedance measurements in order to perform corrections of the polarization curves. The 0.01 X cm2 value obtained is considered as negligible, leading to a minor change in Tafel slope values and in the current corrosion. Moreover, according to some authors ([6], see references therein), the liquid junction potential was estimated to be insignicant for HCl concentration >1 N. The HCl concentration was varied between 0.5 and 9 M. Increasing the HCl concentrations shifted the polarization curves to anodic direction. This means that the rate of anodic reaction is increased by both acidity and Cl ions. For all the HCl concentrations below 3 M, a Tafel slope of approximately ba = 70 mV dec1 was obtained in the vicinity of the corrosion potential. For concentrations higher than 3 M, an increase of the anodic Tafel slope is obtained, indicating that a change in the mechanism of iron dissolution occurs. For [HCl] = 8 M, values of ba are quite high (130140 mV dec1) showing that the dissolution mechanism is not a kinetically simple one. The dependence of the corrosion current icorr on Hammett acidity function is shown in Fig. 3. A linear relationship is obtained for dlogicorr % 0:5. For all the linear regreslog icorr vs. (H00 ) with a slope dH 0 0 sion curves of this study, the evaluation of errors in the slope (b) of the best-t line was determined by Patnaik [10] using 95% for the condence interval. For weak acidic solutions, the reaction order with respect to hydrogen ion concentration for iron dissolution can be determined, without correction of polarization curves, by a plot of log anodic current vs. (H00 ) at a constant potential situated in the Tafel region (Fig. 4).This plot indicates when HCl concentration increases, the

Fig. 1. Evolution of acidity H00 vs. acid concentration of perchloric, sulphuric and hydrochloric acid in pure aqueous solution.

A. Kriaa et al. / Corrosion Science 50 (2008) 34873493 Table 1 Electrochemical parameters for iron dissolution in aqueous HCl HCl (mol l1) 0.1 0.5 1 3 5 6 8 9 H00 0.24 0.21 0.18 1.06 1.75 2.12 2.79 3.16 Ecorr (mV vs. SCE) 542 569 553 542 525 519 490 490 icorr (lA cm2) 151 251 380 501 1660 1738 5129 8913 +ba (mV) 79 68 65 80 120 104 136 172

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bc (mV) 117 119 122 130 130 130 130 127

Ecorr: Corrosion potential. icorr: Corrosion current extrapolated from anodic and cathodic segments. ba: Anodic slope (mV dec1). bc: Cathodic slope (mV dec1).

Table 2 Water activity of different HCl concentrations HCl (mol l1) 0.5 1 3 6 8 9 m (mol/kg) 0.43 0.87 2.78 6.18 8.90 10.44 log aH2O 0.0066 0.014 0.058 0.179 0.327 0.41 aH2 O a 0.985 0.968 0.875 0.662 0.471 0.385

a The water activity values were calculated from osmotic coefcient values of HCl solutions, published in the literature [12], for a given molality.

Fig. 3. Evolution of the logarithm of the corrosion rates vs. H00 in water-HCl solutions, at different ionic strengths (R2 is the correlation coefcient).

Table 3 Effect of NaCl addition on current corrosion HCl (mol l1) 3 3 5 5 8 8 NaCl (mol l1) 0 1 0 1 0 1 Ecorr (mV vs. SCE) 544 525 500 482 500 480 icorr (lA cm2) 501 400 1660 759 5129 2400 ba (mV) 78 76 110 95 130 110

Fig. 4. Evolution of the logarithm of anodic current densities vs.H00 , for iron dissolution, Ea = 470 mV.

logarithm of anodic current dissolution is stabilized. At low concentrations (HCl concentrations 63 M) the initial anodic slope value tends to 0.8. If we assume that activity of H+ is assimilated to concentration of the same species, the data would yield a reaction order with respect to the hydrogen ion concentration of 0.8, which is close to the values reported by other workers for the same system [6,7]. When HCl concentration is P3 M, the stabilization of the logarithm of anodic current dissolution may be due to change of water activity and the effect of chlorides in these media. It is well known that water activity decreases when the HCl concentration increases (Table 2). Accordingly, one can assume that this stabilization of anodic current is due to a decreasing of water activity that will decrease rates of corrosion process [11]. This seems to be contradictory with most kinetic studies of iron corrosion that presume an accelerating effect of water on dissolution process. Another factor that can be taken into account is the activity of chlorides. A previous work in this laboratory has shown that the chlorides have an inhibiting effect for iron dissolution, in these highly acidic solutions [1]. The results are summarized in Table 3.

The reaction order with respect to chloride ion activity for iron dissolution can be obtained either by plotting the correlation (log ia + g log aCl) vs. (H00 ) or by maintaining the acidity constant at varying NaCl concentrations [5,6]. In our study, a good linear relationship is obtained, corresponding to g = 1 (see Fig. 5) with a correlation coefcient R2 = 0.99. In this case the reaction order with respect to activity of chloride is $0.8 which is close to 1. We must emphasize that no data exist in literature for the activity values of anions in concentrated acidic media. In our study, the activity of Cl are based on activity coefcients (ci) taken from Harmer and Wu [12]. The activity of HCl aHCl is given by aHCl = a+ a = a2. As usual, ai = ci mi, where ci is the molal activity coefcient. Denition of the mean molal activity coefcient as c2 = c+ c gives a = c mHCl In order to recapitulate, we envisage the following effects that govern iron corrosion (i) a promoting effect of H+ ions in agreement with other ndings [6,13], (ii) The effects of changes in water activity on the electrochemical behaviour of iron, and (iii) an inhibiting effect of chloride ion activity for iron dissolution in highly concentrated HCl solutions. The anodic current density can be written under the form:

ia kF

d aa H2 O aH

ag Cl

  Ea exp 2:3 ba

RT with ba a ; where k is the rate constant, F the Faraday number, Ea nF the anodic electrode potential, n the number of electrons transferred and a transfer coefcient.

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Fig. 5. Plot of log ialog aCl vs. H00 for iron dissolution, at different HCl concentrations.

Fig. 6. Plots of log iaa log aH2O vs. (H00 ) in concentrated acidic chloride media.

With an additional hypothesis, that at vicinity of Ecorr, the global process has to be assumed as under anodic control, the current corrosion can also be expressed by

icorr kF

d aa H2 O aH

ag Cl

  Ecorr exp 2:3 ba

In order to facilitate a graphical exploitation of the results, Eq. (1) can be written as follows:

kinetic parameters. Moreover, the experimental procedures for preparing the iron electrodes used by some investigators [5,6,11], have presumably a direct effect on the electrochemical reaction orders values of iron dissolution. The fact that iron electrodes were annealed at 700 C or 800 C in vacuum for 12 h, rehomogenize the metal structure by minimizing for example dislocations and structure defects. 3.2. Analysis of polarization curves at constant ionic strength To complete these results, we have performed a similar study for constant chloride solutions (xNaCl + yHCl; [Cl] = 4.8 M) in order to determine the electrochemical reaction order with respect to protons. In this set of experiments, we can notice that ionic strength was kept constant by adding corresponding NaCl and we can assume that water activity is constant because the activity coefcients depend of ionic strength. This view point has been veried by Mc Cafferty and Hackerman [5] for 6 N chloride solutions. Firstly, we have characterized the acidity of these solutions by measuring the Hammett acidity function of these acidic solutions with [Cl] = 4.8 M. The results are summarized in Table 4. Fig. 7. shows anodic and cathodic polarization curves for iron in 4.8 M chloride solutions of varying hydrogen ion concentration. The main results are listed in Table 5. In general, we can notice that the anodic Tafel slopes values ba are increased comparatively to solutions without NaCl addition. This phenomenon has been reported in other ndings [1,5] where the ba values are higher than 100 mV dec1. On the other hand, the cathodic Tafel slopes-Ecorr values bc are nearly the theoretical values of bc = 120 mV dec1., in agreement with values obtained in the literature.

log ia Cst d

H00

 d log

fB

fBH

g log aCl

Ea a log aH2 O ba
We have assumed that the ratio (f fB ) is almost constant because BH till now, no experimental method available in the literature allows to determine it. In this case the Hammett acidity function is directly proportional to activity of protons. As consequent, Eq. (1) becomes:

log ia Cst d H00 g log aCl a log aH2 O

Ea ba

On the other hand, it is well known that at high ionic strengths, the activity of water falls below unity. It seems appropriate to consider the inuence of decrease in water activity upon reaction rates in concentrated electrolyte solutions. Since water is known to be one of the reacting species in governing electrochemical mechanisms of corrosion, changes in this variable are rarely considered. In this context, some authors [11,16] show that in sufciently concentrated solutions, the corrosion is strongly decreased by decreasing the water remaining free in the solution. In order to determine the electrochemical reaction order with respect to water, we have plotted the correlation (log iaa log aH2O) vs. H00 for a = 1, 2, 3. The results are presented in Fig. 6 where a better linear relationships are obtained for a ranging between 2 and 3, with a correlation coefcient R2 = 0.99. It should be pointed out, that Smart and Bockris [11], show that the electrochemical reaction order with respect to water is ranging between 1.6 and 2 for iron corrosion. From our experimental results, one can conclude that the reaction order with respect to water is somewhat slightly higher and would be expected to lie between 2 and 3. This result is novel in the eld of metals corrosion and it reveals that adsorption of H2O molecules on such a hydrophilic metal as Armco iron is very substantial. In our previous works [1], we have shown that Armco iron corrosion in concentrated acidic hydro-organic solutions increases with the relative amount of water in the medium. On the other hand, it is well known that the iron mechanism is sensitive to the quality of iron and its surface state and that the presence of imperfections or high or low densities of grain boundaries in the meal structure, involves to a change of iron corrosion mechanism and consequently to its

Table 4 Hammet acidity function H00 values determined spectrophotometrically with anilines as indicators [H+] (mol l1) 0.1 0.2 0.3 0.4 0.5 0.7 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 H00 HCl 0.98 0.6 0.4 0.3 0.21 0.1 0.18 0.46 0.69 0.87 1.06 1.24 1.42 1.6 1.77 1.94 2.12 H00 HCl NaCl 0.58 0.19 0.1 0.21 0.42 0.62 0.77 1 1.17 1.28 1.39 1.47 1.59 1.66

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Fig. 7. Polarization curves of iron in 4.8 M chloride solutions of varying acidity.

Table 5 Electrochemical parameters of iron dissolution in HCl solutions with [Cl] = 4.8 M [HCl] (mol l1) 0.5 1 2 3 4 H00 0.42 0.77 1.17 1.39 1.59 log icorr (lA cm2) 2.99 3.25 3.49 3.78 3.99 Ecorr (mV vs. SCE) 458 456 451 448 444 log ic (lA cm2) 2.6 2.75 3 3.1 3.25 ba (mV dec1) 100 100 130 83 87 bc (mV dec1) 124 125 131 131 137

Fig. 8. log icorr vs. (H00 ) in concentrated chloride medium at [Cl] = 4.8 M.

Fig. 9. Evolution of Ecorr with Hammett acidity function in concentrated chloride medium, [Cl] = 4.8 M.

Due to the dispersion of experimental data, we have chosen to analyse the corrosion currents (log icorr) vs. (H00 ) in order to determine electrochemical reaction order related to H+ for iron corrosion. The plot of logicorr vs. (H00 ) is given in Fig. 8. From our experimental results, a good t of the data is observed for logicorr vs. (H00 ) and the reaction order with respect to H+ can be deduced from the slope of the straight line. It is found as:

d log icorr 0:83 0:1 dH00

This kinetic data is close to unity and this in agreement with the most frequently encountered value for iron electrochemical dissolution in literature. Other kinetic orders, between 0 and 2, have been obtained depending on H+ and Cl concentrations [5,1316]. The evolution of(Ecorr) vs. (H00 ) is illustrated in the Fig. 9. As we can observe, when acidity is increased, the corrosion potential is shifted towards anodic potentials and our results show that a

straight line is obtained with a slope of about 8.0 mV per unity of (H00 ). Similarly, the reaction order with respect to the hydrogen ions for hydrogen evolution is determined from a plot (log ic) vs. (H00 ) at constant potential in the cathodic Tafel region. A linear relationship is obtained between acidity and the parameter log ic. d log ic % 0:7 which is also close to unity. Fig. 10 shows that d H0
0

3.3. Data analysis and interpretation The electrochemical study of acidic HCl solutions at variable ionic strength has conducted us to write the corrosion current density into the form:

log icorr Cst d H00 g logaCl a log aH2 O

Ecorr ba

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[H+], [Cl] are the bulk concentrations of hydrogen and chloride ions respectively This system of Eqs. (1)(4) is described by

d/H 2 k1 1 /H /Cl a H k1 k3 aH2 O /H 0 dt d/ b Cl k2 1 /H /Cl a Cl k2 aH2O /Cl 0 dt

10 11

With /X the fractional coverage surface of FeX ads ; and /H 0. /T = /H + /X % 1. In the steady-state approximation, b dd t Simultaneous solution of Eqs. (8) and (9) then yield
Fig. 10. Reaction order plot with respect to H00 for the hydrogen evolution reaction, Ec = 550 mV.

" # /H k1 aH k2 aH2 O /Cl k2 aCl k1 k3 a2 H2 O

12

On the other hand, at constant ionic strength, the water activity is considered as constant because activity coefcient depends on ionic strength value according to DebyeHuckel theory. Also, during the anodic polarization curves of concentrated chloride media, the chloride activity should be constant at the electrode surface. This hypothesis was already used by some authors [5] and accordingly, we can write Eq. (5) as follow:

With the assumption of complete surface coverage by the anions (/ X ! 1), the rate dissolution [4] is written then according to the expression [11]:

" # k2 aH2 O ia k1 aH 2 2k3 baH2 O 2 F k1 k3 aH2 O k2 k2 aCl

or

13

log icorr Cst d

H00

Ecorr ba

In the plot of logicorr vs. H00 , the slope of the curve obtained is:

" #   k2 aH2 O ia k1 aH FE 2 exp 2k3 baH2 O RT F k2 aCl k1 k3 a2 H2 O

14

d log icorr 1 dEcorr d ba dH00 dH00

The correction produced by the corrosion potential can be estimated by taking an average anodic Tafel slope value ba of 100 mV

With necessary conditions v3 ( v1, the resulting expression for ia is

    ia k2 k1 aH 3 FE 2bk3 aH2 O exp RT F k1 k2 aCl

15

1 dEcorr % 8=100 % 0:08 mV=unity of H00 ba dH00

icorr Finally, ddlog % 0:83 0:08 % 0:75 which close to unity. The H0 0 following mechanism is proposed for iron dissolution in deaerated medium:

The Eq. (15) that takes into account the kinetic parameters found in this study, must be modied by introducing Hammett acidity function

h0 a H

fB fBH

The nal equation of anodic current can be written as

FeH2 O H FeH3 O ads

k1

k1

3 4 5 6

ia

FeH2 O Cl

k2

k2

FeClads RDS 3

H2 O

FeH3 O ads 2H2 O ! FeOH 2H3 O 2e FeOH H ! Fe2 H2 O

k4

  k0 h0 FE a3 exp H2 O RT aCl   k2 k1 fBH With k0 2bFk3 k1 k2 fB

Under logarithmic form, the Eq. (16) becomes

16 17

From this reaction scheme, it can be seen that the rate of iron dissolution reaction should increase with increasing H2O in the solution. The formal rate expression for the above sequence is derived as follows. The anodic current density is

log ia log k0 log aCl H00 3 log aH2 O

Or by rearranging Eq. (18)

FE 2:; 3RT

18

log ia log aCl 3 log aH2 O

 log k0

 FE H00 2:; 3RT

19

ia 2Fk3 ba2 H2 O /H F

4. Conclusion This study has established that Hammett acidity function, namely H00 is a correct measurement of the acid strength of the proton in aqueous HCl solutions. This function is particularly suitable in highly acidic solutions as compared to conventional pH values or aHCl in these media. Linear relationships were obtained between the acidity and the parameters log icorr, log ic, log ia a logH2O and log ia + g log Cl for iron concentrated HCl solutions. These relationships agree well with experimental results. A detailed mechanism has been proposed involving Hammett acidity functions and water activities in the electrode kinetics mechanism. These considerations are novel in the eld of corrosion, giving better understanding of iron corrosion process. At high [H+] and [Cl-]

Where /H is the fractional surface coverage of adsorbed Fe(H3O+)ads, aH2O is the water activity, b is a proportionality constant proposed by Kelly [17] and ki is the electro-chemical rate constant dened as

  azF ki ki exp E RT

With E the electrode potential, n the number of electrons transferred, a the transfer coefcient, and the plus and minus signs refer to the anodic and cathodic processes, respectively. The concentrations of chemical adsorbed species at the iron surface (mol/cm2) are represented by

H ads b/H

and Cl ads b/Cl

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concentrations, iron dissolution is promoted by hydrogen ions rather than by hydroxyl ions but is decreased by the inhibiting role of halide ions. Our results show that in sufciently concentrated solutions, the corrosion is strongly increased by increasing the water remaining free in the solution. References
[1] [2] [3] [4] [5] M. Tzinmann, A. Kiaa, C. Fiaud, Electrochim. Acta 32 (6) (1987) 887890. E. Heitz, Adv. Corros. Sci. Technol. 4 (1975) 149. C.A. Farina, G. Faita, F. Olivani, Corros. Sci. 18 (1978) 465. P.L. De Anna, Corros. Sci. 25 (1985) 43. E. Mc cafferty, N. Hackerman, J. Electrochem. Soc. Electrochem. Sci. Technol. 119 (8) (1972) 9991009. [6] R.J. Chin, K. Nobe, J. Electrochem. Soc.:Electrochem. Sci. Technol. 119 (11) (1972) 14571460.

[7] W.J. Lorenz, H. Yamaoka, H. Fisher, Ber. Bunsenges. Phys. Chem. 67 (1963) 932. [8] F. Coussement, M. Helin, B. Torck (Eds.), Les fonctions dacidit et leurs utilisations en catalyse acido-basique, Gordon and Breach, 1969. [9] N.D. Greene, R.H. Ganghi, Mat. Perf. 21 (1982) 34. [10] P. Patnaik, Deans analytical chemistry handbook, second ed., McGraw-Hill Companies Inc., 1995 (copyright 2004). [11] N.G. Smart, J.OM. Bockris, Corrosion 48 (4) (1992). [12] W.J. Harmer, Y.C. Wu, J. Phys. 1 (4) (1972) 10471099 (Chemical reference data reprints). [13] N.A. Darwish, F. Hilbert, W.J. Lorenz, H. Rosswag, Electrochim. Acta 18 (1973) 421. [14] L.P. Mack, K. Nobe, Corrosion 40 (1984) 215. [15] A. Atkinson, A. Marshall, Corros. Sci. 18 (1978) 427. [16] N.G. Smart, M. Gamboa-Aldeco, J.OM. Bockris, Corros. Sci. 34 (5) (1993) 759 777. [17] E.J. Kelly, J. Electrochem. Soc. 112 (1965) 124.