Corrosion Science 46 (2004) 16131620 www.elsevier.

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Adsorption characteristics of corrosion inhibitors from corrosion rate measurements

M. Christov *, A. Popova
Department of Physical Chemistry, University of Chemical Technology and Metallurgy, Bul. Sv. Kl. Okhridski 8, Soa 1756, Bulgaria Received 14 May 2002; accepted 9 October 2003 Available online 29 November 2003

Abstract Corrosion rate data have been used for the determination of the adsorption parameters of the Frumkin isotherm in the system steel/acid solution/inhibitor. The inhibitors are derivatives of benzimidazole. The maximal amount of adsorbed inhibitor, the interaction parameter a and the equilibrium constant B of the isotherm are found simultaneously by using the SOLVER option of Excel. The statistical analysis of the results shows that this isotherm describes well the adsorption behaviour in the systems studied. 2003 Elsevier Ltd. All rights reserved.
Keywords: Corrosion inhibition; Benzimidazoles; Adsorption; Frumkin isotherm

1. Introduction The use of corrosion inhibitors increases continually [13]. The mechanism of their action can be dierent, depending on the metal, the medium and the structure of the inhibitor. One possible mechanism is the adsorption of the inhibitor, which blocks the metal surface and thus do not permit the corrosion process to take place. If only this mechanism is considered to be responsible for the inhibition eect, it would be possible to construct the adsorption isotherm using corrosion rate data. On the other hand a reasonable isotherm could be considered as an indirect proof for the adsorption mechanism of inhibition.

Corresponding author. Tel.: +359-2-6254282; fax: +359-2-687543. E-mail address: chr@uctm.edu (M. Christov).

0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2003.10.013

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Dierent adsorption isotherms were found to describe the adsorption of inhibitors on steel: Langmuir [413], Temkin [1417], Frumkin [9,1820], Flory Huggins [2123], DharFloryHuggins and BockrisSwinkels [22], Freundlich [24,25]. We have chosen to try if the Frumkin isotherm can describe the adsorption behaviour of benzimidazole derivatives on steel, because the Langmuir can be considered as a limiting case of the Frumkin isotherm (with an interaction parameter equal to zero). The FloryHuggins isotherm has a more complicated form and should be used, if there is evidence that several water molecules are displaced by the adsorbed organic species. The aim of this paper is to test a non-linear optimisation procedure for determining the parameters of the Frumkin isotherm using corrosion rate data.

2. Description of the method The well known Frumkin adsorption isotherm can be written in the form: h B c e2ah ; 1h 1

where h is the coverage degree, cthe concentration of the adsorbate, B has the meaning of an equilibrium constant, and a is an interaction parameter, taking into account the attraction (a > 0) or repulsion (a < 0) between the adsorbed species. For a 0 (no interaction) this isotherm becomes equivalent to the Langmuir isotherm. In literature there are dierent methods for determining the parameters B and a. One of them is based on linearisation of the isotherm in the form lnh=1 hc f h [26]. The logarithmic term is very sensitive to inaccuracy in determining h at very low and very high coverage degrees. One other method [27] uses the concentration, at which h 0:5. It has the disadvantage of using an interpolation value for all calculations. A computer program has been applied [28] for determination of the adsorption parameters, nding the minimum of the residual sum of squares. In all these cases the maximum amount of adsorbed species has to be found in advance. To use them the knowledge of h is assumed. A complicated iterative method has been used to determine a, B and the maximum coverage [29,30]. Our aim is to propose a very simple method for the simultaneous determination of all the three parameters a, B and maximum coverage. The coverage degree is usually dened as h Nocc q ; Ntot qmax 2

Nocc being the number of occupied and Ntot the total number of the adsorption sites. q and qmax are the corresponding amounts of adsorbed species. If every adsorbed molecule occupies only one adsorption site, then qmax would be proportional to Ntot . For larger molecules this assumption cannot be valid. In this case only a

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Fig. 1. Schematic presentation of the metal surface.

fraction c of the total surface can be covered by adsorbed species, the rest (1 c) being accessible for adsorption of smaller molecules, or, in the case of a metal in an aggressive medium, the corrosion process can take place on this fraction of the surface. A similar approach was used by Bagotskii [31] for the determination of the adsorption of organic molecules on platinum. Fig. 1 shows a schematic presentation of the metal surface. The hatched area corresponds to the covered fraction of the surface. qmax is the maximal coverage, which can be achieved by the large adsorbed species, while q0max the maximal coverage, attained by smaller species and proportional to the total surface area. So in the absence of an inhibitor the corrosion rate wo (or corrosion current density jo ) will be proportional to the total surface. In its presence the corrosion process can take place with a corrosion rate w (or corrosion current density j) on the whole noncovered surface, proportional to q0max q. It follows that two types of denition can be postulated for the coverage degree the one based on the total surface h0 q=q0max and another oneon the surface fraction which corresponds to the maximum amount of adsorbed molecules h q=qmax . h0 can be easily obtained from corrosion rate measurements, as it is closely related to the eciency of the inhibitor and can have values between 0 (no inhibition) and c (maximal possible protection for a given inhibitor), while h can reach a maximal value of 1: h0 jo j c h: jo 3

There are three parameters to be determined: c, a and B. In all optimisation procedures it is very important to start with good estimates of the parameters. We preferred to present the experimental data as h0 vs. log c, because normally the concentration is varied on a logarithmic scale. For the rst derivative one nds: oh0 2:303c : o logc h0 =c1 h0 =c1 2a 4

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Fig. 2. Determination of the parameters a, c and B, used as rst estimates in the optimisation.

For h0 c=2, from Eqs. (1) and (4): ! oh0 2:303c ; log B log ch0 c=2 a=2:303: 4 2a o logc 0
h c=2

Fig. 2 shows a typical isotherm, represented as h0 vs. log c. Its form is S-shaped, tending to zero at very low concentrations and to the value of c at the highest concentrations. An inection is observed at h0 c=2, where the slope reaches its maximal value. For medium coverage degrees the isotherm looks almost like a straight line (there is therefore very dicult to distinguish between Temkin and Frumkin isotherm). Its slope at h0 c=2 equals 2:303c=4 2a and enables the estimation of a. It should be noted, that for a > 2 a negative slope is expected, which corresponds to a hysteresis in the experimental isotherm. Finally, the value of B can be obtained from the concentration, at which h0 c=2. We used the SOLVER option of Excel to nd the parameters, using as a criterion the least squares. The main dierence between this method and the optimisation procedure of Damaskin [28] consists in including c as a parameter and the use of Excel rather than writing a special computer program. To calculate h for a given concentration the Newtons method was used as this is one of the fastest methods for nding zeros of functions when the initial guess is fairly close to the answer. The curve (in our case this is the function f h h=1 h Bc exp2ah) is approximated by the straight line tangent to the curve at the current point hi (guess of the ith iteration). If f 0 hi is the slope of the curve at the point hi (it is the rst derivative of f h), then the approximation is given by f hi1  f hi f 0 hi hi1 hi . The zero of the approximation f hi1 0 is computed to get the Newton formula hi1 hi f hi =f 0 hi . The calculations started for the lowest concentration and as initial guess the value of h0 105 was taken. For the next (higher) concentration the result of the previous calculation was taken as the starting value. Normally 45 iterations are sucient to calculate h for which (f h < 106 and jhi1 hi j < 104 ). Then the residual sum squares P h0exp;I h0calc;i2 was minimised using the SOLVER option by changing simultaneously all three parameters c, a and log B, h0calc;i being determined according to Eq. (3).

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3. Experimental The corrosion rate of mild steel in 1 M HCl was determined gravimetrically in pure acid solutions and in the presence of inhibitors. The mild steel used had the following chemical composition (wt%): C0.16; Mn0.35; Si0.016; P0.01; S 0.029; Cr0.06; Cu0.010; Febalance. Following inhibitors were used: benzimidazole (BI), 2-mercaprobenzimidazole (2SHBI), 5(6)-carboxybenzimidazole (COOHBI) and 2-pyridylbenzimidazole (2-PyrBI). The solution concentrations varied from 106 to 0.03 M. The preparation of the samples included pickling in a concentrated HNO3 + H2 SO4 solution at the volume ratio 2:1, washing in warm water and drying. For weighing a Sartorius analytic balance of precision 0.1 mg was used. In order to prevent the formation of saturated solutions of the corrosion products, beakers, containing 250 ml of the examined solutions were used. Three samples were immersed in each beaker. The samples with a total area of 11.3 cm2 had a round shape to avoid eects of the edges where the corrosion rates are higher. Minimum 9 samples were used to determine the mean corrosion rate in each solution. The inhibitor action of the compounds was studied at the denite time interval of 24 h at room temperature (20 1 C) without stirring and at free air access. The uniform corrosion observed on the samples surface enables the calculation of the inhibitor eciency (IE) according to the following relation: IE wo w ; wo 6

where wo (g m2 h1 ) is the average corrosion rate in the rst 24 h without inhibitor and win the solution of the inhibitor. The standard deviations of w were less than 2%. A more detailed description of the experiments is given elsewhere [32]. As the corrosion rates are proportional to the corrosion currents, the inhibitor eciency coincides with the coverage degree h0 dened by Eq. (3).

4. Results and discussion To check the applicability of the proposed method, four inhibitors among a greater numbers of inhibitors investigated at our laboratory were chosen [32,33], having dierent values of the attraction parameter a. As a guide-line for this choice served the slope of the experimental curves inhibitor eciencylog c according to Eq. (4) at values of IE close to 0.5. In Fig. 3 are presented the experimental results (points), compared with the curves calculated as described in the previous section. The values of the parameters derived are summarized in Table 1. Two of the inhibitors (BI and 2SHBI) have negative values of a, COOHBI shows a quasiLangmuir behaviour (a is very close to zero), while the value of a for 2PyrBI is very close to the critical value of +2.

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Fig. 3. Comparison of the experimental coverage degrees h0 vs. log c (points) with the Frumkin isotherms, calculated with the parameters of Table 1 (lines). Table 1 Adsorption parameters (Frumkin isotherm) and statistical data for the adsorption of benzimidazoles on steel in 1 M HCl BI c B log B a Number of points, n Mean residue Standard deviation Condence interval DW R=s 0.907 2.46 102 2.390 )0.68 6 7.08 103 2.14 102 1.71 102 2.16 2.3 < 2.8 < 3.0 2SHBI 0.950 3.00 104 4.477 )1.85 8 )2.20 103 1.64 102 1.14 102 2.34 2.5 < 3.0 < 3.4 COOHBI 0.940 1.80 103 3.255 )0.05 9 )6.11 103 1.84 102 1.20 102 2.15 2.6 < 3.0 < 3.5 2PyrBI 0.937 1.51 106 6.179 1.73 10 0.70 103 1.91 102 1.18 102 2.12 2.6 < 3.5 < 3.6

It is seen that in all cases the experiments are described well by the Frumkin isotherm. Some additional statistical tests were performed in order to prove the reliability of the model. 4.1. Residual analysis The residuals, dened as the dierence between the experimental and the computed coverage degree at a given concentration, ei h0exp h0calc , were calculated for all substances. The average values, the standard deviations and the condence intervals (at a condence level of 95%) are presented in Table 1. If the model is adequate, the average values should equal zero. In all cases the condence intervals (less than 0.02) are greater than the average values, which is an indication that the zero hypothesis Ho (mean residual 0) cannot be rejected at a signicance level of 0.05.

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Fig. 4. Random distribution of the residuals.

Fig. 4 shows the residuals as a function of the experimental values of the coverage degree. It is a good illustration of a stochastic distribution and no tendency can be observed. None of the residuals is greater than the estimated experimental error of 0.05). To test the auto-correlation, the DurbinWatson-coecient [34] was calculated: P 2 ei ei1 P 2 DW : 7 ei All values of DW are very close to 2 (Table 1). A great deviation from this value should indicate an inappropriate choice of the mathematical model. To test the normal distribution of the residuals, the test of David et al. [35] was applied. The test quantity is R=s, where R is the dierence between the maximal and minimal value and sthe standard deviation of the residuals. It is compared with two critical valuesa lower and an upper one, which depend on the number of the experimental points and the chosen signicance level. The hypothesis of normal distribution is rejected, when the test value lies out of this range. In Table 1 are shown the results for this test for a signicance level of 0.05. As all test quantities lie between the two critical values, the normal distribution of the residuals cannot be rejected.

5. Conclusions It has been shown that corrosion rate data can be used for determination of adsorption parameters, if the inhibition mechanism consists in blocking of the metal surface by the adsorbed inhibitor. The presentation of the adsorption results as adsorbed quantity h0 vs. log c have some advantages in comparison to the most common presentations h0 vs. c or different linearised forms of the Frumkin isotherm. It enables a good estimation of the

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adsorption parameters c (or qmax ), B and a, which can be easily used as rst approximations in the SOLVER option of Excel. This procedure provides simultaneously the values of these parameters and a good t of the calculated isotherm to the experimental data. The statistical analysis shows that the residuals are normally distributed without auto-correlation to the coverage degrees, having a mean value of zero within the range of the condence interval. This means that the chosen isotherm describes satisfactorily the inhibiting action of the examined benzimidazoles.

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