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Thin Solid Films 516 (2008) 1020 – 1024 www.elsevier.com/locate/tsf

Experimental and theoretical elucidation on the inhibition mechanism of 1-methyl-5-mercapto-1,2,3,4-tetrazole self-assembled films on corrosion of iron in 0.5 M H2SO4 Solutions
Hongfang Ma ⁎, Tao Song, Hua Sun, Xiao Li
Department of materials, Shandong Jianzhu University, Jinan 250101, PR China Received 19 June 2006; received in revised form 15 June 2007; accepted 30 June 2007 Available online 13 July 2007

Abstract The self-assembled films of 1-methyl-5-mercapto-1,2,3,4-tetrazole (MMT) were prepared on the iron surface. By means of electrochemical impedance spectroscopy in 0.5 M H2SO4 solutions, the inhibition ability of the film was investigated. Results were discussed through changing the concentrations of the inhibitor and the pH values of the self-assembly solutions. Quantum chemical calculation was applied to elucidate the adsorption mechanism of the inhibitor molecule to iron atom. The study shows that MMT is a good inhibitor for iron in 0.5 M H2SO4 solutions. The self-assembled films formed in 10−2 M acidic solutions have the best protection effect and the inhibition efficiency in 0.5 M H2SO4 solutions is 98.0%. Density functional theory proves that MMT molecule is adsorbed on the iron surface by the most negatively charged nitrogen atom and the adsorption can occur spontaneously. © 2007 Elsevier B.V. All rights reserved.
Keywords: Self-assembled films; Inhibition efficiency; Adsorption mechanism; Quantum chemical calculation

1. Introduction Organic compounds are usually used to protect metal against corrosion as inhibitors in acidic media [1–5]. Heterocyclic compounds containing N and S atoms, such as azoles and their derivatives, have attracted much attention because of the efficient inhibition abilities to the metal [6–8]. Heteroatoms, for example, N and S, usually become the active center. When metal is immersed in the inhibiting solutions, N and S atoms donate lone pair electrons to the unoccupied orbits of the metal atom. Strong and stable bonds are formed between the inhibitor and the metal surface during the self-assembling process. Iron is a widely used metal with extensive applications in industry and the study of its corrosion inhibition has attracted lots of interest [9–11]. But it is difficult to form self-assembled films on the iron surface because of its spontaneous oxidation trend in

⁎ Corresponding author. Tel.: +86 531 86367035; fax: +86 531 886367034. E-mail address: mahongfangsd@yahoo.com.cn (H. Ma). 0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2007.06.225

atmosphere. K. Nozawa et al. [12] used self-assembled films of alkanethiols for corrosion protection to iron. But the application of thiol-compounds is limited due to their toxicity [13]. Ilona Felhösi et al. [13] studied the formation of self-assembled films of alkane monophosphonic acids on the iron surface and explored the protection mechanism. Considering the characteristic of the heteroatoms, 1-methyl-5-mercapto-1,2,3,4-tetrazole (MMT) was used as the inhibitor for iron. Electrochemical impedance spectroscopy (EIS) is often used to study the inhibiting process and to probe the action mechanism [14,15]. Quantum chemical calculation is usually used to study the correlations between the corrosion inhibition and molecular properties of the inhibitor [16–18]. The properties include orbital energies, charge density and combined energies, etc. [19]. The purpose of this study is to determine the inhibition efficiency of MMT self-assembled films to iron with EIS. Ab initio quantum chemical calculation is used to gain insight into the mechanism of the corrosion inhibition. It shows that the selfassembled films formed in 10−2 M acidic solutions have the best

/ Thin Solid Films 516 (2008) 1020–1024 Fig. 1021 .H. Measured Nyquist impedance diagrams for iron electrodes in 0. Ma et al. 1. (b) modified with 10−3 M MMT acidic solution. (c) modified with 10−2 M MMT neutral solution. (d) modified with 10−2 M MMT acidic solution.5 M H2SO4 solutions: (a) modified with 10−3 M MMT neutral solution.

0 96.9 72. .7 79. Results and discussion 3.1.1.7 25.5 M H2SO4 solutions. It was in a separate compartment connected with the main part by a fine Luggin capillary to minimize ohmic resistance.1 63.5 M H2SO4 solutions is 98. EIS measurement EIS experiments were carried out in a three-electrode cell.1022 H. Preparation of the samples and films MMT (A. 2.3. Table 1 Impedance data of iron in 0.5 103.0 693. After rinsed with tridistilled water and absolute ethanol. Measured and fitted Nyquist impedance diagrams for iron electrode in 0.0 61.2 434.8 96.2 1244. The diameter of the capacitive loop is associated with the corrosion resistance of the self-assembled films [21].7 146.6 1848.7 84.8 98.1 267. 2. 2.R.9 90.5 M H2SO4 solutions (electrode modified with 10−2 M MMT acidic solution for 8 hours).9% pure iron rod. And all potential values were referred to the SCE. the electrode was etched in a 0. The 0. and polished with 1 μm diamond spray until a mirror surface was obtained.8 98. All spectra exhibit capacitive loops. 3.8 85.5 59.2.6 88.5 M H2SO4. while Rct is the charge transfer resistance at the iron/solution interface [22]. All quantum calculations were accomplished by program Gaussian 98 [20]. All impedance spectra can be analyzed and fitted with the equivalent circuit in Fig. 3. Calculation method Considering the accuracy and convenience of ab initio method. The working electrode was made from a 99.4 44. 2.2 218.5) immediately. the electrode was rinsed with tridistilled water again. Experimental details 2. Considering that the capacity of the double layer is different from the ideal capacitor.9 109.4 190. Germany). / Thin Solid Films 516 (2008) 1020–1024 EIS measurements were conducted with an IM6 impedance and electrochemical measurement system (ZAHNER. The electrode was embedded in epoxy resin and only its top surface was exposed to the solution. B3LYP method of density functional theory (DFT) on the basis set of LANL2DZ was used to perform a full geometry optimization of the MMT molecule and the accomplished system after the MMT molecule adsorbed on the iron surface. Electrochemical impedance spectroscopy Fig.6 P% – 49.4 94. Fig.5 M H2SO4 solutions with and without the MMT films Iron electrodes Bare 10−3M neutral solution Immersion time – 15 min 30 min 3 hour 8 hour 12 hour 15 min 30 min 3 hour 8 hour 12 hour 15 min 30 min 3 hour 8 hour 12 hour 15 min 30 min 3 hour 8 hour 12 hour Rct (Ω cm2) 39. Then it was rinsed with water again as soon as possible.4 359. The exposed surface was ground with emery paper of different grit sizes up to 1600.2 1222. Ma et al. In Fig.3 71. and immersed in MMT solutions (pH = 2 and pH = 6. The counter electrodes were two sheets of platinum placed in two sides of the working electrode respectively. 2.1 140.4 2006.9 23.0%. 2. The pH value of the solution was adjusted by 0. All tests were carried out in 0. Q represents CPE in Fig.2 97.7 10−3 M acidic solution 10−2 M neutral solution 10−2 M acidic solution Fig. Equivalent circuit of the iron/solution interface. The measured and calculated data of the electrode modified by MMT films protection effect for iron and the inhibition efficiency in 0. EIS tests were performed in a frequency range of 60 kHz to 20 mHz under excitation of a sinusoidal perturbation signal of 5 mV amplitude at open circuit potential.2 251.1 81. grade) was dissolved in tridistilled water with the controlled concentrations (10−3 M and 10−2 M). Rs is the solution resistance between the work electrode and the reference electrode.2 M H2SO4 solution for 15 s in order to obtain an active iron surface.8 52. 2. a constant phase element (CPE) is used as a substitute for the capacitor.9 79.2 53.5 M H2SO4 solutions were prepared with concentrated H2SO4 and tridistilled water. After the formation of the self-assembled films. The reference electrode was a saturated-calomel electrode (SCE).3 72. 1 represents the Nyquist impedance spectra for bare iron electrode and the electrodes modified with MMT self-assembled films.

hence too long film formation time is detrimental to the quality of the films.46 – Complex 1. when using the 10−3 M solutions. good inhibition efficiency is observed in the neutral solution. At first. 3. the corrosion inhibition of the film first increases with the self-assembling time and then decreased. (immersed in 10−2 M MMT acidic solution for 8 h) are both displayed in Fig. Good quality films can be obtained in 10−2 M MMT solutions with pH = 2. and the result is shown in Fig.28 128. which is better than the inhibition efficiency of the neutral solution (pH = 6.8483 100. 3. Optimized complex of 1-methyl-5-mercapto-1. a full geometry optimization of the MMT molecule is performed with the B3LYP/LANL2DZ method.2. The reason is that the self-assembled films are formed on the iron surface by the molecules of the inhibitor spontaneously.42 119.8225 1. According to the experimental data.04 131.0%.3490 – 108.67 Band angle (°) .2.49 143. 4. The self-assembling process is a dynamic process.8024 1.0846 −0. and the iron will dissolve immediately at the beginning of the self-assembling process if it is immersed in 10−3 M solutions.5271 1. we can see that the selfassembled films formed in 10−2 M solutions have more effective inhibition efficiency than that of 10−3 M.66 121.1074 −0.0616 concentration (10−3 M) of the inhibitor cannot produce compact films on the electrode in a short time. we can see that the calculated values fit the measured data well. In these systems. Quantum chemical calculations In order to investigate the adsorption mode between the MMT and the iron. In the 10−2 M solutions.4-tetrazole molecule and iron atom. 5. 3. Optimized structure of 1-methyl-5-mercapto-1.H. From Fig. 3 h may be characterized as the appropriate self-assembly time.4628 1. It is good for the film formation when time is prolonged until equilibrium is attained.4718 1.3640 1. In this self-assembled system.3.03 124. The fitted data and inhibition efficiencies of the films are listed in Table 1. In acidic self-assembly solutions. some protonated nitrogen atoms are positively charged and iron surface is negatively charged because of the adsorption of sulphate ions from the solution [24]. large quantities of molecules can form condense films on the iron surface.1225 −0. So the MMT molecules can adsorb on the iron surface through positively charged nitrogen atoms by electrostatic action and the protection barrier is formed.3.0428 0. The inhibition efficiency (P%) of the self-assembled films can be calculated by the following formula [23]: P% ¼ 100ðRct À R0 Þ=Rct ct Where R0ct and Rct are charge transfer resistances of bare electrode and electrode modified with self-assembled films respectively. Fig.10 126. From Fig. However.2. we carried quantum chemical calculations. which includes the adsorption of the inhibitor to the electrode and desorption from the electrode.4057 1.4605 1. / Thin Solid Films 516 (2008) 1020–1024 1023 Fig.0525 0. Ma et al. 4. However further increase of the self-assembling time cause desquamation of the films formed on the iron surface.5).4-tetrazole. It shows that the MMT molecule has a planar Table 3 Bond properties of the MMT molecule and the complex including MMT and iron MMT molecule Bond distance (Å) N4–C1 N4–C2 N4–N6 C1–S8 C1–N5 N4–Fe N6–N4–C1 C1–N4–C2 S8–C1–N4 N5–C1–S8 Fe–N4–C2 1. both the concentration of the inhibitor and the pH value of the solution affect the formation of the film. 1 and Table 1.1952 −0. The highest inhibition efficiency is 98.4893 1. The reason is that low Table 2 Mulliken charges of the MMT molecule Atom δ(C1) δ(C2) δ(N3) δ(N4) δ(N5) δ(N6) δ(S8) Charge −0.

Chem. Maccafferty. J. entropies (S) and free energy changes (ΔG) of the MMT and iron system H(hartree) Iron atom MMT molecule Complex (MMT–Fe) ΔH (J/mol) ΔS (J/mol·K) ΔG (J/mol) −123. B. Gaussian 98. K. Sci. Aramaki. Mater. L. Martin. Binkley. Electrochim. Trabanelli. Dikshit. Coord. Electrochim. 41 (1999) 1715. Appl. Electrochem. Vračar. the MMT molecule can be adsorbed on the metal surface. The MMT molecule links to the iron surface by sharing of electrons between the nitrogen and the iron atoms. Sci. J. Corros. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] G. J. V.H. Wong. The calculated results of enthalpies (H).T.J. 135 (1998) 307. Pálinkás. Nozawa.A. Robb. Corros. / Thin Solid Films 516 (2008) 1020–1024 Table 4 Calculated results of enthalpies (H). In order to investigate the spontaneity of the self-assembly process. 39 (1997) 243. Zhu. K.5 M [21] [22] [23] [24] . Ayala. Al-Laham. Polyhedron 12 (1993) 759.. Adv. Replogle. 39 (1997) 1625. Tsuji. Montgomery. Sci. Chen. Corros. 33 (2003) 179. Gaussian Inc.L. G.Q. Head-Gordon. Appl. Sci. Kerit. X.L. Revision A. J. C. T. which is shown in Fig. ΔS is the entropy change of the self-assembly process. N.493 −430. Peyrimhoff.L. we use one iron atom instead of iron surface to investigate the adsorption mechanism.A. Lendvay-Győrik. M. which shows that atom 4 N has the biggest electron density and it may be the reactive center of the MMT molecule. The adsorption structure for the complex of MMT molecule and iron atom is optimized with the same method. We consider this simplification is permitted and sound in the quantum chemical calculation. 44 (2002) 703.L. Qi. Chen. Lazarova. Kálmán. Johnson. Some nitrogen atoms can be protonated in acidic solution and be adsorbed on the negatively charged iron surface. Corros. Kalcheva. Because 4N atom of the MMT molecule will donate its lone electron pair to the unfilled orbit of the metal atom. M. Stoyanova.Y. D.4 381. Appl. S. K.Y. Acknowledgement This work was supported by the Outstanding Middleaged Scientists Foundation of Shandong Province of China (2005BS009). Xue. Surf. 42 (2000) 1669. Pittsburgh. Corros. and T is the absolute temperature. Quan. N.J. Y. Li.A. The most important explanation of the adsorption mechanism is obtained by the DFT. H. Rev. G. G. S. Gomperts.792 −125901. therefore the self-assembling process is spontaneous. Phys. ΔH is the enthalpy change. we calculated the free energy changes by: DG ¼ DH À T DS where ΔG is the free energy change. E. Ma et al. Corros. The calculated result of ΔG is −90597. 42 (2000) 79. T. Defrees. Hackerman. Sci. Fox.S. G.F. Surf. 30 (2000) 561. Corrosion 47 (1991) 410. Sci. Stoyanov. N. C.B. R. the planar structure of the MMT molecule is changed and distorted. K. T. E. Zakrzewski.S. 82 (2003) 949. Chen. Z. Wang. 43 (2001) 919. P. J.H.6 −90597. entropies (S) and free energy changes (ΔG) of MMT and iron system are presented in Table 4. M. Corros.M. Ma. Acta 48 (2003) 2635. Khalil.0%. Lj M. Pople. Andres. Chem. we find that the MMT molecule is connected with the iron atom through its 4 N atom. H. J.L. J. Corros. 129 (1994) 91. 279 (2002) 1. Frisch. E. Acta 47 (2002) 2335. J. Mészáros.D.Y. Chem.F. B. Singh. N. M. Langmuir 11 (1995) 2231. In order to simplify the calculation.A. C.B. Electrochim.251 −307. Stewart. W. G. Sci. J. Cheng. I. Acta 48 (2003) 2715.W. Nishihara. Raper.9. Z. This study is helpful in exploring the protection of self-assembled films to iron in practice. Lengyel. Khaled.Y. Peng. Yankova.V. J. S. B.W.P. Nozawa. Li. E. X. Phys. four nitrogen atoms. 44 (2002) 1669.M. Keith. Corros. 93 (1996) 59. Appl.S. Mészáros.J.H.R.1 J/mol. Gonzalez. X. R. Trucks. Hammouti. Gill. Ortiz. R.G. Ye. J. X. Another kind of adsorption is by electrostatic action in acidic solution. S. Mater. S. Gojić. The self-assembling process is performed at the room temperature. G. After adsorption. 5. Petersson.R. Martin Stratmann.8 −118. 42 (2000) 1523. Schlegel. Cheeseman. Moreover.S. From Fig. two carbon atoms and one sulfur atom are all in one plane.1 S(J/mol·K) 158. M. Raghavachari. S. J. Hackerman. Neykov. Cui. S. Ma. The adsorption is enhanced by these two actions in 10−2 M MMT acidic solutions and the best inhibition efficiency is obtained. Sci. Sci. A. G. Aleksiev.1024 H. Electrochem. J. K. Khaled. which might be caused by the intensive interactions between the MMT molecule and the iron atom.G. Xin.W. Lazarova. E. Dražić. which accords completely with the former theoretical predication. H. P. Petkova. Aramaki.Q. K.4 H2SO4 solutions. E. Felhösi. The best inhibition efficiency of MMT for iron is 98. Chen.8 341. C. Aramaki. corresponding bond distance became long and bond angle became small.J. structure. H. D. D. B. Conclusion The self-assembled films of heterocyclic compound MMT are found to be effective in inhibiting corrosion of iron in 0. K. N. 5. Sci. that is. G.G. K. PA. 4. 1999. M. 2 (1990) 191. Teleddi.K. Yankova. Foresman. Mulliken charges of the atoms in MMT molecule are calculated and listed in Table 2. Sci. Baker.A. Bond distance and bond angle of the MMT molecule before and after the adsorption are listed in Table 3.