Quantum Chemical Study of Some Benzimidazole Derivatives as Corrosion Inhibitors of Copper in 1M HNO 3.

Australian Journal of Basic and Applied Sciences, 5(11): 309-317, 2011 ISSN 1991-8178 Quantum Chemical Study of Some Benzimidazole Derivatives as Corrosion Inhibitors of Copper in 1M HNO 3. 1 P.M. Niamien, 1 F.K. Essy, 1 A. Trokourey, 1 A. Yapi, 1 H. K.Aka and 1,3 D. Diabate 1 Laboratoire de chimie physique. Université de Cocody-Abidjan. 3 Institut UTINAM-UMR CNRS 6213 Equipe capteurs et membranes 25013 Besançon cedex. 22 BP 582 Abidjan 22(Côte d'ivoire) Abstract: Quantum chemical calculations of electronic molecular parameters of 2- thiobenzylbenzimidazole (TBBI), 2-thiomethylbenzimidazole (TMBI), 2-Hydroxymethylbenzimidazole (HMBI), 2-mercaptobenzimidazole (MBI) were performed. The correlation between molecular structure of these compounds and their inhibition efficiency against copper corrosion in 1M HNO 3 was found by considering Density Functional theory (DFT) B3LYP/6-31G(d,p) level. The properties most relevant to their potential action as corrosion inhibitors has been calculated: highest occupied molecular orbital energy (E HOMO ), lowest unoccupied molecular orbital energy (E LUMO ), energy gap (ΔE), dipole moment (µ) and parameters that provide informations about the chemical reactivity: electronegativity (χ), global hardness(η). All calculations have been performed using the Gaussian 03W suite of programs. It was found that theoretical data support experimental results. Key words: Density Functional theory (DFT), adsorption isotherm, free enthalpy, energy gap, dipole moment, theoretical calculation. INTRODUCTION The corrosion problems are of great interest for the industries because they are translated in great economic losses for them. Nowadays the research of novel inhibitors for metals or alloys is an important industrial and academic topic and the most efficient alternatives to protect metals and alloys of this phenomenon are the use of substances that being adsorbed on metallic surface (Ali et al., 2003). It had been suggested that most effective factors for inhibiting effects are the presence of polar atoms such as O, N, S, P (Hongfang et al., 2008; Popova et al., 2007), the unsaturated bonds, such as double bonds or triple bonds (Chetouani et al., 2005; Abd El Maksoud, 2003) and the plane conjugated systems including all kind of aromatic cycles (Durnie et al., 1999; Sastri and Paerumareddi, 1997) which can offer special active electrons or vacant orbital to donate or accept electrons. A large number of organic molecules have at least one of the above-mentioned characteristics in their molecular structure according to diversity of organic compounds. The primary step in the action of organic corrosion inhibitors in the solution is usually attributed to the adsorption process (Yildirim and Cetin, 2008). Studies (Kaled Hackerman, 2003) report that adsorption process depends on the physico-chemical properties of the inhibitor molecule, related to the electronic density of donor atoms and on the possible steric effects. The problem of the relationship between the molecular structure and the inhibition efficiency of the organic inhibitors of corrosion attracts the attention of many investigators (Growcock, 1989; Lazarova et al., 2000). Recently, the density functional theory (DFT) was successfully applied to describe the structural importance of corrosion inhibitors and their adsorption efficiency on the metal surface (Cruz et al., 2005; Cruz et al., 2004): the electronic properties of the corrosion inhibitors such as highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), energy difference between E HOMO and E LUMO, atomic charge and dipole moments have been achieved the appropriate correlation. In this work, the corrosion inhibition behavior of 2-thiobenzylbenzimidazole (TBBI), 2-thiomethylbenzimidazole (TMBI), 2-hydroxymethylbenzimidazole (HMBI) and 2-mercaptobenzimidazole (MBI) against copper corrosion in 1M HNO 3 was investigated by weight loss. Quantum chemistry studies have been performed in order to relate the inhibition efficiency to the molecular properties of these compounds. The molecular structure and the electronic parameters that can be obtained through theoretical calculations, as the HOMO (higher occupied molecular orbital) energy, the LUMO (lower unoccupied molecular orbital) energy, Corresponding Author: P.M. Niamien, Laboratoire de chimie physique. Université de Cocody-Abidjan. E-mail: niamienfr@yahoo.fr 309

the energy gap (ΔE=E LUMO -E HOMO ), dipole moments (µ), are involved in the activity of the inhibitors. We have also determined the parameters that give valuable information about the reactive behavior of these molecules: electronegativity χ and global hardness η that can be treated by means of the HSAB theory (Blajiev and Hubin, 2004). Materials: MATERIALS AND METHODS Fig. 1: Optimized Chemical structures of TBBI, TMBI, MBI and HMBI. These organic compounds have been synthesized in the Laboratory. Their molecular structures have been identified by RMN -1 H and 13 C spectroscopies, mass spectroscopy and X-rays. 2.2 Weight loss measurements: The weight loss measurements were performed with samples of copper in the form of rods measuring 10 mm by 2.2 mm of diameter that were cut from commercial pure copper (Cu: 99.5 %). The corrosive solution of 1M HNO 3 was prepared by dilution of analytical grade 65% HNO 3 from MERCK with bidistilled water. The samples were polished with different emery papers, washed thoroughly with bidistilled water, degreased and dried with acetone. The samples were kept in a desiccator, weighed and immersed in the corrosive medium (50 ml of 1M HNO 3 ) with or without the tested inhibitors. A water thermostat SELECTA (FRIGITERM) controlled to ± 0.5 C maintained the temperatures. After 1 hour, the specimens were removed, washed in 65% nitric acid for 5 s to remove the corrosion products, using bristle brush and rinsed with bidistilled water, dried, kept in a desiccator and then reweighed. All tests were made in aerated solutions and were run triplicate to guarantee the reliability of the results. 2.3 Computational Details: All the calculations have been performed by resorting to density functional theory (DFT) methods using the Gaussian 03 W suite of programs. The calculations were based on 6-31G (d,p) basis set. This basis set provided accurate geometry and electronic properties for a wide range of organic compounds (Becke, A. D., 1993; Lee et al., 1988). The calculations of quantum chemical parameters (E LUMO, E HOMO, ΔE = E HOMO - E LUMO and the dipole moment μ) were carried at density functional theory (DFT) method level by B3LYP. RESULTS AND DISCUSSION 3.1 Inhibition Efficiency: The corrosion rate (W) and the inhibition efficiencies IE (%) were calculated using the following equations: 310

(1) (2) Where m 1 and m 2 are respectively the weight ( in g) before and after immersion, S the total surface of the sample (in cm 2 ) and t the immersion time (in h); w 0 and w are respectively the corrosion rates of copper in the absence and presence of the tested compounds. The values of inhibition efficiencies IE(%) and corrosion rates W obtained from weight loss measurements in 1.0 M HNO 3 after 1 h immersion at T = 298K and C inh = 10-3 M are listed in Table 1. Table1: Efficiencies of the studied molecules at T = 298 K and C inh = 10-3 M. Compound m 1 - m 2 (g) IE (%) Blank 0.0802 - TBBI 0.0080 90.02 TMBI 0.0090 88.78 HMBI 0.0118 85.27 MBI 0.0099 87.26 It can be concluded that the inhibition ability is in descent order as TBBI > TMBI > MBI > HMBI. This can be attributed to the molecular structure and the physico-chemical properties of these molecules. The molecular structure of an adsorption type inhibitor has been determined as a major factor that influences adsorption interaction between the inhibitor molecules and the metal surface, and consequently the inhibitor effiency (Bereket et al., 2003). 3.2 Adsorption isotherm: The adsorption of an organic inhibitor on the surface of a corroding metal may be regarded as a substitution process between the organic compound in aqueous phase and water molecules adsorbed on the metal surface (Oguzie et al., 2007): The surface coverage (θ) was calculated from weight loss as follows: (3) Basic information on the interaction between the inhibitor and the copper surface can be provided by the adsorption isotherm. In order to obtain the isotherm, linear relation between θ values and inhibitor concentration C inh must been found. Attempts were made to fit the θ values to various isotherms including Langmuir, Temkin, Frumkin and Freundlich. The best fit was obtained with the Langmuir isotherm (Fig.2). The plots of C inh /θ versus inhibitor concentration C inh (Fig.3) yield straight lines; the correlation coefficients and the slopes are listed in table 2. Table 2: Correlation coefficients and slopes of the Langmuir straight lines. Correlation coefficient slope TBBI 0.999 0.996 TMBI 0.999 0.996 HMBI 0.997 0.968 MBI 0.999 0.968 The values of the correlation coefficients and the slopes of these straight lines are all very close to 1, confirming that the adsorption of these molecules on copper surface obeys the Langmuir isotherm. This adsorption isotherm is described by the following equation: 311

Fig. 2: Langmuir adsorption plots for copper in 1M HNO 3 (4) Where C inh is the inhibitor concentration, θ is the fraction of the surface covered and K ads the equilibrium constant of the adsorption process. Change in free energy of adsorption can be calculated using equation (5). The numeral of 55.5 is the molar concentration of water in the solution. (5) The obtained values of equilibrium constant and free energy at T = 298K and C inh = 10-3 M are summarized in the following table. Table 3: Equilibrium constant and change in free energy of adsorption onto copper surface in 1M HNO 3 at T = 298K and C inh = 10-3 M. Compound K ads (M -1 ) TBBI 9025.0-32.50 TMBI 9176.8-32.54 HMBI 5097.0-31.08 MBI 7101.0-31.90 The negative values of indicates spontaneous adsorption of the molecules on copper surface. According to several authors (Szklarska-Smialowska, 1978; Yurt et al., 2006), it is accepted that for the values of up to -20 kj.mol -1 the type of adsorption is physisorption while the values smaller than - 40 kj.mol-1 is seen as chemisorption. In our case, the values of range from -31 kj.mol -1 to -33 kj.mol -1 : it is suggested that the adsorption of these molecules involves both types of interactions, physisorption and chemisorption. The inhibitive actions of organic compounds depend on the electron densities around the adsorption centers (polar atoms); the higher the electron density at the centre, the more efficient is the inhibitor. Protection efficiency depends on several factors such as the number of adsorption sites, their charge density, the molecular size, the mode of interaction with the metal surface, the electronic properties of the corrosion inhibitors such 312

as highest occupied molecule orbital (HOMO), the lowest unoccupied molecule orbital (LUMO), energy difference between E HOMO and E LUMO, atomic charge and dipole moments (Fouda et al., 2009). 3.3 Quantum Chemistry Calculations: The geometry of the molecules (Fig.1) were optimized by the density functional theory (DFT) method level with B3LYP exchange correlation functional, using 6-31G(d,p) basis set. We have determined quantum chemical parameters such as E LUMO, E HOMO, ΔE = E LUMO - E HOMO, dipole moment μ, ionization potential (I = -E HOMO ) and electron affinity (A = -E LUMO ) of the studied molecules. The obtained values of I and A were considered for the calculation of the electronegativity χ and the global hardness η in each of the tested molecule using the following relations (Pearson, 1989): (6) The calculated parameters are summarized in table 4. Table 4: The calculated quantum chemical properties for tested compounds. TBBI TMBI HMB I MBI E(ZPE) (ev) -28517.6-22236.1-13451.1-21163.3 EHOMO (ev) -5.606-5.856-6.069-6.033 ELUMO (ev) -0.484-0.556-0.493-0.639 ΔE=E LUMO -E HOMO (ev) 5.122 5.300 5.575 5.394 µ (D) 1.8779 1.7862 3.6071 3.8428 I(eV) 5.606 5.856 6.069 6.033 A (ev) 0.484 0.556 0.493 0.639 Mwt (amu) 240.07 164.04 148.06 150.02 χ 3.192 3.084 3.077 3.257 η 2.570 2.729 2.834 2.783 ΔN 0.378 0.334 0.304 0.305 The fraction of electrons transferred from the inhibitor molecule to the metallic atom (ΔN) (Table 4) was calculated according to Pearson's formula (Michaelson, 1977): (7) (8) The idea behind this is that in the reaction of two systems with different electronegativity as a metallic surface and an inhibitor molecule, the following mechanism will take place: the electron flow will happen from the molecule with the low electronegativity towards that of a higher value until the chemical potential are the same. In order to calculate the fraction of electrons transferred, a theoretical value of electronegativity of bulk copper was used χ Cu =4.98 ev (Dewar et al., 1985) and a global hardness η Cu =0 assuming that for a metallic bulk I = A [24] because they are softer than the neutral metallic atoms. An attempt has been made to correlate corrosion inhibition efficiency (dependent variable) and the set of some independent variables like highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), dipole moment etc. According to the frontier molecular orbital theory, the formation of a transition state is due to an interaction between frontier orbitals (HOMO and LUMO) of reacting species (Fukui, 1975). Thus, the treatment of the frontier molecular orbitals separately from the other orbitals is based on the general principles governing the nature of chemical reactions. HOMO is often associated with the electron donating ability of a molecule. High E HOMO values indicate that the molecule has a tendency to donate electrons to appropriate acceptor molecules with low energy empty molecular orbital. Increasing values of the E HOMO facilitate adsorption (and therefore inhibition) by influencing the transport process through the adsorbed layer (Gece, 2008). E LUMO indicates the ability of the molecules to accept electrons. The lower values of E LUMO, the more probable it is that the molecule would accept electrons (Fukui, 1975). Low values of the energy band gap (ΔE) gives good inhibition efficiencies, because the energy to remove an electron from the last occupied orbital will be low (Gece, 2008). In our case, the values of E HOMO, E LUMO and those of ΔE (Table 4) allowed concluding that inhibition 313

ability is in descent order as TBBI > TMBI > MBI > HMBI. Besides, it is possible to observe from Table 4, that the fraction of electrons transferred from the studied molecules to the metallic surface (N) is in the same descent order, confirming the results obtained from weight loss measurements. The experimentally found inhibition efficiencies of the studied molecules (Table 1) allowed making some correlation between experimental values and the theoretical parameters from quantum chemical approach (Figs.3 and 4). Fig. 3: Relationship between Inhibition efficiency and energy gap Fig. 3 shows the relationship between inhibition efficiency and energy gap: the lower is the value of the energy gap; the higher is the inhibition efficiency. Figs. 4 and 5 show that there is a linear correlation between the inhibition efficiency and E HOMO for TBBI, TMBI and MBI. Fig. 4: Relationship between Inhibition efficiency and E HOMO. From these figures it can be cleary seen that TBBI has the smallest HOMO-LUMO gap (i.e. 5.122), while MBI has the highest energy gap (i.e.5.394). We can also see that inhibition efficiency decreases as E HOMO level decreases. MBI has the lowest E LUMO value meaning the worst inhibition efficiency. TBBI has the highest E LUMO value, therefore the best inhibition efficiency. The higher inhibition effects of TBBI as compared to TMBI and MBI can be attributed to the presence of the aromatic cycle which increases the electronic density of TBBI. 314

Fig. 5: Relationship between Inhibition efficiency and E HOMO TMBI has a higher inhibition efficiency compared to MBI because of the presence of the methyl group (CH 3 ): methyl group is electron donors; it increases electron density of TMBI. HMBI has the lower inhibition efficiency because of the presence of oxygen instead of sulfur: the inhibition efficiency of organic compounds containing donor atoms is in the sequence S > N > O (Lece et al., 2008). According to Zhang et al. (2004) the introduction of mercapto group to a heterocyclic compound can vary the disturbance and orbital energy configurations of electrons, thus enhancing the inhibition. Frontier MO energy level may indicate the tendency of forming a chelate bond with metal surface. Further study on the probable center of chelating site in inhibitors requires knowledge of the spatial distribution of electronic density (Table 5) for the given molecules. Table 5: Atomic charges with hydrogen summed into heavy atoms. Compound N N S TBBI - 0.674025-0.344472-0.354045 TMBI - 0.651433-0.294465-0.257838 MBI - 0.538551-0.295407-0.066943 Fig.6. presents the correlation between the inhibition efficiency and the electronic charges on S. Fig. 6: Relationship between inhibition efficiency and electronic charge on S. 315

From table 5, it can be seen that charges on nitrogen are nearly similar, but great differences exist between charges on S. The HOMO of the TBBI, TMBI and MBI are made up predominantly of 3px of S atom in each molecule which contribute respectively to the electronic charge density of their HOMO levels. S of TBBI has the highest contribution, while that of MBI has the lowest one. This can be associated with the dominative contribution of the S atom according to the frontier orbital approximation; the region of highest density is generally the site of electrophilic attack (Fang and Li, 2002). For the dipole moment, we have not found a linear correlation with inhibition efficiency. Dipole moment (µ) is relating to the hydrophobic character of the molecules; the obtained values suggest that the molecules of lower dipole moment are more favoring the accumulation of the inhibitor molecules on the metal surface. Similar results can be found in the literature (Gao and Liang, 2007) even if survey of the literature reveals that several irregularities appeared in the case of the correlation of dipole moment with inhibitor efficiency (Khaled et al., 2005; Bereket et al., 2002). Conclusions: Through DFT quantum chemical calculations, a correlation between parameters related to the electronic structures of 2-thiobenzylbenzimidazole (TBBI), 2-thiomethylbenzimidazole (TMBI), 2-hydroxymethyl-benzimidazole (HMBI) and 2-mercaptobenzimidazole (MBI) and their inhibition efficiencies have been established. Most of the calculated molecular parameters of the inhibitors calculated by B3LYP/6-31G (d,p) level show excellent correlation with inhibition efficiency of the studied inhibitors. From the theoretical data, the inhibitive effectiveness order is TBBI > TMBI > MBI > HMBI and this agrees well with experiment. REFERENCES Abd El Maksoud, S.A., 2003. The influence of some Arylabenzoyl acetonitrile derivatives on the behavior of carbon steel in acidic media. Appl. Surf. Sci., 206: 129-136. Ali, S.A., M.T. Saeed, S.V. Rahman, 2003. The isoxazolidines: a new class of corrosion inhibitors of mild steel in acidic medium. Corros. Sci., 45: 253-266. Bereket, G., E. Hür, C. Ögretir, 2002. Quantum chemical studies on some imidazole derivatives as corrosion inhibitors for iron in acidic medium. J. Mol. Struct. (Teochem) 578: 79-88. Becke, A.D., 1993. Density-functional thermochemistry. The role of exact exchange. J. Chem. Phys., 98: 5648-5652. Bereket, G., C. Ogretir, C. Ozsahim, 2003. Chemical studies on the inhibition efficiencies of some piperazine derivatives for corrosion steel in acidic medium. J. Mol. Struct. (Theochem) 663: 39-46. Blajiev, O., A. Hubin, 2004. Inhibition of copper corrosion in chloride solutions by amino-mercapto-thiadiazol and methyl- mercapto- thiadiazol: an impedance spectroscopy and a quantum chemical investigation. Electrochimica Acta, 49: 2761-2770. Chetouani, A., B. Hammouti, T. Benhadda, M. Daoudi, 2005. Inhibitive action of bipyrazolic type organic compounds towards corrosion of pure iron in acidic media. Appl. Surf. Sci., 249: 375-385. Cruz, J., T. Pandiyan, E. Garcia-Ochoa, 2005. A new inhibitor for mild carbon steel: electrochemical and DFT studies. J.Electroanal. Chem, 583: 8. Cruz, J., R. Martinez, J. Genesca, E. Garcia-Ochoa, 2004. Experimental and theoretical study of 1-(2-ethylamino)-2-methylimidazoline as an inhibitor of carbon steel. J. Electroanal. Chem, 566: 111-121. Dewar, M.J.S., E.G. Zoebisch, E.F. Heali, J.J.P. Stewart, 1985. A new general purpose quantum mechanical molecular model. J. Am. Chem. Soc., 85: 8245. Durnie, W., R. de Marco, A. Gefferson, B. Kinsella, J. Electrochem, (1999) Soc., 146: 1751. Fang, J., J. Li, 2002. Quantum chemistry study on the relationship between molecular structure and corrosion inhibition efficiency of amides. J. of Mol. Struct. (Theochem) 593: 179-185. Fouda, A.S., F.E. Heakal, M.S. Radwan, 2009. Role of some thiadiazole derivatives as inhibitors for the corrosion of carbone steel in 1M H2SO4. J. Appl. Electrochem, 39: 391-402. Fukui, K., 1975. Theory of Orientation and Stereoselection, Springer verlaz, New York. Gao, G., C. Liang, 2007. Electrochemical and DFT studies of β-amino-alcohols as corrosion inhibitors for brass. Electrochimica Acta, 52: 4554-4559. Gece, G., 2008. The use of quantum chemical methods in corrosion inhibitor studies. Corros. Sci., 50: 2981-2992. 316

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