Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment

Rokia Hadja Toure; Aphouet Aurelie Koffi; Mougo Andre Tigori; Paulin Marius Niamien

doi:doi:10.11648/j.ajac.20241206.12

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Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment

Rokia Hadja Toure, Aphouet Aurelie Koffi^*

, Mougo Andre Tigori, Paulin Marius Niamien

Published in American Journal of Applied Chemistry (Volume 12, Issue 6)

Received: 6 November 2024 Accepted: 19 November 2024 Published: 12 December 2024

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Abstract

Organic inhibitors are crucial for preserving metals from corrosion in acidic environments. In this regard, the methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate (M-41HBI-2MTMB) was synthesized and investigated as an eco-friendly inhibitor for aluminum in a molar nitric acid solution (1 M HNO₃). The gravimetric technique was used to study the inhibitory properties of the molecule, and the density functional theory (DFT) was conducted to elucidate the corrosion inhibition mechanism. The experimental data indicated that M-41HBI-2MTMB reduced the corrosion of the metal with a significant inhibition efficiency. The corrosion inhibition increased with an increase in the concentration of the molecule, reaching an efficiency of 98.5% at a concentration of 5.10^-3 M, and a temperature of 298 K. Adsorption isotherms and thermodynamic parameters were studied to elucidate the interactions between M-41HBI-2MTMB and the metal surface. The inhibitor adsorbed spontaneously onto the aluminum surface following the Villamil model (modified Langmuir isotherm). Additionally, the Gibbs free energy less than - 40 kJ.mol^-1 and the negative value of the enthalpy of adsorption suggested mixed-type adsorption with a predominance of physical interactions. The theoretical findings of DFT calculations revealed a positive fraction of electrons transferred (ΔN = 0.247 eV), a high value of the electrophilicity index (ω = 3.807 eV) as well as a low energy gap (ΔE = 4.478 eV) showing favorable interactions of M-41HBI-2MTMB with its environment. The active sites of the molecule were highlighted at the level of carbon atoms, and a corrosion inhibition mechanism was proposed.

Published in	American Journal of Applied Chemistry (Volume 12, Issue 6)
DOI	10.11648/j.ajac.20241206.12
Page(s)	135-148
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Aluminum, Methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate (M-41HBI-2MTMB), Gravimetric Measurement, Density Functional Theory (DFT)

1. Introduction

Industries commonly use acid solutions to seal and clean metal systems

[1]

. These industrial processes ensure the smooth running and efficiency of the plant. However, corrosion occurs during these processes, and aluminum structures are not spared

[2]

. Beyond the huge economic losses, corrosion causes environmental degradation and risks human health. Corrosion of materials is, therefore, a significant global problem

[3, 4]

Appropriate techniques can be used to protect against corrosion and its effects, such as applying potential corrosion inhibitors and protective coatings

[5]

. The commonly used method to mitigate corrosion of metals in an aqueous environment is the addition of inhibitors, classified into organic and inorganic compounds

[6-8]

. For example, inorganic inhibitors such as chromate, molybdate, and vanadate ions exhibit excellent corrosion protection capability. However, these compounds are hazardous and harmful

[5, 9]

When selecting inhibitors, efforts are made to protect humans and the environment. Thus, non-toxic and biodegradable organic compounds are preferred

[10-12]

. Many organic inhibitors have been studied to reduce the corrosion rate of aluminum structures, including nitroimidazopyridinehydrazone derivatives

[13]

, theophylline

[14]

, and thiophene

[6]

. These molecules protect the metal by adsorbing physically or chemically on the substrate surface. The inhibitor's capacity to get adsorbed depends on the molecule's structure (heteroatoms and π bonds), the type of electrolyte, the excess surface charge of the metal, and the working conditions

[15, 16]

It is in this imperative of research on green inhibitors that this work was carried out. The inhibitory properties of methyl 4-(((1-H benzo [d] imidazole-2-yl) methyl) thio) methyl) benzoate on the corrosion of aluminum in 1 M HNO₃ solution was investigated. The molecule of interest belongs to the benzimidazole derivatives. It contains heteroatoms (N, O, and S) and aromatic rings that can facilitate its interactions with the metal surface because the adsorption process is essential in the inhibitory effectiveness of an organic compound

[17-19]

Several authors have reported the inhibitory properties of benzimidazole derivatives in acidic environments. For instance, Timoudan et al.

[20]

studied the corrosion inhibition properties of (1H-benzimidazol-2-yl)methanethiol (LF1) and 1-dodecyl-2-((dodecylthio)methyl)-1H benzimidazole (LF2) in 1 M hydrochloric acid solution by numerous methods. The inhibition rate reached 88.2% and 95.4% for LF1 and LF2, respectively. Likewise, Guendouz and al.

[21]

investigated the inhibitory properties of two newly synthesized benzimidazole derivatives, namely 1-(cyclohex-1-en-1-yl)-3-[(3-phenyl-1,2-oxazol-5-yl)methyl]-2,3-dihydro-1H-1,3-benzodiazol-2-one (Benz1) and 1-(cyclohex-1-en-1-yl)-3-[(3-phenyl-4, 5-dihydro-1,2-oxazol-5-yl)methyl]-2,3-dihydro-1H-1,3-benzodiazol-2-one (Benz2). In this study, Benz1 and Benz2 were evaluated as corrosion inhibitors using both experimental methods and computational approaches.

Many other benzimidazole derivatives have attracted much interest in metal corrosion protection

[22]	Marinescu, M. Recent advances in the use of benzimidazoles as corrosion inhibitors. BMC Chemistry. 2019, 13, 136. https://doi.org/10.1186/s13065-019-0655-y View Article
[23]	Nagy, H. A. E., Tamany, E. H. E., Ashour, H., El-Azabawy, O. E., Zaki, Elsayed, G., Elsaeed, S. M. Polymeric Ionic Liquids Based on Benzimidazole Derivatives as Corrosion Inhibitors for X‑65 Carbon Steel Deterioration in Acidic Aqueous Medium: Hydrogen Evolution and Adsorption Studies. ACS Omega. 2020, 5(47), 30577–30586. https://doi.org/10.1021/acsomega.0c04505 View Article
[24]	Ran, B., Wei, Z., Yu, S., Zhi, H., Yan, S., Cai, S., Wen, L., Fan, B., Wang, J., Wang, K., Luo, X. The study on corrosion inhibition effect of 2-Phenylbenzimidazole for X70 steel in HCl solution at 308K. International Journal of Electrochemical Science. 2023, 18, 100032. https://doi.org/10.1016/j.ijoes.2023.100032 View Article
[25]	Yousif, Q. A, Fadel, Z., Abuelela, A. M, Alosaimi, E. H., Melhi, S., Bedair, M. A. Insight into the corrosion mitigation performance of three novel benzimidazole derivatives of amino acids for carbon steel (X56) in 1 M HCl solution. RSC Advances. 2023, 13(19), 13094–13119. https://doi.org/10.1039/d3ra01837g View Article
[26]	Khormali, A., Ahmadi, S. Experimental and modeling analysis on the performance of 2-mercaptobenzimidazole corrosion inhibitor in hydrochloric acid solution during acidizing in the petroleum industry. Journal of Petroleum Exploration and Production Technology. 2023, 13, 2217–2235. https://doi.org/10.1007/s13202-023-01675-6 View Article
[27]	Liu, Q., Xiao, W., Ge, P., Long, W., Gao, S., Liu, X., Chen, Y. Corrosion Inhibition Effect of 2-Chloro-1-(4-fluorobenzyl) benzimidazole on Copper in 0.5 M H₂SO₄ solution. International Journal of Electrochemical Science. 2022, 17, 221299. https://doi.org/10.20964/2022.12.110 View Article
[28]	Zhang, J., Li, H. 2-(2-chlorophenyl)-1H-Benzimidazole as a New Corrosion Inhibitor for Copper in Sulfuric Acid. International Journal of Electrochemical Science. 2020, 15, 5362 – 5372. https://doi.org/10.20964/2020.06.63 View Article
[29]	Rouifi, Z., Rbaa, M., Abousale, A. S., Benhiba, F., Laabaissi, T., Oudda, H., Lakhrissi, B., Guenbour, A., Warad, I., Zarrou, A. Synthesis, characterization and corrosion inhibition potential of newly benzimidazole derivatives: Combining theoretical and experimental study. Surfaces and Interfaces. 2020, 18, 100442. https://doi.org/10.1016/j.surfin.2020.100442 View Article

[22-29]

. These molecules were synthesized and studied in extremely aggressive environments, such as acidic solutions as well as in sodium hydroxide and salt media. Also, the metals tested are diverse. All these benzimidazole derivatives exhibited good inhibitory performances.

This study aims to synthesize and investigate the anticorrosion behavior of methyl 4-(((1-H benzo [d] imidazole-2-yl) methyl) thio) methyl) benzoate using experimental and theoretical techniques. On the one hand, the corrosion rate of aluminum and the inhibition efficiency of the molecule studied were evaluated using gravimetric measurements. On the other hand, the corrosion inhibition mechanism was elucidated through thermodynamic parameters and Density Functional Theory (DFT) calculations.

2. Materials and Methods

2.1. Aluminium Samples and Electrolyte Medium

Gravimetric tests were performed using high-purity (99.6%) aluminum rods cut into 1 cm lengths. Each aluminum sample was subjected to polishing with abrasive paper, washing with distilled water, and degreasing with an acetone solution; then oven drying at 353 K for 10 minutes. Subsequently, each sample was weighed and immersed in 50 mL of 1 M HNO₃ without and with M-41HBI-2MTMB in a concentration range from 0.001 to 5 mM. After one hour, the sample was removed from the solution and rinsed thoroughly with distilled water. This is followed by oven drying and re-weighing. Each test was repeated at least three times to check the reproducibility of the results.

2.2. Inhibitor Synthesis

The synthesis of methyl 4-((((1-H benzo [d] imidazole-2-yl) methyl) thio) methyl) benzoate followed the procedure outlined by Souleymane Coulibaly et al

[30]

. It was carried out in two reaction steps, summarized in Figure 1. First, isothiouronium-1-H-benzimidazole salt is formed by adding 7g of ortho phenylenediamine to 7g of 2-chloroacetic acid in 60 ml of 4 N hydrochloric acid solution. Then, the formed salt was added to methyl-4-bromomethyl benzoate in a sodium hydroxide solution.

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Figure 1. Synthesis of methyl 4-(((1-H benzo [d] imidazole-2-yl) methyl) thio) methyl) benzoate.

2.3. Gravimetry Method

The corrosion rate 𝑊 (g. cm⁻². h⁻¹) of the sample and the inhibition efficiency 𝐸 (%) of the M-41HBI-2MTMB molecule were determined using the equations below:

W = \frac{ m}{S \times t}

(1)

E = \frac{W_{0} - W}{W_{0}} \times 100

(2)

Here ∆𝑚 represents the mass loss (g); 𝑆 denotes the total area of the specimen (cm²); 𝑡 represents the immersion time (h);

W_{0}

and 𝑊 are the corrosion rates without and with inhibitor, respectively.

2.4. Density Functional Theory Calculations

To explore the reactivity of the molecule under investigation, quantum chemistry calculations were carried out employing the Gaussian 09W software package at DFT/B3LYP method with a 6-311G++ (d, p) basis set

[31]

. Before calculations, the molecule was drawn, and the structure was preoptimized using GaussView 5.0.8. Then, the descriptors of the global reactivity, namely the energy of the highest occupied molecular orbital (E_HOMO) and the lowest unoccupied molecular orbital (E_LUMO), as well as the dipole moment (µ) and the total energy (E_T) were obtained. Subsequently, the electronegativity (χ), the electrophilicity index (ω), the fraction of electrons transferred (ΔN), and the energy gap (ΔE) were determined using the following equations:

χ = - \frac{(E_{HOMO} + E_{LUMO})}{2}

(3)

ω = \frac{^{2}}{2 }

(4)

ΔN = \frac{_{Al} - _{inh}}{2 (_{Al} + _{inh})}

(5)

Δ E = E_{LUMO}

−

E_{HOMO}

(6)

Where

_{Al} = 0 eV

and

_{inh}

are the hardness of aluminium and the inhibitor, respectively. The work function

_{Al} = 4.28 eV

was used instead because the electronegativity

_{Al}

is conceptually wrong here

[32]

To further understand the reactivity of the M-41HBI-2MTMB molecule, the Fukui functions (

f_{k}^{+}

and

f_{k}^{-}

) used to specify the sites prone to electrophilic and nucleophilic attack are determined by the equations above:

f_{k}^{+} = q_{k} (N + 1) - q_{k} (N)

(7)

f_{k}^{-} = q_{k} (N) - q_{k} (N - 1)

(8)

In these expressions,

q_{k} (N)

q_{k} (N + 1)

and

q_{k} (N - 1)

are the Mulliken charges of the atom

k

in the neutral, anionic, and cationic forms, respectively.

3. Results and Discussions

3.1. Gravimetric Results

3.1.1. Effect of M-41HBI-2MTMB on the Aluminium Corrosion

Figure 2 below shows the corrosion rate of aluminum investigated in 1M HNO₃ solution. This figure indicates that the aluminum sample dissolves in the corrosive medium. Dissolution increases particularly with rising temperature. Indeed, thermal agitations facilitate the movements of the reactants in the solution

[33, 34]

. However, by adding M-41HBI-2MTMB in the corrosive environment, the corrosion rate decreased significantly.

The effectiveness of this inhibitor is evaluated as shown in Figure 3. The inhibition rate of the molecule increases from 65.27 % to 98.51 % at 298 K, which means that the inhibitory barrier becomes increasingly dense with the inhibitor concentration. It is reported that in an acidic environment, an organic species exerts its inhibitory action by getting adsorbed on the surface of the metal to be protected

[17-19]

. The decrease observed when the temperature reaches 338 K is due to the desorption of inhibitory species from the surface of the metal

[35]

. Despite a weaker adsorption process of M-41HBI-2MTMB species at higher temperatures, the metal is effectively protected with an inhibitory efficiency of 74.3% at a concentration of 5.10^-3 M.

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Figure 2. Corrosion rate of aluminium in 1M HNO₃ environment versus M-41HBI-2MTMB concentration, at different temperatures.

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Figure 3. Inhibition efficiency versus M-41HBI-2MTMB concentration, at different temperatures.

3.1.2. Adsorption Isotherms and Thermodynamic Parameters

The study of isotherms is crucial because it is necessary to elucidate the nature of the interactions between an inhibitor and the metal surface. Thus, the modeling of adsorption was carried out using the surface coverage (θ) through various models. The appropriate model that best fits the surface coverage is given by the coefficients of determination closest to unity. The Langmuir isotherm (Figure 4) presents the highest fitting line coefficients (Table 1), but the slopes do not equal unity. Therefore, the modified Langmuir isotherm (Villamil isotherm

[36]

) of equation (9) below better describes the adsorption of M-41HBI-2MTMB species onto the aluminum surface in 1M HNO₃ medium, suggesting the presence of interactions between adsorbed species, a non-uniform distribution of adsorption sites on the metal surface, and the formed multilayer adsorption

[37]

\frac{C_{inh}}{θ} = \frac{n}{K_{ads}} + {n C}_{inh}

(9)

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Figure 4. Langmuir isotherm applied to the adsorption of M-41HBI-2MTMB molecule on the aluminum surface in 1 M HNO₃ solution.

Table 1. Langmuir isotherm parameters for M-41HBI-2MTMB on the aluminum surface.

T (K)	Equation	R²	$K_{ads}$ (10^-3 M)
298	$C_{inh} / θ = 1.0127 C_{inh} + 0.026$	0.9997	38950
308	$C_{inh} / θ = 1.0570 C_{inh} + 0.028$	0.9996	37750
318	$C_{inh} / θ = 1.1052 C_{inh} + 0.033$	0.9994	33491
328	$C_{inh} / θ = 1.1570 C_{inh} + 0.035$	0.9996	33057
338	$C_{inh} / θ = 1.2223 C_{inh} + 0.039$	0.9995	31341

The key parameters including the adsorption free energy (

{∆ G}_{ads}

), the adsorption enthalpy (

{∆ H}_{ads}

) and the adsorption entropy (

{∆ S}_{ads}

) are determined through the following equations:

{∆ G}_{ads} = - RTLn (55.5 K_{ads})

(10)

{\ln K}_{ads} = \frac{{- ∆ H}_{ads}}{RT} + \frac{{∆ S}_{ads}}{R}

(11)

55.5 represents the water’s molar concentration, R is the universal gas constant (8.31 J.mol^-1.K^-1) and T denotes the absolute temperature (K).

From the results (Table 2), the negative values of

{∆ G}_{ads}

highlight the spontaneous adsorption process of M-41HBI-2MTMB on the aluminium surface. Furthermore, the values vary between – 40 and – 20 kJ.mol^-1 assuming both chemisorption and physisorption processes

[19, 38]

. The negative sign of

{∆ H}_{ads}

indicates an exothermic process associated with the physical adsorption type of M-41HBI-2MTMB

[39, 40]

. From the positive value of the entropy, it could be concluded that an increase in disorder accompanies the adsorption of the inhibitory species due to the desorption of water molecules previously adsorbed on the aluminum surface

[35]

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Figure 5. Plot of

{Ln K}_{ads}

versus

T

of M-41HBI-2MTMB on the aluminum surface.

Table 2. Adsorption parameters of M-41HBI-2MTMB on the aluminium surface.

T (K)	${- ∆ G}_{ads}$ (kJ.mol^-1)	$- {∆ H}_{ads}$ (kJ.mol^-1)	${∆ S}_{ads}$ (J.mol^-1.K^-1)
298	36.122	4.762	47.869
308	37.254
318	38.147
328	39.311
338	40.360

The adsorption phenomenon was also investigated by plotting

log W

and

\log (W / T

) versus

1000 / T

using linear forms of the Arrhenius relation (Equation 12) and the transition state relation (Equation 13). In these relations, the parameters sought are the energy (

E_{a}^{*}

), the enthalpy variation (

{∆ H}_{a}^{*}

) and the entropy variation (

{∆ S}_{a}^{*}

) of activation.

\log W = - \frac{E_{a}^{*}}{2.303 RT} + \log k_{0}

(12)

\log \frac{W}{T} = - \frac{{∆ H}_{a}^{*}}{2.303 RT} + \frac{{∆ S}_{a}^{*}}{2.303 R} + \log \frac{R}{Nh}

(13)

Figure 6 and Table 3 represent the results obtained. The literature reports that upon the addition of an inhibitor in an acidic medium, an increase in

E_{a}^{*}

is associated with physisorption. Still, the decrease in activation energy is attributed to chemisorption

[39-41]

. Remarkably, the higher values of

E_{a}^{*}

in the inhibited acidic solutions could be related to a physical barrier formed by the adsorption of the M-41HBI-2MTMB species. The

∆ H_{a}^{*}

values are positive, indicating that the dissolution of aluminim in this corrosive environment is a heat-consuming process. Similarly, the

∆ S_{a}^{*}

values are positive meaning that the corrosion of aluminim is accompanied by an increase in disorder due to a dissociative mechanism of the activated complex

[42]

. Furthermore, increasing the concentration of M-41HBI-2MTMB promotes the increase of

E_{a}^{*}

∆ H_{a}^{*}

and

∆ S_{a}^{*}

. The adsorption of this inhibitor improves the inhibitory barrier and contributes to the disorder.

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Figure 6. Plots of (a)

log W

and (b)

\log (W / T)

versus

1000 / T

of aluminium in 1 M HNO₃ without and with M-41HBI-2MTMB.

Table 3. Activation parameters of aluminium surface in 1M HNO₃ medium without and with M-41HBI-2MTMB.

C_inh (mM)	$E_{a}^{*}$ (kJ.mol^-1)	$∆ H_{a}^{*}$ (kJ.mol^-1)	$∆ S_{a}^{*}$ (J.mol^-1K^-1)
Blank	55.03	52.40	301.08
0.001	66.74	64.10	331.59
0.005	67.60	64.97	333.33
0.01	70.09	67.46	340.30
0.05	71.58	68.95	343.69
0.1	70.24	67.60	337.79
0.5	77.05	74.42	356.66
1	81.84	79.20	369.54
5	104.42	101.78	437.82

3.2. Theoretical Study and Inhibition Mechanism

3.2.1. Quantum Calculations

The adsorption mechanism of the molecule under investigation was further discussed with quantum chemistry. Thus, the global and local reactivity parameters of the M-41HBI-2MTMB molecule were determined using Density Functional Theory (DFT) calculations. The analysis of the defined parameters informs us about the molecule's active sites and capability to share electrons with its environment. The optimized molecule and the frontier orbitals are depicted in Figure 7. From the figure, it is noticed that the HOMO density is distributed over the benzimidazole ring, and the LUMO electron density is concentrated around the carboxybenzene. Consequently, the active sites of the inhibitor could be located at any atom.

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Figure 7. Optimized structure and HOMO and LUMO orbitals of M-41HBI-2MTMB.

The energies of the frontier orbitals (E_HOMO and E_LUMO) as well as the fraction of electrons transferred (ΔN) and the electrophilicity index (ω) are indicated in Table 4. The global descriptors of the molecule studied are consistent with the literature values

[31, 32, 43-45]

. E_HOMO is high characterizing the molecule's tendency to donate electrons, while E_LUMO is low demonstrating its ability to accept electrons. Therefore, M-41HBI-2MTMB can interact with its environment which is supported by a low energy gap (ΔE = 4.478 eV). Furthermore, the high value of the electrophilicity index (ω = 3.807 eV) confirms the electrophilic nature of the studied molecule, and the fraction of electrons transferred (ΔN = 0.247 eV) indicates that M-41HBI-2MTMB donates electrons to the surface of aluminum. In sum, the global descriptors suggest favorable interactions between the molecule and its environment.

Table 4. Global reactivity descriptors of M-41HBI-2MTMB.

$E_{HOMO}$ $(eV)$	$E_{LUMO}$ $(eV)$	$ΔE$ $(eV)$	$μ$ $(D)$	$E_{T}$ $(ua)$	$χ$ $(eV)$	$η$ $(eV)$	$S$ $({eV}^{- 1})$	$ω$ $(eV)$	$ΔN$
-6.368	-1.890	4.478	1.997	-1315.889	4.129	2.239	0.447	3.807	0.247

Table 5 provides the index dual that specifies the electrophilic and nucleophilic attack sites involved in these interactions. This descriptor is determined from the Fukui functions as:

{∆ f}_{k} = f_{k}^{+} - f_{k}^{-}

(14)

Here,

f_{k}^{+}

and

f_{k}^{-}

are the nucleophilic and electrophilic Fukui functions.

According to the literature

[46-48]

, the zones sensitive to nucleophilic attack are highlighted by the highest values of the dual descriptor. In contrast, the lowest values of

{∆ f}_{k}

underscore the sites prone to electrophilic attack. In this study, the C(15) and C(18) carbon atoms exhibit the highest values of

{∆ f}_{k}

and may serve as the nucleophilic attack sites. On the contrary, the lowest dual index identifies C(7) and C(21) as potential electrophilic attack sites.

Table 5. Mulliken charges, Fukui functions and dual descriptor of pertinent atoms of M-41HBI-2MTMB.

Atom N°	$q_{k} (N - 1)$	$q_{k} (N)$	$q_{k} (N + 1)$	$f_{k}^{+}$	$f_{k}^{-}$	${∆ f}_{k}$
C(1)	0.534	0.502	0.615	0.113	-0.032	0.145
C(2)	0.443	0.232	0.021	-0.211	-0.211	0.000
C(3)	-0.377	-0.374	-0.222	0.152	0.003	0.149
C(4)	-0.465	-0.417	-0.302	0.115	0.048	0.067
C(5)	-0.208	-0.250	-0.223	0.027	-0.042	0.069
C(6)	-0.653	-0.622	-0.389	0.233	0.031	0.202
C(7)	-0.110	0.597	-0.025	-0.622	0.707	-1.329
N(13)	-0.094	-0.081	0.043	0.124	0.013	0.111
N(14)	-0.061	-0.112	-0.079	0.033	-0.051	0.084
C(15)	-0.449	-1.017	-0.719	0.298	-0.568	0.866
C(18)	-0.201	-1.12	-0.831	0.289	-0.919	1.208
C(21)	0.998	1.543	1.016	-0.527	0.545	-1.072
C(22)	-0.695	-0.502	-0.507	-0.005	0.193	-0.198
C(23)	-0.568	-0.512	-0.488	0.024	0.056	-0.032
C(24)	-0.485	-0.347	-0.383	-0.036	0.138	-0.174
C(26)	-0.566	-0.322	-0.355	-0.033	0.244	-0.277
C(28)	0.594	0.524	0.593	0.069	-0.070	0.139
S(31)	-0.459	-0.000	0.398	0.398	0.459	-0.061
C(32)	-0.086	-0.167	-0.184	-0.017	-0.081	0.064
O(33)	-0.327	-0.266	-0.244	0.022	0.061	-0.039
O(34)	-0.140	-0.119	-0.120	-0.001	0.021	-0.022
C(35)	-0.234	-0.216	-0.221	-0.005	0.018	-0.023

3.2.2. Proposed Inhibition Mechanism

Literature reported that corrosion inhibition in an acidic environment occurs through adsorption of the inhibitor onto the metal surface

[20, 22, 46, 48]

. The adsorption process includes physical or chemical interactions, or a combination of the two, influenced by several factors such as the metal's surface charge and the inhibitor's chemical structure. Several mechanisms could be proposed.

When exposed to an acidic environment, the aluminum surface takes on a positive charge. The chloride ions present in the solution are then adsorbed onto the positively charged metal surface. Besides, in an acidic environment, an organic molecule undergoes protonation. Subsequently, interactions occur between the protonated inhibitor and previously adsorbed chloride ions

[49]

. In this work, the most favorable site in M-41HBI-2MTMB for protonation is the N(13) atom. The protonated inhibitor (M-41HBI-2MTMBH⁺) can be physically adsorbed onto the aluminum surface as shown in Figure 8. M-41HBI-2MTMBH⁺ could also be chemically adsorbed onto the metal surface. The presence of the aromatic ring facilitates this chemisorption which could notably occur at the level of C(7) and C(21) atoms.

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Figure 8. Adsorption process of the protonated inhibitor on the aluminum surface.

It is also possible that M-41HBI-2MTMB formed metal complexes with

{Al}^{3 +}

released in the acidic solution

[50]

. These cations contribute to the inhibition of the aluminum surface by physical adsorption. Moreover, protonated M-41HBI-2MTMB can compete with

H^{+}

ions at the cathodic sites on the aluminum surface, by accepting electrons formed during the metal oxidation

[51]

. This mechanism agrees with DFT results as certified by the positive ΔN parameter. In addition, the inhibitor can cover a larger metal surface contributing to high inhibition efficiency.

4. Conclusions

The molecule methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate was explored as a corrosion inhibitor of aluminum in a 1 M HNO₃ solution using a combination of gravimetric analysis to examine the compound's effectiveness and the DFT calculations to provide additional insights into the molecular behavior.

Experimental results revealed that adding this molecule to the acidic medium significantly reduced the corrosion of aluminum, thus demonstrating its inhibitory properties. The inhibition efficiency increased with higher concentrations, from 10^-6 M to 5.10^-3 M, reaching up to 98.5 % at a temperature of 298 K. The adsorption of methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate followed the Villamil isotherm, suggesting repulsive interactions and formation of multiple layers on the metal surface. Analysis of thermodynamic parameters suggested a predominance of physisorption.

Density Functional Theory (DFT) calculations highlighted distinct distributions of the HOMO and LUMO electron densities of the molecule. Theoretical results also suggested a high reactivity due to a low energy gap. The active sites identified by the Fukui functions are C(15) and C(18) for electrophilic attack, C(7), and C(21) for nucleophilic attack. Additionally, electrons are transferred from the methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate molecule to the metal surface with a positive fraction of electron transfer (ΔN = 0.247 eV). Experimental and theoretical approaches are consistent with the inhibitory behavior of the molecule and the mechanism underlying its adsorption mode.

Abbreviations

DFT	Density Functional Theory
HOMO	Highest Occupied Molecular Orbital
LUMO	Lowest Unoccupied Molecular Orbital
M-41HBI-2MTMB	Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate

Author contributions

Rokia Hadja Touré: Investigation, Validation, Formal Analysis, Methodology, Software.

Aphouet Aurelie Koffi: Writing – original draft, Data curation, Writing – review & editing, Formal Analysis, Methodology.

Mougo André Tigori: Writing – original draft, Data curation, Writing – review & editing, Formal Analysis, Methodology.

Paulin Marius Niamien: Conceptualization, Supervision, Data curation, Validation, Methodology, Visualization.

Funding

No funding was received during the preparation of this manuscript.

Conflicts of Interest

The authors declare no conflicts of interest.

References

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Toure, R. H., Koffi, A. A., Tigori, M. A., Niamien, P. M. (2024). Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment. American Journal of Applied Chemistry, 12(6), 135-148. https://doi.org/10.11648/j.ajac.20241206.12

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Toure, R. H.; Koffi, A. A.; Tigori, M. A.; Niamien, P. M. Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment. Am. J. Appl. Chem. 2024, 12(6), 135-148. doi: 10.11648/j.ajac.20241206.12

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Toure RH, Koffi AA, Tigori MA, Niamien PM. Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment. Am J Appl Chem. 2024;12(6):135-148. doi: 10.11648/j.ajac.20241206.12

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@article{10.11648/j.ajac.20241206.12,
  author = {Rokia Hadja Toure and Aphouet Aurelie Koffi and Mougo Andre Tigori and Paulin Marius Niamien},
  title = {Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment
},
  journal = {American Journal of Applied Chemistry},
  volume = {12},
  number = {6},
  pages = {135-148},
  doi = {10.11648/j.ajac.20241206.12},
  url = {https://doi.org/10.11648/j.ajac.20241206.12},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajac.20241206.12},
  abstract = {Organic inhibitors are crucial for preserving metals from corrosion in acidic environments. In this regard, the methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate (M-41HBI-2MTMB) was synthesized and investigated as an eco-friendly inhibitor for aluminum in a molar nitric acid solution (1 M HNO3). The gravimetric technique was used to study the inhibitory properties of the molecule, and the density functional theory (DFT) was conducted to elucidate the corrosion inhibition mechanism. The experimental data indicated that M-41HBI-2MTMB reduced the corrosion of the metal with a significant inhibition efficiency. The corrosion inhibition increased with an increase in the concentration of the molecule, reaching an efficiency of 98.5% at a concentration of 5.10-3 M, and a temperature of 298 K. Adsorption isotherms and thermodynamic parameters were studied to elucidate the interactions between M-41HBI-2MTMB and the metal surface. The inhibitor adsorbed spontaneously onto the aluminum surface following the Villamil model (modified Langmuir isotherm). Additionally, the Gibbs free energy less than - 40 kJ.mol-1 and the negative value of the enthalpy of adsorption suggested mixed-type adsorption with a predominance of physical interactions. The theoretical findings of DFT calculations revealed a positive fraction of electrons transferred (ΔN = 0.247 eV), a high value of the electrophilicity index (ω = 3.807 eV) as well as a low energy gap (ΔE = 4.478 eV) showing favorable interactions of M-41HBI-2MTMB with its environment. The active sites of the molecule were highlighted at the level of carbon atoms, and a corrosion inhibition mechanism was proposed.
},
 year = {2024}
}

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TY  - JOUR
T1  - Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment

AU  - Rokia Hadja Toure
AU  - Aphouet Aurelie Koffi
AU  - Mougo Andre Tigori
AU  - Paulin Marius Niamien
Y1  - 2024/12/12
PY  - 2024
N1  - https://doi.org/10.11648/j.ajac.20241206.12
DO  - 10.11648/j.ajac.20241206.12
T2  - American Journal of Applied Chemistry
JF  - American Journal of Applied Chemistry
JO  - American Journal of Applied Chemistry
SP  - 135
EP  - 148
PB  - Science Publishing Group
SN  - 2330-8745
UR  - https://doi.org/10.11648/j.ajac.20241206.12
AB  - Organic inhibitors are crucial for preserving metals from corrosion in acidic environments. In this regard, the methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate (M-41HBI-2MTMB) was synthesized and investigated as an eco-friendly inhibitor for aluminum in a molar nitric acid solution (1 M HNO3). The gravimetric technique was used to study the inhibitory properties of the molecule, and the density functional theory (DFT) was conducted to elucidate the corrosion inhibition mechanism. The experimental data indicated that M-41HBI-2MTMB reduced the corrosion of the metal with a significant inhibition efficiency. The corrosion inhibition increased with an increase in the concentration of the molecule, reaching an efficiency of 98.5% at a concentration of 5.10-3 M, and a temperature of 298 K. Adsorption isotherms and thermodynamic parameters were studied to elucidate the interactions between M-41HBI-2MTMB and the metal surface. The inhibitor adsorbed spontaneously onto the aluminum surface following the Villamil model (modified Langmuir isotherm). Additionally, the Gibbs free energy less than - 40 kJ.mol-1 and the negative value of the enthalpy of adsorption suggested mixed-type adsorption with a predominance of physical interactions. The theoretical findings of DFT calculations revealed a positive fraction of electrons transferred (ΔN = 0.247 eV), a high value of the electrophilicity index (ω = 3.807 eV) as well as a low energy gap (ΔE = 4.478 eV) showing favorable interactions of M-41HBI-2MTMB with its environment. The active sites of the molecule were highlighted at the level of carbon atoms, and a corrosion inhibition mechanism was proposed.

VL  - 12
IS  - 6
ER  -

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Rokia Hadja Toure

Laboratory of Constitution and Reaction of Matter, Training and Research Unit of Sciences of Structure, Matter and Technology, Felix Houphouet Boigny University, Abidjan, Ivory Coast
Aphouet Aurelie Koffi

Laboratory of Constitution and Reaction of Matter, Training and Research Unit of Sciences of Structure, Matter and Technology, Felix Houphouet Boigny University, Abidjan, Ivory Coast

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http://orcid.org/0000-0003-2306-7593
Mougo Andre Tigori

Laboratory of Environmental Sciences and Technologies, Training and Research Unit of Environment, Jean Lorougnon Guede University, Daloa, Ivory Coast
Paulin Marius Niamien

Laboratory of Constitution and Reaction of Matter, Training and Research Unit of Sciences of Structure, Matter and Technology, Felix Houphouet Boigny University, Abidjan, Ivory Coast

http://orcid.org/0000-0002-0744-9623

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Toure, R. H., Koffi, A. A., Tigori, M. A., Niamien, P. M. (2024). Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment. American Journal of Applied Chemistry, 12(6), 135-148. https://doi.org/10.11648/j.ajac.20241206.12

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Toure, R. H.; Koffi, A. A.; Tigori, M. A.; Niamien, P. M. Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment. Am. J. Appl. Chem. 2024, 12(6), 135-148. doi: 10.11648/j.ajac.20241206.12

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Toure RH, Koffi AA, Tigori MA, Niamien PM. Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment. Am J Appl Chem. 2024;12(6):135-148. doi: 10.11648/j.ajac.20241206.12

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@article{10.11648/j.ajac.20241206.12,
  author = {Rokia Hadja Toure and Aphouet Aurelie Koffi and Mougo Andre Tigori and Paulin Marius Niamien},
  title = {Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment
},
  journal = {American Journal of Applied Chemistry},
  volume = {12},
  number = {6},
  pages = {135-148},
  doi = {10.11648/j.ajac.20241206.12},
  url = {https://doi.org/10.11648/j.ajac.20241206.12},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajac.20241206.12},
  abstract = {Organic inhibitors are crucial for preserving metals from corrosion in acidic environments. In this regard, the methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate (M-41HBI-2MTMB) was synthesized and investigated as an eco-friendly inhibitor for aluminum in a molar nitric acid solution (1 M HNO3). The gravimetric technique was used to study the inhibitory properties of the molecule, and the density functional theory (DFT) was conducted to elucidate the corrosion inhibition mechanism. The experimental data indicated that M-41HBI-2MTMB reduced the corrosion of the metal with a significant inhibition efficiency. The corrosion inhibition increased with an increase in the concentration of the molecule, reaching an efficiency of 98.5% at a concentration of 5.10-3 M, and a temperature of 298 K. Adsorption isotherms and thermodynamic parameters were studied to elucidate the interactions between M-41HBI-2MTMB and the metal surface. The inhibitor adsorbed spontaneously onto the aluminum surface following the Villamil model (modified Langmuir isotherm). Additionally, the Gibbs free energy less than - 40 kJ.mol-1 and the negative value of the enthalpy of adsorption suggested mixed-type adsorption with a predominance of physical interactions. The theoretical findings of DFT calculations revealed a positive fraction of electrons transferred (ΔN = 0.247 eV), a high value of the electrophilicity index (ω = 3.807 eV) as well as a low energy gap (ΔE = 4.478 eV) showing favorable interactions of M-41HBI-2MTMB with its environment. The active sites of the molecule were highlighted at the level of carbon atoms, and a corrosion inhibition mechanism was proposed.
},
 year = {2024}
}

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TY  - JOUR
T1  - Investigation on the Properties of Methyl 4-(((1-H benzo[d]imidazol-2-yl) methyl)thio)methyl)Benzoate on Aluminum Corrosion in Acidic Environment

AU  - Rokia Hadja Toure
AU  - Aphouet Aurelie Koffi
AU  - Mougo Andre Tigori
AU  - Paulin Marius Niamien
Y1  - 2024/12/12
PY  - 2024
N1  - https://doi.org/10.11648/j.ajac.20241206.12
DO  - 10.11648/j.ajac.20241206.12
T2  - American Journal of Applied Chemistry
JF  - American Journal of Applied Chemistry
JO  - American Journal of Applied Chemistry
SP  - 135
EP  - 148
PB  - Science Publishing Group
SN  - 2330-8745
UR  - https://doi.org/10.11648/j.ajac.20241206.12
AB  - Organic inhibitors are crucial for preserving metals from corrosion in acidic environments. In this regard, the methyl 4-(((1-H benzo[d]imidazol-2-yl)methyl)thio)methyl)benzoate (M-41HBI-2MTMB) was synthesized and investigated as an eco-friendly inhibitor for aluminum in a molar nitric acid solution (1 M HNO3). The gravimetric technique was used to study the inhibitory properties of the molecule, and the density functional theory (DFT) was conducted to elucidate the corrosion inhibition mechanism. The experimental data indicated that M-41HBI-2MTMB reduced the corrosion of the metal with a significant inhibition efficiency. The corrosion inhibition increased with an increase in the concentration of the molecule, reaching an efficiency of 98.5% at a concentration of 5.10-3 M, and a temperature of 298 K. Adsorption isotherms and thermodynamic parameters were studied to elucidate the interactions between M-41HBI-2MTMB and the metal surface. The inhibitor adsorbed spontaneously onto the aluminum surface following the Villamil model (modified Langmuir isotherm). Additionally, the Gibbs free energy less than - 40 kJ.mol-1 and the negative value of the enthalpy of adsorption suggested mixed-type adsorption with a predominance of physical interactions. The theoretical findings of DFT calculations revealed a positive fraction of electrons transferred (ΔN = 0.247 eV), a high value of the electrophilicity index (ω = 3.807 eV) as well as a low energy gap (ΔE = 4.478 eV) showing favorable interactions of M-41HBI-2MTMB with its environment. The active sites of the molecule were highlighted at the level of carbon atoms, and a corrosion inhibition mechanism was proposed.

VL  - 12
IS  - 6
ER  -

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