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Synthesis, inhibition effects and quantum chemical studies of a novel coumarin derivative on the corrosion of mild steel in a hydrochloric acid solution
© Al-Azawi et al. 2016
Received: 9 January 2016
Accepted: 11 April 2016
Published: 27 April 2016
The acid corrosion inhibition process of mild steel in 1 M HCl by 4-[(2-amino-1, 3, 4-thiadiazol-5-yl)methoxy]coumarin (ATC), has been investigated using weight loss technique and scanning electron microscopy (SEM). ATC was synthesized, and its chemical structure was elucidated and confirmed using spectroscopic techniques (infrared and nuclear magnetic resonance spectroscopy).
The results indicated that inhibition efficiencies were enhanced with an increase in concentration of inhibitor and decreased with a rise in temperature. The adsorption equilibrium constant (K) and standard free energy of adsorption (ΔGads) were calculated. Quantum chemical parameters such as highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy (EHOMO and ELUMO, respectively) and dipole moment (μ) were calculated and discussed. The results showed that the corrosion inhibition efficiency increased with an increase in both the EHOMO and μ values but with a decrease in the ELUMO value.
Our research show that the synthesized macromolecule represents an excellent inhibitor for materials in acidic solutions. The efficiency of this macromolecule had maximum inhibition efficiency up to 96 % at 0.5 mM and diminishes with a higher temperature degree, which is revealing of chemical adsorption. An inhibitor molecule were absorbed by metal surface and follow Langmuir isotherms low and establishes an efficient macromolecule inhibitor having excellent inhibitive properties due to entity of S (sulfur) atom, N (nitrogen) atom and O (oxygen) atom.
It is very important to use corrosion inhibitors to prevent metal dissolution and minimize acid consumption [1–4]. The majority of well-known acid inhibitors are organic compounds that contain nitrogen, sulfur and oxygen atoms. The inhibitory action exercised by organic compounds on the dissolution of metallic species is normally related to adsorption interactions between the inhibitors and the metal surface. The planarity (p) and lone pairs of electrons present on N, O and S atoms are important structural features that control the adsorption of these molecules onto the surface of the metal [5–7]. The effective and efficient corrosion inhibitors are those compounds that have π-bonds, contain hetero-atoms such as sulfur, nitrogen, oxygen and phosphorous and allow the adsorption of compounds on the metal surface [8–11]. The organic inhibitors decrease the corrosion rate by adsorbing on the metal surface and blocking the active sites by displacing water molecules, leading to the formation of a compact barrier film on the metal surface. Coumarins exhibit pharmacological activities, such as anticancer, anti-inflammatory , anti-influenza, antituberculosis , anti-HIV, antiviral, antialzheimer and antimicrobial activities . Nowadays researchers go for coumarins to used as corrosion inhibitors due to the electronic structure, planarity, lone pairs of electrons present on oxygen and stability [15–17]. The successful control of corrosion develops the life of mechanical hardware. Nowadays corrosion inhibitors have more significant, due to their usage in industries. Organic inhibitors considered as eco-friendly much more than inorganic one. Organic inhibitors decreasing the corrosion rate by adsorbing onto the surface of the metal through the active sites namely phosphorus, sulfur, oxygen, nitrogen atoms or pi-bonds . Recently the quantum chemical computations based on density function theory (DFT) become powerful investigation theoretical tool for researchers to investigate the ability of organic molecules as corrosion inhibitions. This tool offers a glance at physical insights on corrosion inhibition mechanisms . In continuation of previous work [20–27], we focus herein on the design our approach to increase the inhibitive properties based on conjugated system and electron density, in addition to applied the theoretical studies to associate the inhibitive properties with electronic structures. Initially we were starting from 4-hydroxycoumarin as starting material for the synthesis of 4-[(2-amino-1, 3, 4-thiadiazol-5-yl)methoxy]coumarin (ATC) contain 1, 3, 4-thiadiazol moiety.
The chemicals utilized were supplied by Sigma-Aldrich and the purity checked by TLC (thin layer chromatography). Infrared spectra were obtained on a Thermo Scientific, NICOLET 6700 FTIR spectrometer. Nuclear magnetic resonance spectra were obtained on a JEOL JNM-ECP 400. Elemental microanalysis, was carried out using a model 5500-Carlo Erba C.H.N elemental analyzer.
Synthesis of corrosion inhibitor “4-[(2-amino-1, 3, 4-thiadiazol-5-yl)methoxy]coumarin (ATC)”
This compound was synthesized in good yield according to the previously described procedures [28, 29]. Phosphorus oxychloride (20 ml) was added to 2-(2-oxo-2H-chromen-4-yloxy) acetic acid (0.05 mol) and the mixture was stirred for I h at room temperature. Thiosemicarbazide (4.56 g, 0.05 mol) was added and the mixture was heated and reflux for 5 h. On cooling, the mixture was poured on to ice. After 4 h stir for 15 min to decompose the excess phosphorusoxychloride, then heated under reflux for 30 min, cooling, the mixture was neutralized by 5 % potassium hydroxide, the precipitated was filtered, washed with water, dried and crystallized. Recrystallization from dichloromethane yields 55 %, m.p. 99 °C; 1H-NMR (CDCl3): δ 5.62 (s, 1H, –C=C–H), δ 4.91 and δ 5.33 (d, 2H, t, 2H, for OCH2), δ 7.23–7.87 (m, 1H, C–H aromatic ring), δ5.21 (s, NH2); IR: 3314.5 and 3375.1 cm−1 (s, H, amine), 291.2 (C–H alkane); 3079.1 (C–H aromatic),1752.3 cm−1 (C=O, lactone), 1591.1 cm−1(C=N, imine), 1635.3 cm−1 (C=C aromatic); Anal. Calcd. for C12H9N3O3S: C 52.36 %, H 3.30 %, N 15.26 %. Experimentally: C 51.64 % H 2.92 % and N 14.94 %s.
Mild steel specimens utilized throughout our work were supplied from “Metal-Samples-Company” (St. Marys, PA, United States). The weight composition percentages of the MS were: Iron, 99.21; Carbon, 0.21; Silicon, 0.38; Phosphorous, 0.09; S, 0.05; Manganese, 0.05; and Alaminuim, 0.01. The specimens were cleaned using the chemical cleaning procedures described in ASTM G1-03 test method . All experiments were done in aerated and non stirred hydrochloric acid mediums contain various concentrations of (ATC).
Weight loss techniques
Quantum chemical calculations
The molecular optimization was carried out using the density function theory (DFT)/B3LYP with basis set 6-31G. Quantum chemical calculations such as E HOMO (highest occupied molecular orbital energy), E LUMO (lowest unoccupied molecular orbital energy) and μ (dipole moment) were calculated and discussed.
Results and discussion
Weight loss method
Effect of concentration
Effect of temperature
Scanning electron microscopy, SEM
Adsorption isotherm and mechanism of corrosion and inhibition
Suggested mechanisms of actions of coumarin as inhibitor
Quantum chemical calculations
Calculated quantum chemical properties for the most stable conformation of (ATC)
f − max
f + max
Charges (Mulliken charges) for the ATC
Our research demonstrate that the synthesized macromolecule represents an excellent inhibitor for materials in acidic solutions. The efficiency of this macromolecule had maximum inhibition efficiency up to 96 % at 0.5 mM and diminish with a higher temperature degree, which is revealing of chemical adsorption. Inhibitor molecules were absorbed by metal surface and follow Langmuir isotherms low and establishes an efficient macromolecule inhibitor hading excellent inhibitive properties due to entity of S (sulfur) atom, N (nitrogen) atom and O (oxygen) atom. SEM (Scanning electron microscope) measurements were confirming the figuration of a protective metal surface. Inhibition study of synthesized macromolecules obviously expose their function in the protection of MS in 1 M HCl.
AAA the principle investigator and wrote the main manuscript text. KFA and SBA evaluated the corrosion inhibitor with surface characterization, AZM, SAM and TKA were synthesis the inhibitor and prepared Figures while ABM and AHK were co-investigators and prepared part of characterization. All authors read and approved the final manuscript.
The authors gratefully acknowledge the Universiti Kebangsaan Malaysia under Grant DIP-2012-02.
The authors declare that they have no competing interests.
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