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.
Keywords(thiadiazol-5-yl)methoxy)coumarin Corrosion inhibitor Isotherm Weight loss
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.
Open AccessThis article is 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, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.
- Al-Amiery A, Binti Kassim F, Kadhum V, Mohamad A (2016) Synthesis and characterization of a novel eco-friendly corrosion inhibition for mild steel in 1 M hydrochloric acid. Sci Rep 6:19890. doi: 10.1038/srep19890
- Sing DN, Dey AK (1993) Synergistic effects of inorganic and organic cations on inhibitive performance of propargyl alcohol on steel dissolution in boiling hydrochloric acid solution. Corrosion 49:594–600View ArticleGoogle Scholar
- Al-Amiery AA, Kadhum AAH, Mohamad AB, Musa AY, Li CJ (2013) Electrochemical study on newly synthesized chlorocurcumin as an inhibitor for mild steel corrosion in hydrochloric acid. Materials 6:5466–5477View ArticleGoogle Scholar
- Arab ST, Noor EA (1993) Inhibition of acid corrosion of steel by some S-Alkylisothiouronium. Corrosion 49:122–129View ArticleGoogle Scholar
- Khaled FH (2003) Investigation of the inhibitive effect of ortho-substituted on corrosion of iron in 0.5 M H2SO4 solutions. Mater Chem Phys 82:949–960View ArticleGoogle Scholar
- Lin W (2001) Inhibiting effect of 2-mercaptopyrimidine on the corrosion of a low carbon steel in phosphoric acid. Corros Sci 43:1637–1644View ArticleGoogle Scholar
- Shorky H, Yuasa M, Sekine I, Issa RM, El-Baradie HY, Gomma GK (1998) Corrosion inhibition of mild steel by schiff base compounds in various aqueous solutions. Corros Sci 40:2173–2186View ArticleGoogle Scholar
- Cang H, Shi WY, Shao JL, Xu Q (2012) Synthesis and some physical properties of magnetite (Fe3O4) nanoparticles. Int J Electrochem Sci 7:5626Google Scholar
- Ma H, Song T, Sun H, Li X (1020) Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces. Thin Solid Films 2008:516Google Scholar
- El Ashry EH, El Nemr AS, Essawy A, Ragab S (2008) Problems and progress in organic coatings science and technology. Prog Org Coat 61:11View ArticleGoogle Scholar
- Ju H, Kai ZP, Li Y (2008) Corrosion behaviour of magnesium/aluminium alloys in 3.5 wt.% NaCl. Corros Sci 50:865View ArticleGoogle Scholar
- Egan D, O’Kennedy R, Moran E, Cox D, Prosser E, Thornes RD (1990) The pharmacology, metabolism, analysis, and applications of coumarin and coumarin-related compounds. Drug Metab Rev 22:503–529View ArticleGoogle Scholar
- Devji T, Reddy C, Woo C, Awale S, Kadota S, CorrioMoniz D (2011) Pancreatic Anticancer activity of a novel geranylgeranylated coumarin derivative. Bioorg Med Chem Lett 21:57705773View ArticleGoogle Scholar
- Yeh J-Y, Coumar MS, Horng J-T, Shiao H-Y, Lee H-L (2010) anti-influenza drug discovery: structure-activity relationship and mechanistic insight into novel angelicin derivatives. J Med Chem 53:1519–1533View ArticleGoogle Scholar
- Al-Amiery AK, Mohamad A, How C, Junaedi S (2014) Inhibition of mild steel corrosion in sulfuric acid solution by new Schiff base. Materials 7(2):787–804View ArticleGoogle Scholar
- Mohamad AB, Kadhum AAH, Al-Amiery AA, Ying LC, Musa AY (2014) Synergistic of a coumarin derivative with potassium iodide on the corrosion inhibition of aluminum alloy in 1.0 M H2SO4. Met Mater Int 20(3):459–467. doi:10.1007/s12540-014-3008-3 View ArticleGoogle Scholar
- Kadhum AAH, Mohamad AB, Hammed LA, Al-Amiery AA, San NH, Musa AY (2014) Inhibition of mild steel corrosion in hydrochloric acid solution by new coumarin. Materials 7(6): 4335–4348. doi:10.3390/ma7064335
- Banerjee G, Malhotra SN (1992) Contribution to adsorption of aromaticamines on mild-steel surface from HCl solutions by impedance, UV, and raman-spectroscopy. Corrosion 48:10View ArticleGoogle Scholar
- Gece G (2008) The use of quantum chemical methods in corrosion inhibitor studies. Corros Sci 50:2981View ArticleGoogle Scholar
- Al-Amiery AA, Al-Bayati R, Saour K, Radi M (2012) Cytotoxicity, antioxidant and antimicrobial activities of novel 2-quinolone derivatives derived from coumarins. Res Chem Intermed 38(358):559–569View ArticleGoogle Scholar
- Al-Amiery A.A, Al-MajedyKadhum A.A.H, Mohamad A (2015) Novel macromolecules derived from coumarin: synthesis and antioxidant activity. Sci Rep 5: 11825. doi:10.1038/srep11825)
- Al-Amiery AA, Musa AY, Kadhum AAH, Mohamad A (2011) The antioxidant activity of new coumarin derivatives. Int J Mol Sci 12:5757–5761Google Scholar
- Al-Amiery A, Kadhum A, Alobaidy A, Mohamad A, Hoon P (2014) Novel corrosion inhibitor for mild steel in HCl. Materials 7(2):662–672View ArticleGoogle Scholar
- Al-Amiery AA, Kadhum AAH, Mohamad A (2012) Antifungal and antioxidant activities of pyrrolidonethiosemicarbazone complexes. Bioinorg Chem Appl 2012:1–5View ArticleGoogle Scholar
- Al-Amiery AA (2012) Synthesis and antioxidant, antimicrobial evaluation, DFT studies of novel metal complexes derivate from Schiff base. Res Chem Intermed 38:745–759View ArticleGoogle Scholar
- Obayes H, Alwan G, Alobaidy A, Al-Amiery A, Kadhum A, Mohamad A (2014) Quantum chemical assessment of benzimidazole derivatives as corrosion inhibitors. Chem Cent J 8:21View ArticleGoogle Scholar
- Al-Amiery AA, Kadhum AAH, Mohamad A (2012) Antifungal activities of new coumarins. Molecules 17:5713–5723View ArticleGoogle Scholar
- Al-Majedy Y, Kadhum K, Al-Amiery AAH (1982) A synthesis and characterization of some new 4-Hydroxy-coumarin derivatives. Molecules 19(8):11791–11799View ArticleGoogle Scholar
- Kadhum AA, Al-Amiery AA, Shikara M, Kadhum AA, Al-Bayati R (1980) Synthesis, structure elucidation and DFT studies of new thiadiazoles. Int J Phys Sci 6:6692–6697Google Scholar
- Junaedi S, Kadhum AAH, Al-Amiery AA, Mohamad AB, Takriff MS (2012) Synthesis and characterization of novel corrosion inhibitor derived from oleic acid: 2-Amino 5-Oleyl-1,3,4Thiadiazol (AOT). Int J Electrochem Sci 7:3543–3554Google Scholar
- Deng Q, Shi HW, Ding NN, Chen BQ, He XP, Liu G, Tang Y, Long YT, Chen GR (2012) Novel triazolylbis-amino acidderivatives readily synthesized via click chemistry as potentialcorrosion inhibitors for mild steel in HCl. Corros Sci 57:220–227View ArticleGoogle Scholar
- Tao Z, Hea W, Wang S, Zhang S, Zhou G (2012) A study of differential polarization curves and thermodynamic properties for mild steel in acidic solution with nitrophenyltriazole derivative. Corros Sci 60:205–213View ArticleGoogle Scholar
- Ji Gopal, Dwivedi P, Sundaram S, Prakash R (2013) Inhibitive effect of chlorophytum borivilianum root extract on mild steel corrosion in HCl and H2SO4 solutions. Ind Eng Chem Res 52(10673):10681Google Scholar
- Gopal J, Shukla SK, Dwived P, Sundaram S, Prakash R (2011) Inhibitive effect of argemone mexicana plant extract on acid corrosion of mild steel. Ind Eng Chem Res 50:11954–11959View ArticleGoogle Scholar
- Zhang QB, Hua YX (2009) Corrosion inhibition of mild steel by alkylimidazolium ionic liquids in hydrochloric acid. Electrochim Acta 54:1881–1887View ArticleGoogle Scholar
- Khaled KF (2010) Understanding corrosion inhibition of mild steel in acid medium by some furan derivatives: a comprehensive overview. J Electrochem Soc 157:C116–C124View ArticleGoogle Scholar
- Aytac AU, Ozmen M, Kabasakaloğlu M (2005) Investigation of some Schiff bases as acidic corrosion of alloy AA3102. Mater Chem Phys 89:176–181View ArticleGoogle Scholar
- Dandia A, Gupta L, Singh P, Quraishi MA (2013) Ultrasound-assisted synthesis of pyrazolo[3,4b]pyridines as potential corrosion inhibitors for mild steel in 1.0 M HCl. ACS Sustain. Chem Eng 1:1303–1310Google Scholar
- Al-Amiery AA, Al-Majedy YK, Kadhum AAH, Mohamad AB (2015) New coumarin derivative as an eco-friendly inhibitor of corrosion of mild steel in acid medium molecules. Molecules 20:366–383View ArticleGoogle Scholar
- Bavarian B, Kim Yeob, Reiner L (2003) Corrosion protection of steel rebar in concrete by migrating corrosion inhibitors, CORROSION 2003. Appl Electrochem 34:95Google Scholar
- Al-Amiery AA, Kadhum AAH, Mohamad AB, Junaedi S (2013) A novel hydrazinecarbothioamide as a potential corrosion inhibitor for mild steel in HCl. Materials 6:1420–1430View ArticleGoogle Scholar
- Rubaye A, Abdulwahid A, Al-Baghdadi S, Al-Amiery A, Kadhum A, Mohamad A (2015) Cheery sticks plant extract as a green corrosion inhibitor complemented with LC-EIS/MS Spectroscopy. Int J Electrochem Sci 10:8200–8209Google Scholar
- Al-Amiery AA, Musa AY, Kadhum AAH, Mohamad A (2011) The use of umbelliferone in the synthesis of new heterocyclic compounds. Molecules 16:6833–6843View ArticleGoogle Scholar
- Ebenso EE, Isabirye DA, Eddy NO (2010) Adsorption and quantum chemical studies on the inhibition potentials of some thiosemicarbazides for the corrosion of mild steel in acidic medium. Int J Mol Sci 11:2473–2498View ArticleGoogle Scholar
- Ashassi-Sorkhabi H, Shaabani B, Seifzadeh D (2005) Effect of some pyrimidinic Schiff bases on the corrosion of mild steel in HCl solution. Electrochim Acta 50:3446–3452View ArticleGoogle Scholar
- Khaleda KF, Fadl-Allahb SA, Hammoutic B (2009) Some benzotriazole derivatives as corrosion inhibitors for copper in acidic medium: experimental and quantum chemical molecular dynamics approach. Mater Chem Phys 117:148–155View ArticleGoogle Scholar
- Bahrami MJ, Hosseini SMA, Pilvar P (2010) Experimental and theoretical investigation of organic compounds as inhibitors for mild steel corrosion in sulfuric acid medium. Corros Sci 52:2793–2803View ArticleGoogle Scholar
- Cruz J, Pandiyan T, Garcıa-Ochoa E (2005) A new inhibitor for mild carbon steel: electrochemical and DFT studies. J Electroanal Chem 583:8–16View ArticleGoogle Scholar
- Costa JM, Lluch JM (1984) The use of quantum mechanics calculations for the study of corrosion inhibitors. Corros Sci 24:924–933View ArticleGoogle Scholar
- Khalil N (2003) Quantum chemical approach of corrosion inhibition. Electrochim Acta 48:2635–2640View ArticleGoogle Scholar
- Al-Amiery AA (2012) Antimicrobial and antioxidant activities of new metal complexes derived from (E)-3-((5-phenyl-1,3,4-oxadiazol-2-ylimino)methyl)naphthalen-2-ol. Med Chem Res 21:3204–3213View ArticleGoogle Scholar
- Xia S, Qiu M, Yu L, Liu F, Zhao H (2008) Molecular dynamics and density functional theory study on relationship between structure of imidazoline derivatives and inhibition performance. Corros Sci 50:2021–2029View ArticleGoogle Scholar
- Musa AY, Kadhum AH, Mohamad AB, Rahoma AB, Mesmari H (2010) Electrochemical and quantum chemical calculations on 4,4-dimethyloxazolidine-2-thione as inhibitor for mild steel corrosion in hydrochloric acid. J Mol Struct 969:233–327View ArticleGoogle Scholar
- Obot IB, Ebenso EE, Akpan IA, Gasem ZM, Alfobi Ayo S (2012) Thermodynamic and density functional theory investigation of sulphathiazole as green corrosion inhibitor at mild steel/hydrochloric acid interface. Int J Electrochem Sci 7:1978–1996Google Scholar
- Obot IB, Obi-Egbedi NO (2011) Anti-corrosive properties of xanthone on mild steel corrosion in sulphuric acid: experimental and theoretical investigations. Curr Appl Phys 11:382–392View ArticleGoogle Scholar
- Obot IB, Obi-Egbedi NO, Eseola AO (2011) Anticorrosion potential of 2-Mesityl-1H-imidazo[4,5-f][1,10]phenanthroline on mild steel in sulfuric acid solution: experimental and theoretical study. Ind Eng Chem Res 50:2098–2110View ArticleGoogle Scholar
- Obot IB, Obi-Egbedi NO (2010) Theoretical study of benzimidazole and its derivatives and their potential activity as corrosion inhibitors. Corros Sci 52:657–660View ArticleGoogle Scholar