Quinoline Carbonitriles as Novel Inhibitors for N80 Steel Corrosion in Oil-Well Acidizing: Experimental and Computational Insights

 Mohammad Salman Mohammad Salman, Vandana SrivastavaVandana Srivastava, M. A. QuraishiM. A. Quraishi, Dheeraj Singh ChauhanDheeraj Singh Chauhan, K. R. AnsariK. R. Ansari, Jiyaul HaqueJiyaul Haque
Российский электрохимический журнал
Abstract / Full Text

Three quinoline derivatives as corrosion inhibitors for N80 steel 15% HCl solutions. Influence of the –H, –OCH3 groups and the introduction of π bonding are reported in the present report. Experimental studies were performed using gravimetric tests, electroanalytical methods, and surface analysis. The cinnamaldehyde derivative displayed the maximum inhibition efficiency of 95% at 300 mg L–1, followed by the –OCH3 and the –H derivatives. The inhibitor adsorption on the metal surface obeyed the Langmuir isotherm with a mixed mode of physical and chemical adsorption. Impedance measurements revealed an increase in the charge transfer resistance with the addition of increasing inhibitor dosage, which supported the inhibitor adsorption. Frequency modulations displayed a lowering in the corrosion current density upon the addition of the corrosion inhibitors. Polarization studies revealed that all the three inhibitors showed a mixed-type inhibition behavior with cathodic prevalence. SEM and FTIR of the inhibitor-adsorbed steel surface affirmed the adsorption of inhibitor and improvement in the surface smoothness of the N80 steel. The pKa analysis revealed that all the three inhibitors undergo protonation at the pyridine Nitrogen at the experimental pH. The DFT studies showed that the protonated form of the inhibitors is more active compared to the neutral form.

Author information
  • Department of Chemistry, Indian Institute of Technology, Banaras Hindu University, 221005, Varanasi, India Mohammad Salman, Vandana Srivastava & Jiyaul Haque
  • Center of Research Excellence in Corrosion, Research Institute, King Fahd University of Petroleum and Minerals, 31261, Dhahran, Saudi ArabiaM. A. Quraishi, Dheeraj Singh Chauhan & K. R. Ansari
  1. Quraishi, M.A., Chauhan, D.S., and Saji, V.S., Heterocyclic Organic Corrosion Inhibitors: Principles and Applications, Amsterdam: Elsevier, 2020.
  2. Ansari, K.R., Chauhan, D.S., Singh, A., Saji, V.S., and Quraishi, M.A., Corrosion inhibitors for acidizing process in oil and gas sectors, in Corrosion Inhibitors in the Oil and Gas Industry, Saji, V.S. and Umoren, S.A., Eds., Wiley-VCH, 2020.
  3. Schmitt, G., Application of inhibitors for acid media: report prepared for the European federation of corrosion working party on inhibitors, Brit. Corros. J., 1984, vol. 19, no. 4, p. 165.
  4. Chauhan, D.S., Quraishi, M.A., Carrière, C., Seyeux, A., Marcus, P., and Singh, A., Electrochemical, ToF-SIMS and computational studies of 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol as a novel corrosion inhibitor for copper in 3.5% NaCl, J. Mol. Liq., 2019, vol. 289, p. 111113.
  5. Chauhan, D.S., Sorour, A.A., and Quraishi, M.A., An overview of expired drugs as novel corrosion inhibitors for metals and alloys, Int. J. Chem. Pharm. Sci., 2016, vol. 4, no. 12, p. 680.
  6. El-Hajjaji, F., Messali, M., Aljuhani, A., Aouad, M., Hammouti, B., Belghiti, M., Chauhan, D.S., and Quraishi, M.A., Pyridazinium-based ionic liquids as novel and green corrosion inhibitors of carbon steel in acid medium: electrochemical and molecular dynamics simulation studies, J. Mol. Liq., 2018, vol. 249, p. 997.
  7. Singh, P., Chauhan, D.S., Chauhan, S.S., Singh, G., and Quraishi, M.A., Chemically modified expired Dapsone drug as environmentally benign corrosion inhibitor for mild steel in sulphuric acid useful for industrial pickling process, J. Mol. Liq., 2019, vol. 286, p. 110903.
  8. Singh, P., Chauhan, D.S., Chauhan, S.S., Singh, G., and Quraishi, M.A., Bioinspired synergistic formulation from dihydropyrimdinones and iodide ions for corrosion inhibition of carbon steel in sulphuric acid, J. Mol. Liq., 2019, vol. 298, p. 112051.
  9. Cicileo, G., Rosales, B., Varela, F., and Vilche, J., Inhibitory action of 8-hydroxyquinoline on the copper corrosion process, Corros. Sci., 1998, vol. 40, no. 11, p. 1915.
  10. Ebenso, E.E., Obot, I.B., and Murulana, L.C., Quinoline and its derivatives as effective corrosion inhibitors for mild steel in acidic medium, Int. J. Electrochem. Sci., 2010, vol. 5, p. 1574.
  11. Verma, C., Olasunkanmi, L., Obot, I.B., Ebenso, E.E., and Quraishi, M.A., 5-arylpyrimido-[4,5-b] quinoline-diones as new and sustainable corrosion inhibitors for mild steel in 1 M HCl: a combined experimental and theoretical approach, RSC Adv., 2016, vol. 6, no. 19, p. 15639.
  12. Jiang, L., Qiang, Y., Lei, Z., Wang, J., Qin, Z., and Xiang, B., Excellent corrosion inhibition performance of novel quinoline derivatives on mild steel in HCl media: experimental and computational investigations, J. Mol. Liq., 2018, vol. 255, p. 53.
  13. Singh, P., Ebenso, E.E., Olasunkanmi, L.O., Obot, I., and Quraishi, M.A., Electrochemical, theoretical, and surface morphological studies of corrosion inhibition effect of green naphthyridine derivatives on mild steel in hydrochloric acid, J. Phys. Chem. C, 2016, vol. 120, no. 6, p. 3408.
  14. Chauhan, D.S., Quraishi, M.A., Sorour, A.A., Saha, S.K., and Banerjee, P., Triazole-modified chitosan: a biomacromolecule as a new environmentally benign corrosion inhibitor for carbon steel in a hydrochloric acid solution, RSC Adv., 2019, vol. 9, no. 26, p. 14990.
  15. Swain, M., Chemicalize.org, J. Chem. Inform. Model., 2012, vol. 52, no. 2, p. 613.
  16. Becke, A.D., Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., 1993, vol. 98, p. 5648.
  17. Frisch, M., Trucks, G., Schlegel, H. B., Scuseria, G., Robb, M., Cheeseman, J., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G., Gaussian 09, Revision A. 02, Inc., Wallingford, CT, 2009, vol. 200.
  18. Baboian, R., Corrosion Tests and Standards: Application and Interpretation, ASTM Int., 2005.
  19. ASTM Committee G-1 on Corrosion of Metals, Standard Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens, ASTM Int., 2017.
  20. Barsoukov, E. and Macdonald, J.R., Impedance Spectroscopy: Theory, Experiment, and Applications, John Wiley & Sons, 2018.
  21. Barsukov, Y. and Macdonald, J.R., in Characterization of Materials, Kaufmann, E.N., Ed., John Wiley & Sons, 2002, p. 1.
  22. Döner, A., Solmaz, R., Özcan, M., and Kardaş, G., Experimental and theoretical studies of thiazoles as corrosion inhibitors for mild steel in sulphuric acid solution, Corros. Sci., 2011, vol. 53, no. 9, p. 2902.
  23. Solmaz, R., Investigation of adsorption and corrosion inhibition of mild steel in hydrochloric acid solution by 5-(4-dimethylaminobenzylidene) rhodanine, Corros. Sci., 2014, vol. 79, p. 169.
  24. Solmaz, R., Kardaş, G., Culha, M., Yazıcı, B., and Erbil, M., Investigation of adsorption and inhibitive effect of 2-mercaptothiazoline on corrosion of mild steel in hydrochloric acid media, Electrochim. Acta, 2008, vol. 53, no. 20, p. 5941.
  25. Marcus, P. and Mansfeld, F.B., Analytical Methods in Corrosion Science and Engineering, CRC Press, 2005.
  26. Popova, A. and Christov, M., Evaluation of impedance measurements on mild steel corrosion in acid media in the presence of heterocyclic compounds, Corros. Sci., 2006, vol. 48, no. 10, p. 3208.
  27. Popova, A., Christov, M., Raicheva, S., and Sokolova, E., Adsorption and inhibitive properties of benzimidazole derivatives in acid mild steel corrosion, Corros. Sci., 2004, vol. 46, no. 6, p. 1333.
  28. Popova, A., Raicheva, S., Sokolova, E., and Christov, M., Frequency dispersion of the interfacial impedance at mild steel corrosion in acid media in the presence of benzimidazole derivatives, Langmuir, 1996, vol. 12, no. 8, p. 2083.
  29. Chauhan, D.S., Kumar, A.M., and Quraishi, M.A., Hexamethylenediamine functionalized glucose as a new and environmentally benign corrosion inhibitor for copper, Chem. Eng. Res. Des., 2019, vol. 150, p. 99.
  30. Chauhan, D.S., Ansari, K.R., Sorour, A.A., Quraishi, M.A., Lgaz, H., and Salghi, R., Thiosemicarbazide and thiocarbohydrazide functionalized chitosan as ecofriendly corrosion inhibitors for carbon steel in hydrochloric acid solution, Int. J. Biol. Macromol., 2018, vol. 107, p. 1747.
  31. Singh, P., Chauhan, D.S., Srivastava, K., Srivastava, V., and Quraishi, M., Expired atorvastatin drug as corrosion inhibitor for mild steel in hydrochloric acid solution, Int. J. Ind. Chem., 2017, vol. 8, no. 4, p. 363.
  32. Özcan, M., Dehri, I., and Erbil, M., Organic sulphur-containing compounds as corrosion inhibitors for mild steel in acidic media: correlation between inhibition efficiency and chemical structure, Appl. Surf. Sci., 2004, vol. 236, no. 1, p. 155.
  33. McCafferty, E., Validation of corrosion rates measured by the Tafel extrapolation method, Corros. Sci., 2005, vol. 47, no. 12, p. 3202.
  34. McCafferty, E., Introduction to Corrosion Science, Springer Science & Business Media, 2010.
  35. Gupta, R.K., Malviya, M., Ansari, K.R., Lgaz, H., Chauhan, D.S., and Quraishi, M.A., Functionalized graphene oxide as a new generation corrosion inhibitor for industrial pickling process: DFT and experimental approach, Mater. Chem. Phys., 2019, vol. 236, p. 121727.
  36. Chauhan, D.S., Srivastava, V., Joshi, P.G., and Quraishi, M.A., PEG cross-linked chitosan: a biomacromolecule as corrosion inhibitor for sugar industry, Int. J. Ind. Chem., 2018, vol. 9, p. 363.
  37. Srivastava, V., Chauhan, D.S., Joshi, P.G., Maruthapandian, V., Sorour, A.A., and Quraishi, M.A., PEG-functionalized chitosan: a biological macromolecule as a novel corrosion inhibitor, Chem. Select, 2018, vol. 3, no. 7, p. 1990.
  38. Geerlings, P., De Proft, F., and Langenaeker, W., Conceptual density functional theory, Chem. Rev., 2003, vol. 103, no. 5, p. 1793.
  39. Obot, I., Macdonald, D., and Gasem, Z., Density functional theory (DFT) as a powerful tool for designing new organic corrosion inhibitors. Part 1: an overview, Corros. Sci., 2015, vol. 99, p. 1.
  40. Dohare, P., Chauhan, D.S., and Quraishi, M.A., Expired Podocip drug as potential corrosion inhibitor for carbon steel in acid chloride solution, Int. J. Corros. Scale Inhib., 2018, vol. 7, no. 1, p. 25.
  41. Dohare, P., Chauhan, D.S., Sorour, A.A., and Quraishi, M.A., DFT and experimental studies on the inhibition potentials of expired Tramadol drug on mild steel corrosion in hydrochloric acid, Mater.Discovery, 2017, vol. 9, p. 30.
  42. Dohare, P., Chauhan, D.S., Hammouti, B., and Quraishi, M.A., Experimental and DFT investigation on the corrosion inhibition behavior of expired drug lumerax on mild steel in hydrochloric acid, Anal. Bioanal. Electrochem., 2017, vol. 9, p. 762.
  43. Pearson, R.G., Absolute electronegativity and hardness correlated with molecular orbital theory, Proc. Nat. Acad. Sci., 1986, vol. 83, no. 22, p. 8440.
  44. Pearson, R.G., Absolute electronegativity and hardness: application to inorganic chemistry, Inorg. Chem., 1988, vol. 27, no. 4, p. 734.
  45. Pearson, R.G., The principle of maximum hardness, Acc. Chem. Res., 1993, vol. 26, no. 5, p. 250.
  46. Parr, R.G. and Pearson, R.G., Absolute hardness: companion parameter to absolute electronegativity, J. Am. Chem. Soc., 1983, vol. 105, no. 26, p. 7512.
  47. Jupp, A.R., Johnstone, T.C., and Stephan, D.W., The global electrophilicity index as a metric for Lewis acidity, Dalton T., 2018, vol. 47, no. 20, p. 7029.
  48. Kokalj, A. and Kovačević, N., On the consistent use of electrophilicity index and HSAB-based electron transfer and its associated change of energy parameters, Chem. Phys. Lett., 2011, vol. 507, nos. 1–3, p. 181.
  49. Parr, R.G., Szentpaly, L.V., and Liu, S., Electrophilicity index, J. Am. Chem. Soc., 1999, vol. 121, no. 9, p. 1922.
  50. Kokalj, A., Is the analysis of molecular electronic structure of corrosion inhibitors sufficient to predict the trend of their inhibition performance, Electrochim. Acta, 2010, vol. 56, no. 2, p. 745.
  51. Kokalj, A., On the HSAB based estimate of charge transfer between adsorbates and metal surfaces, Chem. Phys., 2012, vol. 393, no. 1, p. 1.
  52. Kokalj, A., Kovačević, N., Peljhan, S., Finšgar, M., Lesar, A., and Milošev, I., Triazole, benzotriazole, and naphthotriazole as copper corrosion inhibitors: I. Molecular electronic and adsorption properties, ChemPhysChem, 2011, vol. 12, no. 18, p. 3547.
  53. Guo, L., Obot, I.B., Zheng, X., Shen, X., Qiang, Y., Kaya, S., and Kaya, C., Theoretical insight into an empirical rule about organic corrosion inhibitors containing nitrogen, oxygen, and sulfur atoms, Appl. Surf. Sci., 2017, vol. 406, p. 301.
  54. Baig, N., Chauhan, D.S., Saleh, T.A., and Quraishi, M.A., Diethylenetriamine functionalized graphene oxide as a novel corrosion inhibitor for mild steel in hydrochloric acid solutions, New J. Chem., 2019, vol. 43, p. 2328.
  55. Haque, J., Srivastava, V., Chauhan, D.S., Lgaz, H., and Quraishi, M.A., Microwave-induced synthesis of chitosan schiff bases and their application as novel and green corrosion inhibitors: experimental and theoretical approach, ACS Omega, 2018, vol. 3, no. 5, p. 5654.
  56. Saady, A., El-Hajjaji, F., Taleb, M., Alaoui, K.I., El Biache, A., Mahfoud, A., Alhouari, G., Hammouti, B., Chauhan, D.S., and Quraishi, M.A., Experimental and theoretical tools for corrosion inhibition study of mild steel in aqueous hydrochloric acid solution by new indanones derivatives, Mater. Discovery, 2018, vol. 12, p. 30.
  57. Onyeachu, B., Chauhan, D.S., Ansari, K.R., Obot, I., Quraishi, M.A., and Alamri, A.H., Hexamethylene-1, 6-bis (N–D-glucopyranosylamine) as a novel corrosion inhibitor for oil and gas industry: electrochemical and computational analysis, New J. Chem., 2019, vol. 43, p. 7282.
  58. Obot, I., Haruna, K., and Saleh, T., Atomistic simulation: a unique and powerful computational tool for corrosion inhibition research, Arab. J. Sci. Eng., 2019, vol. 44, no. 1, p. 1.