Share This Article:

DFT Calculations for Corrosion Inhibition of Ferrous Alloys by Pyrazolopyrimidine Derivatives

Abstract Full-Text HTML Download Download as PDF (Size:376KB) PP. 6-14
DOI: 10.4236/ojpc.2014.41002    5,119 Downloads   8,625 Views   Citations

ABSTRACT

The inhibition performance of 5-tolyl-2-phenylpyrazolo[1,5-c] pyrimidine-7(6H)thione (Tolyl), 5-tolyl-2-pheenylpyrazolo [1,5-c]pyrimidine-7(6H)one (Inon) was investigated as corrosion inhibitors using density functional theory (DFT) at the B3LYP/6-31 + G(d,p) level of theory. The calculated quantum chemical parameters correlated to the inhibition efficiency are: the highest occupied molecular orbital energy(EHOMO), the lowest unoccupied molecular orbital energy (ELUMO), the energy gap (ΔEL-H), dipole moment (μ), ionization energy (Ι), electron affinity (Α), absolute electronegativity (χ), absolute hardness (η), absolute softness (σ), the fraction of electron transferred (ΔN), and the total energy (Etot) which were calculated. The local reactivity has been analyzed through the Fukui function and local softness indices in order to compare the possible sites for nucleophilic and electrophilic attacks. The success of DFT calculations in predicting the inhibition efficiency was assessed.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

N. Wazzan and F. Mahgoub, "DFT Calculations for Corrosion Inhibition of Ferrous Alloys by Pyrazolopyrimidine Derivatives," Open Journal of Physical Chemistry, Vol. 4 No. 1, 2014, pp. 6-14. doi: 10.4236/ojpc.2014.41002.

References

[1] N. O. Obi-Egbedi, I. B. Obot, M. I. El-khaiary, S. A. Umoren and E. E. Ebenso, “Computational Simulation and Statistical Analysis on the Relationship between Corrosion Inhibition Efficiency and Molecular Structure of Some Phenanthroline Derivatives on Mild Steel Surface,” International Journal of Electrochemical Science, Vol. 6, No. 11, 2011, p. 5649.
[2] I. B. Obot and N. O. Obi-Egbedi, “Inhibitory Effect and Adsorption Characteristics of 2,3-Diaminonaphthalene at Aluminum/Hydrochloric Acid Interface: Experimental and Theoretical Study,” Surface Review and Letters, Vol. 15, No. 6, 2008, pp. 903-910. http://dx.doi.org/10.1142/S02186 25X08012074
[3] H. Ju, Z.-P. Kai and Y. Li, “Aminic Nitrogen-Bearing Polydentate Schiff Base Compounds as Corrosion Inhibitors for Iron in Acidic Media: A Quantum Chemical Calculation,” Corrosion Science, Vol. 50, No. 3, 2008, pp. 865-871. http://dx.doi.org/10.1016/j.corsci.2007.10.009
[4] S. A. Umoren and I. B. Obot, “Polyvinylpyrollidone and Polyacrylamide as Corrosion Inhibitors for Mild Steel in Acidic Medium,” Surface Review and Letters, Vol. 15, No. 3, 2008, pp. 277-286.
http://dx.doi.org/10.1142/S0218625X08011366
[5] S. A. Umoren, I. B. Obot, E. E. Ebenso and N. O. Obi-Egbedi, “Synergistic Inhibition between Naturally Occurring Exudate Gum and Halide Ions on the Corrosion of Mild Steel in Acidic Medium,” International Journal of Electrochemical Science, Vol. 3, No. 9, 2008, pp. 1029-1043.
[6] D. Wang, S. Li, Y. Ying, M. Wang, H. Xiao and Z. Chen, “Theoretical and Experimental Studies of Structure and Inhibition Efficiency of Imidazoline Derivatives,” Corrosion Science, Vol. 41, No. 10, 1999, pp. 1911-1919. http://dx.doi.org/10.1016/S0010-938X(99)00027-X
[7] H. Wang, X. Wang, H. Wang, L. Wang and A. Liu, “DFT Study of New Bipyrazole Derivatives and Their Potential Activity as Corrosion Inhibitors,” Journal of Molecular Modeling, Vol. 13, No. 1, 2007, pp. 147-153. http://dx.doi.org/10.1007/s00894-006-0135-x
[8] P. Udhayakala, T. V. Rajendiran and S. Gunasekaran, “Theoretical Approach to the Corrosion Inhibition Efficiency of Some Pyrimidine Derivatives Using DFT Method,” Journal of Computational Methods in Molecular Design, Vol. 2, No. 1, 2012, pp. 1-15.
[9] M. Finsgar, S. Fassbender, F. Nicolini and I. Milosev, “Polyethyleneimine as a Corrosion Inhibitor for ASTM 420 Stainless Steel in Near-Neutral Saline Media,” Corrosion Science, Vol. 51, No. 3, 2009, pp. 525-533. http://dx.doi.org/10.1016/j.corsci.2008.12.006
[10] S. A. Awad and K. M. Kamel, “Mechanism of CorrosionInhibition and Corrosion-Promotion of Zinc by Phosphate Ions,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 24, No. 1, 1970, pp. 217-225. http://dx.doi.org/10.1016/S0022-0728(70)80023-7
[11] S. A. Awad, K. M. Kamel, Z. Abd El-Hadi and H. A. Bayumi, “Mechanism of Anodic Dissolution of Copper in Aqueous Acidified Solutions of Different Anions,” Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 199, No. 2, 1986, pp. 341-350. http://dx.doi.org/10.1016/0022-0728(86)80008-0
[12] F. M. Mahgoub, B. A. Abdel-Nabey and Y. A. El-Samadisy, “Adopting a Multipurpose Inhibitor to Control Corrosion of Ferrous Alloys in Cooling Water Systems,” Materials Chemistry and Physics, Vol. 120, No. 1, 2010, pp. 104-108. http://dx.doi.org/10.1016/j.matchemphys.2009.10.028
[13] H. Baba and T. Kodama, “Corrosion Inhibition and Characteristics of the Triazinedithiol Surface Film on Copper Under Potentiostatic Anodization,” Corrosion Science, Vol. 41, No. 10, 1999, pp. 1987-2000. http://dx.doi.org/10.1016/S0010-938X(99)00030-X
[14] T. Zhao and G. Mu, “The Adsorption and Corrosion Inhibition of Anion Surfactants on Aluminium Surface in Hydrochloric Acid,” Corrosion Science, Vol. 41, No. 10, 1999, pp. 1937-1944.
http://dx.doi.org/10.1016/S0010-938X(99)00029-3
[15] M. S. Masoud, M. K. Awad, M. A. Shaker and M. M. T. El-Tahawy, “The Role of Structural Chemistry in the Inhibitive Performance of Some Aminopyrimidines on the Corrosion of Steel,” Corrosion Science, Vol. 52, No. 7, 2010, pp. 2387-2396. http://dx.doi.org/10.1016/j.corsci.2010.04.011
[16] M. K. Awad, F. M. Mahgoub and M. M. El-iskandarani, “Theoretical Studies of the Effect of Structural Parameters on the Inhibition Efficiencies of Mercapto-1,2,4-triazoline Derivatives,” Journal of Molecular Structure: THEOCHEM, Vol. 531, No. 1-3, 2000, pp. 105-117. http://dx.doi.org/10.1016/ S0166-1280(00)00437-1
[17] M. K. Awad, “Semiempirical Investigation of the Inhibition Efficiency of Thiourea Derivatives as Corrosion Inhibitors,” Journal of Electroanalytical Chemistry, Vol. 567, No. 2, 2004, pp. 219-225. http://dx.doi.org/10.1016/j.jelechem.2003.12.028
[18] M. A. M. Ibrahim, S. S. Abd El Rehim and M. M. Hamza, “Corrosion Behavior of Some Austenitic Stainless Steels in Chloride Environments,” Materials Chemistry and Physics, Vol. 115, No. 1, 2009, pp. 80-85. http://dx.doi.org/10.1016/j.matchemphys.2008.11.016
[19] L. Feng, H. Yang and F. Wang, “Experimental and Theoretical Studies for Corrosion Inhibition of Carbon Steel by Imidazoline Derivative in 5% NaCl Saturated Ca(OH)2 Solution,” Electrochimica Acta, Vol. 58, 2011, pp. 427-436. http://dx.doi.org/10.1016/j.electacta.2011.09.063
[20] P. Hohenberg and W. Kohn, “Inhomogeneous Electron Gas,” Physical Review, Vol. 136, No. 3, 1964, pp. B864-B871. http://dx.doi.org/10.1103/PhysRev.136.B864
[21] W. Kohn and L. J. Sham, “Self-Consistent Equations Including Exchange and Correlation Effects,” Physical Review, Vol. 140, No. 4, 1965, pp. A1133-A1138. http://dx.doi.org/10.1103/PhysRev.140. A1133
[22] R. G. Parr and W. Yang, “Density-Functional Theory of Atoms and Molecules,” Oxford University Press, Oxford, 1989.
[23] N. I. Levine, “Quantum Chemistry,” Prentice Hall, Englewood Cliffs, 2000.
[24] W. Kohn, “Nobel Lecture: Electronic Structure of Matter —Wave Functions and Density Functionals,” Reviews of Modern Physics, Vol. 71, No. 5, 1999, pp. 1253-1266. http://dx.doi.org/10.1103/RevMod Phys.71.1253
[25] L. M. Rodríguez-Valdez, A. Martínez-Villafane and D. Glossman-Mitnik, “CHIH-DFT Theoretical Study of Isomeric Thiatriazoles and Their Potential Activity as Corrosion Inhibitors,” Journal of Molecular Structure: THEOCHEM, Vol. 716, No. 1-3, 2005, pp. 61-65. http://dx.doi.org/10.1016/j.theochem. 2004.10.082
[26] G. K. Gece and S. BilgiA, “Quantum Chemical Study of Some Cyclic Nitrogen Compounds as Corrosion Inhibitors of Steel in NaCl Media,” Corrosion Science, Vol. 51, No. 8, 2009, pp. 1876-1878. http://dx.doi.org/10.1016/j.corsci.2009.04.003
[27] A. Y. Musa, A. A. H. Kadhum, A. B. Mohamad, A. A. B. Rahoma and H. Mesmari, “Electrochemical and Quantum Chemical Calculations on 4,4-Dimethyloxazolidine-2-thione as Inhibitor for Mild Steel Corrosion in Hydro-chloric Acid,” Journal of Molecular Structure, Vol. 969, No. 1-3, 2010, pp. 233-237. http://dx.doi.org/10.1016/j.molstruc.2010.02.051
[28] R. M. Issa, M. K. Awad and F. M. Atlam, “Quantum Chemical Studies on the Inhibition of Corrosion of Copper Surface by Substituted Uracils,” Applied Surface Science, Vol. 255, No. 5, 2008, pp. 2433-2441. http://dx.doi.org/10.1016/j.apsusc.2008.07.155
[29] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and A. D. J. Fox, Gaussian, Inc., Wallingford, 2009, p. 09.
[30] A. D. Becke, “Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior,” Physical Review A, Vol. 38, No. 6, 1988, pp. 3098-3100. http://dx.doi.org/10.1103/PhysRevA.38.3098
[31] C. Lee, W. Yang and R. G. Parr, “Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density,” Physical Review B, Vol. 37, No. 2, 1988, pp. 785-789.
http://dx.doi.org/10.1103/PhysRevB.37.785
[32] R. G. Pearson, “Absolute Electronegativity and Hardness: Application to Inorganic Chemistry,” Inorganic Chemistry, Vol. 27, No. 4, 1988, pp. 734-740. http://dx.doi.org/10.1021/ic00277a030
[33] R. G. Parr and R. G. Pearson, “Absolute Hardness: Companion Parameter to Absolute Electronegativity,” Journal of the American Chemical Society, Vol. 105, No. 26, 1983, pp. 7512-7516. http://dx.doi.org/10.1021/ja00364a005
[34] R. G. Parr, L. V. Szentpaly and S. Liu, “Electrophilicity Index,” Journal of the American Chemical Society, Vol. 121, No. 9, 1999, pp. 1922-1924. http://dx.doi.org/10.1021/ja983494x
[35] E. S. H. El Ashry, A. El Nemr, S. A. Esawy and S. Ragab, “Corrosion Inhibitors: Part II: Quantum Chemical Studies on the Corrosion Inhibitions of Steel in Acidic Medium by Some Triazole, Oxadiazole and Thiadiazole Derivatives,” Electrochimica Acta, Vol. 51, No. 19, 2006, pp. 3957-3968.
http://dx.doi.org/10.1016/j.electacta.2005.11.010
[36] X. Li, S. Deng, H. Fu and T. Li, “Adsorption and Inhibition Effect of 6-Benzylaminopurine on Cold Rolled Steel in 1.0 M HCl,” Electrochimica Acta, Vol. 54, No. 16, 2009, pp. 4089-4098.
http://dx.doi.org/10.1016/j.electacta.2009.02.084
[37] K. R. Sandip, N. Islam and D. G. Ghosh, Journal of Quantum Information Science, Vol. 1, 2011, pp. 87-95.
[38] P. Geerlings and F. D. Proft, “Chemical Reactivity as Described by Quantum Chemical Methods,” International Journal of Molecular Sciences, Vol. 3, No. 4, 2002, pp. 276-309.
http://dx.doi.org/10.3390/i3040276
[39] E. E. Ebenso, D. A. Isabirye and N. O. Eddy, “Adsorption and Quantum Chemical Studies on the Inhibition Potentials of Some Thiosemicarbazides for the Corrosion of Mild Steel in Acidic Medium,” International Journal of Molecular Sciences, Vol. 11, No. 6, 2010, pp. 2473-2498.
http://dx.doi.org/10.3390/ijms11062473
[40] I. Lukovits, E. Kalman and F. Zucchi, “Corrosion Inhibitors—Correlation between Electronic Structure and Efficiency,” Corrosion, Vol. 57, No. 1, 2001, pp. 3-8. http://dx.doi.org/10.5006/1.3290328
[41] E. G. Lewars, “Computational Chemistry Introduction to the Theory and Applications of Molecular and Quantum Mechanics,” Springer, London, 2011.
[42] P. Fuentealba, P. Perez and R. Contreras, “On the Condensed Fukui Function,” The Journal of Chemical Physics, Vol. 113, 2000, pp. 2544-2551. http://dx.doi.org/10.1063/1.1305879

  
comments powered by Disqus

Copyright © 2020 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.