Resumo

ELMSELLEM, H et al. Quantum Chemical Studies and Corrosion Inhibitive Properties of Mild Steel by Some Pyridine Derivatives in 1 N HCl Solution. Port. Electrochim. Acta [online]. 2014, vol.32, n.2, pp.77-108. ISSN 0872-1904.  https://doi.org/10.4152/pea.201402077.

The influence of 2,6-bis-(hydroxy)-pyridine (P1), 2,6-bis-(chloro)-pyridine (P2) and diethyl 1,1'-(pyridine-2,6-diyl)bis(5-methyl-1H-pyrazol2-3-carboxylate ( P3) on the corrosion of steel in 1 N HCl solution has been studied by weight loss measurements, potentiodynamic and impedance spectroscopy methods. The inhibiting action increases with the concentration of these compounds to attain 91,5% at 10^-3 M for P3. We note good agreement between gravimetric and electrochemical methods. The polarisation measurements show also that the pyridines act essentially as mixed inhibitors and the cathodic curves indicate that the reduction of proton at the steel surface happens with an activating mechanism. The temperature effect on the corrosion behaviour of iron in 1 M HCl without and with these inhibitors at different concentrations was studied in the temperature range from 313 to 353 K, and allows deducing the apparent activation energy, enthalpy and entropy of the dissolution process and the free energy were determined and discussed. The inhibitors were adsorbed on the iron surface according to the Langmuir adsorption isotherm model at different temperatures and some thermodynamic data for the adsorption process are calculated. The experimental study has been finished by quantum theoretical study; the quantum chemical calculations, based on DFT methods at B3LYP/6-31G** level of theory, were performed, by means of the GAUSSIAN 03 set of programs. Structural parameters, such as the frontier molecular orbital energies (E_HOMO and E_LUMO), gap of energy ΔE, charge distribution, absolute hardness η and softens σ, fraction of electrons ΔN transferred from pyridine molecules to steel, as well as electronic parameters such as Mulliken atomic populations have been determined. The objective of this quantum theoretical treatment is to attempt to find relationships between their molecular and electronic structures and inhibition efficiency.

Palavras-chave : Pyridine; Inhibition; Corrosion; Steel; Acid; quantum chemical; DFT methods; B3LYP/6-31G base; GAUSSIAN 03.

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