The influence of some new 2,5-disubstituted 1,3,4-thiadiazoles on the corrosion behaviour of mild steel in 1 M HCl solution: AC impedance study and theoretical approach

The new 2,5-disubstituted 1,3,4-thiadiazoles were investigated as corrosion inhibitors of mild steel in 1 M HCl using AC impedance technique. Four of these compounds exhibit good inhibition properties, while two of them, 2,5-bis(4-nitrophenyl)-1,3,4-thiadiazole and 2,5-bis(4-chlorophenyl)-1,3,4-thiadiazole, stimulate the corrosion process especially at low concentrations. The experimental data obtained from this method show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. Possible correlations between experimental inhibition efficiencies and quantum chemical parameters such as dipole moment (μ), highest occupied (E_HOMO) and lowest unoccupied (E_LUMO) molecular orbitals were investigated. The models of the inhibitors were optimised with the Density Functional Theory formalism (DFT) using hybrid B3LYP/6-31G (2d,2p) as a higher level of theory. The Quantitative Structure Activity Relationship (QSAR) approach has been used and composite index of some quantum chemical parameters were constructed in order to characterize the inhibition performance of the tested molecules.     

Enhanced corrosion resistance of carbon steel in normal sulfuric acid medium by some macrocyclic polyether compounds containing a 1,3,4-thiadiazole moiety: AC impedance and computational studies

We report here the use of macrocyclic polyether compounds containing a 1,3,4-thiadiazole moiety (n-MCTH) in the corrosion inhibition of C38 carbon steel in 0.5 M H₂SO₄ acid medium.

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The aim of this work is devoted to study the inhibition characteristics of these compounds for acid corrosion of C38 steel using electrochemical impedance spectroscopy (EIS). Data obtained from EIS show a frequency distribution and therefore a modeling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The experimental results obtained revealed that these compounds inhibited the steel corrosion in acid solution and the protection efficiency increased with increasing inhibitors concentration. The difference in their inhibitive action can be explained on the basis of the number of oxygen atoms present in the polyether ring which contribute to the chemisorption strength through the donor acceptor bond between the non bonding electron pair and the vacant orbital of metal surface. Adsorption of n-MCTH was found to follow the Langmuir’s adsorption isotherm. The thermodynamic functions of adsorption process were calculated and the interpretation of the results is given. These results are complemented with quantum chemical study in order to provide an explanation of the differences between the probed inhibitors. Correlation between the inhibition efficiency and the structure of these compounds are presented.     

Inhibitive properties, adsorption and a theoretical study of 3,5-bis(n-pyridyl)-4-amino-1,2,4-triazoles as corrosion inhibitors for mild steel in perchloric acid

Corrosion inhibition of mild steel in molar perchloric acid by 3,5-bis(n-pyridyl)-4-amino-1,2,4-triazoles (n-PAT, n = 2, 3 and 4) was studied at 30 °C using gravimetric and electrochemical impedance spectroscopy techniques. Protection efficiencies of 95% and 92% were obtained with 12 × 10⁻⁴ M of 3-PAT and 4-PAT, respectively; while 2-PAT reached only 65%. The inhibiting properties of n-PAT were found to depend on the concentration and the order of increasing inhibition efficiency was correlated with the modification of the position of the nitrogen atom in the pyridinium substituent. It was shown that adsorption of 4-aminotriazole derivatives on the steel surface is consistent with the Langmuir adsorption isotherm and the obtained standard free energy of adsorption () values indicate that the corrosion inhibition of the mild steel in 1 M HClO₄ is depends on both physic-and chemisorption. A significant correlation is obtained between inhibition efficiency and quantum chemical parameters using semi-empirical quantitative structure-activity relationships (QSAR) approach.     

Corrosion inhibition of C38 steel in 1 M hydrochloric acid medium by alkaloids extract from Oxandra asbeckii plant

The inhibition effect of alkaloids extract from Oxandra asbeckii plant (OAPE) on the corrosion of C38 steel in 1 M hydrochloric acid solution has been investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The corrosion inhibition efficiency increases on increasing plant extracts concentration. Cathodic and anodic polarization curves show that OAPE is a mixed-type inhibitor. The effect of temperature on the corrosion behavior of C38 steel in 1 M HCl with and without addition of plant extract was studied in the temperature range 25–55 °C. The thermodynamic functions of dissolution and adsorption processes were calculated from experimental polarization data and the interpretation of the results are given. The adsorption of this plant extract on the C38 steel surface obeys the Langmuir adsorption isotherm. Surface analysis (Raman) was also carried out to establish the corrosion inhibitive property of this plant extract in HCl solution.     

Mixed and hybrid finite element methods for convection-diffusion equations and their relationships with finite volume

Abstract We study the relationship between finite volume and mixed finite element methods for the the hyperbolic conservation laws, and the closely related convection-diffusion equations. A general framework is proposed for the derivation and a functional framework is developed which could allow the analysis of relating finite volume (FV) schemes. We show via two non-standard formulations, that numerous FV schemes, including centred, upwind, Lax-Friedrichs, Roe, Engquist-Osher, the central Nessyahu-Tadmor schemes, etc., can be recovered in the unique dual mixed and hybrid (DMH) finite element framework. That makes possible a better understanding of these FV schemes. Moreover, the large number of DMH finite element results available can then give the analysis of these FV methods in a unified fashion. Furthermore, stabilized methods are proposed. In particular, interpretation in terms of the Lagrange multiplier of flux-limiter is given.We end by presenting numerical results to validate the newly proposed stabilized schemes.     

ac impedance, X-ray photoelectron spectroscopy and density functional theory studies of 3,5-bis(n-pyridyl)-1,2,4-oxadiazoles as efficient corrosion inhibitors for carbon steel surface in hydrochloric acid solution

The corrosion inhibition properties of a new class of oxadiazole derivatives, namely 3,5-bis(n-pyridyl)-1,2,4-oxadiazoles (n-DPOX) for C38 carbon steel corrosion in 1 M HCl medium were analysed by electrochemical impedance spectroscopy (EIS). An adequate structural model of the interface was used and the values of the corresponding parameters were calculated and discussed. The experimental results showed that these compounds are excellent inhibitors for the C38 steel corrosion in acid solution and that the protection efficiency increased with increasing the inhibitors concentration. Electrochemical impedance data demonstrate that the addition of the n-DPOX derivatives in the corrosive solution decreases the charge capacitance and simultaneously increases the function of the charge/discharge of the interface, facilitating the formation of an adsorbed layer over the steel surface. Adsorption of these inhibitors on the steel surface obeys to the Langmuir adsorption isotherm. X-ray photoelectron spectroscopy (XPS) and the thermodynamic data of adsorption showed that inhibition of steel corrosion in normal hydrochloric solution by n-DPOX is due to the formation of a chemisorbed film on the steel surface. Quantum chemical calculations using the Density Functional Theory (DFT) and the Quantitative Structure Activity Relationship (QSAR) approach were performed on n-DPOX derivatives to determine the relationship between molecular structure and their inhibition efficiencies. The results of the quantum chemical calculations and experimental inhibition efficiency were subjected to correlation analysis and indicate that their inhibition effect is closely related to E_HOMO, E_LUMO, and dipole moment (μ).     

Synergistic effect of iodide ions on inhibitive performance of 2,5-bis(4-methoxyphenyl)-1,3,4-thiadiazole during corrosion of mild steel in 0.5?M sulfuric acid solution

The synergistic effect of iodide ions on the corrosion inhibition of mild steel in 0.5 M H₂SO₄ solutions by 2,5-bis(4-methoxyphenyl)-1,3,4-thiadiazole (4-MTH) has been studied using electrochemical impedance spectroscopy (EIS) and the Tafel polarisation method. The results showed that the inhibition efficiency increased with 4-MTH concentration while the potential of desorption (E _d) remained unchanged. The addition of potassium iodide (KI) in the acid solution stabilized the adsorption of 4-MTH molecules on the metal surfaces and, therefore, enhanced the inhibition efficiency of 4-MTH and increased the value of E _d. The synergistic effect was observed between KI and 4-MTH with an optimum mass ratio of [4-MTH]/[KI] = 5/5. The calculated values of synergism parameter (S _θ) from the coverage of the surface were found to be more than unity in most cases. This clearly showed the synergistic influence of iodide ions on the corrosion inhibition of mild steel in 0.5 M H₂SO₄ by 4-MTH. The adsorption of this inhibitor alone and in combination with iodide ions followed Langmuir’s adsorption isotherm.     

Electrochemical and quantum chemical studies of new thiadiazole derivatives adsorption on mild steel in normal hydrochloric acid medium

In this work, a new class of thiadiazole derivatives, namely 3,5-bis(2-thienyl)-1,3,4-thiadiazole (2-TTH) and 3,5-bis(3-thienyl)-1,3,4-thiadiazole (3-TTH), have been studied as possible corrosion inhibitors for mild steel in molar hydrochloric acid (1 M HCl). Weight loss measurements, polarisation curves and AC impedance methods have been used. These studies have shown that the thiadiazole derivatives were very good inhibitors for mild steel in 1 M HCl. Comparison of results showed that 3-TTH was the best inhibitor. The potential of zero charge (PZC) of mild steel was studied by AC impedance method, and the mechanism of adsorption has been predicted. X-ray photoelectron spectroscopy surface analysis with thiadiazole derivatives shows that it chemisorbed at the mild steel/HCl interface. The adsorption of these inhibitors followed Langmuir’s adsorption isotherm. The electronic properties of 2-TTH and 3-TTH, obtained using the AM1 semi-empirical quantum chemical approach, were correlated with their experimental efficiencies using the linear resistance model (LR). These inhibitors are considered as non-cytotoxic substances.