2,5-Bis(4-dimethylaminophenyl)-1,3,4-oxadiazole and 2,5-bis(4-dimethylaminophenyl)-1,3,4-thiadiazole as corrosion inhibitors for mild steel in acidic media

2,5-Bis(4-dimethylaminophenyl)-1,3,4-oxadiazole (DAPO) and 2,5-bis(4-dimethylaminophenyl)-1,3,4-thiadiazole (DAPT) have been synthesised and their inhibiting action on the corrosion of mild steel in 1 M HCl and 0.5 M H₂SO₄ at 30 °C has been investigated by various corrosion monitoring techniques. At constant acid concentration, the inhibitor efficiency of both the compounds is found to increase with inhibitor concentration. DAPT is slightly more efficient in 0.5 M H₂SO₄ than in 1 M HCl whereas DAPO is more efficient in 1 M HCl. Of the two, DAPT appears to be a better inhibitor. Potentiostatic polarisation studies show that both are mixed-type inhibitors in 1 M HCl but cathodic-type in 0.5 M H₂SO₄. The inhibitors function through adsorption following Langmuir isotherm in both the acids. The electronic properties of DAPO and DAPT, obtained using the AM1 semi-empirical quantum chemical approach, have been correlated with their experimental inhibition efficiencies using the linear resistance model (LR). These inhibitors are considered as a non-cytotoxic substances.     

Thermodynamic characterization of metal dissolution and inhibitor adsorption processes in mild steel/2,5-bis(n-thienyl)-1,3,4-thiadiazoles/hydrochloric acid system

The corrosion inhibition of mild steel in 1 M hydrochloric acid solution by some 2,5-bis(n-thienyl)-1,3,4-thiadiazoles (n-TTH) has been studied in relation to the concentration of the inhibitors as well as the temperature using chemical (weight loss) and electrochemical (ac impedance and dc polarisation) techniques. All the methods employed are in reasonable agreement. The protection efficiency increases with increasing inhibitors concentration and with increasing temperature. The thermodynamic functions of dissolution and adsorption processes were calculated from experimental polarisation data and the interpretation of the results are given. Adsorption of n-TTH was found to follow the Langmuir’s adsorption isotherm and the ability of the molecule to chemisorb on the steel surface was dependent on the position of the sulphur atom on the thienyl substituent.     

Study of the mechanism and inhibiting efficiency of 3,5-bis(4-methylthiophenyl)-4H-1,2,4-triazole on mild steel corrosion in acidic media

The efficiency of a new triazole derivative, namely, 3,5-bis(4-methylthiophenyl)-4H-1,2,4-triazole (4-MTHT) has been studied for corrosion inhibition of mild steel in 1 M hydrochloric acid (HCl) and 0.5 M sulphuric acid (H₂SO₄). Corrosion inhibition was studied using electrochemical methods and weight loss measurements. These studies have shown that 4-MTHT was a very good inhibitor. 4-MTHT behaved better in 1 M HCl than in 0.5 M H₂SO₄ and inhibition efficiencies up to 99% and 80% can be obtained in 1 M HCl and 0.5 M H₂SO₄, respectively. Activation energies (E_a) in the presence and absence of 4-MTHT were obtained by measuring the temperature independence of the corrosion current. The potential of zero charge of mild steel was studied by ac impedance method, and the mechanism of adsorption has been discussed. The adsorption of 4-MTHT followed Langmuir's adsorption isotherm in both acids.     

The inhibition of mild steel corrosion in acidic solutions by 2,5-bis(4-pyridyl)-1,3,4-thiadiazole: Structure-activity correlation

The effect of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (4-PTH) on the corrosion of mild steel in acidic media (1 M HCl, 0.5 M H₂SO₄, 1 M HClO₄) has been investigated using weight loss measurements, electrochemical impedance spectroscopy and potentiodynamic polarisation. These studies have shown that 2,5-bis(4-pyridyl)-1,3,4-thiadiazole is good inhibitor for mild steel in 1 M HCl, 0.5 M H₂SO₄ and 1 M HClO₄ solutions, the better performances are seen in the case of 1 M HCl solutions. But in 1 M HClO₄, the 4-PTH stimulates corrosion at low concentrations. Polarisation curves indicate that the 4-PTH is a mixed-type inhibitor in all acidic media and E (%) is temperature-dependent. Adsorption on the mild steel surface follows the Langmuir isotherm model in all acidic media. The electronic properties obtained using the Hartree-Fock AB initio 3-21G quantum chemical approach, were correlated with the experimental efficiencies.     

Corrosion inhibition of mild steel by the new class of inhibitors [2,5-bis(n-pyridyl)-1,3,4-thiadiazoles] in acidic media

The inhibitor effect of 2,5-bis(n-pyridyl)-1,3,4-thiadiazoles (n-PTH) on the corrosion of mild steel in 1 M HCl and 0.5 M H₂SO₄ have been investigated using weight loss and electrochemical impedance spectroscopy. Results obtained reveal that these compounds are mixed-type inhibitors and behave better in 1 M HCl than in 0.5 M H₂SO₄. The adsorption of n-PTH on the mild steel surface in both acidic media follows a Langmuir isotherm model.     

Quantum chemical studies on the corrosion inhibition of some sulphonamides on mild steel in acidic medium

Quantum chemical calculations using the density functional theory (DFT) and some semi-empirical methods were performed on four sulphonamides (sulfaguanidine, sulfamethazine, sulfamethoxazole and sulfadiazine) used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies. The results of the quantum chemical calculations and experimental %IE were subjected to correlation analysis and indicate that their inhibition effect are closely related to E_HOMO, E_LUMO, hardness, polarizability, dipole moment and charges. The %IE increased with increase in the E_HOMO and decrease in E_HOMO − E_LUMO. The negative sign of the E_HOMO values and other kinetic and thermodynamic parameters indicates that the data obtained support physical adsorption mechanism.     

Electrochemical and theoretical investigation on the corrosion inhibition of mild steel by thiosalicylaldehyde derivatives in hydrochloric acid solution

Inhibitory effect of three Schiff bases 2-{[(2-sulfanylphenyl)imino]methyl}]phenol (A), 2-{[(2)-1-(4-methylphenyl)methylidene]amino}-1-benznethiol (B), and 2-[(2-sulfanylphen-yl)ethanimidoyl)]phenol (C) on corrosion of mild steel in 15% HCl solution has been studied using weight loss measurements, polarization and electrochemical impedance spectroscopy (EIS) methods. The results of the investigation show that the compounds A and B with mean efficiency of 99% at 200 mg/L additive concentration have fairly good inhibiting properties for mild steel corrosion in hydrochloric acid, and they are as mixed inhibitor. All measurements show that inhibition efficiencies increase with increase in inhibitor concentration. This reveals that inhibitive actions of inhibitors were mainly due to adsorption on mild steel surface. Adsorption of these inhibitors follows the Langmuir adsorption isotherm. Thermodynamic adsorption parameters (K_ads, ΔG_ads) of studied Schiff bases were calculated using the Langmuir adsorption isotherm. Activation parameters of the corrosion process such as activation energies, E_a, activation enthalpies, ΔH^∗, and activation entropies, ΔS^∗, were calculated by the obtained corrosion currents at different temperatures. Obvious correlation was found between the corrosion inhibition efficiency and the calculated parameters. The obtained theoretical results have been adapted with the experimental data.     

Inhibition of mild steel corrosion in phosphoric acid solution by triazole derivatives

Corrosion inhibition by triazole derivatives (n-PAT) on mild steel in phosphoric acid (H₃PO₄) solutions has been investigated by weight loss and polarization methods. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions with emphasis on the former and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. Some kinetic parameters are obtained.     

Adsorption and inhibitive properties of benzimidazole derivatives in acid mild steel corrosion

Eight diazoles were investigated as corrosion inhibitors of mild steel in 1 M hydrochloric acid using gravimetric and polarization techniques. It was found that the inhibition efficiency increased with the increase of organic substrate concentration, while the adsorption followed the Frumkin isotherm. A correlation between the electronic parameters (induction and mesomeric effects of the substituents, ionization potential values) as well as those of the chemical structure (molecular area) of diazoles molecules and their inhibiting properties was looked for. The results obtained show that a definite interdependence exists but it is not as simple and straightforward as might be expected.     

The isoxazolidines: the effects of steric factor and hydrophobic chain length on the corrosion inhibition of mild steel in acidic medium

Several new isoxazolidines having varying degree of steric environment and hydrophobic chain length, prepared efficiently using single-step nitrone cycloaddition reactions, are tested for corrosion inhibition of mild steel in 1 M and 5 M HCl at 50-70 °C range by gravimetric and electrochemical methods. All compounds have shown very good corrosion inhibition efficiency (IE%) in acidic solution. Steric crowding around the nitrogen centres and hydrophobic chain lengths as well as increase in temperature (in the presence of the inhibitor in the higher concentration range 100-400 ppm) are found to increase the inhibition efficiency of the isoxazolidines. Thermodynamic parameters (ΔG°_ads, ΔH°_ads, ΔS°_ads) for the adsorption process and kinetic parameters for the metal dissolution (or hydrogen evolution) reaction in the presence of one of the isoxazolidines were determined. Experimental results agree with the Temkin adsorption isotherm. The inhibition of corrosion in 1 M HCl, influenced by both physi- and chemi-sorption, was found to be under mixed control, but predominantly under cathodic control.     

Electrochemical and quantum chemical studies of some azomethine compounds as corrosion inhibitors for mild steel in 1 M hydrochloric acid

The corrosion inhibition effect of new azomethine compounds: PhNNC (COCH₃)NC₆H₄Y {Y = OCH₃ (SB₁), CH₃ (SB₂), H (SB₃), Br (SB₄) and Y = Cl (SB₅)} on mild steel in 1 M HCl, was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and quantum chemistry analysis. It has been found that the inhibition efficiency increased with increasing inhibitor concentration. The polarization curves showed that these Schiff bases function as mixed inhibitors. The adsorption of studied compounds on mild steel surface was found to follow the Langmuir isotherm. Molecular modeling was used to correlate corrosion inhibition properties and calculated quantum chemical parameters.     

Lignin terpolymer for corrosion inhibition of mild steel in 10% hydrochloric acid medium

Lignin terpolymer has been obtained by grafting copolymerization of both dimethyl diallyl ammonium chloride (DMDAAC) and acrylamide (AM) onto lignin. The corrosion inhibition properties of the terpolymer were tested. The results showed that the highest corrosion inhibition percentage was over 95% in 10% HCl acid medium at 25 °C and 80 °C. The lignin terpolymer inhibitor adsorption followed Temkin isotherm at 25 °C and 80 °C, and the adsorption capability was in reverse proportion to the temperature according to −ΔG_ads. The effects of corrosion inhibition are the comprehensive synergistic effect through the graft reaction among lignin, AM and DMDAAC.     

The isoxazolidines: a new class of corrosion inhibitors of mild steel in acidic medium

The cycloaddition of the cyclic nitrone-1-pyrroline-1-oxide with a variety of alkenes, phenyl isocyanate and phenyl isothiocyanate afforded a multitude of cycloaddition products (isoxazolidines). One of the cycloadducts on reaction with benzyl and propargyl chloride gave quaternary ammonium salts. All these new isoxazolidines are tested for corrosion inhibition of mild steel in 1 M HCl at 60 °C by gravimetric and electrochemical methods.The inhibition efficiency of this class of compounds are determined for the first time. All compounds have shown excellent corrosion inhibition efficiency (IE%) in acidic solution; IE% in the range 86.7-99.5 are measured by the gravimetric method. Comparable results were obtained by the electrochemical method using Tafel plots for the inhibition efficiency of some of the selected synthesized compounds.     

Electrochemical and quantum chemical studies of 3,4-dihydropyrimidin-2(1H)-ones as corrosion inhibitors for mild steel in hydrochloric acid solution

The inhibition effect of 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) on the corrosion of mild steel in hydrochloric acid medium has been investigated using weight loss measurements, electrochemical impedance spectroscopy, potentiodynamic polarization and quantum chemical study. Among the compounds studied, DHPM-3 exhibited the best inhibition efficiency η (%) 99% at 10 mg L⁻¹ at 308 K. Polarization measurements indicate that all the examined compounds are of mixed-type inhibitor. The adsorption of studied compounds obeyed the Langmuir’s adsorption isotherm. The electronic properties obtained using quantum chemical approach, were correlated with the experimental inhibition efficiencies.     

Experimental and quantum chemical studies on two triazole derivatives as corrosion inhibitors for mild steel in acid media

Two triazole derivatives [1‐phenyl‐2‐(5‐(1,2,4) triazol‐1‐ylmethyl‐(1,3,4) oxadizaol‐2‐ylsulphanyl)‐ethanone (PTOE) and 2‐(4‐tert‐butyl‐benzylsulphanyl)‐5‐(1,2,4) triazol‐1‐ylmethyl‐(1,3,4) oxadiazole (TBTO)] were synthesized as new corrosion inhibitors for the corrosion of mild steel in 1 M hydrochloric acid solutions. The inhibiting efficiency of the different inhibitors was evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. The electrochemical investigation results indicate that these compounds act as mixed‐type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds followed the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated with ab initio calculations. The electronic properties such as highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) energy level, dipole moment (µ) and molecular orbital densities were calculated.     

Hydrophobic-tailed bicycloisoxazolidines: A comparative study of the newly synthesized compounds on the inhibition of mild steel corrosion in hydrochloric and sulfuric acid media

The cycloaddition reactions of the cyclic nitrones 1-pyrroline 1-oxide and 3,4,5,6-tetrahydropyridine 1-oxide with alkenes, 11-phenoxy-1-undecene and 11-p-methoxyphenoxy-1-undecene, afforded cycloaddition products (bicyclic isoxazolidines) in excellent yields. One of the cycloadducts on reaction with propargyl chloride and ring opening with zinc in acetic acid afforded quaternary ammonium salt and aminoalcohol, respectively. All the new inhibitor molecules in the presence of 400 ppm at 60 °C achieved inhibition efficiencies, determined by gravimetric method, in the range 99-99.6% and 85-99% for mild steel in 1 M HCl and 0.5 M H₂SO₄, respectively. Comparable results were obtained by the electrochemical methods using Tafel plots and electrochemical impedance spectroscopy for the synthesized compounds. The isoxazolidine derivatives were also found to be good inhibitors of mold steel corrosion in synthetic brine. Negative values of in the acidic media ensured the spontaneity of the adsorption process. While the corrosion inhibition by these molecules was predominantly under cathodic control in 1 M HCl, the inhibition in 0.5 M H₂SO₄ was found to be under anodic control. The isoxazolidines and their derivatives were found to be among a rare class of molecules, which provide suitable inhibition mechanism for the corrosion inhibition in HCl as well as in H₂SO₄ media.     

Inhibitive and adsorption behaviour of carboxymethyl cellulose on mild steel corrosion in sulphuric acid solution

Chemical methods were used to assess the inhibitive and adsorption behaviour of carboxymethyl cellulose (CMC) for mild steel in H₂SO₄ solution at 30-60 °C. Results obtained show that CMC act as inhibitor for mild steel in H₂SO₄. The inhibition efficiency was found to increase with increase in CMC concentration but decreased with rise in temperature, which is suggestive of physical adsorption mechanism. The adsorption of the CMC onto the mild steel surface was found to follow Langmuir and Dubinin-Radushkevich adsorption isotherm models. The inhibition mechanism was further corroborated by the values of activation parameters obtained from the experimental data.     

Inhibiting effects of some mercapto-triazole derivatives on the corrosion of mild steel in 1.0 M HCl medium

The effect of some mercapto-triazole derivatives synthesized in the laboratory containing different hetero atoms and substituents in the organic structures on the corrosion and hydrogen permeation of mild steel in 1.0 M HCl was investigated by weight loss and various electrochemical techniques. Results obtained reveal that all the mercapto-triazole derivatives perform excellently as corrosion inhibitors for mild steel in 1.0 M HCl. Potentiodynamic polarization studies have shown that all these compounds suppress both the anodic and cathodic process and they behave as mixed-type inhibitors. Double layer capacitance and charge transfer resistance values were derived from Nyquist plots obtained from AC impedance studies. Changes in impedance parameters are indicative of the adsorption of these compounds on the metal surface. The inhibition efficiency mainly depends on the nature of the investigated compounds. The values of the inhibition efficiency calculated from these techniques are in reasonably good agreement. The extent of reduction of hydrogen permeation current through mild steel surface was studied by the hydrogen electropermeation technique. The adsorption of these compounds on mild steel surface is found to obey Langmuir adsorption isotherm. The free energy of adsorption for inhibiting process was determined on the basis of Langmuir adsorption isotherm.     

Corrosion control of mild steel using 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole in normal hydrochloric acid medium

The inhibition performance of the 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT) on mild steel in normal hydrochloric acid medium (1 M HCl) at 30 °C was tested by weight loss, potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. This organic compound inhibits the acidic corrosion even at very low concentration, reaching a value of inhibition efficiency up to 98% at a concentration of 3 × 10⁻⁴ M. The results obtained from the different corrosion evaluation techniques are in good agreement. Polarisation curves indicate that 4-MAT is a mixed inhibitor, affecting both cathodic and anodic corrosion currents. Data, obtained from EIS measurements, were analyzed to model the corrosion inhibition process through appropriate equivalent circuit model, a constant phase element (CPE) has been used. The adsorption of 4-MAT on the steel surface, in 1 M HCl solution, obeys to Langmuir’s isotherm with a very high negative value of the free energy of adsorption ΔG°_ads (chemisorption). X-ray photoelectron spectroscopy (XPS) was carried out to establish the mechanism of corrosion inhibition of mild steel in 1 M HCl medium in the presence of 3,5-bis(4-methoxyphenyl)-4-amino-1,2,4-triazole (4-MAT).