[en] An examination of quantum chemical and corrosion inhibition studies were carried out to investigate whether any clear links exist between the results of quantum chemical calculations and the experimental efficiencies of urea (U), thiourea (TU), acetamide (A), thioacetamide (TA), semicarbazide (SC), thiosemicarbazide (TSC), methoxybenzaldehydethiosemicarbazone (MBTSC), 2-acetylpyridine-(4phenyl) thiosemicarbazone (2AP4PTSC), 2-acetylpyridine-(4-methyl) thiosemicarbazone (2AP4MTSC), benzointhiosemicarbazone (BZOTSC) and benzilthiosemicarbazone (BZITSC) being corrosion inhibitors. The quantum chemical calculations have been performed by using DFT, ab-initio molecular orbital and semi-empirical methods for some amides and thiosemicarbozone derivatives being corrosion inhibitors. The highest occupied molecular orbital energy (E _HOMO), lowest unoccupied molecular orbital energy (E _LUMO), the energy gap between E _HOMO and E _LUMO (ΔE _HOMO-LUMO), dipole moments (μ), charges on the C, O, N, S atoms, the total energies of the molecules and the polarizabilities <α>, the coefficients of the development of the MO over the atomic orbital (AO) corresponding to the between atoms which a new bond is established have been calculated. The results of quantum chemical calculations and experimental efficiencies of inhibitors were subjected to correlation analysis. We have reached the conclusion that the synthesis of better corrosion inhibitors can be achieved by controlling all electronic properties and parameters of a selected group of molecules

[en] 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

[en] Highlights: ► Azure A molecule is found to be a good inhibitor for mild steel in HCl solution. ► SEM results clearly indicate that a protective film formation occurred on the mild steel surface. ► The long term corrosion tests are cleared that the Azure A has effectively protected the mild steel in HCl solution. ► The quantum chemical measurements were cleared the reactive sites and charges of atoms in the molecule. - Abstract: In this study, inhibition effect of Azure A on mild steel in 1.0 M HCl were evaluated by using electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and potentiodynamic polarization and scanning electron microscope (SEM) methods. These studies were carried out at different concentrations, temperatures and durations. The inhibitor molecules were chemisorbed on electrode surface according to the Langmuir adsorption isotherm. The quantum chemical calculations were employed to give further insight into the inhibition mechanism of Azure A.

[en] Research highlights: → TX-305 exhibits inhibiting properties for iron corrosion more than TX-165 and TX 100. → Inhibition efficiency increases with temperature, suggesting chemical adsorption. → The three tested surfactants act as mixed-type inhibitors with cathodic predominance. → Validation of corrosion rates measured by Tafel extrapolation method is confirmed. - Abstract: The inhibition characteristics of non-ionic surfactants of the TRITON-X series, namely TRITON-X-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on the corrosion of iron was studied in 1.0 M HCl solutions as a function of inhibitor concentration (0.005-0.075 g L^-1) and solution temperature (278-338 K). Measurements were conducted based on Tafel extrapolation method. Electrochemical frequency modulation (EFM), a non-destructive corrosion measurement technique that can directly give values of corrosion current without prior knowledge of Tafel constants, is also presented. Experimental corrosion rates determined by the Tafel extrapolation method were compared with corrosion rates obtained by the EFM technique and an independent method of chemical analysis. The chemical method of confirmation of the corrosion rates involved determination of the dissolved cation, using ICP-AES (inductively coupled plasma atomic emission spectrometry). The aim was to confirm validation of corrosion rates measured by the Tafel extrapolation method. Results obtained showed that, in all cases, the inhibition efficiency increased with increase in temperature, suggesting that chemical adsorption occurs. The adsorptive behaviour of the three surfactants followed Temkin-type isotherm. The standard free energies of adsorption decreased with temperature, reflecting better inhibition performance. These findings confirm chemisorption of the tested inhibitors. Thermodynamic activation functions of the dissolution process were also calculated as a function of each inhibitor concentration. All the results obtained from the methods employed are in reasonable agreement.

[en] Graphical abstract: . Display Omitted Research highlights: → The inhibition effect of TX-100, TX-165 and TX-305 on iron corrosion in 1.0 M HCl was studied. → TX-305 inhibited iron corrosion more effectively than TX-100 and TX-165. → In most cases, inhibition efficiency increased with time during the first 60 min of immersion, then decreased. → Calculated quantum chemical parameters confirmed the experimental inhibition efficiencies of the tested surfactants. - Abstract: The inhibition performance of three selected non-ionic surfactants of the TRITON-X series, namely TRITONX-100 (TX-100), TRITON-X-165 (TX-165) and TRITON-X-305 (TX-305), on the corrosion of iron was studied in 1.0 M HCl solutions as a function of inhibitor concentration (0.01-0.20 g L^-1) and immersion time (0.0-8 h) at 298 K. Measurements were conducted based on Tafel polarization, LPR and impedance studies. At high frequencies, the impedance spectrum showed a depressed capacitive loop in the complex impedance plane, whose diameter is a function of the immersion time and the type and concentration of the introduced surfactant. In all cases, an inductive loop was observed in the low frequency and this could be attributed to the adsorption behavior. The inhibition efficiency increased with immersion time, reached a maximum and then decreased. This was attributed to the orientation change of adsorbed surfactant molecules. TX-305 inhibited iron corrosion more effectively than TX-100 and TX-165. The frontier orbital energies, the energy gap between frontier orbitals, dipole moments (μ), charges on the C and O atoms, the polarizabilities, and the quantum chemical descriptors were calculated. The quantum chemical calculation results inferred that for the HOMO representing the condensed Fukui function for an electrophilic attack (f_k⁺), the contributions belong to the phenyl group and the oxygen atom attached to the phenyl group for each tested surfactant. Quantitative structure-activity relationship (QSAR) approach has also been used and a correlation of the composite index having some of the quantum chemical parameters with average inhibition efficiencies (I_av.(%)) was conducted to determine the inhibition performance of the tested surfactant molecules. The results showed that the values of I_av.(%) of the tested inhibitor molecules were closely related to some of the quantum chemical parameters. The calculated I_av.(%) values were found to be close to the experimental ones. Based on the values of coefficients of correlations at 0.02 level concentration, B3LYP/3-21G^* method outpaced the other two methods namely B3LYP/6-31G and RHF/6-31G^*. The relationship between I_av.(%) and composite index is accounted for by B3LYP/3-21G^*.