Corrosion inhibition and adsorption behavior of methionine on mild steel in sulfuric acid and synergistic effect of iodide ion

The corrosion inhibition of mild steel in sulfuric acid by methionine (MTI) was investigated using electrochemical techniques. The effect of KI additives on corrosion inhibition efficiency was also studied. The results reveal that MTI inhibited the corrosion reaction by adsorption onto the metal/solution interface. Inhibition efficiency increased with MTI concentration and synergistically increased in the presence of KI, with an optimum [KI]/[MTI] ratio of 5/5, due to stabilization of adsorbed MTI cations as revealed by AFM surface morphological images. Potentiodynamic polarization data suggest that the compound functioned via a mixed-inhibition mechanism. This observation was further corroborated by the fit of the experimental adsorption data to the Temkin and Langmuir isotherms. The inhibition mechanism has been discussed vis-à-vis the presence of both nitrogen and sulfur atoms in the MTI molecule.     

Corrosion and corrosion inhibition characteristics of bulk nanocrystalline ingot iron in sulphuric acid

The corrosion and corrosion inhibition of bulk nanocrystalline ingot iron (BNII) fabricated from conventional polycrystalline ingot iron (CPII) by severe rolling was studied in 0.5 M H₂SO₄ solution using electrochemical impedance spectroscopy and potentiodynamic polarization techniques. The results indicate that BNII was more susceptible to corrosion in the acidic environment essentially because of an increase in the kinetics of the anodic reaction. An amino acid cysteine (cys) was employed as a corrosion inhibitor at concentrations of 0.001 and 0.005 M. Tests in inhibited solutions revealed that cys reduced the corrosion rates of both metal specimens by different mechanisms. For CPII cys inhibited the cathodic reaction but had a stimulating effect on the anodic process at low concentration and a trivial effect at higher concentration. For BNII, cys inhibited both the cathodic and the anodic reactions, although the former effect was more pronounced. Iodide ions improved the inhibitive effect of cys without altering the inhibition mechanism.     

Anisotropic Stark effect of carbon monoxide: emergent orbital cooperativity

ABSTRACT

Applying external electric fields to molecules gives rise to spectral shifting and splitting, a phenomenon known as the Stark effect. However, a fundamental question of how electronic structures of molecules are modified by electric fields is still not well understood. By applying electric fields to a carbon monoxide molecule, herein we have successfully addressed the fundamental question at orbital scales and discovered that the Stark effect exhibits anisotropic characters depending on the direction of the electric fields with respect to the molecular axis. Based on the fact that applying electric fields along the molecular axis always preserved the orthogonality between the sigma and pi electrons, we found that orbital resemblance-based cooperativity can only operate within either the sigma system in which sigma electrons somehow prefer to resemble each other or the pi electron system in which the 1π electrons experience polarization-based self-resemblance. However, switching the electric field vertical to the molecular axis breaks down the orthogonality between the sigma system and pi electron systems, opening up electronic channels that allow σ electron systems to resemble π electrons. Such orbital cooperativity represents a new physical effect beyond the conventional Stark effect. Moreover, we have found that applying electric fields to the molecule would modify its molecular orbital diagram, depending on the directions of the electric fields; the electric field along the carbon-to-oxygen direction basically retains the MO diagram of the free CO molecule, with noticeable intra-orbital electron redistributions, whereas the oxygen-to-carbon electric field does create new states of molecular orbital contributions.     

Inhibitory Action of Funtumia elastica Extracts on the Corrosion of Q235 Mild Steel in Hydrochloric Acid Medium: Experimental and Theoretical Studies

The inhibiting effect of aqueous extracts of Funtumia elastica (FE) on mild steel corrosion in 1 M HCl solution was investigated using electrochemical and surface characterization techniques. The results revealed that FE effectively inhibited the corrosion reaction. Polarization data reveal that the extract functioned as a mixed-type inhibitor, while impedance results show that the extract organic matter gets adsorbed on the metal/solution interface. Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy results confirmed the formation of a protective layer of extract adsorbed on the mild steel surface. Adsorption of some organic constituents of FE on mild steel was theoretically described by quantum chemical computations and molecular dynamics simulations, in the framework of the density functional theory.     

Experimental, quantum chemical calculations, and molecular dynamic simulations insight into the corrosion inhibition properties of 2-(6-methylpyridin-2-yl)oxazolo[5,4-f][1,10]phenanthroline on mild steel

2-(6-Methylpyridin-2-yl)oxazolo[5,4-f][1,10]phenanthroline (MOP) was synthesized and characterized by elemental analysis and Fourier-transform infrared (FT-IR), ¹H nuclear magnetic resonance (NMR), and ¹³C NMR spectra. MOP was evaluated as a corrosion inhibitor for carbon steel in 0.5 M H₂SO₄ solution using the standard gravimetric technique at 303–333 K. Quantum chemical calculations and molecular dynamic (MD) simulations were applied to analyze the experimental data and elucidate the adsorption behavior and inhibition mechanism of MOP. Results obtained show that MOP is an efficient inhibitor for mild steel in H₂SO₄ solution. The inhibition efficiency was found to increase with increase in MOP concentration but decreased with temperature. Activation parameters and Gibbs free energy for the adsorption process using statistical physics were calculated and discussed. The adsorption of MOP was found to involve both physical and chemical adsorption mechanisms. Density functional theory (DFT) calculations suggest that nitrogen and oxygen atoms present in the MOP structure were the active reaction sites for the inhibitor adsorption on mild steel surface via donor–acceptor interactions between the lone pairs on nitrogen and oxygen atoms together with the π-electrons of the heterocyclic and the vacant d-orbital of iron atoms. The adsorption of MOP on Fe (1 1 0) surface was parallel to the surface so as to maximize contact, as shown in the MD simulations. The experiments together with DFT and MD simulations provide further insight into the mechanism of interaction between MOP and mild steel.     

Orbital mechanism of upright CO activation on Fe(100)

The knowledge of bond activation forms a cornerstone for modern chemistry, wherein symmetry rules of electronic activation lie in the heart of bond activation. However, the question as to how a chemical bond is activated remains elusive. By taking CO activated on Fe(100), herein, we have resolved the long-standing fundamental question; we have found that excitations in the adsorbate feature the bond activation. We essentially have discovered contrasting electronic processes in respective σ and π electron systems of the adsorbed CO molecule. The σ electron system is involved in reversible hidden excitations/deexcitations between two occupied σ orbitals, whereas the π electron system is subject to irreversible π to π* excitations dispersed along the d-band region, which is coupled to the rotational 2π electron couplings depending on the strength of molecule-metal interactions. The σ excitations pertain to the Pauli repulsion mediated quantum nature with energy and entropy marked by the two energy levels, whereas the π to π* excitations fall into a new category of electronic excitations contributing to energy and entropy exchanges in a wide and continuous d-band region. The findings that the internal states of the adsorbate are excited and that fundamental connections between the frontier orbitals and low-lying orbitals are established as the molecule comes to the surface may open up new channels to realize more efficient bond activation and renew our thinking on probing the quantum mechanical nature of bond activation at surfaces with further possible impact on manipulation of orbital activation in femtochemistry and attochemistry.