• Journal of Electrochemical Science and Technology
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• v.9 no.4
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• pp.260-275
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• 2018

The corrosion inhibition of cast iron in 1 M HCl by Phenanthroline (Phen) was investigated using potentiodynamic polarization (PDP) curves, electrochemical impedance spectroscopy (EIS), surface analysis and theoretical calculations. It is found that Phen exhibits high inhibition activity towards the corrosive action of HCl and its adsorption obeys the Langmuir adsorption isotherm model. The results showed that inhibition efficiency increases with Phen concentration up to a maximum value of 96% at 1.4 mM, and decreases slightly with the increase in temperature. The free adsorption energy value indicates that Phen adsorbs on cast iron surface in 1 M HCl via a simultaneous physisorption and chemisorption mechanism. Scanning electron microscopy (SEM) micrographs, atomic force microscopy (AFM) and FTIR analysis confirmed the formation of a protective film on cast iron surface, resulting in the improvement of its corrosion resistance in the studied aggressive solution. Quantum chemical calculations at the DFT level were achieved to correlate electronic structure parameters of Phen molecules with their adsorption mode.

• Corrosion Science and Technology
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• v.22 no.2
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• pp.73-89
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• 2023

Due to continuous promotion of green alternatives to toxic petrochemicals by government policies, research efforts towards the development of green corrosion inhibitors have intensified recently. The objective of the current work was to develop novel green and sustainable corrosion inhibitors derived from 4-aminoantipyrine to effectively prevent corrosion of mild steel in corrosive environments. Gravimetric methods were used to investigate corrosion inhibition of 4-((furan-2-ylmethylene)amino)antipyrine (FAP) and 4-((pyridin-2-ylmethylene)amino)antipyrine (PAP) for mild steel in 1 M HCl. FAP and PAP were subjected to quantum chemical calculations using density functional theory (DFT). DFT was used to determine the mechanism of mild steel corrosion inhibition using inhibitors tested in HCl. Results demonstrated that these tested inhibitors could effectively inhibit mild steel corrosion in 1.0 M HCl. At 0.0005 M, these inhibitors' efficiencies for FAP and PAP were 93.3% and 96.5%, respectively. The Langmuir adsorption isotherm was obeyed by these inhibitors on the mild steel surface. Values of adsorption free energies, ΔG^o_ads, revealed that FAP followed chemical and physical adsorptions.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.355-363
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• 2023

In this study, we explore the nature of clumped isotopes of H₂O molecule using quantum chemical calculations. Particularly, we estimated the relative clumping strength between diverse isotopologues, consisting of oxygen (¹⁶O, ¹⁷O, and ¹⁸O) and hydrogen (hydrogen, deuterium, and tritium) isotopes and quantify the effect of temperature on the extent of isotope clumping. The optimized equilibrium bond lengths and the bond angles of the molecules are 0.9631-0.9633 Å and 104.59-104.62°, respectively, and show a negligible variation among the isotopologues. The calculated frequencies of the modes of H₂O molecules decrease as isotope mass number increases, and show a more prominent change with varying hydrogen isotopes over those with oxygen isotopes. The equilibrium constants of isotope substitution reactions involving these isotopologues reveal a greater effect of hydrogen mass number than oxygen mass number. The calculated equilibrium constants of clumping reaction for four heavy isotopologues showed a strong correlation; particularly, the relative clumping strength of three isotopologues was 1.86 times (HT¹⁸O), 1.16 times (HT¹⁷O), and 0.703 times (HD¹⁷O) relative to HD¹⁸O, respectively. The relative clumping strength decreases with increasing temperature, and therefore, has potential for a novel paleo-temperature proxy. The current calculation results highlight the first theoretical study to establish the nature of clumped isotope fractions in H₂O including ¹⁷O and tritium. The current results help to account for diverse geochemical processes in earth's surface environments. Future efforts include the calculations of isotope fractionations among various phases of H₂O isotopologues with a full consideration of the effect of anharmonicity in molecular vibration.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.564-570
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• 2012

s-Tetrazine is the essential candidate of many energetic compounds due to its high nitrogen content, enthalpy of formation and thermal stability. The present study explores the design of s-tetrazine derivatives in which different $-NO_2$, $-NH_2$ and $-N_3$ substituted azoles are attached to the tetrazine ring via C-N linkage. The density functional theory (DFT) is used to predict the geometries, heats of formation (HOFs) and other energetic properties. The predicted results show that azide group plays a very important role in increasing HOF values of the s-tetrazine derivatives. The densities for designed molecules were predicted by using the crystal packing calculations. The introduction of $-NO_2$ group improves the density as compared to $-N_3$, and $-NH_2$ groups and hence the detonation performance. Bond dissociation energy analysis and insensitivity correlations revealed that amino derivatives are better candidates considering insensitivity and stability.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2093-2098
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• 2013

Density functional theory (DFT) was used to determine the ground state geometries of indigo and new design dyes (IM-Dye-1 IM-Dye-2 and IM-Dye-3). The time dependant density functional theory (TDDFT) was used to calculate the excitation energies. All the calculations were performed in both gas and solvent phase. The LUMO energies of all the dyes were above the conduction band of $TiO_2$, while the HOMOs were below the redox couple (except IM-Dye-3). The HOMO-LUMO energy gaps of new design dyes were smaller as compared to indigo. All new design dyes were strongly red shifted as compared to indigo. The improved light harvesting efficiency (LHE) and free energy change of electron injection ${\Delta}G^{inject}$ of new designed sensitizers revealed that these materials would be excellent sensitizers. The broken coplanarity between the benzene near anchoring group having LUMO and the last benzene attached to TPA unit in all new design dyes consequently would hamper the recombination reaction. This theoretical designing will the pave way for experimentalists to synthesize the efficient sensitizers for solar cells.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2588-2592
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• 2010

The potential energy surfaces (PESs) for the primary and secondary dissociations of the phenylarsane molecular ion (1a) were determined from the quantum chemical calculations using the G3(MP2)//B3LYP method. Several pathways for the loss of $H{\cdot}$ were determined and occurred though rearrangements as well as through direct bond cleavages. The kinetic analysis based on the PES for the primary dissociation showed that the loss of $H_2$ was more favored than the loss of $H{\cdot}$, but the $H{\cdot}$. loss competed with the $H_2$ loss at high energies. The bicyclic isomer, 7-arsa-norcaradiene radical cation, was formed through the 1,2 shift of an $\alpha$-H of 1a and played an important role as an intermediate for the further rearrangements in the loss of $H{\cdot}$ and the losses of $As{\cdot}$ and AsH. The reaction pathways for the formation of the major products in the secondary dissociations of $[M-H]^+$ and $[M-H_2]^{+\cdot}$. were examined. The theoretical prediction explained the previous experimental results for the dissociation at high energies but not the dissociation at low energies.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2345-2350
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• 2009

As part of an effort to discover bioactive natural products from marine sources, we investigated the bioactive secondary metabolites from two marine isolates of the fungi, Trichoderma viride and Rhizopus stolonifer. Three cyclopentenones, myrothenones A (1) and B (2) and trichodenone A (3), were isolated from T. viride and two cyclopentenones, 2-bromomyrothenone B (4) and botrytinone (5), were isolated from R. stolonifer. The molecular structures and absolute stereochemistries of the cyclopentenones were determined from chemical and physicochemical evidence, including quantum chemistry calculations, X-ray analysis, and the circular dichroism (CD) exciton chirality method. Myrothenone A (1) displays tyrosinase inhibitory activity, with an I$C_{50}$ value of 6.6 ${\mu}M$, and is therefore more active than the positive control, kojic acid.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.243-243
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• 2012

Self-assembled monolayers (SAMs) prepared by aromatic thiols on gold surfaces have much larger potential for electronic device applications due to their electronic properties. In this study, the formation and structures of SAMs prepared by benzenethiol (BT), toluenethiol (TT), 2-fluorobenzenethiol (2-FBT), 3-fluorobenzenethiol (3-FBT), 4-fluorobenzenethiol (4-FBT), 4-chlorobenzenethiol (4-CBT), 4-fluorobenzenemethanethiol (4-FBMT), and 4-chlorobenzenemethanethiol (4-CBMT) on Au(111) were examined using scanning tunneling microscopy (STM) and Kelvin probe (KP) to explore the structure and electronic interface properties of eight differently substituted aromatic thiol SAMs on Au(111). And these values are compared with gas phase dipole moments computed by quantum chemical calculations for individual thiol molecules. It was revealed that all eight thiol-molecules form uniform SAMs on Au(111) at $75^{\circ}C$ compared to lower solution temperature by STM observation. The work function change obtained in the KP measurements and calculated molecular dipole moments have the linear relationship while the 4-FBMT and 4-CBMT deviate from this tendency.

• Journal of Electrochemical Science and Technology
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• v.6 no.1
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• pp.7-15
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• 2015

3-(4-Iodophenyl)-2-imino-2,3-dihydrobenzo[d]oxazol-5-yl 4-methylbenzenesulfonate (4-IPhOXTs) was synthesized and its inhibiting action on the corrosion of stainless steel 316L (SS) in sulfuric acid was investigated by means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results of the investigation show that this compound has excellent inhibiting properties for SS corrosion in sulfuric acid. Inhibition efficiency increases with increase in the concentration of the inhibitor. The adsorption of 4-IPhOXTs onto the SS surface followed the Langmuir adsorption model with the free energy of adsorption ΔG⁰_ads of −8.45 kJ mol⁻¹ . Quantum chemical calculations were employed to give further insight into the mechanism of inhibition action of 4-IPhOXTs.

• Journal of Electrochemical Science and Technology
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• v.12 no.3
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• pp.365-376
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• 2021

Two arylamino substituted mercaptoimidazole derivatives namely 4,5-dimethyl-1-(phenylamino)-1H-imidazole-2(3H)-thione (I1) and 4,5- dimethyl-1-((p-chlorophenyl)amino)- 1H-imidazole-2(3H)-thione (I2) were synthesized and investigated as corrosion inhibitors for carbon steel in 0.5 M HCl solution by means of electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, ATR-FTIR spectroscopy and SEM. The results showed that the investigated mercaptoimidazole derivatives act as mixed type inhibitors and inhibition efficiency follows the I2>I1 order. Adsorption of inhibitors on metal surface was found to obey the Langmuir adsorption isotherm. Thermodynamic parameters revealed that adsorption of the inhibitors has both physisorption and chemisorption adsorption mechanism. Electrochemical test results were supported by quantum chemical parameters obtained from DFT calculations.