• Bulletin of the Korean Chemical Society
• /
• v.11 no.6
• /
• pp.521-527
• /
• 1990

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

• Composites Research
• /
• v.33 no.6
• /
• pp.336-340
• /
• 2020

In this study, carbon aerogels (CA) were prepared by sol-gel polycondensation of resorcinol and furfural in isopropanol using hexamethylenetetramine as a catalyst, and then directly drying the organic gels under isopropanol freeze-drying conditions, followed by carbonization under a nitrogen atmosphere. The preparation conditions of the CA were explored by changing the mole ratio of resorcinol to furfural. The effect of the preparation conditions on the pore structure of the CA was studied by nitrogen adsorption isotherms. The characteristics of the CA were studied by scanning and transition electron microscopy, and infrared spectrometry. The accessibility of pores and performance of the CA as an electrode in electric double layer capacitors were also electrochemically investigated. As a result, BET surface area and specific capacitance increased with the molar ratio of resorcinol to catalyst (R/C) ratio; the maximum values of 765 ㎡/g and 132 F/g were achieved at the R/C ratio of 200, respectively. Consequently, it was confirmed that increasing the R/C ratio increased the average pore size of the CA electrode, which improved the rate capability of the system.

• Corrosion Science and Technology
• /
• v.21 no.3
• /
• pp.230-241
• /
• 2022

Austenitic stainless steel has been widely used because of its good corrosion resistance and mechanical properties. However, intergranular corrosion can occur if the alloy is welded or aged. The objective of this study was to determine intergranular corrosion behaviors of austenitic medium carbon (0.05 wt%) and low carbon (0.02 wt%) stainless steel aged at several conditions. Alloys were evaluated according to ASTM A262 Practice A, ISO 12732 DL-EPR (double loop-electrochemical potentiokinetic reactivation) test, and ASTM A262 Practice C. The degree of sensitization and intergranular corrosion rate were obtained. The relationship between the degree of sensitization and the intergranular corrosion rate showed a very large fluctuation. Such behavior might be related to whether two-dimension tests or three-dimension tests were performed. On the other hand, regardless of carbon content of alloys, when the intergranular corrosion rate increased, the degree of sensitization also increased. However, the DL-EPR test showed a higher sensitivity than the Huey test for differentiating the intergranular corrosion property at a low intergranular corrosion rate, while the Huey test had a higher sensitivity than the DL-EPR test for distinguishing the intergranular corrosion property at a high intergranular corrosion rate.

• Korean Chemical Engineering Research
• /
• v.61 no.1
• /
• pp.155-161
• /
• 2023

Ion concentration polarization (ICP) is one of the essential important mechanisms for biomolecule preconcentration devices as well as a fundamental transport phenomenon found in electrodialysis, electrochemical cell, etc. The ICP triggered by externally applied voltage enables the biomolecular analyte to be preconcentrated at an arbitrary position by a locally amplified electric field inside the microchannel. Conventional preconcentration methodologies using the ICP have two limitations: uncertain equilibrium position and hydrodynamic instability of preconcentration plug. In this work, a new preconcentration method in the dead-end microchannel around cation exchange membrane was numerically studied to resolve the limitations. As a result, the numerical model showed that the analyte was concentrated at a shock front developed in a geometrically confined dead-end channel. Furthermore, the electrokinetic behaviors for preconcentration dynamics were analyzed by changing microchannel's applied voltage and volumetric charge concentration of microchannel as key parameters to describe the dynamics. This work would provide an effective means for a point-of-care platform that requires ultra-fast preconcentration method.

• Korean Chemical Engineering Research
• /
• v.61 no.4
• /
• pp.604-610
• /
• 2023

The nitrogen reduction reaction (NRR), which produces NH₃ by reducing N₂ under ambient conditions, is attracting attention as a promising technology that can reduce energy consumption in industrial processes. We investigated the adsorption behaviors at various active sites on the Ni (100) surface, which is widely used among catalytic metal surfaces capable of adsorbing and activating N₂, based on density-functional theory calculations. We also investigated two N₂ adsorption structures, so-called end-on and side-on structures. We find that for the end-on case, N₂ is adsorbed on a top site, and the reaction proceeded in a distal pathway, while for the side-on case, N₂ is adsorbed on a bridge site, and the reaction proceeded with enzymatic pathway. Finally, this study provides insight into the adsorption of metal catalyst surfaces for the NRR reactions based on the calculated Gibbs free energy profiles of the thermodynamically most favorable pathways.

• Analytical Science and Technology
• /
• v.22 no.5
• /
• pp.432-438
• /
• 2009

In order to develop the analytical method for the pharmaceutical tablets containing ranitidine HCl by square wave voltammetry (SWV), $5.00{\times}10^{-5}M$ ranitidine HCl solutions prepared with phosphate buffers of various pH values were investigated by SWV. The well defined main peak due to the electrochemical reduction of $-NO_2$ in the structure of ranitidine moved towards the cathodic direction by -70 mV/pH as the pH values were increased indicating the involvement of hydrogen in its reduction. The calibration curve, the plot of peak currents (Ip) vs. concentrations of ranitidine HCl in the range between $1.00{\times}10^{-7}M$ and $1.00{\times}10^{-5}M$ showed linearity with slopes of $232,530{\mu}A/M$ (pH 6.14), $289,015{\mu}A/M$ (pH 7.07) and $232,843{\mu}A/M$ (pH 8.01). When one pharmaceutical tablet was simply dissolved in the phosphate buffer with a pH value of 6.14 and determined by standard addition method using SWV, the within-day precision study (n=4) resulted in the contents of ranitidine HCl as $171{\pm}2.1mg$ ($102{\pm}1.3%$ of the specified contents, RSD of 1.2%) in a tablet of Curan$^{(R)}$. The inter-day precision for 5 days was 1.1% of RSD. For Zantac$^{(R)}$ the within-day precision study (n=4) showed the contents of ranitidine HCl as $167{\pm}0.8mg$ ($99{\pm}0.5%$ of the specified contents, RSD of 0.5%) in a tablet and the inter-day precision for 5 days was 0.3% of RSD.

• Applied Chemistry for Engineering
• /
• v.18 no.3
• /
• pp.205-212
• /
• 2007

In this work, polyacrylonitrile (PAN) fiber was prepared by electrospinning methods from dimethyl formamide solutions with various conditions, such as 8~20 kV applied voltage, 5~15 wt% PAN concentration, and 15 cm tip-to-collector distance (TCD). The nanofibers were stabilized by oxidation at $250^{\circ}C$ for 1 h, and then subsequently carbonized at $800{\sim}1000^{\circ}C$ for 1 h. The structured characteristics of the nanofibers before and after carbonization were studied by Fourier transform infrared spectroscopy. The resulting diameter distribution and morphologies of the nanofiber were evaluated by scanning electron microscope analysis. The electrochemical behaviors of the nanofiber were observed by cyclic voltammetry tests. From the results, the diameter of electrospinning nanofibers was predominantly influenced by the concentration of polymer solution and the applied voltage. The average diameter of the fibers was decreased with increasing the polymer concentration up to 10wt%. It was also found that the nanofibers with uniform diameter distribution and fine diameter could be achieved at 15kV input voltage and 15 cm TCD.

• Applied Chemistry for Engineering
• /
• v.9 no.1
• /
• pp.44-51
• /
• 1998

In this work, the in-situ viscoelastic characteristics of electropolymerized polypyrrole (PPy) thin film were investigated in the electrolyte solutions of $NaClO_4$, $LiClO_4$, and $KClO_4$ by using quartz crystal analyzer (QCA). One side of quartz crystal was used as a working electrode mounted in a special fabricated QCA electrochemical ceil. The resonant frequency and resonant resistance diagram (F-R diagram) was used to interpret the viscoelastic characteristics of Pby thin film and compared with AFM photograph. The resonant frequency, resonant resistance, and current were measured to analyze the redox reaction behaviors when the cyclic voltammetry was performed using AT-cut quartz crystal electrode coated with galvanostatically polymerized Ppy film. The result suggests that the Ppy film polymerized onto the crystal behaves as a rigid elastic layer at the initial stage of electropolymerization, while the film becomes a viscoelastic layer the polymerization proceeds further. At the same time, the film thickness increases and some morphological changes take place due to the penetration of electrolyte solution into the film. These phenomena take place when cyclic voltammetry was performed using different electrolyte solution compared with polymerization process.

• Analytical Science and Technology
• /
• v.6 no.5
• /
• pp.417-424
• /
• 1993

Eight-coordinate tetrakis molybdenum(IV) complexes containing 5,7-dichloro-8-hydroxyquinolinol(Hdcq) and 2-mercaptopyrimidine(Hmpd) has been prepared. $Mo(mpd)_4$, $Mo(dcq)(mpd)_3$, $Mo(dcq)_2(mpd)_2$, $Mo(dcq)_3(mpd)$ and $Mo(dcq)_4$ complexes have been isolated by thin-layer chromatography on silicagel plates. These complexes have been charaterized by $^1H-nmr$ spectrum and UV-Vis. spectrum. The chemical shift values of the protons ${\alpha}$ to the nitrogen in the ligands are shifted to down field. The relative intensities of the peaks which are positioned at the same proton of $Mo(dcq)(mpd)_3$ and $Mo(dcq)_3(mpd)$ are observed in 2:1 ratio, in case of $Mo(dcq)_2(mpd)_2$ appears in approximately a 1:1 ratio. The stereochemistry of the complexes in discussed in terms of their nmr spectrum and Orgel's rule. By vertue of the intensities (${\varepsilon}$>10,000~25,000) the low energy($16,600{\sim}19,800cm^{-1}$) bands are observed for the electronic spectra of the complexes are assigned as charge transfer bands.

• Journal of the Microelectronics and Packaging Society
• /
• v.18 no.2
• /
• pp.43-48
• /
• 2011

The maximum current density of copper electrorefining is 350 A/$m^2$ and the higher current density is required to promote the copper productivity. The 1000 A/$m^2$ high current density is possible when rotating disc electrode is employed to reduce diffusion thickness. The copper electroplating with 1000 A/$m^2$ is possible at 400 rpm. Thiourea and glue were used to improve the electrodeposition behaviors during copper electrorefining process. Potentiodynamic polarization tests were conducted to investigate the effects of additives on copper electrodeposition. Galvanostatic tests were also conducted at 1000 A/$m^2$. Copper were electroplated on cylindrical rotating electrodes to give the uniform flow on the electrode surface. The lowest surface roughness was obtained when 16 ppm thiourea was added to the electrolytes. The surface roughness was increased with glue concentration. The surface hardness was not influenced by addition of glue. The copper nuclei were getting smaller with thiourea concentration, however there is no glue effects on copper nucleation.