• Title/Summary/Keyword: Kinetic Method

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Determination of Adsorption Isotherms of Hydrogen at an Ir Electrode Interface Using the Phase-Shift Method and Correlation Constants (Ir 전극 계면에서 위상이동 방법 및 상관계수를 이용한 수소의 흡착동온식 결정)

  • Jeon, Sang-K.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.132-140
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    • 2007
  • The phase-shift method and correlation constants for studying a linear relationship between the behavior ($-{\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and that (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}\theta{\geq}0$) have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) at noble metal/aqueous electrolyte interfaces. At an Ir/0.1 M KOH aqueous electrolyte interface, the Langmuir and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=3.3{\times}10^{-4}\;mol^{-1}$ for the Langmuir and $K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}$ for the Temkin adsorption isotherm), interaction parameter (g = 4.6 for the Temkin adsorption isotherm), and standard free energies (${\Delta}G_{ads}^0=19.9kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-4}\;mol^{-1}$ and $16.5<{\Delta}G_{\theta}^0<23.3\;kJ\;mol^{-1}\;for\;K=3.3{\times}10^{-3}{\exp}(-4.6{\theta})\;mol^{-1}\;and\;0.2<\theta<0.8$) of H for the cathodic $H_2$ evolution reaction are determined using the phase-shift method and correlation constants. The inhomogeneous and lateral interaction effects on the adsorption of H are negligible. At the intermediate values of ${\theta},\;i.e,\;0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms (${\theta}\;vs.\;E$) and related electrode kinetic and thermodynamic parameters(K, g, ${\Delta}G_{ads}^0, {\Delta}G_{\theta}^0$).

Small Animal PET Imaging Study of 68Ga-BAPEN (68Ga-BAPEN 소동물 PET영상 연구)

  • Kim, Ji-Who;Lee, Jae-Sung;Yang, Bo-Yeun;Kim, Su-Jin;Kim, Joong-Hyun;Jeong, Jae-Min;Lee, Dong-Soo
    • Progress in Medical Physics
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    • v.22 no.4
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    • pp.172-177
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    • 2011
  • The purpose of this study was to analyze $^{68}Ga$-BAPEN dynamic PET image in rat myocardium to evaluate potential of this radiotracer as a perfusion imaging agent. Animal PET/CT scan was done in 9 rats during 120 minutes. Especially we synthesized $^{68}Ga$-BAPEN with kit which is simple and low cost method. PET images showed the in vivo dynamic distribution of $^{68}Ga$-BAPEN in the chest region of rats. Initially $^{68}Ga$-BAPEN PET images showed aorta and liver activities and a few minutes later, $^{68}Ga$-BAPEN moved to myocardium. Regions of interest were drawn on myocardium, liver, lung and blood pool. Time-activity curves showed significant uptake of $^{68}Ga$-BAPEN in myocardium. The contrast ratios of myocardial to blood pool, lung and liver at 60 minutes after injection were 1.66, 2.82 and 0.60. To estimate accurate kinetic parameters, 60 minutes after injection was required to PET scan as myocardium image contrast ratios reached to constant values. As a result, $^{68}Ga$-BAPEN would be suitable radiotracer for PET which can applied to diagnosis of myocardial perfusion diseases after further preclinical and clinical investigations.

The Kinetics of Delignification in Oxygen·Alkali pulping (효소(酵素)·알칼리 증해(蒸解)의 탈(脱)리그닌에 관(関)한 동역학적(動力學的) 분석(分析))

  • Jo, Byoung Muk;Shin, Dong So
    • Journal of Korean Society of Forest Science
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    • v.56 no.1
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    • pp.26-50
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    • 1982
  • In order to obtain more detailed information concerning the degradation of lignin in the oxygen alkali pulping single stage isothermal delignification of pine wood meal (Pinus koraiensis S. et Z.) was studied in the oxygen alkali system at five temperature level ($110^{\circ}C$, $120^{\circ}C$, $130^{\circ}C$, $140^{\circ}C$, $150^{\circ}C$) for 60 min.. The rate constant, activation energy, oxygen and alkali consumption during the oxygen alkali delignification were determined by the kinetic method. The 2/5 of total lignin was eliminated at the start of the reaction. The delignification rate constant was about 3 times that of caustic soda pulping. The activation energy was about 1/3 lower than in caustic soda pulping. Like oxygen consumption, alkali consumption was also rapid early at the reaction and almost ceased after about 10 min.. The degradation reaction of lignin was strongly dependent upon the pH decrease of the cooking liquor by organic acid generated in pulping. The lignin in the oxygen alkali pulping degraded into lover molecular weight and had more hydrophillic properties. The methoxyl group decreased considerably at the first of oxygen alkali delignification, while the carbonyl, carboxyl and phenolic hydroxyl group increased rapidly.

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Synthesis and Characterization of Some Transition Metal Complexes of Unsymmetrical Tetradentate Schiff Base Ligand (비대칭 Tetradentate Schiff 염기 리간드의 전이금속 착물에 대한 합성 및 특성)

  • Munde, A. S.;Jagdale, A. N.;Jadhav, S. M.;Chondhekar, T. K.
    • Journal of the Korean Chemical Society
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    • v.53 no.4
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    • pp.407-414
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    • 2009
  • The solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with 4-hydroxy-3-(1-{2-(2-hydroxybenzylidene)- amino phenylimino}-ethyl)-6-methy-pyran-2-one (H2L) derived from o-phenylenediamine, 3-acetyl- 6-methyl-(2H) pyran, 2,4 (3H)-dione (dehydroacetic acid or DHA) and salicylic aldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-visible, IR, $^1H$-NMR spectra, X-ray diffraction, thermal analysis, and screened for antimicrobial activity. The IR spectral data suggest that the ligand behaves as a dibasic tetradentate ligand with ONNO donor atoms sequence towards central metal ion. From the microanalytical data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand). The physico-chemical data suggests square planar geometry for Cu(II) and Ni(II) complexes and octahedral geometry for Co(II), Mn(II) and Fe(III) complexes. The x-ray differaction data suggests orthorhombic crystal system for Cu(II) complex, monoclinic crystal system for Ni(II), Co(II) and Fe(III) and tetragonal crystal system for Mn(II) complex. Thermal behaviour (TG/DTA) of the complexes was studied and kinetic parameters were determined by Coats-Redfern method. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus Niger and Trichoderma.

A Study on the Ionic Dissociation Rate of $\alpha$-Chlorobenzyl Ethyl Ether by Dynamic NMR Spectroscopy-Chlorobenzyl Ethyl Ether by Dynamic NMR Spectroscopy (動的 NMR에 依한 $\alpha$-Chlorobenzyl Ethyl Ether의 이온解離速度에 關한 硏究)

  • Chang-Yol Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.44-52
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    • 1980
  • Ionic dissociation rates of $\alpha$-chlorobenzyl ethyl ether in each solvent of toluene-$d_8$ and carbon tetrachloride were measured by the method of dynamic NMR spectroscopy. The spin system of these 1H NMR spectra was $AB_3$. The theoretical spectrum was calculated by computer simulation of dynamic NMR spectra, which agreed very well with observed spectra. From this computer simulation, the ionic dissociation rate constant k was obtained, and by Eyring plot with it, slope and intercept length was gained, from which kinetic parameters were calculated.The easiness of ionic dissociation depended upon solvent polarity. Activation enthalpy was 4.7 kcal/mole in toluene-$d_8$, 10.7 kcal/mole in carbon tetrachloride, and activation entropy was -35. 8 e.u. in toluene-$d_8$, -14.4 e.u. in carbon tetrachloride. It was understood that though the ${\Delta}H^{neq}$ value was small, this ionic dissociation had an easier procession in nonpolar solvents with increasing temperatures. Considering that the ionic dissociation could be thought as the first step of $S_N1$ mechanism, attention might be paid to the results that the value of ${\Delta}S^{neq}$ had a large negative value in comparison with a small ${\Delta}H^{neq}$.

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A Study on Catalytic Activity of Oxygen Reduction Reaction and Performance of PEMFC using Pt/C Synthesized by Modified Polyol (수정된 폴리올법으로 합성된 Pt/C를 이용한 산소환원반응성 및 고분자전해질 연료전지 성능 연구)

  • Yang, Jongwon;Chu, Cheonho;Kwon, Yongchai
    • Journal of Energy Engineering
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    • v.23 no.3
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    • pp.157-162
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    • 2014
  • In this research, we investigate electrical performance and electrochemical properties of carbon supported Pt (Pt/C) that is synthesized by polyol method. With the Polyol_Pt/C that is adopted for oxygen reduction reaction (ORR) as cathode of proton exchange membrane fuel cells (PEMFCs), their catalytic activity and ORR performance and electrical performance are estimated and compared with commercial Pt/C(Johnson Mattey) catalyst. Their electrochemically active surface (EAS) area are measured by cyclic voltammetry (CV), respectively. On the other hand, regarding ORR activity and electrical performance of the catalysts, (i) linear sweeping voltammetry by rotating disk electrode and (ii) PEMFC single cell tests are used. The CV measurement demonstrate EAS of Polyol_Pt/C is compared with commercial JM_Pt/C. In case of Polyol_Pt/C, its half-wave potential, kinetic current density are excellent. Based on data obtained by half-cell test, when PEMFC single cell tests are carried out, current density measured at 0.6V and maximum power density of the PEMFC single cell employing Polyol_Pt/C are better than those employing commercial Pt/C. Conclusively, Polyol_Pt/C synthesized by modified polyol process shows better ORR catalytic activity and PEMFC performance than other catalysts.

The Development of Iodine-123 with MC-50 Cyclotron (MC-50 싸이클로트론을 이용한 $^{123}I$ 제법 연구)

  • Suh, Yong-Sup;Yang, Seung-Tae;Chun, Kown-Soo;Lee, Jong-Doo;Han, Hyon-Soo
    • The Korean Journal of Nuclear Medicine
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    • v.25 no.2
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    • pp.286-293
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    • 1991
  • $^{123}I$, which is applied for the thyroid and other in vivo kinetic study, has a special role in life sciences. The 159 KeV $\gamma-ray$ from $^{123}I$ is almost ideally appropriate for the current imaging instrumentation. Its decay mode (electron capture) and short half-life (13.3 hr) reduced the burden of radiation dose to the patients, and its chemical property makes it easy to synthesize the labelling compounds. In this experiment, the production of $^{123}I$ via the nuclear reaction $^{124}Te(p,2n)^{123}I$ with 28 MeV protons was sutdied. $TeO_2$ is used as a target material, because it has good physical properties. The target was prepared with $TeO_2$ powder and was molten into a ellipsoidal cavity (a=14 mm, b=10 mm, $270.8mg/cm^2$ thick) of pure platinum. The irradiation was carried out in the external proton beam with incident energies range from 28 MeV to 22 MeV, and current was $30{\mu}A$. The loss of $TeO_2$ target was significantly reduced by using $4\pi-cooling$ system in irradiation. The dry distillation method was adopted for the separation of $^{123}I$ from irradiated target, and when it was kept 5 minutes at $780^{\circ}C$, its result was quantitative. The loss of the target material $(TeO_2)$ was below 0.2% for each production run and $^{123}I$ from the dry distillation apparatus was captured with 0.01 N NaOH in $Na^{123}I$ form, then the pH of the solution was adjusted to $7.5\sim9.0$ with HC1/NaOH. The $Na^{123}I$ solution was passed through $0.2{\mu}m$ membrane filter, and sterilized under high pressure and temperature for 30 minutes. The production of $^{123}I$ is acceptable for clinical application based on the quality of USP XXI.

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A Consideration on its Kinetics for shelf-life Prediction of Meat Sausage (축육소시지 저장성 산출을 위한 속도론적 고찰)

  • Kim, Soo-Min
    • Korean Journal of Food Science and Technology
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    • v.24 no.3
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    • pp.256-260
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    • 1992
  • This study was conducted to calculate and predict the shelf-life of meat sausage through physicochemical and biological analysis. Judging from physico-chemical components, it can be found out the most effective indicator in meat sausage. And also, the materials used for packaging is cellulose #23 in inner-packaging and CN/HDPE laminating film in outer-packaging. The changes of the most effective indicator were discussed through the method of kinetic analysis. Judging from physico-chemical components, VBN was the most available component in quality judgement of meat sausage and their upper limiting contents were 20 mg%. It is possible to calculate and predict the shelf-life of meat sausage through the regression equation and $Q_{10}$ value. As a result, the shelf-life prediction was $58{\sim}63$ days at $10^{\circ}C$, $47{\sim}51$ days at $20^{\circ}C$ and 26 days at $40^{\circ}C$, respectively, but the difference between two methods showed about $4{\sim}5$ days. $Q_{10}$ value on the changes contents was 1.35 at acceralated temperature $40^{\circ}C$. The reaction rate of VBN contents could be interpreted as a first order reaction that divided into 2 periods with different reaction rate constants. The corresponding Arrhenius activation energies were 2.959 Kcal/mole and 3.632 Kcal/mole, respectively.

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DEVELOPMENT OF SAFETY-BASED LEVEL-OF-SERVICE PARAMETERS FOR TWO-WAY STOP-CONTROLLED INTERSECTIONS (무신호 교차로의 안전 -서비스 수준 측정에 관한 연구-)

  • 이수범
    • Proceedings of the KOR-KST Conference
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    • 1996.02a
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    • pp.59-86
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    • 1996
  • Current methods for evaluating unsignalized intersections, and estimating level-of-service (LOS) is determined from efficiency-based criteria such as little or no delay to very long delays. At present, similar procedures to evaluate intersections using safety-based criteria do not exist. The improvement of sight distances at intersections is the most effective way of improving intersection safety. However, a set of procedures is necessary to account for the limitations in current methodology. Such an approach would build upon such methods, but also account for: deficiencies in the current deterministic solution for the determination of intersection sight distances; opportunity for an accident and severity of an accident; and cost-effectiveness of attaining various levels of sight distances. In this research, a model that estimates the degree of safety at two-way stop-controlled intersections is described. Only crossing maneuvers are considered in this study because accidents caused by the crossing maneuvers are the dominate type among intersection accidents. Monte Carlo methods are used to estimate the hazard at an intersection as a function of roadway features and traffic conditions. Driver`s minimum gap acceptance in the crossing vehicles and headway distribution on the major road are used in the crossing vehicles and headway distribution on the major road are used in the model to simulate the real intersectional maneuvers. Other random variables addressed in the model are: traffic speeds; preception-reaction times of both drivers in the crossing vehicles and drivers in oncoming vehicles on the major road; and vehicles on the major roads. The developed model produces the total number of conflicts per year per vehicle and total potential kinetic energy per year per vehicle dissipated during conflicts as measurements of safety at intersections. Based on the results from the developed simulation model, desirable sight distances for various speeds were determined as 350 feet, 450 feet and 550 feet for 40 mph, 50 mph and 60 mph prevailing speed on the major road, respectively. These values are seven to eight percent less than those values recommended by AASHTO. A safety based level-of-service (LOS) is also developed using the results of the simulation model. When the total number of conflicts per vehicle is less than 0.05 at an intersection, the LOS of the intersection is `A' and when the total number of conflicts per vehicle is larger than 0.25 at an intersection, the LOS is `F'. Similarly, when the total hazard per vehicle is less than 350, 000 1b-ft2/sec2, the LOS is `F'. Once evaluation of the current safety at the intersection is complete, a sensitivity analysis can be done by changing one or more input parameters. This will estimate the benefit in terms of time and budget of hazard reduction based upon improving geometric and traffic characteristics at the intersection. This method will also enable traffic engineers in local governments to generate a priority list of intersection improvement projects.

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Trace impurity analysis of Cu films using GDMS: concentration change of impurities by applying negative substrate bias voltage (글로우방전 질량분석법을 이용한 구리 박막내의 미량불순물 분석: 음의 기판 바이어스에 의한 불순물원소의 농도변화)

  • Lim Jae-Won;Isshiki Minoru
    • Journal of the Korean Vacuum Society
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    • v.14 no.1
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    • pp.17-23
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    • 2005
  • Glow discharge mass spectrometry(GDMS) was used to determine the impurity concentrations of the deposited Cu films and the 6N Cu target. Cu films were deposited on Si (100) substrates at zero substrate bias voltage and a substrate bias voltage of -50 V using a non-mass separated ion beam deposition method. Since do GDMS has a little difficulty to apply to thin films because of the accompanying non-conducting substrate, we have used an aluminum foil to cover the edge of the Cu film in order to make an electrical contact of the Cu film deposited on the non-conducting substrate. As a result, the Cu film deposited at the substrate bias voltage of -50 V showed lower impurity contents than the Cu film deposited without the substrate bias voltage although both the Cu films were contaminated during the deposition. It was found that the concentration change of each impurity in the Cu films by applying the negative substrate bias voltage is related to the difference in their ionization potentials. The purification effect by applying the negative substrate bias voltage might result from the following reasons: 1) Penning ionization and an ionization mechanism proposed in the present study, 2) difference in the kinetic energy of accelerated Cu+ ions toward the substrate with/without the negative substrate bias voltage.