• Bulletin of the Korean Chemical Society
• /
• v.26 no.12
• /
• pp.1981-1985
• /
• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• Journal of Korean Society of Environmental Engineers
• /
• v.33 no.8
• /
• pp.606-616
• /
• 2011

The objectives of this study were to evaluate the applicability of adsorption models for adsorption properties of adsorbents. For this study, adsorption experiment of $NO_3^-$ ion using anion exchange resin has been investigated under adsorption equilibrium and kinetic in bach process. Adsorption equilibrium experiment were carried out that two conditions is change of adsorbate concentration and change of adsorbent weight. Experiment results have been analyzed by adsorption isotherm models, energy models and kinetic models. Under the condition of change of adsorbate concentration was best described by Sips and Redlich-Perterson isotherm models. However case of change of adsorbent weight was described by Langmuir isotherm models. It seems reasonable to assume that isotherm model was dominated by multiple mechanism according to experiment condition.

• Wind and Structures
• /
• v.25 no.1
• /
• pp.63-77
• /
• 2017

When railway vehicles run by towers of long span bridges, the railway vehicles might experience a sudden load-off and load-on phenomenon in crosswind conditions. To ensure the running safety of the railway vehicles and the running comfort of the passengers, some studies were carried out to investigate the impacts of sudden changes of aerodynamic loads on moving railway vehicles. In the present study, the aerodynamic coefficients which were measured in wind tunnel tests using a moving train model are converted into the aerodynamic coefficients in the actual scale. The three-component aerodynamic loads are calculated based on the aerodynamic coefficients with consideration of the vehicle movement. A three-dimensional railway vehicle model is set up using the multibody dynamic theory, and the aerodynamic loads are treated as the inputs of excitation varied with time for kinetic simulations of the railway vehicle. Thus the dynamic responses of the railway vehicle passing by the bridge tower can be obtained from the kinetic simulations in the time domain. The effects of the mean wind speeds and the rail track positions on the running performance of the railway vehicle are discussed. The three-component aerodynamic loads on the railway vehicle are found to experience significant sudden changes when the vehicle passes by the bridge tower. Correspondingly, such sudden changes of aerodynamic loads have a large impact on the dynamic performance of the running railway vehicle. The dynamic responses of the railway vehicle have great fluctuations and significant sudden changes, which is adverse to the running safety and comfort of the railway vehicle passing by the bridge tower in crosswind conditions.

• Journal of Microbiology and Biotechnology
• /
• v.17 no.11
• /
• pp.1789-1796
• /
• 2007

A ${\beta}$-glucosidase with the molecular mass of 160,000 Da was purified to homogeneity from cell extract of a cellulolytic bacterium, Cellulomonas uda CS1-1. The kinetic parameters ($K_m$ and $V_{max}$) of the enzyme were determined with pNP-cellooligosccharides (DP 1-5) and cellobiose. The molecular orbital theoretical studies on the cellulolytic reactivity between the pNP-cellooligosaccharides as substrate (S) molecules and the purified ${\beta}$-glucosidase (E) were conducted by applying the frontier molecular orbital (FMO) interaction theory. The results of the FMO interaction between E and S molecules verified that the first stage of the reaction was induced by exocyclic cleavage, which occurred in an electrophilic reaction based on a strong charge-controlled reaction between the highest occupied molecular orbital (HOMO) energy of the S molecule and the lowest occupied molecular orbital (LUMO) energy of the hydronium ion ($H_3O^+$), more than endocyclic cleavage, whereas a nucleophilic substitution reaction was induced by an orbital-controlled reaction between the LUMO energy of the oxonium ion ($SH^+$) protonated to the S molecule and the HOMO energy of the $H_2O_2$ molecule. A hypothetic reaction route was proposed with the experimental results in which the enzymatic acid-catalyst hydrolysis reaction of E and S molecules would be progressed via $SN_1$ and $SN_2$ reactions. In addition, the quantitative structure-activity relationships (QSARs) between these kinetic parameters showed that $K_m$ has a significant correlation with hydrophobicity (logP), and specific activity has with dipole moment, respectively.

• Korean Journal of Microbiology
• /
• v.41 no.2
• /
• pp.112-116
• /
• 2005

Moderately halophilic bacterium, Kordia algicida gen. nov., sp. novo was isolated from seawater of Masan Bay, Korea, during algal blooming caused by Skeletonema costatum. This bacterium was grown on the ZoBell 2216e medium supplied aged seawater, but not grown the medium supplied $3\%$ NaCl. This bacterium showed absolute requirements for mono and divalent cations such as $Na^+,\;Mg^{2+}\;and\;Ca^{2+}$, since no growth was observed in the medium, which is not supplemented with one of $Na^+,\;Mg^{2+}\;and\;Ca^{2+}$ ions. In kinetic studies for three kinds of cation, Km values of $Na^+,\;Ca^{2+}\;and\;Mg^{2+}$ were determined to 0.202 M, 0.089 mM, and 0.189 mM, respectively. Also, $V_{max}({\mu}max)$ was 0.442 h, 0.411 hand 0.316 h. The bacterial cells were quickly lysed in the condition limited by the cations. This result should be suggested that Kordia algicida originated from marine.

• Journal of the Korean Geotechnical Society
• /
• v.18 no.2
• /
• pp.97-105
• /
• 2002

Random properties of discontinuities were attributed to the limitation of test methods and lack of obtained data. Therefore, the uncertainties are pervasive and inevitable in rock slope engineering as well as other geotechnical engineering fields. The probabilistic analysis has been proposed to deal properly with the uncertainty. However, previous probabilistic approaches do not take account of the condition of kinematic instability but consider only kinetic instability. In this study, in order to overcome the limitation of the previous studies, the geometric characteristics as well as the shear strength characteristics in discontinuities are taken account into the probabilistic analysis. Then, the new approach to evaluate the probability of failure is suggested. The results of the deterministic analysis which was carried out to compare with the result of the probabilistic analysis, are somewhat different from those of the probabilistic approach. This is because the selected and used data in the deterministic approach do not take account of the random properties of discontinuities.

• Journal of the Korean earth science society
• /
• v.32 no.1
• /
• pp.46-56
• /
• 2011

The purpose of this paper is to evaluate the wind energy resources with high spatial resolution in Sunghak and Guduck mountains in Busan Metropolitan area under the various atmospheric stabilities. The numerical model used in this research is A2C (Atmosphere to CFD), mainly applied to assess the regional scale and microscale meteorological phenformin. Wind under the strong atmospheric stability moves around mountain side smoothly due to the strong potential energy. On the other hand, the cavity region on the lee side of mountain tends to be created and expanded as the atmospheric stability decrease. Annually the average distribution of wind power density, turbulence kinetic energy, and vertical wind shear help to explain quantitatively that wind resource near the northern side of Guduck mountain top is more suitable to establish wind energy complex than that in any other regions in the target area.

• Atmosphere
• /
• v.26 no.3
• /
• pp.401-412
• /
• 2016

A 3D sonic anemometer has been installed at Yongpyong alpine slope since Oct. 23th 2014 to observe the slope winds and to analyze turbulent characteristics with the change in surface cover (grass and snow) and the synoptic wind strength. Eddy covariance method has been applied to calculate the turbulent quantity after coordinate transformation of a planar-fit rotation. We have carefully selected 3 good episodes in the winter season (23 October 2014 to 28 February 2015) for each category (9 days in total), such as grass and snow covers in case of weak synoptic wind condition, and grass cover of strong synoptic wind. The diurnal variations of the slope winds were well developed like the upslope wind in the daytime and downslope wind in the nighttime for both surface covers (grass and snow) in the weak synoptic forcing, when accordingly both heat and momentum fluxes significantly increased in the daytime and decreased in the nighttime. Meanwhile, diurnal variation of heat flux was not present on the snow cover probably in associated with significant fraction of sunlight reflection due to high albedo especially during the daytime in comparison to those on the grass cover. In the strong synoptic regime, the most dominant feature at Yongpyong, only the southeasterly downslope winds were steadily generated irrespective of day and night with significant increases in momentum flux and turbulent kinetic energy as well, which could suggest that local circulations are suppressed by the synoptic scale forcing. In spite of only one season analysis applied to the limited domain, this kind of an observation-based study will provide the basis for understanding of the local wind circulation in the complex mountain domain such as Gangwon in Korea.

• Journal of the Korean Chemical Society
• /
• v.30 no.2
• /
• pp.231-236
• /
• 1986

Oxidation of $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$ with hydrogen chromate yields the molybdenum (VI) complex, $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$. Stoichiometry for the reaction of $[Mo_2O_4(C_2O_4)_2(OH_2)_2]^{2-}$ with hydrogen chromate are expressed as ${3Mo_2}^V+2Cr^{VI}\;{\rightleftharpoons}\;{3Mo_2}_{VI}+2Cr^{III}$. Observed rate constants are dependent on $[H+]^2$. The kinetic data are consistent with a mechanism in which three successive single-electron steps convert $Cr^{VI}$to $Cr^{III}$ by way of intermediate Cr^V$ and $Cr^{IV}$. Mechanism of the reaction are presented and discussed.

• Journal of Ocean Engineering and Technology
• /
• v.31 no.1
• /
• pp.36-46
• /
• 2017

Most of the studies on the hydraulic characteristics of wave-current interaction have used 2-D hydraulic experiments or 2-D numerical simulations. However, it is difficult to understand the wave-current interaction found in actual estuaries using these. Therefore, a numerical water tank was constructed in this study to perform simulations involving a 3-D river mouth. The result showed a change in the water surface at the river mouth from the wave-current interaction. With an increase in the ratio ($V_c/C_i$) between the river current and wave celerity, the wave height and mean water level of the river increased at the wave and current meeting point. A higher $V_c/C_i$ caused a stronger wave-current interaction and increased the turbulence kinetic energy. Thus, the wave height attenuation became larger by the wave-current interaction with a higher $V_c/C_i$. In addition, it was possible to understand the flow characteristics in the vicinity of the river mouth as a result of the wave-current interaction using the mean flow and mean time-averaged velocity at the mid-cross section of river.