• Title/Summary/Keyword: Reaction rate equation

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Electrochemical Propertics and Oxidation Reaction of Hydrazobenzene by Oxygen Adducted Tetradentate Schiff Base Cobalt(II)(3MeOSED) Activated Catalyst in Aprotic Solvents(I) (비수용매에서 산소첨가된 네자리 Schiff Base Cobalt(II)(3MeOSED) 활성촉매에 의한 Hydrazobenzene의 산화반응과 전기화학적 성질 (제 1 보))

  • Ki-Hyung Chjo;Yong-Kook Choi;Sang-Bock Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.261-272
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    • 1992
  • Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

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Adsorption Characteristics Analysis of 2,4-Dichlorophenol in Aqueous Solution with Activated Carbon Prepared from Waste Citrus Peel using Response Surface Modeling Approach (반응표면분석법을 이용한 폐감귤박 활성탄에 의한 수중의 2,4-Dichlorophenol 흡착특성 해석)

  • Lee, Chang-Han;Kam, Sang-Kyu;Lee, Min-Gyu
    • Korean Chemical Engineering Research
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    • v.55 no.5
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    • pp.723-730
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    • 2017
  • The batch experiments by response surface methodology (RSM) have been applied to investigate the influences of operating parameters such as temperature, initial concentration, contact time and adsorbent dosage on 2,4-dichlorophenol (2,4-DCP) adsorption with an activated carbon prepared from waste citrus peel (WCAC). Regression equation formulated for the 2,4-DCP adsorption was represented as a function of response variables. Adequacy of the model was tested by the correlation between experimental and predicted values of the response. A fairly high value of $R^2$ (0.9921) indicated that most of the data variation was explained by the regression model. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. These results showed that the model used to fit response variables was significant and adequate to represent the relationship between the response and the independent variables. The kinetics and isotherm experiment data can be well described with the pseudo-second order model and the Langmuir isotherm model, respectively. The maximum adsorption capacity of 2,4-DCP on WCAC calculated from the Langmuir isotherm model was 345.49 mg/g. The rate controlling mechanism study revealed that film diffusion and intraparticle diffusion were simultaneously occurring during the adsorption process. The thermodynamic parameters indicated that the adsorption reaction of 2,4-DCP on WCAC was an endothermic and spontaneous process.

Adsorption Characteristics of CO2 on Activated Carbons Treated with Alkali-metal Salts (알칼리금속염으로 처리된 활성탄에 대한 CO2의 흡착특성)

  • Ryu, Dong Kwan;Kim, Sung Hyun
    • Applied Chemistry for Engineering
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    • v.9 no.2
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    • pp.286-293
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    • 1998
  • Two methods were used to enhance the adsorption capacity of activated carbons. One is to impregnate activated carbons with chemical compounds which have a good affinity for $CO_2$. The other is to activate by heat-treating after impregnation with KOH on activated carbons(AC). The chemical compounds impregnated on AC were alkali metal, alkaline earth metal, and transition metal chlorides. The adsorption capacity of $CO_2$ on AC impregnated with these metals was less than that of pure AC. These compounds have not the chemical affinity for $CO_2$ and obstruct the micropore of AC. The experiment of breakthrough for $CO_2$ on AC impregnated with KOH showed the increase of the adsorbed amount of $CO_2$ in influent gases containing water vapor. This means that KOH adsorbes $CO_2$ gas. However, the adsorbents impregnated with KOH had not the reproducibility because of the production of $K_2CO_3$ by the reaction of KOH with $CO_2$. The amount of $CO_2$ adsorbed on the heat-treated AC at $800^{\circ}C$ increased with the amount of impregnation. The adsorption capacity of $CO_2$ was the largest when the ratio of weight of KOH to AC equal to 4. The isosteric heat of adsorption was calculated by the equation of Clausius-Clapeyron form adsorption capacity data of $CO_2$ for the temperature change. In addition, the characteristics of $CO_2$ breakthrough curve were surveyed for the change of flow rate and concentration.

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Studies on the Stability of Multivitamin Solutions (종합비타민 액제의 안정성에 대한 연구)

  • Park, Hong-Koo
    • Applied Biological Chemistry
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    • v.43 no.1
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    • pp.39-45
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    • 2000
  • The stability of vitamin A, $B_1,\;B_2,\;B_6$, C in aqueous multivitamin solutions was carried out by means of estimation of reaction velocity and the results are described in this paper. The stability of vitamin A, $B_1$ and C due to thermal degradation method in aqueous multivitamin solutions was evaluated at 40, 50, 60 and $70^{\circ}C$ up to 40 days. The shelf-lives of vitamin A, B₁ and C in this preparation, calculated using the Arrhenius equation, were 1493, 449 and 639 days at $25^{\circ}C$ respectively. Examination was made on the effect of initial concentration of vitamin $B_2$$(C_0)$ on light fading of vitamin $B_2$ in aqueous multivitamin solutions and it was found that the fading progressed according to the following formula : $-{\frac {dc}{dt}}=K_c\;{\frac C{C_0}}$ where Kc is apparent light-fading rate constant relate to $C_0$. Photodecomposition of vitamin $B_6$ in aqueous multivitamin solutions was apparently first order kinetics and was stable in polyethylene>brown color>glass container to sunlight. Photodecomposition of vitamin $B_6$ in four seasons also investigated.

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Adsorption of Dyes with Different Functional Group by Activated Carbon: Parameters and Competitive Adsorption (활성탄에 의한 작용기가 다른 염료의 흡착: 파라미터 및 경쟁 흡착)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.33 no.2
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    • pp.151-158
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    • 2022
  • In this paper, parameter characteristics such as pH effect, isotherm, kinetic and thermodynamic parameters and competitive adsorption of dyes including malachite green (MG), direct red 81 (DR 81) and thioflavin S (TS), which have different functional groups, being adsorbed onto activated carbon were investigated. Langmuir, Freundlich and Temkin isotherm models were employed to find the adsorption mechanism. Effectiveness of adsorption treatment of three dyes by activated carbon were confirmed by the Langmuir dimensionless separation factor. The mechanism was found to be a physical adsorption which can be verified through the adsorption heat calculated by Temkin equation. The adsorption kinetics followed the pseudo second order and the rate limiting step was intra-particle diffusion. The positive enthalpy and entropy changes showed an endothermic reaction and increased disorder via adsorption at the S-L interface, respectively. For each dye molecule, negative Gibbs free energy increased with the temperature, which means that the process is spontaneous. In the binary component system, it was found that the same functional groups of the dye could interfere with the mutual adsorption, and different functional groups did not significantly affect the adsorption. In the ternary component system, the adsorption for MG lowered a bit, likely to be disturbed by the other dyes meanwhile DR 81 and TS were to be positively affected by the presence of MG, thus resulting in much higher adsorption.

Numerical Analysis of Unstable Combustion Flows in Normal Injection Supersonic Combustor with a Cavity (공동이 있는 수직 분사 초음속 연소기 내의 불안정 연소유동 해석)

  • Jeong-Yeol Choi;Vigor Yang
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2003.05a
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    • pp.91-93
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    • 2003
  • A comprehensive numerical study is carried out to investigate for the understanding of the flow evolution and flame development in a supersonic combustor with normal injection of ncumally injecting hydrogen in airsupersonic flows. The formulation treats the complete conservation equations of mass, momentum, energy, and species concentration for a multi-component chemically reacting system. For the numerical simulation of supersonic combustion, multi-species Navier-Stokes equations and detailed chemistry of H2-Air is considered. It also accommodates a finite-rate chemical kinetics mechanism of hydrogen-air combustion GRI-Mech. 2.11[1], which consists of nine species and twenty-five reaction steps. Turbulence closure is achieved by means of a k-two-equation model (2). The governing equations are spatially discretized using a finite-volume approach, and temporally integrated by means of a second-order accurate implicit scheme (3-5).The supersonic combustor consists of a flat channel of 10 cm height and a fuel-injection slit of 0.1 cm width located at 10 cm downstream of the inlet. A cavity of 5 cm height and 20 cm width is installed at 15 cm downstream of the injection slit. A total of 936160 grids are used for the main-combustor flow passage, and 159161 grids for the cavity. The grids are clustered in the flow direction near the fuel injector and cavity, as well as in the vertical direction near the bottom wall. The no-slip and adiabatic conditions are assumed throughout the entire wall boundary. As a specific example, the inflow Mach number is assumed to be 3, and the temperature and pressure are 600 K and 0.1 MPa, respectively. Gaseous hydrogen at a temperature of 151.5 K is injected normal to the wall from a choked injector.A series of calculations were carried out by varying the fuel injection pressure from 0.5 to 1.5MPa. This amounts to changing the fuel mass flow rate or the overall equivalence ratio for different operating regimes. Figure 1 shows the instantaneous temperature fields in the supersonic combustor at four different conditions. The dark blue region represents the hot burned gases. At the fuel injection pressure of 0.5 MPa, the flame is stably anchored, but the flow field exhibits a high-amplitude oscillation. At the fuel injection pressure of 1.0 MPa, the Mach reflection occurs ahead of the injector. The interaction between the incoming air and the injection flow becomes much more complex, and the fuel/air mixing is strongly enhanced. The Mach reflection oscillates and results in a strong fluctuation in the combustor wall pressure. At the fuel injection pressure of 1.5MPa, the flow inside the combustor becomes nearly choked and the Mach reflection is displaced forward. The leading shock wave moves slowly toward the inlet, and eventually causes the combustor-upstart due to the thermal choking. The cavity appears to play a secondary role in driving the flow unsteadiness, in spite of its influence on the fuel/air mixing and flame evolution. Further investigation is necessary on this issue. The present study features detailed resolution of the flow and flame dynamics in the combustor, which was not typically available in most of the previous works. In particular, the oscillatory flow characteristics are captured at a scale sufficient to identify the underlying physical mechanisms. Much of the flow unsteadiness is not related to the cavity, but rather to the intrinsic unsteadiness in the flowfield, as also shown experimentally by Ben-Yakar et al. [6], The interactions between the unsteady flow and flame evolution may cause a large excursion of flow oscillation. The work appears to be the first of its kind in the numerical study of combustion oscillations in a supersonic combustor, although a similar phenomenon was previously reported experimentally. A more comprehensive discussion will be given in the final paper presented at the colloquium.

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Potassium and Clay Minerals in Upland Soils (밭 토양(土壤)의 점토(粘土) 광물(鑛物)과 가리(加里))

  • Kim, Tai-Soon
    • Korean Journal of Soil Science and Fertilizer
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    • v.10 no.3
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    • pp.135-151
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    • 1977
  • The present paper summerizes the studies on clay mineralogical characteristics of Korean soil, relationship between potassium and clay minerals, potassium release pattern of clay minerals and utilization of clay minerals for soil conditioner and fertilizers, which have been carried out in this laboratory. 1. The red yellow podzolic soil is mostly abundant in the upland of Korea and mainly consists of halloysite and weathered intermediates of mica such as illite and vermiculite. 2. With regard to soil parent material, kaolin mineral occurs abundant in soils derived from granite and granite gneiss. Mica is dominant in basaltic soil. The main clay mineral of the soil, originated from the Tertiary, is found montmorillonite and the volcanic soil of Jeju Island has plenty of allophane as its main clay mineral. 3. It is confirmed that the soil fertility depends on the composition of clay minerals. The red yellow podzolic soil, containing lot of kaolin, shows low productivity while the montmorillonite soil has higher productivity. 4. The release rate of solid phase potassium (micas and fixed potassium) follows the 1st order reaction equation in the equilibrium solution of $IN-NH_4OAc$. The potassium release constant is positively correlated with the mica content of the clay but negatively correlated with the content of $14.5{\AA}$ minerals. On the other hand, the potassium release constant has very high correlation with the ratio(Kex/Kt) of exchangeable potassium(Kex) to total potassium(Kt). 5. It is also found that Kex/Kt has rather high correlation with the content of mica and $14.5{\AA}$ minerals existed in the clay as well as the mica content of the soil.

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Electrochemical Characteristic on Hydrogen Intercalation into the Interface between Electrolyte of the 0.1N H2SO4and Amorphous Tungsten Oxides Thin Film Fabricated by Sol-Gel Method (졸-겔법으로 제조된 비정질의 텅스텐 산화물 박막과 황산 전해질 계면에서 일어나는 수소의 층간 반응에 대한 전기화학적 특성)

  • Kang, Tae-Hyuk;Min, Byoung-Chul;Ju, Jeh-Beck;Sohn, Tae-Won;Cho, Won-Il
    • Applied Chemistry for Engineering
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    • v.7 no.6
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    • pp.1078-1086
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    • 1996
  • The peroxo-polytungstic acid was formed by the direct reaction of tungsten powder with the hydrogen peroxide solution. Peroxo-polytungstic powder were prepared by rotary evaporator using the fabricated on to ITO coated glass as substrate by dip-coating method using $2g/10mL(W-IPA/H_2O)$ sol solution. A substrate was dipped into the sol solution and after a meniscus had settled, the substrate was withdrawn at a constant rate of the 3mm/sec. Thicker layer could be built up by repeated dipping/post-treatment 15 times cycles. The layers dried at the temperature of $65{\sim}70^{\circ}C$ during the withdrawn process, and then tungsten oxides thin film was formed by final heating treatment at the temperature of $230{\sim}240^{\circ}C$ for 30min. A linear rotation between the thickness of thin film and the number of dipping/post-treatment cycles for tungsten oxides thin films made by dip-coating was found. The thickness of thin film had $60{\AA}$ after one dipping. From the patterns of XRD, the structure of tungsten oxides thin film identified as amorphous one and from the photographs of SEM, the defects and the moderate cracks were observed on the tungsten oxides thin film, but the homogeneous surface of thin films were mostly appeared. The electrochemical characteristic of the $ITO/WO_3$ thin film electrode were confirmed by the cyclic voltammetry and the cathodic Tafel polaization method. The coloring bleaching processes were clearly repeated up to several hundreds cycles by multiple cyclic voltammetry, but the dissolved phenomenon of thin film revealed in $H_2SO_4$ solution was observed due to the decrease of the current densities. The diffusion coefficient was calculated from irreversible Randles-Sevick equation from the data obtained by the cyclic voltammetry with various scan rates.

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Geochemical Equilibria and Kinetics of the Formation of Brown-Colored Suspended/Precipitated Matter in Groundwater: Suggestion to Proper Pumping and Turbidity Treatment Methods (지하수내 갈색 부유/침전 물질의 생성 반응에 관한 평형 및 반응속도론적 연구: 적정 양수 기법 및 탁도 제거 방안에 대한 제안)

  • 채기탁;윤성택;염승준;김남진;민중혁
    • Journal of the Korean Society of Groundwater Environment
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    • v.7 no.3
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    • pp.103-115
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    • 2000
  • The formation of brown-colored precipitates is one of the serious problems frequently encountered in the development and supply of groundwater in Korea, because by it the water exceeds the drinking water standard in terms of color. taste. turbidity and dissolved iron concentration and of often results in scaling problem within the water supplying system. In groundwaters from the Pajoo area, brown precipitates are typically formed in a few hours after pumping-out. In this paper we examine the process of the brown precipitates' formation using the equilibrium thermodynamic and kinetic approaches, in order to understand the origin and geochemical pathway of the generation of turbidity in groundwater. The results of this study are used to suggest not only the proper pumping technique to minimize the formation of precipitates but also the optimal design of water treatment methods to improve the water quality. The bed-rock groundwater in the Pajoo area belongs to the Ca-$HCO_3$type that was evolved through water/rock (gneiss) interaction. Based on SEM-EDS and XRD analyses, the precipitates are identified as an amorphous, Fe-bearing oxides or hydroxides. By the use of multi-step filtration with pore sizes of 6, 4, 1, 0.45 and 0.2 $\mu\textrm{m}$, the precipitates mostly fall in the colloidal size (1 to 0.45 $\mu\textrm{m}$) but are concentrated (about 81%) in the range of 1 to 6 $\mu\textrm{m}$in teams of mass (weight) distribution. Large amounts of dissolved iron were possibly originated from dissolution of clinochlore in cataclasite which contains high amounts of Fe (up to 3 wt.%). The calculation of saturation index (using a computer code PHREEQC), as well as the examination of pH-Eh stability relations, also indicate that the final precipitates are Fe-oxy-hydroxide that is formed by the change of water chemistry (mainly, oxidation) due to the exposure to oxygen during the pumping-out of Fe(II)-bearing, reduced groundwater. After pumping-out, the groundwater shows the progressive decreases of pH, DO and alkalinity with elapsed time. However, turbidity increases and then decreases with time. The decrease of dissolved Fe concentration as a function of elapsed time after pumping-out is expressed as a regression equation Fe(II)=10.l exp(-0.0009t). The oxidation reaction due to the influx of free oxygen during the pumping and storage of groundwater results in the formation of brown precipitates, which is dependent on time, $Po_2$and pH. In order to obtain drinkable water quality, therefore, the precipitates should be removed by filtering after the stepwise storage and aeration in tanks with sufficient volume for sufficient time. Particle size distribution data also suggest that step-wise filtration would be cost-effective. To minimize the scaling within wells, the continued (if possible) pumping within the optimum pumping rate is recommended because this technique will be most effective for minimizing the mixing between deep Fe(II)-rich water and shallow $O_2$-rich water. The simultaneous pumping of shallow $O_2$-rich water in different wells is also recommended.

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