• Title/Summary/Keyword: Formation Kinetics

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A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols using Cr(VI)-Heterocyclic Complex(Cr(VI)-Isoquinoline) (Cr(VI)-헤테로고리 착물(Cr(VI)-Isoquinoline)를 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구)

  • Park, Young-Cho;Kim, Young-Sik
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.14 no.11
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    • pp.6000-6007
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    • 2013
  • Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

The Measurement and Analysis of LiF:Mg, Cu, Na, Si TL Material by Thermoluminescence Spectrum (LiF:Mg, Cu, Na, Si TL 물질의 열자극발광스펙트럼 측정 및 분석)

  • Lee, J.I.;Moon, J.H.;Kim, D.H.
    • Journal of Korean Ophthalmic Optics Society
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    • v.6 no.1
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    • pp.149-153
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    • 2001
  • Three-dimensional thermoluminescence(TL) spectra of LiF: Mg, Cu, Na, Si TL material based on temperature, wavelength and intensity were measured and analyzed. The glow curves were obtained by integration of luminescence intensity for wavelength at each temperature, and various trapping parameters related to the trap formation were determined by analyzing these curves. Computerized glow curve deconvolution(CGCD) method which based on general order kinetics(GOK) model were used for the glow curve analysis. The glow curves of LiF:Mg, Cu, Na, Si TL material were deconvoluted to six isolated glow curves which have peak temperature at 333 K, 374 K, 426 K, 466 K, 483 K and 516 K, respectively. The 466 K main glow peak had an activation energy of 2.06 eV and a kinetic order of 1.05. This TL material was also found to have three recombination centers, 1.80 eV, 2.88 eV and 3.27 eV by TL spectra analysis based on Franck-Condon model. It showed that 2.88 eV is the dominant center, followed by 3.27 eV level, and 1.80 eV center is ascertained as emission center of this material even though its very weak emission intensity.

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Production and Characterization of a Transgenic Mouse Model of Human Liver Cancer (형질 전환 기법을 이용한 인체 간암의 마우스 모델 제작 및 특성 규명)

  • Li, Zhong-Shu;Lee, Jung-Woong;Hyun, Byung-Hwa;Lee, Chul-Ho;Jeong, Kyu-Shick;Fang, Nan-Zhu;Yeom, Young-Il
    • Reproductive and Developmental Biology
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    • v.31 no.3
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    • pp.145-152
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    • 2007
  • Transgenic mice were generated by microinjecting a plasmid DNA containing the SV40 (simian virus 40) large T antigen (Tag) gene fused with mouse albumin promoter/enhancer sequences into fertilized one-cell mouse embryos. Among eleven founder transgenic animals, four developed hepatocellular carcinoma, two showed kidney cancer and one developed skin and brain tumors. Three stable transgenic lines, #1-2, #1-6 and #1-11 were established. Members of the lines #1-6 and #1-11 reproducibly developed liver tumors by 8 to 10 weeks of age but did not exhibit any phenotypic changes in other tissues. Histological changes loading to liver tumor formation occurred with predictable kinetics and could be classified into three distinct stages; (a) newborn to 3 weeks of age, characterized by hyperplastic hepatocytes with reduced amounts of cytoplasm without any nuclear alterations, (b) between 4 to 8 weeks of age, characterized by diffuse liver cell dysplasia without observable tumor nodules, and (c) 9 weeks of age and thereafter, characterized by hepatocellular carcinomas in the background of extensive liver dysplasia. Metastasis to the lung from a liver carcinoma was observed in #1-11 founder animal. This transgenic mouse system displays similarities with human liver cancers in a number of aspects and provides a useful model for the study of molecular events involved in hepatocarcinogenesis.

Kinetics of the Reaction of Phenacyl Bromide with Anilines in Methanol and Dimethylformamide (Phenacyl Bromide와 置換아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Soo-Dong Yoh;Doo-Jung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.376-382
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    • 1981
  • The rates and the activation parameters for the reaction of phenacyl bromide with substituted anilines in methanol and dimethylformamide were measured. The effects of substituted anilines were discussed. The rate of the reaction was increased with the electron donating power of substituent and showed larger value in DMF than in MeOH. The isokinetic relationship was shown between ${\delta}H^{\neq}$ and ${\delta}S^{\neq}$, isokinetic temperature was 539 and $400^{\circ}C$ in MeOH and DMF respectively, but p-nitro aniline was deviated from linearity in both solvents caused by solvent effects. The excellent linear relationship between log k and p$K_a$ of substituted anilines was observed by following equation. log k = 0.57p$K_a$-1.28 (r = 0.996) in MeOH at $45^{\circ}C$, log k = 0.65p$K_a$-0.88 (r = 0.970) in DMF at $45^{\circ}C$. From the Hammett plot, this reaction was a nucleophilic displacement of aniline to phenacyl bromide and the following equation was obtained at $45^{\circ}C$. log k/$k_0$ = -2.00${\sigma}$ + 0.06 (r = 0.985) in MeOH; log k/$k_0$ = -2.22${\sigma}$ + 0.08 (r = 0.995) in DMF. Large deviation of p-nitro aniline in DMF is resulted from solvent effects too. From above results, the substituent effect of this reaction can be described as $S_N2$ mechanism and bond formation more proceeds in DMF relative to MeOH.

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Effects of Membrane Size and Organic Matter on Membrane Fouling (천연유기물질의 특성과 막의 종류에 따른 막오염 메카니즘 분석)

  • Jung, Chul-Woo;Son, Hee-Jong
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.10
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    • pp.1046-1054
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    • 2006
  • The raw water DOC contained 39.3% of hydrophilics, 42.9% of hydriophobic, and 17.8% of transphilic. The hydrophobic fraction in this raw water was mostly fulvic acid. Fulvic acid comprised of 62% and the rest was humic acid(38%). There was more carboxylic acid functional group(64%) than phenolic group(36%). HPI-N and HPI-C comprised of 17% and 22% in the hydrophilic portion, respectively. The fouling mechanisms on the membrane surface and into its porous structure were analyzed in terms of several kinetic models. In order to analyze the fouling kinetics, the various kinetic models described in this paper were used to fit the experimental results. The kinetic models and kinetic constants obtained for each operation condition. The permeate flux was rapidly declined by simultaneous pore blocking and cake formation. Also, the permeate flux declined with decreasing internal pore size resulted from organic deposition into the membrane pore. The results of the membrane fouling test using UF membrane according to NOM fractions. HPI-N caused more fouling than HPI-C. Humic acid caused more fouling than fulvic acid probably due to higher adsorption capacity. Since humic acid has higher adsorption capacity than fulvic acid, it would be more adsorbed onto the membrane pores.

Kinetics for the Transformation of Outer Charge Transfer Complex to Inner Complex (Outer Charge Transfer Complex가 Inner Complex로의 변환에 따른 속도론적 연구)

  • Kwon Oh-Yun;Paek U-Hyon;Kim Eung-Ryul
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.343-349
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    • 1991
  • Formation of charge transfer complex between iodine and substituted aniline [aniline, N,N-dimethylaniline(N,N-DMA), 2,6-dimethylaniline(2,6-DMA), 2,4,6-trimethylaniline(2,4,6-TMA)] in CHCl$_3$, CH$_2$Cl$_2$ : CHCl$_3$ (1 : 1), and CH$_2$Cl$_2$ have been studied kinetically by using conductivity method. In the transformation of initially formed outer charge transfer complex to inner complex, the effects of substituted aniline as electron donor and polar medium on the reaction were investigated. The rate of transformation depend on the dielectric contribution of medium and pK$_a$ value of substituted aniline. The order of rate increasing is 2,4,6-TMA, 2,6-DMA, aniline, and N,N-DMA. The activation enthalpy ${\Delta}H^{\neq}$ for 2.5 M-substituted aniline in CHCl$_3$ at 25$^{\circ}C$ is respectively N,N-DMA, 3.47 kcal/mol; aniline, 4.25 kcal/mol; 2,6-DMA, 7.79 kcal/mol and 2,4,6-TMA, 7.96 kcal/mol; and activation entropy ${\Delta}S^{\neq}$ is large and negative value of -41 ~ -55 cal/mol${\cdot}$K.

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Characteristics of LSC coated Metallic Interconnect for Solid Oxide Fuel Cell (LSC가 코팅된 고체산화물 연료전지용 금속연결재의 특성 연구)

  • Pyo, Seong-Soo;Lee, Seung-Bok;Lim, Tak-Hyoung;Park, Seok-Joo;Song, Rak-Hyun;Shin, Dong-Ryul
    • Korean Chemical Engineering Research
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    • v.48 no.2
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    • pp.172-177
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    • 2010
  • This study reports the high-temperature oxidation kinetics, ASR(area specific resistance), and interfacial microstructure of metallic interconnects coated with conductive oxides in oxidation atmosphere at $800^{\circ}C$, The conductive material LSC($La_{0.8}Sr_{0.2}CoO_3$, prepared by Solid State Reaction) was coated on the Crofer22APU. The contact behavior of coating layer/metal substrate was increased by sandblast. The electrical conductivity of the LSC coated Crpfer22APU was measured by a DC two probe four wire method for 4000hr, in air at $800^{\circ}C$. Microstructure and composition of the coated layer interface were investigated by SEM/EDS. These results show that a coated LSC layer prevents the formation and growth of oxide scale such as $Cr_2O_3$ and enhances the long-term stability and electrical performance of metallic interconnects for SOFCs.

Determination of HONO Concentration and Investigation on Its Formation Mechanism Using a Continuous Measurement System in Indoor Environment of an Apartment (아파트 실내 환경에서 실시간 측정시스템을 활용한 HONO 농도 측정 및 생성기작 연구)

  • Park, Seung-Shik;Hong, Jin-H.;Lee, Jai-H.;Kim, Young-J.;Cho, Sung-Y.;Kim, Seung-J.
    • Journal of Korean Society for Atmospheric Environment
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    • v.24 no.1
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    • pp.16-29
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    • 2008
  • Nitrous acid (HONO) can be produced by heterogenous reactions of nitrogen dioxide on surface materials and direct emission from combustion sources. However, a little is known of indoor HONO levels or the relationship between residential HONO, NO, and $NO_2$ concentrations in occupied houses. Therefore, we measured simultaneously NO, $NO_2$, and HONO concentrations in living room of an apartment using continuous analyzers to study the production of HONO (June $22{\sim}30$, 2006). The 4-min average concentrations of indoor NO, $NO_2$, and HONO were 4.3 (range: $0.4{\sim}214.3$), 10.3 ($2.0{\sim}87.3$), and 1.8 ppb ($0.3{\sim}7.7$), respectively. Peak levels of HONO up to 7.7 ppb and 24-hr averages as high as 1.7 ppb were measured. In agreement with previous studies, indoor HONO concentrations increased during operation of an unvented gas range. Examination of the observed kinetics suggests that the secondary production of indoor HONO, possibly as a result of heterogeneous reactions involving $NO_2$ and $H_2O$ is associated with $[NO_2]^2[H_2O]\;(r^2=0.88)$ rather than with $[NO][NO_2][H_2O]\;(r^2=0.75)$. Three combustion experiments at nighttime were also carried out to investigate the effects of vented combustion on the HONO, NO, and $NO_2$ concentrations. It was found to release HONO for $10{\sim}15$ minutes after NO and $NO_2$ source was turned off, and peak values were finally attained. Compared to unvented combustion, peak $NO_2$ and HONO concentrations were 3.2 and 2.0 times lower at weak vented combustion (air flow: $340\;m^3/hr$) and 4.9 and 2.4 times lower at strong vented combustion (air flow: $540\;m^3/hr$), respectively, emphasizing importance of operating ventilation hood fan during combustion to improve indoor air quality.

THE EFFECT OF THE SUPERSATURATED SOLUTIONS CONTAINING HIGH CONCENTRATIONS OF FLUORIDE ON SEEDED CRYSTAL GROWTH (고농도의 불소를 포함하는 과포화용액이 apatitic crystal growth에 미치는 영향)

  • Kwun, Jung-Won;Kum, Kee-Yeon;Lee, Seung-Jong;Jung, Il-Young;Lee, Chan-Young
    • Restorative Dentistry and Endodontics
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    • v.24 no.2
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    • pp.330-336
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    • 1999
  • In biological systems, the mineral that forms hard tissue is of an apatitic nature, and hydroxyapatite($Ca_5OH(PO_4)_3$: HA) is generally considered as the prototype for such a mineral. Thus, the precipitation of HA, having biological implications, has been the subject of several investigations. Crystal growth studies using HA seeds in supersaturated solutions have enhanced our understanding of the process and mechanism involved in seeded crystal growth. From these studies, it has become apparent that the precipitation rate of HA onto the seed crystals depends on the various conditions, especially on the additives. The relation between the supersaturated solution containing fluoride and the process of HA crystal growth enhances the understanding of mechanism of HA crystal growth. Until recently, the studies have been on the crystal growth of enamel minerals and synthetic HA seeds in the supersaturated solution containing 1~2 ppm fluoride. The purpose of the present investigation is to study the effect that fluoride of high concentration has on the crystal growth kinetics of HA. In order to produce the composition found in the secretory enamel fluid, experimental solutions of 1mM Ca, 3mM P, and 100mM Tris as background electrolyte were used. Then this experimental solutions were added to 0, 2, 4, 6, 8, 10 ppm fluoride. The effect of fluoride at high concentrations on the precipitation was examined in a bench-top crystal growth model adopting a miniaturized reaction column. Chemical analysis was employed for characterization of working solutions before and after the experimentation. Remarkable findings were : 1) the amount of crystal growth was gradually accelerated as the fluoride concentration increased until 6 ppm, but decreased in 8 and 10 ppm fluoride; 2) the amount of fluoride ion consumed in crystal formation was constant despite the increase in fluoride concentration.

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Numerical Sudy on Bubbling Fluidized Bed Reactor for Fast Pyrolysis of Waste Lignocelluosic Biomass (폐목질계 바이오매스의 급속열분해 기포유동층 반응기에 대한 수치해석적 연구)

  • Lee, Ji Eun;Choi, Hang Seok
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.10
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    • pp.710-716
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    • 2013
  • New and renewable energy sources have drawn attention because of climate change. Many studies have been carried out in waste-to-energy field. Fast pyrolysis of waste lignocelluosic biomass is one of the waste-to-energy technologies. Bubbling fluidized bed (BFB) reactor is widely used for fast pyrolysis of the biomass. In BFB pyrolyzer, bubble behavior influences on the chemical reaction. Accordingly, in the present study, hydrodynamic characteristics and fast pyrolysis reaction of waste lignocellulosic biomass occurring in a BFB pyrolyzer are scrutinized. The computational fluid dynamics (CFD) simulation of the fast pyrolysis reactor is carried out by using Eulerian-Granular approach. And two-stage semi-global kinetics is applied for modeling the fast pyrolysis reaction of waste lignocellulosic biomass. To summarize, generation and ascendant motion of bubbles in the bed affect particle behavior. Thus biomass particles are well mixed with hot sand and consequent rapid heat transfer occurs from sand to biomass particles. As a result, primary reaction is observed throughout the bed. And reaction rate of tar formation is the highest. Consequently, tar accounts for 66wt.% of the product gas. However, secondary reaction occurs mostly in the freeboard. Therefore, it is considered that bubble behavior and particle motions hardly influences on the secondary reaction.