• Title/Summary/Keyword: 활성화 에너지값

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Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures (압력변화에 따른 퀴놀린 유도체와 p-치환 염화벤조일류의 속도론적 연구)

  • Jong-Wan Lim;Se-Kyong Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.206-212
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    • 2003
  • The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

Kinetic study of perovskite catalyst for water-gas shift reaction (수성가스전환반응 페로브스카이트구조 촉매 반응속도 연구)

  • Jun, Seunghyun;Bae, Joongmyeon;Lim, Sungkwang;Kim, Kihyun
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.11a
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    • pp.77.2-77.2
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    • 2010
  • 일산화탄소를 수소로 변환하는 수성가스전환반응(WGSR)은 수소 생산, 연료개질 시스템뿐만 아니라 암모니아 제조, 제철소 제련과정등 일선 산업현장에서 널리 활용되고 있다. 상용공정에서의 WGS반응은 두 단계의 반응기(HTS/LTS)에서 각각 Fe/Cr, Cu/Zn기반 촉매를 사용하여 이루어진다. 하지만 이러한 촉매들은 공기중 자연발화성이 있고 사용전 환원과정이 필요하다. 또한 최근에 많은 연구가 진행되고 있는 귀금속 담지 촉매는 기존 촉매의 단점을 극복하고 활성이 높은 장점이 있다. 이에 본 연구에서 제시한 페로브스카이트 촉매는 상용 촉매, 귀금속 담지촉매 시스템과의 비교를 위하여 제작된 촉매를 사용한 반응시스템과 기존 상용촉매를 사용한 반응시스템을 비교하여 개발 촉매의 성능 수준을 검토하였다. 이러한 결과 페로브스카이트 구조 촉매는 상용촉매의 공정상의 단점과 귀금속 담지촉매의 가격적인 측면에서의 단점을 동시에 극복한 촉매로서 성능 및 메탄화반응 억제 측면에서 우수성을 보유하고 있다는 것을 증명하였다. 이러한 페로브스카이트 구조 촉매의 반응특성을 규명하기 위해 문헌조사해본 결과 기존 수성가스전환반응에서 쓰이는 촉매들의 반응매카니즘은 대표적으로 formate와 redox 반응 두가지가 있었다. 페로스브스카이트 구조 촉매는 그 구조와 귀금속 함량, 활성 등 성능측면에서 귀금속 촉매와 상당히 유사한 측면이 있기 때문에 귀금속 담지 촉매의 반응속도식을 기본으로 하여 실험결과와 일치시켜 페로브스카이트구조 촉매에 맞는 반응속도식을 제시하고 이를 통한 반응파라미터 값을 도출하였다.

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Rheological Properties of Various Gelatinized Potato Starch Pastes (품종별 감자 전분 호화액의 리올로지 특성)

  • 정란희;김경애
    • Korean journal of food and cookery science
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    • v.7 no.3
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    • pp.1-6
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    • 1991
  • Potato starches are obtained from Irish Cobbler (the dry type), Shepody and superior (the intermediate type) and Dejima (the moist type). Rheological properties of heat-gelatinized potato starch paste were studied to elucidate difference of various potato starches. Heat-gelatinized 3 to 7% potato starch paste showed pseudo plasticity in yield stress. As starch paste concentration increased, the values of consistency index was increased. Relationship between logarithmic consistency index and concentration of potato starch paste was linear at 5% starch concentration. Concentration dependence of consistency index and yield stress of Shepody was highest. As measuring temperature increased, the value of consistency index was decreased. Irish Cobbler starch paste at $50^{\circ}C$, Shepody, Superior and Dejima starch paste at $60^{\circ}C$ showed linear relationships with different slopes. The activation energies of Shepody starch paste was 3.97㎉l/㏖.

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Sintering phenomena and grain growth of ultra-fine spinel($MgAl_2O_4$);(II) (순수 스피넬($MgAl_2O_4$)의 입성장 및 소결현상)

  • 이형복;한영환
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.8 no.3
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    • pp.498-502
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    • 1998
  • Sintering phenomena at refractory temperature ranges, from $1400^{\circ}C$ to $1700^{\circ}C$, of the pure spinel $(MgAl_2O_4)$ are analysed and compared to the experimental data from other researchers in terms of grain size(G), density($\rho$), and activation energy(Q). The grain size and relative density relationships for the spinels present very similar trends. They exhibit two distinct regions, an intermediate sintering stage to about the 85~90% density level and what appears to be the final stage sintering region above that transition-density level. The activation energy in terms of the grain size (G) and density ($\rho$) is determined to be 670$\pm$48 (kJ/mol) in this spinel and about 590 kJ/mol for the overall temperature range in other's spinel. These values are close to other published data, 360 to 580 kJ/mol.

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Effect of lipid contents on the physicochemical characteristics of acorn starch (지방함량 변화에 따른 도토리전분의 이화학적 특성)

  • Ahn, Ho-Kyoung;Kil, Hun-Bae;Yoo, Hae-Euy;Oh, Doo-Hwan
    • Applied Biological Chemistry
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    • v.33 no.4
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    • pp.293-300
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    • 1990
  • The physical and chemical properties of dry acorn starch(DS), defatted acorn starch (DFS) and reincorporated acorn starch(RIS) were investigated. Swelling power and solubility of all starch sample, were exhibited two stage behavior. It had a little change on the pasting temperature of DS and DFS but the peak viscosity and breakdown value of DFS was somewhat higher than those of DS and RIS. Flow behavior of gelatinized starch pastes showed a pseudoplastic behavior and flow behavior index was lower than unit The consistency coefficient showed concentration and temperature dependency. The activation energies of DS, DFS and RIS were from $1.70Kca1/g\;{\cdot}\;mol$ to $3.75Kca1/g\;{\cdot}\;mol$.

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Kinetics of Base Hydrolysis of Some Chromen-2-one Indicator Dyes in Different Solvents at Different Temperatures (여러 온도 및 용매 하에서 수행된 chromen-2-one 지시약 염료들의 염기성 가수분해 반응에 대한 속도론적 연구)

  • Abu-Gharib, Ezz A.;EL-Khatib, Rafat M.;Nassr, Lobna A.E.;Abu-Dief, Ahmed M.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.346-353
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    • 2011
  • Base hydrolysis of 7-hydroxy-2H-chromen-2-one (HC) and 7-hydroxy-2H-chromen-2-one-4-acetic acid (HCA) in aqueous-methanol and aqueous-acetone mixtures were studied kinetically at temperature range from 283 to 313 K. The activation parameters of the reactions were evaluated and discussed. Moreover, the change in the activation energy barrier of the investigated compounds from water to water-methanol and water-acetone mixtures was estimated from the kinetic data. It is observed that the change in activation barriers is more or less the same for the hydrolysis of HC and HCA. Base hydrolysis of HC and HCA follows a rate law with $k_{obs}=k_2[OH^-]$. The decrease in the rate constants of HC and HCA as the proportion of methanol or acetone increases is due to the destabilization of $OH^-$ ion. The high negative values of entropy of activation support the proposal mechanism, i.e. the investigated reaction takes place via the formation of an intermediate complex. Moreover, these values refer to the rigidity and stability of the intermediate complex. Thus, the ring opening of the intermediate complex would be the rate controlling step.

Study on Adsorption Kinetic Characteristics of Propineb Pesticide on Activated Carbon (활성탄에 대한 프로피네브 농약의 흡착동력학적 특성 연구)

  • Lee, Jong-Jib;Cho, Jung-Ho;Kim, Heung-Tae
    • Clean Technology
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    • v.17 no.4
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    • pp.346-352
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    • 2011
  • The adsorption characteristics of propineb pesticide onto activated carbon has been investigated for the adsorption in aqueous solution with respect to initial concentration, contact time and temperature in batch experiment. The Langmuir and Freundlich adsorption models were applied to described the equilibrium isotherms and isotherm constants were also determined. The Freundlich model agrees with experimental data well. slope of isotherm line indicate that activated carbon could be employed as effective treatment for removal of propineb. The pseudo first order, pseudo second order kinetic models were use to describe the kinetic data and rate constants were evaluated. The adsorption process followed a pseudo second order model, and the adsorption rate constant($k_2$) decreased with increasing initial concentration of propineb. The activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption. The estimated values for change of free energy were -7.28, -8.27 and -11.66 kJ/mol over activated carbon at 298, 308 and 318 K, respectively. The results indicated toward a spontaneous process. The positive value for change of enthalpy, 54.46 kJ/mol, found that the adsorption of propineb on activated carbon is an endothermic process.

Preparations of PAN-based Activated Carbon Nanofiber Web Electrode by Electrostatic Spinning and Their Applications to EDLC (정전방사에 의한 PAN계 활성화 탄소 나노섬유 전극 제조와 EDLC 응용)

  • Kim, Chan;Kim, Jong-Sang;Lee, Wan-Jin;Kim, Hyung-Sup;Edie, Dan D.;Yang, Kap-Seung
    • Journal of the Korean Electrochemical Society
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    • v.5 no.3
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    • pp.117-124
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    • 2002
  • Poly(acrylonitrile)(PAN) solutions in dimethylformamide(DMF) were electrospun to prepare webs consisting of 400nm ultra-fine fibers. The webs were oxidatively stabilized, activated by steam and resulted to be activated carbon fibers(ACFs). The specific surface area was $800\~1230 m^2/g$, which showed a trend of a decrease of the surface area with an increase in activation temperature, showing opposite behavior to the other ACFs. The activation energy of the stabilized fibers for the steam activation was determined as 29.2 kJ/mol to be relatively low indicating the easier activation than that of other carbonized fibers. The ACF webs were characterized by pore size and specific surface uea which would be related to the specific capacitance of the electrical double layer capacitor (EDLC). The specific capacitances measured were 27 F/g, 25 F/g, 22 F/g at the respective activation temperature of $700^{circ}C,\;750^{\circ}C\;800^{\circ}C$, showing similar trend with the specific surface area i.e., the higher activation temperature was, the lower specific capacitance resulted.

A Study on Thermally Stimulated Luminescence and Exoelectron Emission Phenomena of MgO Single Crystals (MgO 단결정의 열자극 발광 및 Exo전자 방출 현상에 관한 연구)

  • Doo, Ha-Young;Sim, Sang-Hung;Kim, Hyun-Suk
    • Journal of Korean Ophthalmic Optics Society
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    • v.11 no.3
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    • pp.165-172
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    • 2006
  • On the MgO single crystals doped artificially with Cr, Cu, Fe we observed thermally stimulated luminescence(TSL) glow curves and spectra, and analyzed them in the temperatures range from at liquid nitrogen temperature(77K) to about 500K after excitation with UV or X-ray irradiation. TSL glow curves obtained from these samples show five peaks at 136.5K, 223.5K, 360K, 390K, 440K, and their estimated activation energies are 0.27eV, 0.63eV, 1.08eV, 1.08eV, 1.19eV, and 1.33eV, respectively. When we measured TSL spectrum at the range of 200nm to 650nm on the MgO single crystals. we also analyzed the peak wavelength which obtained at 345nm, 375nm, and 410nm from measurement of TSL spectrum and described their luminescence mechanisms. TSL spectrum peaks emitted from MgO:Cr, MgO:Cu, and MgO:Fe appear at the wavelengths of 345nm, 360nm, and 375nm, respectively.

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Removal of Cs by Adsorption with IE911 (Crystalline Silicotitanate) from High-Radioactive Seawater Waste (IE911 (crystalline silicotitanate) 의한 고방사성해수폐액으로부터 Cs의 흡착 제거)

  • Lee, Eil-Hee;Lee, Keun-Young;Kim, Kwang-Wook;Kim, Ik-Soo;Chung, Dong-Yong;Moon, Jei-Kwon
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.13 no.3
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    • pp.171-180
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    • 2015
  • This study was performed on the removal of Cs, one of the main high- radioactive nuclides contained in the high-radioactive seawater waste (HSW), by adsorption with IE911 (crystalline silicotitanate type). For the effective removal of Cs and the minimization of secondary solid waste generation, adsorption of Cs by IE911 (hereafter denoted as IE911-Cs) was effective to carry out in the m/V (ratio of absorbent weight to solution volume) ratio of 2.5 g/L, and the adsorption time of 1 hour. In these conditions, Cs and Sr were adsorbed about 99% and less than 5%, respectively. IE911-Cs could be also expressed as a Langmuir isotherm and a pseudo-second order rate equation. The adsorption rate constants (k2) were decreased with increasing initial Cs concentrations and particle sizes, and increased with increasing ratios of m/V, solution temperatures and agitation speeds. The activation energy of IE911-Cs was about 79.9 kJ/mol. It was suggested that IE911-Cs was dominated by a chemical adsorption having a strong bonding form. From the negative values of Gibbs free energy and enthalpy, it was indicated that the reaction of IE911-Cs was a forward, exothermic and relatively active at lower temperatures. Additionally, the negative entropy values were seen that the adsorbed Cs was evenly distributed on the IE911.