• Title/Summary/Keyword: Kinetic parameter

검색결과 231건 처리시간 0.036초

고압하의 피리딘 반응에 대한 속도론적 연구 (Kinetic Study for the Reaction of Pyridine under High Pressure)

  • 김명자
    • 한국식품영양학회지
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    • 제16권4호
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    • pp.321-327
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    • 2003
  • The reaction rates of 4-ethyl pyridine with p-methyl benzylbromide have been measured by conductometry in acetonitrile, and the rate constants of these reactions are determined in accordance with various temperatures (20, 25, 30$^{\circ}C$) and pressures (1, 200, 500, 1000 bar). The rate constants increased with the higher pressure and temperature. The activation energies and activation parameter values of these reactions are calculated by determination of the rate constants the same. The activation volume, activation compressibility coefficient and the activation entropy are all negative. The result of kinetic studies for the pressure show that this reaction proceeds in typical bimolecular nucleophilic substitution reaction.

하천 감조부에 있어서 질소의 장기변동에 관한 연구 (Study on the Long-term Change of nitrogen in the Tidal Area of River)

  • 김원규;강주복
    • 물과 미래
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    • 제25권2호
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    • pp.67-78
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    • 1992
  • Several field surveys were conducted to investigate changes of water quality with time in a tidal river. Results indicated that nitrification process were dependent on the change of salinity and suspended solids concenttration. Therefore laboratory batch experiments were conducted, using suspended solids and sediment taken from a tidal river, to study the effect of salinity on nitrification and to estimate kinetic parameters of it in the tidal river. suspended solids and sediment were sampled at a point in the middle stream. Sediments were collect from the aerobic layer of mud. The change of nitrogen concentration with time was clearly explained with Monod groth model and kinetic parameters were obtained by curve fitting method. Changes in NH4-N, NO2-N, and NO3-N concentrations in the river ROKKAU with time were simulated well using Lagrangian reference frame and parameter values obtained in the laboratory tests. T도 mechanism of nitrification by suspended solids and sediment in a tidal river is shown to depend on tidal effects.

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Kinetics and Mechanism of Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile

  • Barai, Hasi Rani;Hoque, Md. Ehtesham Ul;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3811-3816
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    • 2013
  • Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.

Improved modeling of non-hepatic cellular uptake and degradation of low density lipoprotein

  • 임광희;이은주
    • 한국생물공학회:학술대회논문집
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    • 한국생물공학회 2002년도 생물공학의 동향 (X)
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    • pp.524-527
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    • 2002
  • 인간 fibroblasts의 receptor를 통한 LDL의 섭취와 분해에 대하여 보다 개선되어진 수학적/동역학적 모델을 제시하였다. 관련된 동역학적 모델의 hierarchy를 통하여 세포 멤브레인 표면으로 recycle되는 receptor의 선택적 insertion 정도를 나타내는 파라미터, ${\alpha}$를 가지는 모델을 제안하였다. 여러 가지의 LDL 농도의 미디움과 여러 가지의 실험조건에서 모델예측을 수행하였는데, Brown과 Goldstein의 많은 실험데이터에 잘 일치하였다.

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Nucleophilic Substitution Reactions of O-Methyl N,N-Diisopropylamino Phosphonochloridothioate with Anilines and Pyridines

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • 제35권4호
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    • pp.1016-1022
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    • 2014
  • The kinetic studies on the reactions of O-methyl N,N-diisopropylamino phosphonochloridothioate with X-anilines and X-pyridines have been carried out in acetonitrile. The free energy relationship with X in the anilines exhibits biphasic concave upwards with a break region between X = (H and 4-F), giving unusual negative ${\beta}_X$ and positive ${\rho}_X$ values with weakly basic anilines. The unusual phenomenon is rationalized by isokinetic relationship. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the selectivity parameter and variation trend of the deuterium kinetic isotope effects with X. The free energy relationship with X in the pyridines exhibits biphasic concave upwards with a break point at X = 3-MeO. A concerted mechanism is proposed based on relatively small ${\beta}_X$ value, and frontside and backside nucleophilic attack are proposed with strongly and weakly basic pyridines, respectively.

활성탄 흡착에 의한 Ethyl Violet의 공정 파라미터 연구 (Study on Process Parameter of Ethyl Violet by Activated Carbon Adsorption)

  • 이종집
    • 한국수처리학회지
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    • 제26권6호
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    • pp.143-152
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    • 2018
  • The process parameters of ethyl violet from aqueous solution by activated carbon adsorption were carried out as a function of pH, temperature, contact time, initial concentration and temperature. The adsorption equilibrium data can be described well by the Langmuir and Freundlich isotherm models. Base on Langmuir constant ($R_L=0.0343{\sim}0.0523$) and Freundlich constant (1/n=0.1633~0.1974), This process could be employed as effective treatment for adsorption of ethyl violet. The kinetic experimental results showed that the adsorption process can be well described with the pseudo second order model. Based on the positive enthalpy (6.505 kJ/mol), the adsorption of ethyl violet onto granular activated carbon is endothermic. The negative Gibbs free energy (-1.169~-1.681 kJ/mol) obtained indicates that the adsorption process is spontaneous and physisorption.

CALORIMETRIC INVESTIGATION OF SULFUR VULCANIZATION OF NATURAL RUBBER

  • Paik, Nam-Chul;Choi, Sei-Young;Suh, Won-Dong
    • Elastomers and Composites
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    • 제21권1호
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    • pp.13-19
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    • 1986
  • 최근(最近)에 와서는 황(黃)에 의(依)한 고무의 가황반응(加黃反應)이 발열반응(發熱反應)이라는데 주안점(主眼點)을 두어 근래(近來) 고분자화학(高分子化學) 분야(分野)에서 그 활용도(活用度)가 높은 열분석기(熱分析機) (특(特)히 DSC, DTA)가 가황발열현상연구(加黃發熱現象硏究)에 많이 이용(利用)되고 있다. 그러나 고무의 가황반응(加黃反應)을 속도론적(速度論的)으로 연구하여 이론적(理論的) 기초(基礎)를 확립(確立)하여 두는 것이 필요(必要)하다는 것은 여러 학자(學者)들이 전(前)부터 느껴왔으나 고무탄성체(彈性體)는 한번 가황(加黃)되면 일반적(一般的)인 용매(溶媒)에 의(依)한 용해(溶解)가 어렵기 때문에 반응물(反應物)(황, 가황촉진제(黃, 加黃促進劑))이나 생성물(生成物)의 농도측정(濃度測定)에 의(依)한 가황반응(加黃反應)의 속도론적(速度論的) 연구(硏究)가 어려웠다. 그래서 본(本) 연구(硏究)에서는 DSC(Differential Scanning Calorimetry)를 이용(利用)하여 얻은 천연(天然)고무의 가황발열(加黃發熱) thermogram을 Borchardt-Daniel이 제안한 방법으로 분석(分析)하여 kinetic data(즉, rate constant k, frequency factor ko, Activation Energy Ea)를 얻었다. 또한 이 kinetic data가 가황촉진제의 종류(種類)에 따라 어떻게 달라지는지, 실제공정(實際工程)에서 적정가황시간(適正加黃時間), 온도(溫度), 가황촉진제(加黃促進劑)의 종류(種類), 배합량(配合量) 결정(決定)에 활용(活用)할 수 있는 방안(方案)에 대(對)해서도 관심을 두고 검토(檢討)하였다. 한편 DSC에 의(依)한 방법(方法)의 신뢰도를 검토하기 위하여 DSC용(用)으로 쓰여진 것과 동일(同一)한 시료를 사용하여 Oscillating Disk Rheometer에 의한 Cure Curve를 얻고 이 Cure Curve를 분석(分析)하여 얻은 kinetic data를 앞서 구한 data와 비교검토(比較檢討)하였다.

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탄성지반을 고려한 집중질량뜰 갖고 면내력이 작용하는 변단면 보강후판의 진동해석 (Vibration Analysis of Tapered Thick Plate with Concentrated Mass Subjected to In-plane Force on Elastic Foundation)

  • 이용수;김일중;오숙경
    • 한국소음진동공학회논문집
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    • 제18권10호
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    • pp.1033-1041
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    • 2008
  • The purpose of this paper is to investigate natural frequencies of tapered thick plate with concentrated masses subjected to in-plane force on pasternak foundation by means of finite element method and providing kinetic design data for mat of building structures. Finite element analysis of rectangular plate is done by using rectangular finite element with 8-nodes. For analysis, plates is supported on pasternak foundation. The Winkler parameter is varied with 10, 102, the shear foundation parameter is 5. The taper ratio is applied as 0.0, 0.25, 0.5 and the ratio of the concentrated mass to plate mass as 0.25, 0.5 respectively. As results, we can see that when stiffener's sizes or foundation parameter are larger, the natural frequency increases, and when the concentrated mass or taper ratio or in-plane stress is larger, the natural frequency decreases.

활성탄에 의한 아마란스 염료의 흡착동력학에 관한 연구 (Study on Adsorption Kinetic of Amaranth Dye on Activated Carbon)

  • 이종집
    • 청정기술
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    • 제17권2호
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    • pp.97-102
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    • 2011
  • 입상활성탄에 의한 아마란스 염료의 흡착특성을 회분식 실험을 통해 조사하였다. 아마란스 염료의 흡착동력학적 연구는 298, 308, 318 K에서 초기농도 100, 200, 300 mg/L의 수용액을 가지고 수행하였다. 입상활성탄에 의한 아마란스 염료의 흡착 평형관계는 298K에서 Langmuir 등온식이 잘 적용되었다. 유사일차반응속도식과 유사이차반응속도식을 사용하여 동력학 실험값을 평가한 결과, 유사이차반응속도식이 더 잘 맞았으며, 속도상수($k_2$) 값은 아마란스 초기농도 100, 200, 300 mg/L 에 대해 각각 0.1076, 0.0531 및 0.0309 g/$mg{\cdot}h$로 조사되었다. 활성화에너지, 표준엔탈피, 표준엔트로피 및 표준자유에너지를 평가하였다. 조사된 표준자유에너지값은 초기농도 200 mg/L 에서 -5.08 ~ -8.10 kJ/mol로 자발적인 공정임을 알 수 있었다. 엔탈피변화량이 양의 값인 38.89 kJ/mol을 나타내어 활성탄에 대한 아마란스 염료의 흡착이 흡열반응으로 일어난다는 것을 알 수 있었다.