• Title/Summary/Keyword: Kinetic parameter

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

  • 김명자
    • The Korean Journal of Food And Nutrition
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    • v.16 no.4
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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.

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

  • 김원규;강주복
    • Water for future
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    • v.25 no.2
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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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    • v.34 no.12
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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.

Cure Kinetics of Epoxy/Diamine System Modified with Malononitrile by Barrett Method and Integral Method (Malononitrile에 의해 개질된 Epoxy/Diamine계의 경화반응 속도론: Barrett Method와 Integral Method)

  • Cheon, In-Suk;Don, Yun-Seung;Sim, Mi-Ja;Kim, Sang-Uk
    • Korean Journal of Materials Research
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    • v.4 no.5
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    • pp.574-580
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    • 1994
  • This study is about cure kinetics of DGEBA/MDA/MN(malononitrile) system by Barrett method and Integral method using DSC dynamic run. Curing behavior was shown through DSC and the heat change involved in a reaction could be measured directly with DSC. The kinetic parameters such as activation energy, pre-exponential factor and reaction order were given by Barrett method and Integral method obtained in an assumption that the area of DSC enthalpic analysis curve was propotional to the enthalpic change.

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

  • Im, Gwang-Hui;Lee, Eun-Ju
    • 한국생물공학회:학술대회논문집
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    • 2002.04a
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    • pp.524-527
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    • 2002
  • An improved mathematical/kinetic model is proposed to describe receptor-mediated uptake and its degradation of LDL on human fibroblasts. The hierarchy of kinetic models is presented, which leads to the model introducing the parameter of degree of preferential insertion of recy치ed receptors to the surface of cell membrane. The results of its prediction were presented in various types of experimental and in various LDL concentrations. Its ability to predict Brown and Goldstein’s ample experimental data was excellent.

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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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    • v.35 no.4
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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.

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

  • Lee, Jong-Jib
    • Journal of Korean Society of Water Science and Technology
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    • v.26 no.6
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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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    • v.21 no.1
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    • pp.13-19
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    • 1986
  • The effects of several vulcanizing accelerators on the determination of kinetic parameters of natural rubber vulcanizate was studied by DSC. Kinetic parameters were determined by means of the calculation procedures of Borchardt-Daniels and Oscillating Disk Rheometer (ODR) cure curve analysis, using both DSC exothermal thermogram and ODR cure curve. In order to examine the credibility in the DSC method the same compound which was und for DSC method was used for the comparison with the results of ODR data. Upon this method, kinetic rate constant (k), and Arrehenius parameter (Ea, ko, n) have been determined for rubber compounds via a new method using DSC thermogram and ODR cure curve. In the comparison of DSC and ODR results, kinetic parameters has shown good agreements between two results. Consequently, from the present studies, it is shown that the DSC thermoanalytical method can provide an alternate new method of kinetic study of rubber vulcanization.

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

  • Lee, Yong-Soo;Kim, Il-Jung;Oh, Soog-Kyoung
    • Transactions of the Korean Society for Noise and Vibration Engineering
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    • v.18 no.10
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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.

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

  • Lee, Jong-Jib
    • Clean Technology
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    • v.17 no.2
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    • pp.97-102
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    • 2011
  • The adsorption characteristics of amatanth dye by granular activated carbon were experimently investigated in the batch adsorption. Kinetic studies of adsorption of amaranth dye were carried out at 298, 308 and 318 K, using aqueous solutions with 100, 200 and 300 mg/L initial concentration of amatanth. It was established that the adsorption equilibrium of amaranth dye on granular activated carbon was successfully fitted by Langmuir isotherm equation at 298 K. The pseudo first order and pseudo second order models were used to evaluate the kinetic data and the pseudo second order kinetic model was the best with good correlation. Values of the rate constant ($k_2$) have been calculated as 0.1076, 0.0531, and 0.0309 g/mg h at 100, 200 and 300 mg/L initial concentration of amatanth, respectively. Thermodynamic parameter such as activation energy, standard enthalpy, standard entropy and standard free energy were evaluated. The estimated values for standard free energy were -5.08 - -8.10 kJ/mol over activated carbon at 200 mg/L, indicated toward a spontaneous process. The positive value for enthalpy, 38.89 kJ/mol indicates that adsorption interaction of amatanth dye on activated carbon is an endothermic process.