• Title/Summary/Keyword: activation rate constant

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Kinetic Studies on Bromine-Exchange Reactions of Antimony Tribromide with $\alpha$-Phenyl-n-butyl and $\alpha$-Phenyl-i-butyl Bromides in Nitrobenzene$^\dag$

  • Rhyu, Sok-Hwan;Choi, Sang-Up
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.408-414
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    • 1987
  • The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

Delignification Kinetics of Trema orientalis (Nalita) in Kraft Pulping

  • Jahan, M. Sarwar;Rubaiyat, A.;Sabina, R.
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.39 no.5
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    • pp.7-11
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    • 2007
  • Kraft pulping of Trema orientalis (Nalita) was studied in order to find kinetic data for delignification. Pulping runs were carried out in the temperature range of $160-180\;^{\circ}C$ under constant and well-defined conditions. The delignification was found to be first order with respect to residual lignin and was chemically controlled. The rate of delignification reaction was increased 1.11-1.23 for $10\;^{\circ}C$ temperature increase in the range of $160-180\;^{\circ}C$ range. A mean value of 93% of lignin was removed at the transition between bulk and residual delignification. The influence of cooking temperature on the rate constant was expressed by an Arrhenius-type equation. The obtained activation energy of the delignification reaction was 6,164 cal/mol. The transition point between bulk and residual phase was shifted to lower lignin and carbohydrate yield with the increase of temperature.

Effect of Monobutyl Tinoxide Catalyst in Esterification Reaction between Succinic Acid and 1,4-butanediol (Succinic Acid과 1,4-butanediol간의 에스테르화반응에서 Monobutyl Tinoxide 촉매의 영향)

  • Park, Keun-Ho;Kim, Duck-Sool
    • Journal of the Korean Applied Science and Technology
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    • v.26 no.3
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    • pp.362-369
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    • 2009
  • Esterification reaction between succinic acid and 1,4-butanediol was kinetically investigated in the presence of monobutyl tinoxide catalysts at $150{\sim}190^{\circ}C$. The reaction rates measured by the amount of distilled water from the reaction vessel. The esterification reaction was carried out under the first order conditions with respect to the concentration of reactants, respectively. The overall reaction order was 2nd. The linear relationship was shown between apparent reaction rate constant and reciprocal absolute temperature. By the Arrhenius plot the activation energy have been calculated as 87.567 kJ/mol under monobutyl tinoxide catalyst and also apparent reaction rate constant, k' was found to obey first kinetics with respect to the concentration of catalyst.

Drying Characteristics of Fluidized Bed Drying of Naked Barley (쌀보리의 유동층 건조 특성에 관한 연구)

  • Kim, Hee-Yun;Cho, Duk-Jae;Chung, Gea-Hwan;Hur, Jong-Wha
    • Korean Journal of Food Science and Technology
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    • v.25 no.5
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    • pp.558-564
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    • 1993
  • The drying characteristics of fluidized bed drying with different drying conditions using naked barley were carried out. This fluidized drying mechanism of naked barley was consisted of consecutive two falling rate parts, first falling rate period and second falling rate period without showing constant rate period. The drying rate constant was increased with decreasing charged amount and relative humidity and increasing air temperature and air velocity. Since the drying rate constant expressed by Arrhenius type equation in the falling rate period showed good linearity, the falling rate period was considered as the controlling step. The activation energy of first falling step was 1,900 cal/gmol, while for second falling step the values showed 2,500 cal/gmol.

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Evaporation Rate of Lead in Molten Copper Alloy by Gas Injection (가스취입에 의한 용융 동 합금 중 납의 증발속도)

  • Kim, Hang-Su;Jeong, Seong-Yeop;Jeong, U-Gwang;Yun, Ui-Han;Son, Ho-Sang
    • Korean Journal of Materials Research
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    • v.12 no.1
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    • pp.68-74
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    • 2002
  • The lead has to be removed for the recycling of copper alloy. The lead cannot be removed from the copper alloy by oxidation. It can be removed by the evaporation because of its high vapor pressure. However, rare information is found on removal of lead from copper alloy. The purpose of present work is to provide a fundamental knowledges on the removal of lead from the copper alloy by evaporation. Gas injection was made in molten copper alloy, and the evaporation rate of lead was measured. The influence of Ar gas flow rata(2~4 L/min), initial contents of lead(2~4wt%Pb), temperature(1200~140$0^{\circ}C$) was investigated based on the thermodynamic and the kinetics. The rate constant is increased with increasing flow rate of Ar and temperature. Though amount of lead removed is increased with higher initial lead concentration, the rate constant is not changed significantly. The activation energy is estimated from the temperature dependence of the rate constant. Also removal of lead from the copper by adding chloride was made for the comparison.

Performance Analysis of Polymer Electrolyte Membrane Fuel Cell by AC Impedance Measurement (교류 임피던스 측정법을 이용한 고분자 전해질 연료전지의 성능특성 분석)

  • Seo, Sang-Hern;Lee, Chang-Sik
    • Journal of Hydrogen and New Energy
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    • v.20 no.4
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    • pp.283-290
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    • 2009
  • This study focuses on the performance characteristics of polymer electrolyte membrane fuel cell (PEMFC) using the AC impedance technique. The experiment was carried out to investigate the optimal operating conditions of PEMFC such as cell temperature, flow rate, humidified temperature and back-pressure. The fuel cell performance was analyzed by DC electronic-loader with constant voltage mode and expressed by voltage-current density. Additionally, AC impedance was measured to analysis of ohmic and activation loss and expressed by Nyquist plot. The results showed that the cell performance increased with increase of cell temperature, air flow rate, humidified temperature and backpressure. Also, the activation loss decreased as the increase of cell temperature, air flow rate, humidified temperature and backpressure.

Thermal Stability of Lamellar Eutectic Structure in Fe-Ti Alloy (Fe-Ti합금계에서의 충상공정조직의 열적안정성)

  • Wey, Myeong Yong;Hasebe, Mitsuhiro
    • Journal of the Korean Society for Heat Treatment
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    • v.10 no.2
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    • pp.121-127
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    • 1997
  • In order to elucidate thermal stability of Fe-$Fe_2Ti$ eutectic structure, the initial several structures have been investigated in the changes of coarsening and spheroidization during prolonged annealing under the eutectic temperature. The results are as follows: 1) The rate constant of coarsening and spheroidization was formulated as $S^{-n}-S_0^{-n}=k{\cdot}t$, where S is the total area of the interface between ${\alpha}$ and C($Fe_2Ti$) per unit volume, $S_0$ is initial value and k is the rate constant. 2) The coarsening and spheroidization mechanism was described by Ostwald ripening and controlled by diffusion of Ti-atom in ${\alpha}$-phase. 3) The spheroidization rate constant in eutectic lamellar structures was depended upon annealing temperature and showed the Arrhenius relation. The activation energy for spheroidization of lamellar structure was 365 kJ/mole.

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Kinetic Study by Heating Rate Method (가열속도법에 의한 반응속도론 연구)

  • 박영수;양광규;김용태
    • Journal of the Korean Society of Tobacco Science
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    • v.4 no.2
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    • pp.57-61
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    • 1982
  • For evaluating kinetic parameters of various reactions and materials a straight- forward method has been studied by the variable heating rate method in DSC analysis. Based on the linear relationship between the logarithm of the heating rate and reciprocal Peak temperature, this method allows calculation of activation energy and the Arrhenius frequency factor by only one observation of the peak temperature versus the heating rate. According to tile D function, D=-In P(x)/dx, to x(=$\frac{E}{RT}$) we can calculate reasonably accurate activation energy, tile Arrhenius factor and the rate constant, and predict half-life times of various materials from the kinetic calculation.

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Photoionization of N,N,N',N'-Tetramethyl-p-phenylenediamine in Polar Solvents

  • Min Yeong Lee;Du Jeon Jang;Minyung Lee;Du-Jeon Jang;Dongho Kim;Sun Sook Lee;Bong Hyun Boo
    • Bulletin of the Korean Chemical Society
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    • v.12 no.4
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    • pp.429-433
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    • 1991
  • The photoinduced electron transfer reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in various polar solvents were studied by measuring time-resolved fluorescence. The temperature dependence on the fluorescence decay rate in acetonitrile, methanol, ethanol and buthanol was carried out to obtain the activation energy and Arrehnius factor for the photoinduced electron transfer reaction. It was found that as the dielectric constant of the solvent increases, the activation energy and the reaction rate increase. This implys that the Arrehnius factor is important in controlling the photoinduced electron transfer reaction rate. In water, TMPD exists in three forms (cationic, protonated and neutral forms) due to the high dielectric constant and strong proton donating power of water. The photoinduced electron transfer reaction was found to be very fast (< 50 ps) and also the long liverd component in the fluorescence decay profile attributable to the photoexcited protonated form of TMPD was observed. Probably, the reaction pathway and the reaction coordinate seem to be different depending on the solvents studied here.

Basic Studies on Propellant Casting (II). Effects of Solid Additives on Urethane Polymerization (추진제 성형에 관한 기초연구 (제2보). 우레탄 중합에 미치는 첨가제 효과)

  • Young Gu Cheun;Ik Choon Lee;Shi Choon Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.4
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    • pp.214-218
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    • 1981
  • Kinetic studies were carried out on urethane polymerization reaction of hydroxyl-terminated polybutadiene with isophorone diisocyanate under presence of Hexogen as solid additive. The rate was found to increase with the amount of Hexogen added. However the rate acceleration was not a catalytic effect but solely due to an increase of activation entropy. The reaction was a good 2nd order process with nearly constant activation energy of 8.4 kcal/mole.

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