• Title/Summary/Keyword: Arrhenius plot

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Excess proton catalyzed H/D exchange reaction at the ice surface

  • Moon, Eui-Seong;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.333-333
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    • 2011
  • We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.

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A Kinetic Study of Steam Gasification of Rice Straw, Saw Dust Biomass and Coal (볏집, 톱밥 바이오매스와 석탄의 수증기 가스화반응 Kinetics 연구)

  • Song, Byungho;Zhu, Xueyan
    • Korean Chemical Engineering Research
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    • v.50 no.1
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    • pp.76-82
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    • 2012
  • Biomass and coal are great potential energy sources for gasification process. These solids can be gasified to produce syngas and bio-oil which can be upgraded further to transportation fuel. Two biomass and three coals have been gasified with steam in a thermobalance reactor under atmospheric pressure in order to evaluate their kinetic rate information The effects of gasification temperature ($600{\sim}850^{\circ}C$) and partial pressure of steam (30~90 kPa) on the gasification rate have been investigated. The three different types of gas-solids reaction models have been applied to the experimental data to compare their predictions of reaction behavior. The modified volumetric reaction model predicts the conversion data well, thus that model was used to evaluate kinetic parameters in this study. The gasification reactivity of five solids has been compared. The obtained activation energy of coal and biomass gasification were well in the reasonable range. The expression of apparent reaction rates for steam gasification of five solids have been proposed as basic information for the design of coal gasification processes.

pH-Temperature Dependence of the Ca-ATPase Activity in Actomyosin Systems of Rabbit and Frog Skeletal muscle (Actomyosin $Ca^{++}$ Activated Adenosinetriphosphatase 활성도에 대한 pH 및 온도의 영향)

  • Kim, Hee-Joong;Hwang, Ae-Ran;Park, Yang-Saeng;Kang, Doo-Hee
    • The Korean Journal of Physiology
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    • v.11 no.2
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    • pp.1-7
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    • 1977
  • The activity of the $Ca^{++}$ activated adenosinetriphosphatase (Ca-ATPase) of actomyosin systeme of rabbit and frog skeletal muscle has been studied at varying pH and temperature. The PH optima of the Ca-ATPase activity of the rabbit actomyosin was rather broad. Over the temperature range of $16-36^{\circ}C$ activity of the enzyme was not appreciably changed between pH 6.4-8.5; below and above which it rapidly reduced. The pH at the inflection point of the enzyme activity increased as temperature decreased, showing the ${\bigtriangleup}pH\;inflection/{\bigtriangleup}T$ of approximately $-0.018\;unit/^{\circ}C$. Consequently, $(OH^-)/(H^+)$ ratio at the inflection point was constant regardless of assay temperature. In the frog actomyosin systems the Ca-ATPase activity was not apparently altered between PH 6.4-7.0 when the incubation temperature was $15{\sim}30^{\circ}C$. Outside of this range of pH, however, the enzyme activity was dramatically decreased. The pH of the inflection point changed inversely with temperature. ${\bigtriangleup}pH\;inflection/{\bigtriangleup}T$ at the acidic side was approximately $-0.018\;unit/^{\circ}C$, whereas that at the alkaline side it was about $-0.037\;unit/^{\circ}C$. The Arrhenius Plot on the Ca-ATPase activity at constant $(OH^-)/(H^+)$ ratio of 1.0 was not linear, but showed break at arround $20^{\circ}C$ for both rabbit and frog actomyosin Preparations. From these results it was speculated that pH dependence of Ca-ATPase activity of rabbit actomyosin systems might reflect titrations of histidine-imidazole and -SH groups, and that of the frog actomyosin represents titrations of histidine-imidazole and lysyllysine ${\alpha}-NH_2$ groups.

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Microstructures and Proton Conductivities of BaZrO3 Modified by BaCeO3 (BaCeO3가 첨가된 BaZrO3의 미세구조 및 수소이온 전도도)

  • Park, Jong-Sung;Lee, Sung-Myung;Kim, Dong-Wan;Lee, Jong-Ho;Lee, Hae-Won;Choi, Heon-Jin;Kim, Byung-Kook
    • Journal of the Korean Ceramic Society
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    • v.45 no.4
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    • pp.226-231
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    • 2008
  • The dense sintered bodies with >95% theoretical densities were successfully obtained from the $BaZrO_3,\;BaCeO_3,\;Ba(Zr_{0.7}Ce_{0.3})O_3$ solid solution, and core-shell structured $0.7BaZrO_3-0.3BaCeO_3$ composite powders prepared by sol-gel methods. The activation energy of $Ba(Zr_{0.7}Ce_{0.3})O_3$ solid solution calculated from the Arrhenius plot of the proton conductivities was similar to that of $BaZrO_3$. The activation energy of core-shell structured $0.7BaZrO_3-0.3BaCeO_3$ composite, however, was much lower than that of $BaZrO_3$ or $Ba(Zr_{0.7}Ce_{0.3})O_3$ solid solution, and was very similar to that $BaCeO_3$. These results could be assigned to the Ce-rich grain boundary which was clearly observed by EDX in core-shell structured $0.7BaZrO_3-0.3BaCeO_3$ composite.

Production properties of pyrolytic matter of PP and PS plastics in n low temperature pyrolysis condition (저온 열분해조건에서 PP 및 PS계 플라스틱의 열분해물 생성특성 연구)

  • Kim, Sang-Hoon;Jang, Hyun-Tae;Cha, Wang-Seog
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.8 no.4
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    • pp.867-873
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    • 2007
  • Thermal degradation characteristics of polypropylene and polystyrene have been studied in the thermogravimetric(TG) reactor and batch-type microreactor. The dynamic thermogravimetric curve of TG provided a valuable information about pyrolysis temperature. It was found that PS was thermally degraded at lower temperature of $30{\sim}50^{\circ}C$ than PP. It was found that the yield and molecular weight of liquid product in the microreactor were decreased with the increase of reaction temperature and time in the case of PP. The production of styrene monomer was significantly increased by the promotion of depolymerization with the increase of temperature and time. The chain-end scission rate parameters were determined to be 50.0 kcal/mole of PP, 45.2 kcal/mole of PS by the Arrhenius plot.

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Analysis of Electrical Characteristics due to Deep Level Defects in 4H-SiC PiN Diodes (4H-SiC PiN 다이오드의 깊은 준위 결함에 따른 전기적 특성 분석)

  • Tae-Hee Lee;Se-Rim Park;Ye-Jin Kim;Seung-Hyun Park;Il Ryong Kim;Min Kyu Kim;Byeong Cheol Lim;Sang-Mo Koo
    • Korean Journal of Materials Research
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    • v.34 no.2
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    • pp.111-115
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    • 2024
  • Silicon carbide (SiC) has emerged as a promising material for next-generation power semiconductor materials, due to its high thermal conductivity and high critical electric field (~3 MV/cm) with a wide bandgap of 3.3 eV. This permits SiC devices to operate at lower on-resistance and higher breakdown voltage. However, to improve device performance, advanced research is still needed to reduce point defects in the SiC epitaxial layer. This work investigated the electrical characteristics and defect properties using DLTS analysis. Four deep level defects generated by the implantation process and during epitaxial layer growth were detected. Trap parameters such as energy level, capture-cross section, trap density were obtained from an Arrhenius plot. To investigate the impact of defects on the device, a 2D TCAD simulation was conducted using the same device structure, and the extracted defect parameters were added to confirm electrical characteristics. The degradation of device performance such as an increase in on-resistance by adding trap parameters was confirmed.

Effect of Temperature on the Deposition Rate and Bending Strength Characteristics of Chemical Vapor Deposited Silicon Carbide Using Methyltrichlorosilane (메틸트리클로로실란을 이용한 화학증착 탄화규소의 증착율 및 굽힘강도 특성에 미치는 온도의 영향)

  • Song, Jun-Baek;Im, Hangjoon;Kim, Young-Ju;Jung, Youn-Woong;Ryu, Hee-Beom;Lee, Ju-Ho
    • Composites Research
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    • v.31 no.2
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    • pp.43-50
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    • 2018
  • The effects of deposition temperature on chemical vapor deposited silicon carbide (CVD-SiC) were studied to obtain high deposition rates and excellent bending strength characteristics. Silicon carbide prepared at $1250{\sim}1400^{\circ}C$ using methyltrichlorosilane(MTS : $CH_3SiCl_3$) by hot-wall CVD showed deposition rates of $95.7{\sim}117.2{\mu}m/hr$. The rate-limiting reaction showed the surface reaction at less than $1300^{\circ}C$, and the mass transfer dominant region at higher temperature. The activation energies calculated by Arrhenius plot were 11.26 kcal/mole and 4.47 kcal/mole, respectively. The surface morphology by the deposition temperature changed from $1250^{\circ}C$ pebble to $1300^{\circ}C$ facet structure and multi-facet structure at above $1350^{\circ}C$. The cross sectional microstructures were columnar at below $1300^{\circ}C$ and isometric at above $1350^{\circ}C$. The crystal phases were all identified as ${\beta}$-SiC, but (220) peak was observed from $1300^{\circ}C$ or higher at $1250^{\circ}C$ (111) and completely changed to (220) at $1400^{\circ}C$. The bending strength showed the maximum value at $1350^{\circ}C$ as densification increased at high temperatures and the microstructure changed from columnar to isometric. On the other hand, at $1400^{\circ}C$, the increasing of grain size and the direction of crystal growth were completely changed from (111) to (220), which is the closest packing face, so the bending strength value seems to have decreased.

Kinetic Studies on the Thermal Degradation of Ginsenosides in Ginseng Extract (Ginsenosides의 처리온도(處理溫度) 및 시간(時閭)에 따른 반응속도론적(反應速度論的) 연구(硏究))

  • Choi, Jin-Ho;Kim, Doo-Ha;Sung, Hyun-Soon;Kim, Woo-Jung;Oh, Sung-Ki
    • Korean Journal of Food Science and Technology
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    • v.14 no.3
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    • pp.197-202
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    • 1982
  • Kinetic study for the thermal degradation of ginsenosides in ginseng extract was conducted. The results indicate that the thermal degradation followed first order kinetics and rate constants varied substantially depending on the types of ginsenosides and heat treatment temperatures. Activation energy calculated by Arrhenius plots ranged from 16.80 kcal/mole to 30.10 kcal/mole and $Q_{10}$ values ranged from 2.01 to 3.49. Correlation coefficients between the change of ginsenoside contents by thermal degradation and heat treatment temperature were $0.995{\sim}0.999$. The dependence on temperatures of the decomposition rate constant of total ginsenoside can be expressed as $k=4.574{\times}10^8$ exp(8898.8/T).

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Non-Enzymatic Browning Reaction of the Dried File-Fish (건조(乾燥) 말쥐치의 비효소적(非酵素的) 갈변(褐變))

  • Chun, Soon-Sil;Kim, Mu-Nam;Lee, Kang-Ho
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.11 no.3
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    • pp.21-27
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    • 1982
  • A kinetical approach for the non-enzymatic browning reaction of the dried file-fish was studied. The reaction rates revealed a tend to increase with increasing water activity and showed the maximum at $0.75\;a_w$ The activation energies obtained from the Arrhenius plot ranged 12.5 to 16.5 Kcal/mole. From these energies of activation, the $Q_{10}$ values at $45^{\circ}C$ showed 1.9 to 2.3 and both activation energy and $Q_{10}$ values were reduced with increase in $a_w$ Shelf-lives, the time to reach an 0.15 O.D./g solid at which severe brown color change could be de ectable, decreased rapidly as the temperature and water activity increase. A storage study under a square-wave fluctuating temperature condition (at 35 and $55^{\circ}C$ periodically with 7 days interval), the rate constants at all water activities used in the experiments were higher than those at $45^{\circ}C$, the mean temperature of the cycle which affects other kinetic parameters including activation energies, $Q_{10}$ values and finally the shelf-lives. The data obtained from the fluctuating temperaure storage study will be used in prediction of shelf-life. The shelf lives assessed at $25^{\circ}C$ from the accelerated shelf-life tests ranged from 179 daysat $0.75\;a_w$ to 302 days at $0.44\;a_w$.

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Kinetic Study on Char-CO2 Catalytic Gasification of an Indonesian lignite (인도네시아 갈탄의 촤-CO2 촉매가스화 반응특성연구)

  • Lee, Do Kyun;Kim, Sang Kyum;Hwang, Soon Choel;Lee, Si Hoon;Rhee, Young Woo
    • Korean Chemical Engineering Research
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    • v.52 no.4
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    • pp.544-552
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    • 2014
  • In this study, We have investigated the kinetics on the char-$CO_2$ gasification reaction. Thermogravimetric analysis (TGA) experiments were carried out for char-$CO_2$ catalytic gasification of an Indonesian Roto lignite. $Na_2CO_3$, $K_2CO_3$, $CaCO_3$ and dolomite were selected as catalyst which was physical mixed with coal. The char-$CO_2$ gasification reaction showed rapid an increase of carbon conversion rate at 60 vol% $CO_2$ and 7 wt% $Na_2CO_3$ mixed with coal. At the isothermal conditions range from $750^{\circ}C$ to $900^{\circ}C$, the carbon conversion rates increased as the temperature increased. Three kinetic models for gas-solid reaction including the shrinking core model (SCM), volumetric reaction model (VRM) and modified volumetric reaction model (MVRM) were applied to the experimental data against the measured kinetic data. The gasification kinetics were suitably described by the MVRM model for the Roto lignite. The activation energies for each char mixed with $Na_2CO_3$ and $K_2CO_3$ were found a 67.03~77.09 kJ/mol and 53.14~67.99 kJ/mol.