• Title/Summary/Keyword: Arrhenius energy activation

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Oxidation of Chloroethenes by Heat-Activated Persulfate (과황산의 열적활성화 및 염소계용제의 산화분해)

  • Zhang, Hailong;Kwon, Hee-Won;Choi, Jeong-Hak;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.26 no.11
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    • pp.1201-1208
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    • 2017
  • Oxidative degradation of chlorinated ethenes was carried out using heat-activated persulfate. The activation rate of persulfate was dependent on the temperature and the activation reaction rate could be explained based on the Arrhenius equation. The activation energy of persulfate was 19.3 kcal/mol under the assumption that the reaction between the sulfate radical and tricholoroethene (TCE) is very fast. Activation could be achieved at a moderate temperature, so that the adverse effects due to high temperature in the soil environment were mitigated. The reaction rate of TCE was directly proportional to the concentration of persulfate, indicating that the remediation rate can be controlled by the concentration of the injected persulfate. The solution was acidized after the oxidation, and this was dependent on the oxidation temperature. The consumption rate of persulfate was high in the presence of the target organic, but the self-decomposition rate became very low as the target was completely removed.

Computational Study on Unsteady Mechanism of Spinning Detonations

  • Matsuo, Akiko;Sugiyama, Yuta
    • 한국전산유체공학회:학술대회논문집
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    • 2008.03a
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    • pp.367-373
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    • 2008
  • Spinning detonations propagating in a circular tube were numerically investigated with a one-step irreversible reaction model governed by Arrhenius kinetics. Activation energy is used as parameter as 10, 20, 27 and 35, and the specific heat ratio and the heat release are fixed as 1.2 and 50. The time evolution of the simulation results was utilized to reveal the propagation mechanism of single-headed spinning detonation. The track angle of soot record on the tube wall was numerically reproduced with various levels of activation energy, and the simulated unique angle was the same as that of the previous reports. The maximum pressure histories of the shock front on the tube wall showed stable pitch at Ea=10, periodical unstable pitch at Ea=20 and 27 and unstable pitch consisting of stable, periodical unstable and weak modes at Ea=35, respectively. In the weak mode, there is no Mach leg on the shock front, where the pressure level is much lower than the other modes. The shock front shapes and the pressure profiles on the tube wall clarified the mechanisms of these stable and unstable modes. In the stable pitch at Ea=10, the maximum pressure history on the tube wall remained nearly constant, and the steady single Mach leg on the shock front rotated at a constant speed. The high and low frequency pressure oscillations appeared in the periodical unstable pitch at Ea=20 and 27 of the maximum pressure history. The high frequency was one cycle of a self-induced oscillation by generation and decay in complex Mach interaction due to the variation in intensity of the transverse wave behind the shock front. Eventually, sequential high frequency oscillations formed the low frequency behavior because the frequency behavior was not always the same for each cycle. In unstable pitch at Ea=35, there are stable, periodical unstable and weak modes in one cycle of the low frequency oscillation in the maximum pressure history, and the pressure amplitude of low frequency was much larger than the others. The pressure peak appeared after weak mode, and the stable, periodical unstable and weak modes were sequentially observed with pressure decay. A series of simulations of spinning detonations clarified that the unsteady mechanism behind the shock front depending on the activation energy.

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Computational Study on Unsteady Mechanism of Spinning Detonations

  • Matsuo, Akiko;Sugiyama, Yuta
    • 한국전산유체공학회:학술대회논문집
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    • 2008.10a
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    • pp.367-373
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    • 2008
  • Spinning detonations propagating in a circular tube were numerically investigated with a one-step irreversible reaction model governed by Arrhenius kinetics. Activation energy is used as parameter as 10, 20, 27 and 35, and the specific heat ratio and the heat release are fixed as 1.2 and 50. The time evolution of the simulation results was utilized to reveal the propagation mechanism of single-headed spinning detonation. The track angle of soot record on the tube wall was numerically reproduced with various levels of activation energy, and the simulated unique angle was the same as that of the previous reports. The maximum pressure histories of the shock front on the tube wall showed stable pitch at Ea=10, periodical unstable pitch at Ea=20 and 27 and unstable pitch consisting of stable, periodical unstable and weak modes at Ea=35, respectively. In the weak mode, there is no Mach leg on the shock front, where the pressure level is much lower than the other modes. The shock front shapes and the pressure profiles on the tube wall clarified the mechanisms of these stable and unstable modes. In the stable pitch at Ea=10, the maximum pressure history on the tube wall remained nearly constant, and the steady single Mach leg on the shock front rotated at a constant speed. The high and low frequency pressure oscillations appeared in the periodical unstable pitch at Ea=20 and 27 of the maximum pressure history. The high frequency was one cycle of a self-induced oscillation by generation and decay in complex Mach interaction due to the variation in intensity of the transverse wave behind the shock front. Eventually, sequential high frequency oscillations formed the low frequency behavior because the frequency behavior was not always the same for each cycle. In unstable pitch at Ea=35, there are stable, periodical unstable and weak modes in one cycle of the low frequency oscillation in the maximum pressure history, and the pressure amplitude of low frequency was much larger than the others. The pressure peak appeared after weak mode, and the stable, periodical unstable and weak modes were sequentially observed with pressure decay. A series of simulations of spinning detonations clarified that the unsteady mechanism behind the shock front depending on the activation energy.

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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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COMPARISON OF DIFFUSION COEFFICIENTS AND ACTIVATION ENERGIES FOR AG DIFFUSION IN SILICON CARBIDE

  • KIM, BONG GOO;YEO, SUNGHWAN;LEE, YOUNG WOO;CHO, MOON SUNG
    • Nuclear Engineering and Technology
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    • v.47 no.5
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    • pp.608-616
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    • 2015
  • The migration of silver (Ag) in silicon carbide (SiC) and $^{110m}Ag$ through SiC of irradiated tristructural isotropic (TRISO) fuel has been studied for the past three to four decades. However, there is no satisfactory explanation for the transport mechanism of Ag in SiC. In this work, the diffusion coefficients of Ag measured and/or estimated in previous studies were reviewed, and then pre-exponential factors and activation energies from the previous experiments were evaluated using Arrhenius equation. The activation energy is $247.4kJ{\cdot}mol^{-1}$ from Ag paste experiments between two SiC layers produced using fluidized-bed chemical vapor deposition (FBCVD), $125.3kJ{\cdot}mol^{-1}$ from integral release experiments (annealing of irradiated TRISO fuel), $121.8kJ{\cdot}mol^{-1}$ from fractional Ag release during irradiation of TRISO fuel in high flux reactor (HFR), and $274.8kJ{\cdot}mol^{-1}$ from Ag ion implantation experiments, respectively. The activation energy from ion implantation experiments is greater than that from Ag paste, fractional release and integral release, and the activation energy from Ag paste experiments is approximately two times greater than that from integral release experiments and fractional Ag release during the irradiation of TRISO fuel in HFR. The pre-exponential factors are also very different depending on the experimental methods and estimation. From a comparison of the pre-exponential factors and activation energies, it can be analogized that the diffusion mechanism of Ag using ion implantation experiment is different from other experiments, such as a Ag paste experiment, integral release experiments, and heating experiments after irradiating TRISO fuel in HFR. However, the results of this work do not support the long held assumption that Ag release from FBCVD-SiC, used for the coating layer in TRISO fuel, is dominated by grain boundary diffusion. In order to understand in detail the transport mechanism of Ag through the coating layer, FBCVD-SiC in TRISO fuel, a microstructural change caused by neutron irradiation during operation has to be fully considered.

Determination of Kinetic Parameters in Coal Weathering Processes

  • Yun, Yongseung
    • Proceedings of the Korea Society for Energy Engineering kosee Conference
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    • 1993.11a
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    • pp.31-36
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    • 1993
  • Three different methods were employed to measure the degree of aerial oxidation in coal and the resulting oxidation/weathering indices were applied to obtain kinetic parameters of aerial oxidation processes, The index (i.e., slurry pH, Free Swelling Index, weight gain) values were subjected to kinetic analysis based on power-law Arrhenius type reaction model. The results show that activation energy of the aerial oxidation in 20-29$0^{\circ}C$ is in the range of 12-16 ㎉/㏖ and the agreement among three techniques is remarkable. The first order kinetic model is suitable in describing low temperature aerial oxidation process, except in the FSI case where the zero order expression is the best one.

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Kinetic Analyses on Thermal Degradation of Epoxy Based Adhesive for Packaging Application (센서 패키지용 고분자 접착제의 열화 거동 분석)

  • Kim, Yeong K.;Lee, Yoon-Sun
    • Journal of the Microelectronics and Packaging Society
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    • v.24 no.1
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    • pp.67-73
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    • 2017
  • An analysis of thermal degradation of epoxy based adhesive performed by thermogravimetry tests are presented in this study. Six different heating rates were employed for the weight change measurements. Based on the data, an Arrhenius type modeling equation was developed by calculating activation energies and proportional constants, and $n^{th}$ polynomial function was adopted to predict the weight change rates. The prediction results by the modeling was compared with the data using the average activation energy. It was found that the activation energy at the each heating rate was not same due to the different degradation kinetics, especially at the high heating rate. To overcome this pitfall, a new approach using exponential function series was introduced and employed. The calculation results showed very good agreements with the test data regardless of the heating rates.

Mathematical Analysis on TTI's Estimation Accuracy of Food Shelf Life Depending on its Discrepancy in Temperature Dependence (상호 온도의존성의 차이에 따른 TTI의 식품 shelf life 예측 정확성에 대한 수리적 분석)

  • Kang, Jin Won;Choi, Jung Hwa;Park, Soo Yeon;Kim, Min Jung;Kim, Min Jung;Lee, Man Hi;Jung, Seung Won;Lee, Seung Ju
    • KOREAN JOURNAL OF PACKAGING SCIENCE & TECHNOLOGY
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    • v.20 no.3
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    • pp.85-89
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    • 2014
  • TTI is a small label of which the color changes by time-temperature history during food storage. The food shelf life (SL) was compared with that of TTI, the time for TTI to reach the end-point of its color change, for the various discrepancies in two Arrhenius activation energies (Ea), an important parameter of temperature dependence. The SL of TTI and food were mathematically simulated, based on zero-order and first-order kinetics, respectively. In the case Ea of food was smaller than that of TTI, the SL of food was larger than that of TTI, meaning TTI reaches the end-point of color change earlier even though food is still fresh. In the case of Ea of food > Ea of TTI, the food reaches the SL earlier than the TTI. In addition, the magnitude of ${\Delta}Ea$ between food and TTI led to the bigger ${\Delta}SL$. To be safe, $SL_{Food}$ > $SL_{TTI}$ would be practical although $SL_{Food}{\fallingdotseq}SL_{TTI}$ is ideal.

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An improvement on the concrete exothermic models considering self-temperature duration

  • Zhu, Zhenyang;Chen, Weimin;Qiang, Sheng;Zhang, Guoxin;Liu, Youzhi
    • Computers and Concrete
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    • v.19 no.6
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    • pp.659-666
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    • 2017
  • Based on the Arrhenius equations, several hydration exothermic models that precisely calculate the influence of concrete's self-temperature duration on its hydration exothermic rate have been presented. However, the models' convergence is difficult to achieve when applied to engineering projects, especially when the activation energy of the Arrhenius equation is precisely considered. Thus, the models' convergence performance should be improved. To solve this problem and apply the model to engineering projects, the relationship between fast iteration and proper expression forms of the adiabatic temperature rise, the coupling relationship between the pipe-cooling and hydration exothermic models, and the influence of concrete's self-temperature duration on its mechanical properties were studied. Based on these results, the rapid convergence of the hydration exothermic model and its coupling with pipe-cooling models were achieved. The calculation results for a particular engineering project show that the improved concrete hydration exothermic model and the corresponding mechanical model can be suitably applied to engineering projects.

Diffusion of Sodium Chloride in Chinese Cabbage during Salting (배추의 염절임중 소금의 확산에 관한 연구)

  • Cho, Hyung-Yong;Kim, Ju-Bong;Pyun, Yu-Ryang
    • Korean Journal of Food Science and Technology
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    • v.20 no.5
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    • pp.711-717
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    • 1988
  • The diffusivity of sodium chloride in Chinese cabbage was evaluated from its absorption data obtained by immersing the cabbage stalk in a salt solution. By using least squares method, the absorption and desorption diffusivity of NaCl in the cabbage stalk have been estimated to be $1.7{\times}10^{-11}$ and $11.6{\times}10^{-11}m^2/s$, respectively. The apparent diffusivity was not strongly dependent on the concentration of brine and the variety of Chinese cabbage. The influence of temperature on the apparent diffusivity could be expressed as the Arrhenius type equation, in which the activation energy was estimated to be 66 KJ/mol.

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