• Title/Summary/Keyword: kinetics

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Fractal kinetic characteristics of uranium leaching from low permeability uranium-bearing sandstone

  • Zeng, Sheng;Shen, Yuan;Sun, Bing;Tan, Kaixuan;Zhang, Shuwen;Ye, Wenhao
    • Nuclear Engineering and Technology
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    • v.54 no.4
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    • pp.1175-1184
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    • 2022
  • The pore structure of uranium-bearing sandstone is one of the critical factors that affect the uranium leaching performance. In this article, uranium-bearing sandstone from the Yili Basin, Xinjiang, China, was taken as the research object. The fractal characteristics of the pore structure of the uranium-bearing sandstone were studied using mercury intrusion experiments and fractal theory, and the fractal dimension of the uranium-bearing sandstone was calculated. In addition, the effect of the fractal characteristics of the pore structure of the uranium-bearing sandstone on the uranium leaching kinetics was studied. Then, the kinetics was analyzed using a shrinking nuclear model, and it was determined that the rate of uranium leaching is mainly controlled by the diffusion reaction, and the dissolution rate constant (K) is linearly related to the pore specific surface fractal dimension (DS) and the pore volume fractal dimension (DV). Eventually, fractal kinetic models for predicting the in-situ leaching kinetics were established using the unreacted shrinking core model, and the linear relationship between the fractal dimension of the sample's pore structure and the dissolution rate during the leaching was fitted.

Numerical Simulations of Subcritical Reactor Kinetics in Thermal Hydraulic Transient Phases

  • J. Yoo;Park, W. S.
    • Proceedings of the Korean Nuclear Society Conference
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    • 1998.05a
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    • pp.149-154
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    • 1998
  • A subcritical reactor driven by a linear proton accelerator has been considered as a nuclear waste incinerator at Korea Atomic Energy Research Institute(KAERI). Since the multiplication factor of a subcritical reactor is less than unity, to compensate exponentially decreasing fission neutrons from spallation reactions are essentially required for operating the reactor in its steady state. furthermore, the profile of accelerator beam currents is very important in controlling a subcritical reactor, because the reactor power varies in accordance of the profile of external neutrons. We have developed a code system to find numerical solutions of reactor kinetics equations, which are the simplest dynamic model for controlling reactors. In a due course of our previous numerical study of point kinetics equations for critical reactors, however, we learned that the same code system can be used in studying dynamic behavior of the subcritical reactor. Our major motivation of this paper is to investigate responses of subcritical reactors for small changes in thermal hydraulic parameters. Building a thermal hydraulic model for the subcritical reactor dynamics, we performed numerical simulations for dynamic responses of the reactor based on point kinetics equations with a source term. Linearizing a set of coupled differential equations for reactor responses, we focus our research interest on dynamic responses of the reactor to variations of the thermal hydraulic parameters in transient phases.

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Detonation Wave Simulation of Thermally Cracked JP-7 Fuel/Oxygen Mixture using Induction Parameter Modeling (Induction Parameter Modeling을 이용한 열 분해된 JP-7 연료 /산소 혼합기의 데토네이션 파 해석)

  • Cho, Deok-Rae;Shin, Jae-Ryul;Choi, Jeong-Yeol;Yang, Vigor
    • Journal of the Korean Society for Aeronautical & Space Sciences
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    • v.37 no.4
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    • pp.383-391
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    • 2009
  • The detonation wave characteristics of JP-7 and oxygen mixture is investigated by one-step induction parameter model (IPM) obtained from a detailed chemistry mechanism. A general procedure of obtaining reliable one-step kinetics IPM for hydrocarbon mixture from the fully detailed chemistry is described in this study. The IPM is obtained by the reconstruction of the induction time database obtained from a detailed kinetics library. The IPM was confirmed by the comparison of the induction time calculations with that from detailed kinetics. The IPM is later implemented to a fluid dynamics code and applied for the numerical simulation of detonation wave propagation. The numerical results show the detailed characteristics of the detonation wave propagation in JP-7 and oxygen mixture at affordable computing time, which is not be possible by the direct application of the detailed chemical kinetics mechanism of hydrocarbon fuel combustion.

Rheological properties and crystallization kinetics of polypropylene block copolymer with repeated extrusion

  • Sung Yu-taek;Seo Won Jin;Kim Jong Sung;Kim Woo Nyon;Kwak Dong-Hwan;Hwang Tae-Won
    • Korea-Australia Rheology Journal
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    • v.17 no.1
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    • pp.21-25
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    • 2005
  • Rheological properties and crystallization kinetics of the polypropylene (PP) block copolymer and recycled PP block copolymer were studied by advanced rheometric expansion system (ARES), differential scanning calorimetry (DSC), and optical microscopy. In the study of the dynamic rheology, it is observed that the storage modulus and loss modulus for the PP block copolymer and recycled PP block copolymer did not change with frequency. In the study of the effect of the repeated extrusion on the crystallization rate, half crystallization time of the PP samples was increased with the number of repeated extrusion in isothermal crystallization temperature ($T_c$). From the isothermal crystallization kinetics study, the crystallization rate was decreased with the increase of the number of repeated extrusion. Also, from the result of Avrami plot, the overall crystallization rate constant (K) was decreased with the increase of the number of the repeated extrusion. From the study of the optical microscopy, the size of the spherulite of the PP samples did not change significantly with the number of repeated extrusion. However, it was clearly observed that the number of the spherulite growth sites was decreased with the number of repeated extrusion. From the results of the crystallization rate, isothermal crystallization kinetics, Avrami plots, and optical microscopy, it is suggested that the crystallization rate of the PP block copolymer is decreased with the increase of the number of repeated extrusion.

Biodegradation Kinetics of Phenol and pcresol by Micrococcus sp. M1 (Micrococcus sp. M1에 의한 Phenol과 p-Creso의 생분해 Kinetics)

  • Son, Hong-Joo;Jang, Woong-Seok;Lee, Geon;Lee, Sang-Joon
    • Journal of Environmental Science International
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    • v.6 no.2
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    • pp.153-163
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    • 1997
  • In order to fad the most fitted biodegradation model, biodegradation kinetics model to the initial phenol and p-cresot concentrations were investigated and had been fitted by the linear regression. Bacteria capable of degrading p-cresol were isolated from soil by enrichment culture technique. Among them, strain Ml capable of degradillg p.rcresol has also degraded phenal and was identified as the genus Micrococcus from the results from of taxonomical studies. The optimal tonditlons for the biodegradation of phenal and p-cresol by Micrococcus sp. Ml were $NH_4NO_3$ 0.05%, pH 7.0, 3$0^{\circ}C$, respectively, and medium volume 100m1/250m1 shaking flask. iwicrococcus sp. Ml was able to grow on phenal concentration up to 14mM and p-cresol concelltration up to 0.8mM. With increasing substrate concentraction, the lag period increased, but the maximum specific growth rates decreased. The yield coefficient decreased with increasing substrate concentation. The biodegradation kinetics of phenol and p-cresol were best described by Monod with growth model for every experimented concentration. In cultivation of mixed substrate, p-cresol was degraded first and phenol was second. This result implies that p-cresol and phenol was not degraded simultaneously.

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In Vivo $^{13}C$-NMR Spectroscopic Study of Polyhydroxyalkanoic Acid Degradation Kinetics in Bacteria

  • Oh, Jung-Sook;Choi, Mun-Hwan;Yoon, Sung-Chul
    • Journal of Microbiology and Biotechnology
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    • v.15 no.6
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    • pp.1330-1336
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    • 2005
  • Polyhydroxyalkanoic acid (PHA) inclusion bodies were analyzed in situ by $^{13}C$-nuclear magnetic resonance ($^{13}C$-NMR) spectroscopy. The PHA inclusion bodies studied were composed of poly(3-hydroxybutyrate) or poly(3hydroxybutyrate-co-4-hydroxybutyrate), which was accumulated in Hydrogenophaga pseudoflava, and medium-chain-length PHA (MCL-PHA), which was accumulated in Pseudomonas fluorescens BM07 from octanoic acid or 11-phenoxyundecanoic acid (11-POU). The quantification of the $^{13}C$-NMR signals was conducted against a standard compound, sodium 2,2-dimethyl-2-silapentane-5-sulfonate (DSS). The chemical shift values for the in vivo NMR spectral peaks agreed well with those for the corresponding purified PHA polymers. The intracellular degradation of the PHA inclusions by intracellular PHA depolymerase(s) was monitored by in vivo NMR spectroscopy and analyzed in terms of first-order reaction kinetics. The H. pseudoflava cells were washed for the degradation experiment, transferred to a degradation medium without a carbon source, but containing 1.0 g/l ammonium sulfate, and cultivated at $35^{\circ}C$ for 72 h. The in vivo NMR spectra were obtained at $70^{\circ}C$ for the short-chain-length PHA cells whereas the spectra for the aliphatic and aromatic MCL-PHA cells were obtained at $50^{\circ}C\;and\;80^{\circ}C$, respectively. For the H. pseudoflava cells, the in vivo NMR kinetics analysis of the PHA degradation resulted in a first-order degradation rate constant of 0.075/h ($r^{2}$=0.94) for the initial 24 h of degradation, which was close to the 0.050/h determined when using a gas chromatographic analysis of chloroform extracts of sulfuric acid/methanol reaction mixtures of dried whole cells. Accordingly, it is suggested that in vivo $^{13}C$-NMR spectroscopy is an important tool for studying intracellular PHA degradation in terms of kinetics.

Kinetics of In-situ Degradation of Nerve Agent Simulants and Sarin on Carbon with and without Impregnants

  • Saxena, Amit;Sharma, Abha;Singh, Beer;Suryanarayana, Malladi Venkata Satya;Mahato, Timir Haran;Sharma, Mamta;Semwal, Rajendra Prasad;Gupta, Arvind Kumar;Sekhar, Krishnamurthy
    • Carbon letters
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    • v.6 no.3
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    • pp.158-165
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    • 2005
  • Room temperature kinetics of degradation of nerve agent simulants and sarin, an actual nerve agent at the surface of different carbon based adsorbent materials such as active carbon grade 80 CTC, modified whetlerite containing 2.0 and 4.0 % NaOH, active carbon with 4.0 % NaOH, active carbon with 10.0 % Cu (II) ethylenediamine and active carbon with 10.0 % Cu (II) 1,1,1,5,5,5-hexafluoroacetylacetonate were studied. The used adsorbent materials were characterized for surface area and micropore volume by $N_2$ BET. For degradation studies solution of simulants of nerve agent such as dimethyl methylphosphonate (DMMP), diethyl chlorophosphate (DEClP), diethyl cyanophosphate (DECnP) and nerve agent, i.e., sarin in chloroform were prepared and used for the uniform adsorption on the adsorbent systems using their incipient volume at room temperature. Degradation kinetics was monitored by GC/FID and was found to be following pseudo first order reaction. Kinetics parameters such as rate constant and half life were calculated. Half life of degradation with modified whetlerite (MWh/NaOH) system having 4.0 % NaOH was found to be 1.5, 7.9, 1206 and 20 minutes for DECnP, DEClP, DMMP and sarin respectively. MWh/NaOH system showed maximum degradation of simulants of nerve agents and sarin to their hydrolysis products. The reaction products were characterized using NMR technique. MWh/NaOH adsorbent was also found to be active against sulphur mustard.

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An Experimental and Modeling Study on the Oxidation Kinetics of Nitric Oxide over Platinum-based Catalysts (백금계 촉매상에서 산화질소(NO)의 산화반응속도에 관한 실험 및 모델링 연구)

  • Kim, Young-Deuk;Jeong, Soo-Jin;Kim, Woo-Seung
    • Transactions of the Korean Society of Automotive Engineers
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    • v.20 no.5
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    • pp.71-80
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    • 2012
  • To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

Sorption and Desorption Kinetics of Naphthalene and Phenanthrene on Black Carbon in Sediment (퇴적물내 Black Carbon에 대한 Naphthalene과 Phenanthrene의 수착 및 탈착동력학)

  • Oh, Sang-Hwa;Wu, Qi;Song, Dong-Ik;Shin, Won-Sik
    • Journal of Soil and Groundwater Environment
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    • v.16 no.6
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    • pp.79-94
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    • 2011
  • Black carbon (BC), a kind of high surface area carbonaceous material (HSACM), was isolated from Andong lake sediment. Sorption and desorption kinetics of naphthalene (Naph) and phenanthrene (Phen) in organic carbon (OC) and BC in the Andong lake sediment were investigated. Several kinetic models such as one-site mass transfer model (OSMTM), two-compartment first-order kinetic model (TCFOKM), and a newly proposed modified two-compartment first-order kinetic model (MTCFOKM) were used to describe the sorption and desorption kinetics. The MTCFOKM was the best fitting model. The MTCFOKM for sorption kinetics showed that i) the sorbed amounts of PAHs onto BC were higher than those onto OC, consistent with BET surface area; ii) the equilibration time for sorption onto BC was longer than those onto OC due to smaller size of micropore ($11.67{\AA}$) of BC than OC ($38.18{\AA}$); iii) initial sorption velocity of BC was higher than OC; and iv) the slow sorption velocity in BC caused the later equilibrium time than OC even though the fast sorption velocity was early completed in both BC and OC. The MTCFOKM also described the desorption of PAHs from the OC and BC well. After desorption, the remaining fractions of PAHs in BC were higher than those in OC due to stronger PAHs-BC binding. The remaining fractions increased with aging for both BC and OC.

Salinity Effect on the Equilibria and Kinetics of the Formation of CO2 and R-134a Gas Hydrates in Seawater

  • Johanna, Lianna;Kim, A Ram;Jeong, Guk;Lee, Jea-Keun;Lee, Tae Yun;Lim, Jun-Heok;Won, Yong Sun
    • Korean Journal of Materials Research
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    • v.26 no.7
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    • pp.382-387
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    • 2016
  • Gas hydrates are crystalline solids in which gas molecules (guests) are trapped in water cavities (hosts) that are composed of hydrogen-bonded water molecules. During the formation of gas hydrates in seawater, the equilibria and kinetics are then affected by salinity. In this study, the effects of salinity on the equilibria of $CO_2$ and R134-a gas hydrates has been investigated by tracing the changes of operating temperature and pressure. Increasing the salinity by 1.75% led to a drop in the equilibrium temperature of about $2^{\circ}C$ for $CO_2$ gas hydrate and $0.38^{\circ}C$ for R-134a gas hydrate at constant equilibrium pressure; in other words, there were rises in the equilibrium pressure of about 1 bar and 0.25 bar at constant equilibrium temperature, respectively. The kinetics of gas hydrate formation have also been investigated by time-resolved in-situ Raman spectroscopy; the results demonstrate that the increase of salinity delayed the formation of both $CO_2$ and R134-a gas hydrates. Therefore, various ions in seawater can play roles of inhibitors for gas hydrate formation in terms of both equilibrium and kinetics.