• 제목/요약/키워드: activation energies

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Kinetic Investigation of CO2-CH4 Reaction over Ni/La2O3 Catalyst using Photoacoustic Spectroscopy

  • Oh, Hyun-Jin;Kang, Jin-Gyu;Heo, Eil;Lee, Sung-Han;Choi, Joong-Gill
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2615-2620
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    • 2014
  • Ni/$La_2O_3$ with a high dispersion was prepared by reduction of $La_2O_3$ perovskite oxide to examine the catalytic activity for the $CO_2-CH_4$ reaction. The Ni/$La_2O_3$ catalyst was found to be highly active for the reaction. The ratios of $H_2$/CO were measured in a flow of the reaction mixture containing $CO_2/CH_4$/Ar using an on-line gas chromatography system operated at 1 atm and found to be varied with temperature between 0.66 and 1 in the temperature range of $500-800^{\circ}C$. A kinetic study of the catalytic reaction was performed in a static reactor at 40 Torr total pressure of $CO_2/CH_4/N_2$ by using a photoacoustic spectroscopy technique. The $CO_2$ photoacoustic signal varying with the concentration of $CO_2$ during the catalytic reaction was recorded as a function of time. Rates of $CO_2$ disappearance in the temperature range of $550-700^{\circ}C$ were obtained from the changes in the $CO_2$ photoacoustic signal at early reaction stage. The plot of ln rate vs. 1/T showed linear lines below and above $610^{\circ}C$. Apparent activation energies were determined to be 10.4 kcal/mol in the temperature range of $550-610^{\circ}C$ and 14.6 kcal/mol in the temperature range of $610-700^{\circ}C$. From the initial rates measured at $640^{\circ}C$ under various partial pressures of $CO_2$ and $CH_4$, the reaction orders were determined to be 0.43 with respect to $CO_2$ and 0.33 with respect to $CH_4$. The kinetic results were compared with those reported previously and used to infer a reaction mechanism for the Ni/$La_2O_3$-catalyzed $CO_2-CH_4$ reaction.

Adsorption Characteristics and Parameters of Acid Black and Quinoline Yellow by Activated Carbon (활성탄에 의한 Acid Black과 Quinoline Yellow의 흡착특성 및 파라미터)

  • Yi, Kyung Ho;Hwang, Eun Jin;Baek, Woo Seung;Lee, Jong-Jib;Dong, Jong-In
    • Clean Technology
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    • v.26 no.3
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    • pp.186-195
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    • 2020
  • The isothermal adsorption, dynamic, and thermodynamic parameters of Acid black (AB) and Quinoline yellow (QY) adsorption by activated carbon were investigated using the initial concentration, contact time, temperature, and pH of the dyes as adsorption parameters. The adsorption equilibrium data fits the Freundlich isothermal adsorption model, and the calculated Freundlich separation factor values found that activated carbon can effectively remove AB and QY. Comparing the kinetic data showed that the pseudo second order model was within 10% error in the adsorption process. The intraparticle diffusion equation results were divided into two straight lines. Since the slope of the intraparticle diffusion line was smaller than the slope of the boundary layer diffusion line, it was confirmed that intraparticle diffusion was the rate-controlling step. The thermodynamic experiments indicated that the activation energies of AB and QY were 19.87 kJ mol-1 and 14.17 kJ mol-1, which corresponded with the physical adsorption process (5 ~ 40 kJ mol-1). The adsorption reaction was spontaneous because the free energy change in the adsorption of AB and QY by activated carbon was negative from 298 to 318 K. As the temperature increased, the free energy value decreased resulting in higher spontaneity. Adsorption of AB and QY by activated carbon showed the highest adsorption removal rate at pH 3 due to the effect of anions generated by dissociation. The adsorption mechanism was electrostatic attraction.

Microstructure and Electrical Properties of ZnO-Zn2BiVO6-Mn3O4 Varistor (ZnO-Zn2BiVO6-Mn3O4 바리스터의 미세구조와 전기적 특성)

  • Hong, Youn-Woo;Ha, Man-Jin;Paik, Jong-Hoo;Cho, Jeong-Ho;Jeong, Young-Hun;Yun, Ji-Sun
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.31 no.5
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    • pp.313-319
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    • 2018
  • This study introduces a new investigation report on the microstructural and electrical property changes of $ZnO-Zn_2BiVO_6-Mn_3O_4$ (ZZMn), where 0.33 mol% of $Mn_3O_4$ and 0.5 mol% of $Zn_2BiVO_6$ were added to ZnO (99.17 mol%) as liquid phase sintering aids. $Zn_2BiVO_6$ contributes to the decrease of sintering temperatures by up to $800^{\circ}C$, and segregates its particles at the grain boundary, while $Mn_3O_4$ enhances ${\alpha}$, the nonlinear coefficient, of varistor properties up to ${\alpha}=62$. In comparison, when the sintering temperature is increased from $800^{\circ}C$ to $1,000^{\circ}C$, the resistivity of ZnO grains decreases from $0.34{\Omega}cm$ to $0.16{\Omega}cm$, and the varistor property degrades. Oxygen vacancy ($V_o^{\bullet}$) (P1, 0.33~0.36 eV) is formed as a dominant defect. Two different kinds of grain boundary activation energies of P2 (0.51~0.70 eV) and P3 (0.70~0.93 eV) are formed according to different sintering temperatures, which are tentatively attributed to be $ZnO/Zn_2BiVO_6$-rich interface and ZnO/ZnO interface, respectively. Accordingly, this study introduces a progressive method of manufacturing ZnO chip varistors by way of sintering ZZMn-based varistor under $900^{\circ}C$. However, to procure a higher reliability, an in-depth study on the multi-component varistors with double-layer grain boundaries should be executed.

Novel synthesis of nanocrystalline thin films by design and control of deposition energy and plasma

  • Han, Jeon G.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.77-77
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    • 2016
  • Thin films synthesized by plasma processes have been widely applied in a variety of industrial sectors. The structure control of thin film is one of prime factor in most of these applications. It is well known that the structure of this film is closely associated with plasma parameters and species of plasma which are electrons, ions, radical and neutrals in plasma processes. However the precise control of structure by plasma process is still limited due to inherent complexity, reproducibility and control problems in practical implementation of plasma processing. Therefore the study on the fundamental physical properties that govern the plasmas becomes more crucial for molecular scale control of film structure and corresponding properties for new generation nano scale film materials development and application. The thin films are formed through nucleation and growth stages during thin film depostion. Such stages involve adsorption, surface diffusion, chemical binding and other atomic processes at surfaces. This requires identification, determination and quantification of the surface activity of the species in the plasma. Specifically, the ions and neutrals have kinetic energies ranging from ~ thermal up to tens of eV, which are generated by electron impact of the polyatomic precursor, gas phase reaction, and interactions with the substrate and reactor walls. The present work highlights these aspects for the controlled and low-temperature plasma enhanced chemical vapour disposition (PECVD) of Si-based films like crystalline Si (c-Si), Si-quantum dot, and sputtered crystalline C by the design and control of radicals, plasmas and the deposition energy. Additionally, there is growing demand on the low-temperature deposition process with low hydrogen content by PECVD. The deposition temperature can be reduced significantly by utilizing alternative plasma concepts to lower the reaction activation energy. Evolution in this area continues and has recently produced solutions by increasing the plasma excitation frequency from radio frequency to ultra high frequency (UHF) and in the range of microwave. In this sense, the necessity of dedicated experimental studies, diagnostics and computer modelling of process plasmas to quantify the effect of the unique chemistry and structure of the growing film by radical and plasma control is realized. Different low-temperature PECVD processes using RF, UHF, and RF/UHF hybrid plasmas along with magnetron sputtering plasmas are investigated using numerous diagnostics and film analysis tools. The broad outlook of this work also outlines some of the 'Grand Scientific Challenges' to which significant contributions from plasma nanoscience-related research can be foreseen.

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Anomalous Effect of Hydrogenation on the Optical Characterization $In_{0.5}Ga_{0.5}As$ Quantum Dot Infrared Photodetectors (MBE로 성장된 $In_{0.5}Ga_{0.5}As/GaAs$ 양자점 원적외선 수광소자의 수소화 처리가 광학적 특성에 미치는 특이영향)

  • Lim J.Y.;Song J.D.;Choi W.J.;Cho W.J.;Lee J.I.;Yang H.S.
    • Journal of the Korean Vacuum Society
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    • v.15 no.2
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    • pp.223-230
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    • 2006
  • We have investigated the characteristics of hydrogen (H) plasma treated quantum dot infrared photodetectors (QDIPs). The structure used in this study consists of 3 stacked, self assembled $In_{0.5}Ga_{0.5}As/GaAs$ QD layer separated by GaAs barrier layers that were grown by molecular beam epitaxy. Optical characteristics of QDIPs, such as photoluminescence (PL) spectra and photocurrent spectra, have been studied and compared with each other for the as grown and H plasma treated QDIPs. H plasma treatment, resulted in the splitting of PL peak, which can be attributed to the redistribution of the size of QDs. The activation energies estimated from the temperature dependence of integrated PL intensity for as grown and H plasma treated QDIPs are found to be in good agreement with those determined from corresponding peaks of photocurrent spectra. It is also noted that photocurrent is detected up to 130 K for the H plasma treated QDIP, suggesting the future possibility for the development of infrared photodetectors with high temperature operation.

Hydrolysis of Lactose in Milk by Microencapsulated ${\beta}-Galactosidase$ (Microencapsulated ${\beta}-Galactosidase$에 의한 우유 유당의 가수 분해)

  • Baik, Ok-Ryun;Uy, Ro-Sa;Byun, Si-Myung
    • Korean Journal of Food Science and Technology
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    • v.12 no.1
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    • pp.45-52
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    • 1980
  • The nylon (poly 6, 10) microcapsules containing ${\beta}-galactosidase$ were obtained by the interfacial polymerization of 1, 6-diaminohexane and sebacoyl chloride with ${\beta}-galactosidase$ from Escherichia coli. They were generally spherical and had a mean diameter of $80{\mu}$ with 45 % of the activity recovery. In particular, there was no transport hamper of lactose through the membrane of microcapsules. The characteristics of the microencapsulated enzyme were similar to those of soluble enzyme optimal pHs, $7.0{\sim}7.2$ for the soluble and $7.3{\sim}7.5$ for the microencapsulated ; optimal temperatures, $50^{\circ}C$ for both ; apparent $K_m,\;3.33{\times}10^{-4}(on ONPG),$ $2.86{\times}10^{-3}$ M(on lactose) for the soluble and $5.28{\times}10^{-4}$ (on ONPG), $4.25{\times}10^{-3}$ M (on lactose) for the microencapsulated ; activation energies, 8.94 for the soluble and 9.78 Kcal/mole for the microencapsulated enzyme. Using this microencapsulated ${\beta}-galactosidase$, hydrolyses of lactose and milk lactose were carried out and 80 % of 5 % lactose solution and 70 % of lactose in skim milk were hydrolyzed in 40 hr at $27^{\circ}C$. The reusability and operational stability showed that the remaining activity was 50 % of the original activity after 5 runs and 120 hr of total operating time at $27^{\circ}C$.

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The Oxidation Stability of Virgin and Pure Olive Oil on Autoxidation and Thermal Oxidation (자동산화 및 가열산화에 대한 압착 및 혼합 올리브유의 산화안정성)

  • Moon, Joo-Soo;Lee, Ok-Hwan;Son, Jong-Youn
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.34 no.1
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    • pp.93-98
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    • 2005
  • Total tocopherol and phenol contents were determined for virgin and pure oilve oil, and their autoxidation and thermal oxidation were compared with those of commercial soybean oil, in the presence or absence of fluorescent light. The total tocopherol contents of virgin, pure olive oil, and soybean oil were 15.7, 11.2, and 80.7 mg/100 g, respectively. Their total phenol contents were 10.4, 1.6 and 0.5 mg/l00 g, respectively. In autoxidation under dark place at 45$^{\circ}C$, the oxidative stability of the substrate oils decreased in order of virgin oilve oil, pure olive oil, and soybean oil. The average temperature coefficients of the virgin, pure olive oil and soybean oil in the range of 45∼$65^{\circ}C$ were 1.73, 1.83 and 1.64, and the activation energies were 26.86, 29.49, and 24.07 KJ/mol, respectively. In temperature range of 45∼$65^{\circ}C$, pure olive oil was the most susceptible to temperature change, whereas soybean oil the least. In autoxidation under fluorescent light at 45$^{\circ}C$, the oxidative stability of substrate oils decreased in the order of soybean oil, pure olive oil, and virgin olive oil. In thermal oxidation at 18$0^{\circ}C$, the oxidative stability of substrate oils decreased in order of pure olive oil, virgin olive oil, and soybean oil.

Growth of Li2B4O7 Single Crystal and Its Thermoluminescent Properties (Li2B4O7 단결정 성장과 열형광 특성)

  • Park, Kang-Soo;Ahn, Jung-Keun;Kim, Dong-Jin;Hwang, Yoon-Hwae;Kim, Hyung-Kook;Park, Myeong-Hwan;Kang, Hee-Dong;Kim, Do-Sung
    • Journal of Sensor Science and Technology
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    • v.12 no.1
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    • pp.16-23
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    • 2003
  • Thermoluminescent properties of $Li_2B_4O_7$ single crystal grown by Czochralski method have been investigated. The high quality $Li_2B_4O_7$ single crystal without core was obtained at rotation speed of 10 rpm for seed crystal and pulling speed below $0.18\;mm{\cdot}h^{-1}$. The structure of $Li_2B_4O_7$ single crystal was classified as tetragonal by XRD analysis. The TL glow curve was composed with three overlapped peaks which can be easily deconvoluted and the TL response of $Li_2B_4O_7$ single crystal TLD to X-ray radiation is linear within the range of $50\;mGy{\sim}1.5\;Gy$. Activation energies of three TL glow peaks analyzed by the various heating rates method and PL spectrum were 0.93, 1.78 and 2.25 eV, respectively.

Extraction of Valuable Metals from Spent Desulfurizing Catalyst (탈황(脫黃) 폐촉매(廢觸媒)로부터 유가금속(有價金屬) 추출(抽出))

  • Pradhan, Debabrata;Kim, Dong-Jin;Baik, Seung-Bai;Lee, Seoung-Won
    • Resources Recycling
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    • v.20 no.3
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    • pp.48-54
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    • 2011
  • Sulphuric acid leaching was conducted to extract the metal values from spent refinery catalyst. More than 95% of Ni and V and 30% of Mo could be leached out in 1 M sulphuric acid and 1 hr of leaching time. The decrease in Mo leaching was due to typical characteristic of Mo matrix. The activation energies of the leaching reactions showed the dissolution process follows a diffusion control mechanism. In order to leach out all Mo, further the leaching experiments were conducted with sulfur free spent refinery catalyst. For sulfur free spent refinery catalyst, a two step process of leaching with 1 M sulphuric acid followed by sodium carbonate washing showed better leaching than a two step leaching process with sodium carbonate followed by sulphuric acid washing, with almost 99% leaching of Ni, Mo and V. Solvent extraction using LIX 841 were conducted for a leach liquor containing Ni, 2 g/L; V, 9 g/L, Mo, 0.6 g/L. More than 98% of Mo was extracted from the leach liquor at A:O ratio of 5:2 in a 2 stage process. Similarly V was extracted at A:O ratio of 5:3 in a 2 stage process with 82% of total V extraction.

The Roles of Gold Plate (140${\mu}{\textrm}{m}$) Loaded on TLD-100 Chips in the High Energy Radiation Beams (고에너지 광자선속에서 TLD-100 chip 위에 있는 금박막(140 ${\mu}{\textrm}{m}$) 역할)

  • Vahc, Young-Woo;Park, Kyung Ran.
    • Progress in Medical Physics
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    • v.6 no.2
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    • pp.51-60
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    • 1995
  • Lithium Fluoride (LiF; TLD-100) crystal chips are normally used as thermolu minescence dosimeters (abbreviated as NC-100) for estimating the absorbed dose to the skin of a patient or in a solid water phantom undergoing radiotherapy with megavoltage photon (6 and 15MV) beams. In general, investigation has revealed a reduction in the sensitivity of NC-100 chips after many runs through heating cycles. A TLD-100 chip laminated with gold plate (140${\mu}{\textrm}{m}$) on the upper surface layer of its face toward the photon beam (abbreviated as GC-100) has properties different from that of a NC-100 chip activated by incident photons and contaminant electrons with various lower energies coming from the gantry head and air. Activation of the valence band electrons of GC-100 chips by incident photons, positrons and electrons-which come from the gold plate by mainly pair production process and partly from Compton scattering-results in more enhanced signal intensity, higher response per monitor unit, as well as a good linearity with monitor units and independence of dose rate. Since the electron beams (6 and 15 MeV) do not have the probability of pair production process with gold plate, there is only a small difference (about a 3.3% increase for 15 MeV) in the signal gaps in the TL readout for electron beams between GC- and NC-100 chips. The 3.3% increase is entirely due to the buildup caused by the 140 m gold plate. The sensitivity of GC-100 chips is much more susceptible to high energy photon beams than electron one because of pair production. The interaction of high energy photon with a material of high atomic number, such as the good plate in this case, results in a considerably significant probability of pair production. The gold plate on the NC-100 chips acts as not only an intensifier of their signals but also acts as a filter of contaminant electrons in therapeutic high energy X-ray beams.

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