• Title/Summary/Keyword: Activation energies

검색결과 534건 처리시간 0.029초

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

  • 김영득;정수진;김우승
    • 한국자동차공학회논문집
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    • 제20권5호
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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 $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.

EFFECT OF TEMPERATURE ON FLUORESCENCE QUENCHING BY STEADY STATE AND TRANSIENT METHODS IN SOME ORGANIC LIQUID SCINTILLATORS

  • Giraddi, T.P.;Kadadevarmath, J.S.;Chikkur, G.C.;Rath, M.C.;Mukherjee, T.
    • Journal of Photoscience
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    • 제4권3호
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    • pp.97-103
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    • 1997
  • The effect of temperature on the fluorescence quenching of 2-(4-Methoxyphenyl)-5-(1-naphthyl)-1,3,4-oxadiazole (MPNO1), 2-(4-Methoxyphenyl)-5-(2-naphthyl)-1,3,4-oxadiazote(MPNO2), by aniline, and 2-Phenylindole (2-PI) by CCk, in toluene by steady state method and in benzene by time-resolved method have been carried out in the temperature range 30 - 70$\circ$C. The Stem-Volmer (S-V) plots, I$_0$/I against quencher concentration [Q] at different temperanares show positive deviations. The fluorescence lifetimes determined at different temperatures show no systematic variations and the variations being within the experimental error, the average values of lifetimes $ $\tau$ (t) are taken for further calculations. Rate constants such as Stem-Volmer quenching constants K$_sv}$, quenching rate parameters k$_q$ and k'$_q$, static quenching constant V and kinetic distance r are determined using the modified Stem-Volmer equation and sphere of action static quenching model. In order to see whether the reactions are diffusion limited, equations k$_q$ = e$^{-Eq/RT}$ and k'$_q$ = e$^{-Eq/RT}$ are used to determine the values of E$_q$ and E'$_q$, the activation energies for collisional quenching and the values of E$_q$ are 14.53. 17.28 and 16.20 kJ mole$^{-1}$ for MPNO1, MPNO2 and 2-PI respectively and the values of E'$_q$ are 14.62 and 17.73 for MPNO1 and MPNO2 respectively. From the magnitudes of various quantities it has been concluded that the reactions are diffusion limited and the observed positive deviations in the S-V plot are due to static and dynamic quenching.

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폴리에틸렌의 열분해 Kinetics (Thermo-Degradation Kinetics of Polyethylene)

  • 차왕석
    • 공업화학
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    • 제10권3호
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    • pp.432-437
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    • 1999
  • 폴리에틸렌 열분해실험을 반응기 크기가 $10cm^3$인 스테인레스 스틸 반응기에서 수행하였으며 이때 반응온도는 $390{\sim}450^{\circ}C$이었다. 열분해생성물인 반응생성물과 기체생성물을 분리하여 채취하였고 각 생성물의 분자량분포는 HPLC-GPC와 GC분석을 통해 얻었다. 열분해반응의 개시-종료, 전파-비전파반응, 즉 수소탈취반응, 사슬절단, 고분자물질과 라디칼과의 결합반응 등을 설명할 수 있는 random, specific 생성물의 분자랑분포에 대한 distribution balance식을 제안하였다. 말단절단 과정에 의해 저분자량의 비응축성 기체생성물 (C1~C5)이 생성되었으며 이 기체생성물의 평균분자량은 38이었다. 무작위절단과 말단절단의 속도매개변수 중의 하나인 활성화에너지는 각각 35, 17 kcal/mole 이었다.

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쌀보리 전분 호화액의 리올로지 특성 (Rheological Properties of Naked Barley Starches)

  • 박양균;노일환;김관;김성곤;이신영
    • 한국식품과학회지
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    • 제18권4호
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    • pp.278-282
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    • 1986
  • 쌀보리 품종인 송학과 영산 전분의 가열 호화액의 리올로지 특성을 비교하였다. $90^{\circ}C$에서 30분간 호화시킨 3,5,7 및 9% 전분 호화액은 모두 의가소성의 거동을 나타냈고, 점조도지수 K 및 항복을력 $\tau_y$ 값은 송학이 영산보다 컸으며 더 높은 농도의존성을 나타내었다. 전분농도의 증가에 따라 송학과 영산 모두 점조도지수 K값이 지수함수적으로 증가하였으며 5%근처에서는 기울기가 서로 다른 2개의 직선관계를 나타냈다. 아레니우스식에 의해 구한 활성화에너지는 7% 송학과 영산 전분용액에서 각각 4.098 및 3.71kcal/mole 이었다.

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혼합폐플라스틱의 열분해로부터 생성된 고분자성분의 열적분해 (Thermal Degradation of High Molecular Components Obtained from Pyrolysis of Mixed Waste Plastics)

  • 오세천;류재훈;곽현;배성열;이경환
    • 공업화학
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    • 제19권2호
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    • pp.191-198
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    • 2008
  • 혼합폐플라스틱의 열분해로부터 얻어진 고분자성분의 열적분해 특성에 대한 연구를 TGA와 GC-MS를 이용하여 수행하였다. 열적분해의 속도론적 연구는 $10{\sim}50^{\circ}C/min$ 사이의 여러 가열속도에서 비등온 질량감소 기술을 이용하여 수행하였으며 활성화 에너지 및 반응차수 등과 같은 속도 상수들에 대한 정보를 얻기 위하여 문헌에 제시된 여러 가지의 속도론 해석 방법을 이용하여 질량감소 곡선 및 그 미분 값을 해석하였다. 또한 회분식 열분해 반응기를 이용하여 반응온도 및 반응시간에 따른 액상 생성물의 수율변화를 고찰하였으며 GC-MS를 이용하여 반응온도의 증가에 따른 액상 생성물의 특성연구를 수행하였다.

열분석법에 의한 Al-2.1Li-2.9Cu합금이 석출현상에 미치는 In 첨가의 영향 (Effects of In on the Precipitation Phenomena of Al-2.1Li-2.9Cu Alloy by Differential Scanning Calorimetry)

  • 박태원;송영범;이용연
    • 열처리공학회지
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    • 제10권4호
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    • pp.237-245
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    • 1997
  • A study was conducted to examine the effects of In addition on the precipitation behaviors of Al-2.1Li-2.9Cu alloy by differential scanning calorimetry, transmission electron microscopy and micro-hardness tester. DSC analysis was measured over the temperature range of $25{\sim}550^{\circ}C$ at a heating rate of $2{\sim}20^{\circ}C$/min. The heat evolution peaks due to the formation of GP zone and ${\delta}$'phase shift to higher temperature and the peaks to $T_1$ and ${\theta}$'phases shift to lower temperature by In addition. From this result, it was proved that the formation of GP zone and ${\delta}$'phase is suppresed whereas that of $T_1$ and ${\theta}$'phases are accelerated by the In addition of 0.15wt%. The age hardening curve aged at $190^{\circ}C$ showed that the In bearing alloy(alloy B) has more faster age hardening response and a higher peak hardness than In-free alloy(alloy A), attributed to the fine and homogeneous distribution of $T_1$ and ${\theta}$'phases. The activation energies for the formation of ${\delta}$'phase in In-free and In-bearing alloys are 22.3kcal/mol and 18.6kcal/mol, respectively. Those for $T_1(+{\theta}^{\prime})$ phase of In-free and In-bearing alloys are 24.3 and 37.5kcal/mol, respectively. Quenched-in excess vacancies play an important role to the formation of precipitates.

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쌀전분 희석 호화액의 유동학적 특성 (Rheological Properties of Gelatinized Dilute Rice Starch Solutions)

  • 김영숙;김주봉;이신영;변유량
    • 한국식품과학회지
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    • 제16권1호
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    • pp.11-16
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    • 1984
  • 멥쌀 및 찹쌀 전분을 상압과 가압가열 및 알칼리 호화한 회석전분 호화액에 대해 유동특성을 검토하였다. 전분농도 $0.2{\sim}1.0%$의 저농도의 호화전분액은 지수법칙 유체의 유동거동을 나타내었으며 아밀로오스 함량에 따라 크게 좌우되어 아밀로오스 함량이 많은 멥쌀은 점성이 낮고 뉴우톤 유체의 경향을 나타내었으며 농도에 대한 영향이 작았다. 찹쌀 전분은 농도가 증가함에 따라 의가소성 성질이 강해졌으며 농도에 따라 급격히 점도가 증가하였다. 가압호화시킨 경우 찹쌀 전분 호화액의 점조도 지수 및 유동 거동 지수는 상압 호화액에 비하여 거의 변화가 없었으나 멥쌀 전분 호화액의 점조도 지수값은 현저히 증가하는 현상을 보였다. 가압 가열호화 및 알칼리 호화 용액은 상압 가열호화에 비해 훨씬 높은 점성을 보였다. 가열 호화 및 알칼리호화액의 겉보기 점도에 대한 온도의 영향을 검토해 본 결과 아레니우스식의 형태에 따름을 알 수 있었다.

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Photoluminescence of Nanocrystalline CdS Thin Films Prepared by Chemical Bath Deposition

  • Park, Wug-Dong
    • Transactions on Electrical and Electronic Materials
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    • 제11권4호
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    • pp.170-173
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    • 2010
  • Nanocrystalline cadmium sulfide (CdS) thin films were prepared using chemical bath deposition in a solution bath containing $CdSO_4$, $SC(NH_2)_2$, and $NH_4OH$. The CdS thin films were investigated using X-ray diffraction (XRD), photoluminescence (PL), and Fourier transform infrared spectroscopy (FTIR). The as-deposited CdS thin film prepared at $80^{\circ}C$ for 60 min had a cubic phase with homogeneous and small grains. In the PL spectrum of the 2,900 A-thick CdS thin film, the broad red band around 1.7 eV and the broad high-energy band around 2.7 eV are attributed to the S vacancy and the band-to-band transition, respectively. As the deposition time increases to over 90 min, the PL intensity from the band-to-band transition significantly increases. The temperature dependence of the PL intensity for the CdS thin films was studied from 16 to 300 K. The $E_A$ and $E_B$ activation energies are obtained by fitting the temperature dependence of the PL intensity. The $E_A$ and $E_B$ are caused by the deep trap and shallow surface traps, respectively. From the FTIR analysis of the CdS thin films, a broad absorption band of the OH stretching vibration in the range $3,000-3,600\;cm^{-1}$ and the peak of the CN stretching vibration at $2,000\;cm^{-1}$ were found.

ZrO2(Y2O3)계 세라믹스의 소결성과 전기전도도에 대한 M2O3의 영향(III) : ZrO2-Y2O3-Ln2O3계 세라믹스 (Effect of M2O3 on the Sinterbility and Electrical Conductivity of ZrO2(Y2O3) System(III) : Ceramics of the ZrO2-Y2O3-Ln2O3 System)

  • 오영제;정형진;이희수
    • 한국세라믹학회지
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    • 제24권2호
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    • pp.123-132
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    • 1987
  • Yttria-stabilized zirconia with erbia-lanthana were investigated with respect to the amount of Ln2O3 (Ln; Er, La) addition in the range of 0.5∼5 mol% to the base composition of 8 mol% yttriazirconia. Following analysis and measurement were adopted for the characterization of synthesizes of solid electrolyte; phase transformation, lattice parameter, crystallite size, relative density, chemical composition and SEM/EDS. Electrical conductivity by two-probe method versus temperature from 350$^{\circ}C$ to 800$^{\circ}C$ and frequency in the range of 5Hz∼13MHz by complex impedance method was also conducted together with the determination of oxygen ion transference number by EMF method for the evaluation of their electrical properties. The results were as followsing; Electrical conductivity were decreased with increase in Ln2O3 content, but their activation energies increased. In the case of La2O3 addition, espicially, its electrical conductivity was decreased owing to the segregation of second phases at the grain-boundary. Grain-boundary conductivity of the specimen contained 0.5 mol% Er2O3 exhibited a maximum conductivity among thecompositions experimented. However, their bulk conductivities decreased in both case. Oxygen ion transference number was also reduced with decrease in oxygen partial pressure. For example, in the case of Er2O3 addition it retained value in the range of 0.97∼0.94 abvove 4.74${\times}$10-2in oxygen partial pressure. With the increase in the quantities of the evaporation of additive components, the crystallite size of stabilized zirconia decreased, and their relative density also reduced owing to the formation of porosity in their matrices. In the case of La2O3 the sinterbility was improved in the limited amount of addition up to 0.5 mol%, in the same range of addition the strength of sintered bodies were improved perhaps owing to the precipitation of metastable tetragonal phase in the fully stabilized zirconia.

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$GeO_2$의 첨가가 $PbO-Bi_2O_3-Ga_2O_3$ 유리의 안정화에 미치는 영향 (Effects of $GeO_2$ Addition on the Stabilities of $PbO-Bi_2O_3-Ga_2O_3$ Glasses)

  • 최용규;허종;류선윤
    • 한국세라믹학회지
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    • 제32권11호
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    • pp.1269-1275
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    • 1995
  • Effects of GeO2 addition on the thermal and structural stabilities of PbO-Bi2O3-Ga2O3 glasses were studied. Thermal stabilities, as assessed by the weighted thermal stability factors [(Tx-Tg)/Tg], increased with GeO2 concentraton from 0.097 to 0.210 with the addition of 20 mol% GeO2. Increasing GeO2 content resulted in the decrease of apparent density, molar volume, refractive index and thermal expansion. On the other hand, IR transmission cut-off (λT=50%) moved from 6.73${\mu}{\textrm}{m}$ for the ternary PbO-Bi2O3-Ga2O3 glass to shorter wavelength side, 5.98${\mu}{\textrm}{m}$ for a glass containing 20mol% GeO2. There were little change with GeO2 content, however, in the activation energies for the viscous flow of approximately 140 kcal/mole within the temperature interval of 300~50$0^{\circ}C$. Addition of GeO2 to PbO-Bi2O3-Ga2O3 glasses enhanced the thermal and structural stabilities significantly at the expense of their infrared transmittance. An appropriate compsomise between these two opposite trends should be made following the specifications of the final applications.

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