• Title/Summary/Keyword: Hydrogen transfer

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Hydrogenation of trans-Cinnamaldehyde with Hydrido-Carbonyl Osmium(II) Complexes of Chelating Phosphine Ligands

  • 정민교;허성;이원용;전무진
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.806-810
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    • 1997
  • A series of new hydridocarbonyl osmium(Ⅱ) complexes, OsHCl(CO)(PPh3)(L-L)[L-L=Ph2P(CH2)nPPh2 (n=1 (1), 2 (2), 3 (3), cis-Ph2PCH=CHPPh2 (4), and Fe(η5-C5H4PPh2)2 (5)] has been synthesized from OsHCl(CO)(PPh3)3 and chelating diphosphines. These complexes have been characterized by IR, 1H NMR and elemental analysis. The catalytic activities of these complexes both for the transfer hydrogenation of trans-cinnamaldehyde with 2-propanol as the hydrogen donor, and for the selective hydrogenation of trans-cinnamaldehyde with H2, have been examined. Complexes (1)-(5) were shown to have higher selectivities for the transfer hydrogenation of the C=O bond of aldehyde than for the transfer hydrogenation of the C=C bond of aldehyde. The selectivities for the transfer hydrogenation with 2-propanol as well as for the hydrogenation with H2 have been found to decrease in the order 3 > 5 > 2 > 4 > 1. Complex (3) has shown to possess almost 90% of the selectivity to cinnamyl alcohol for transfer hydrogenation. It is also found that there is a correlation between the ν(CO) of each complex and the hydrogenation, of the C=O bond of trans-cinnamaldehyde. Overall, the selectivities with the complexes (1)-(5) are greater for the transfer hydrogenation with 2-propanol than for the hydrogenation with H2.

Variation of Hydrogen Residue on Metallic Samples by Thermal Soaking in an Inert Gas Environment (불활성 가스하 열건조에 따른 금속시험편의 수소잔류물 거동 분석)

  • Lee, Yunhee;Park, Jongseo;Baek, Unbong;Nahm, Seunghoon
    • Transactions of the Korean hydrogen and new energy society
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    • v.24 no.1
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    • pp.44-49
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    • 2013
  • Hydrogen penetration into a metal leads to damages and mechanical degradations and its content measurement is of importance. For a precise measurement, a sample preparation procedure must be optimized through a series of studies on sample washing and drying. In this study, two-step washing with organic solvents and thermal soaking in inert gas were tried with a rod-shaped, API X65 steel sample. The samples were machined from a steel plate and then washed in acetone and etyl-alcohol for 5 minute each and dried with compressed air. After then, the samples were thermally soaked in a home-made nitrogen gas chamber during 10 minute at different heat gun temperatures from 100 to $400^{\circ}C$ and corresponding temperature range in the soaking chamber was from 77 to $266^{\circ}C$ according to the temperature calibration. Hydrogen residue in the samples was measured with a hot extraction system after each soaking step; hydrogen residue of $0.70{\pm}0.12$ wppm after the thermal soaking at $77^{\circ}C$ decayed with increase of the soaking temperature. By adopting the heat transfer model, decay behavior of the hydrogen residue was fitted into an exponential decay function of the soaking temperature. Saturated value or lower bound of the hydrogen residue was 0.36 wppm and chamber temperature required to lower the hydrogen residue about 95% of the lower bound was $360^{\circ}C$. Furthermore, a thermal desorption spectroscopy was done for the fully soaked samples at $360^{\circ}C$. Weak hydrogen peak was observed for whole temperature range and it means that hydrogen-related contaminants of the sample surface are steadily removed by heating. In addition, a broad peak found around $400^{\circ}C$ means that parts of the hydrogen residue are irreversibly trapped in the steel microstructure.

Characterization of Thermal Degradation of Polytrimethylene Terephthalate by MALDI-TOF Mass Spectrometry

  • Jang, Sung-Woo;Yang, Eun-Kyung;Jin, Sung-Il;Cho, Young-Dal;Choe, Eun-Kyung;Park, Chan-Ryang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.833-838
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    • 2012
  • The thermal degradation products of polytrimethylene terephthalate (PTT) obtained by heating the sample in the temperature range of $250-360^{\circ}C$ under non-oxidative conditions was characterized using MALDI-TOF (matrix assisted laser desorption/ionization) mass spectrometry. The structures of the degradation products were determined and the relative compositions were estimated. The MALDI-TOF mass spectra of the thermally degraded PTT sample showed three main series of oligomer products with different end groups, which were carboxyl/carboxyl, carboxyl/allyl, and allyl/allyl. In contrast to the thermal degradation of polyethylene terephthalate (PET), the oligomers containing terephthalic anhydrides were not detected, whereas the formation of oligomers containing the unsaturated allyl ester group was confirmed by mass assignment. From these results, it was concluded that the thermal degradation of PTT proceeds exclusively through the ${\beta}$-CH hydrogen transfer mechanism, which is in accordance with the proposed reaction mechanism for the thermal degradation of polybutylene terephthalate (PBT).

Heat transfer enhancement of metal hydride $(Mm(La_{0.6-0.8})Ni_{4.0}Co_{0.6}Mn_{0.2}Al_{0.2})$ for hydrogen storage (수소저장용 금속수소화물$(Mm(La_{0.6-0.8})Ni_{4.0}Co_{0.6}Mn_{0.2}Al_{0.2})$의 전열촉진)

  • Bae Sang-Chul;Yang Yang;Masanori Monde
    • New & Renewable Energy
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    • v.2 no.2 s.6
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    • pp.75-80
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    • 2006
  • The effective thermal conductivities of $Mm(La_{0.6-0.8})Ni_{4.0}Co_{0.6}Mn_{0.2}Al_{0.2}$ [TL-492] with hydrogen and helium have been examined. Experiment results show that pressure has great influence on effective thermal conductivity in low pressure range [below 0.5 MPa]. And that influence decreases rapidly with increase of gas pressure. The reason is at low pressure, the mean free path of gas becomes greater than effective thickness of gas film which is important to the heat transfer mechanism in this research. And, carbon fibers have been used to try to enhance the poor thermal conductivity of TL-492. Three types of carbon fibers and three mass fractions have been examined and compared. Naturally, the highest effective thermal conductivity has been reached with carbon fiber which has highest thermal conductivity, and highest mass fraction. This method has acquired 4.33 times higher thermal conductivity than pure metal hydrides with quite low quantity of additives, only 0.99 wt% of carbon fiber. This is a good result comparing to other method which can reach higher effective thermal conductivity but needs much higher mass fraction of additives too.

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Reaction Characteristics of Coal and Oxygen Carrier Particle in a Thermogravimetric Analyzer (열중량분석기에서 석탄과 산소공여입자의 반응 특성)

  • Ryu, Ho-Jung;Kim, Young-Joo;Park, Yeong-Seong;Park, Moon-Hee
    • Transactions of the Korean hydrogen and new energy society
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    • v.22 no.2
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    • pp.213-222
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    • 2011
  • To check adaptability of low ash coal(hyper coal) to chemical looping combustion, reaction characteristics of two coals (Roto and Hyper coal) with two oxygen carriers (NiO/bentonite, OCN703-1100) have been investigated in a thermogravimetric analyzer. Hyper coal represented low combustion rate and high ignition temperature, high volatile content and high devolatilization rate, and therefore, showed worse oxygen transfer during successive 10 cycle reduction-oxidation test than Roto coal. Finally we selected Roto coal as the candidate coal for chemical looping combustion. For Roto coal, OCN703-1100 particle showed better oxygen transfer than NiO/bentonite particle. During 10 cycle reduction oxidation test, change of the extent of oxidation (Wo) was negligible and we could conclude that both oxygen carriers have sufficient regeneration ability.

A Real Time Model of Dynamic Thermal Response for 120kW IGBT Inverter (120kW급 IGBT 인버터의 열 응답 특성 실시간 모델)

  • Im, Seokyeon;Cha, Gangil;Yu, Sangseok
    • Transactions of the Korean hydrogen and new energy society
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    • v.26 no.2
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    • pp.184-191
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    • 2015
  • As the power electronics system increases the frequency, the power loss and thermal management are paid more attention. This research presents a real time model of dissipation power with junction temperature response for 120kw IGBT inverter which is applied to the thermal management of high power IGBT inverter. Since the computational time is critical for real time simulation, look-up tables of IGBT module characteristic curve are implemented. The power loss from IGBT provides a clue to calculate the temperature of each module of IGBT. In this study, temperature of each layer in IGBT is predicted by lumped capacitance analysis of layers with convective heat transfer. The power loss and temperature of layers in IGBT is then communicated due to mutual dependence. In the dynamic model, PWM pulses are employed to calculation real time IGBT and diode power loss. Under Matlab/Simulink$^{(R)}$ environment, the dynamic model is validated with experiment. Results showed that the dynamic response of power loss is closely coupled with effective thermal management. The convective heat transfer is enough to achieve proper thermal management under guideline temperature.

Design of Cell Frame Structure of Unit Cell for Molten Carbonate Fuel Cell Using CFD Analysis (CFD를 통한 용융탄산염 연료전지 단위전지용 셀 프레임 구조 설계)

  • LEE, SUNG-JOO;LIM, CHI-YOUNG;LEE, CHANG-WHAN
    • Transactions of the Korean hydrogen and new energy society
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    • v.29 no.1
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    • pp.56-63
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    • 2018
  • In this study, a $100cm^2$ cell frame for a molten carbonate fuel cell was designed using CFD analysis. Electrochemical reactions, gas flow, and the heat transfer in $100cm^2$ cell frame were modeled using COMSOL Multiphysics. Two design variables such as the height of the cell frame and the length of the gas input area were determined to obtain minimized temperature distribution and uniform gas distribution. With two design parameter such as height of the cell frame and the length of the gas flow channel, the temperature difference in the cell fame was decreased to $5^{\circ}C$ and the gas uniformity in the flow channel were achieved.

Lyα Radiative Transfer and The Wouthuysen-Field effect

  • Seon, Kwang-Il;Kim, Chang-Goo
    • The Bulletin of The Korean Astronomical Society
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    • v.42 no.2
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    • pp.43.1-43.1
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    • 2017
  • A three-dimensional (3D) $Ly{\alpha}$ radiative transfer code is developed to study the Wouthuysen-Field effect, which couples the 21 cm spin temperature of neutral hydrogen and the $Ly{\alpha}$ radiation field, and the escape fraction of $Ly{\alpha}$ from galaxies. The Monte Carlo code is capable of treating arbitrary 3D distributions of $Ly{\alpha}$ source, neutral hydrogen and dust densities, gas temperature, and velocity field. It is demonstrated that the resonance-line profile at the center approaches to the Boltzmann distribution with the gas temperature. A plane-parallel ISM model, which is appropriate for the neutral ISM of our Galaxy, is used to calculate the $Ly{\alpha}$ radiation field strength as a function of height above the galactic plane. We also use a two-phase, clumpy medium model which is composed of the cold and warm neutral media (WNM). It is found that the $Ly{\alpha}$ radiation field is strong enough to thermalize the 21 cm spin temperature in the WNM to the gas kinetic temperature. The escape fraction of $Ly{\alpha}$ is found to be a few percent, which is consistent with the $Ly{\alpha}$ observations of our Galaxy and external galaxies.

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Effects of Charge-discharge Rate on Morphology and Resistance of Surface Film on a Graphite Negative Electrode in an Ethylene Carbonate-based Solution (탄산 에틸렌계 용액 중에서 생성되는 흑연 음극 표면피막의 형상 및 저항에 미치는 충방전 속도의 영향)

  • Jeong, Soonki;Kim, Pogyom
    • Transactions of the Korean hydrogen and new energy society
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    • v.24 no.2
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    • pp.179-185
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    • 2013
  • The behavior of surface film formation was greatly dependent on the speed of potential cycling. In $LiClO_4$ / EC + DEC, cyclic voltammetry results showed that the peaks originated from surface film formation on graphite electrode at the high charge-discharge rate was shifted to the lower potentials as the charge-discharge rate decrease. This indicates that surface films with different morphology and thickness were formed by different charge-discharge rate. Transmission electron microscopy (TEM) results indicated that the properties such as thickness and morphology of the surface film were greatly affected by the charge-discharge rate. Electrochemical impedance spectroscopy (EIS) showed that the resistance of surface film was affected by the speed of potential cycling. In addition, the charge transfer resistance was also dependent on the charge-discharge rate indicating that the charge transfer reaction was affected by the nature of surface film. TEM and EIS results suggested that the chemical property as well as the physical property of the surface film was affected by the charge-discharge rate.

Preparation and Permeation Characteristics of PDMS-b-PMMA Copolymer Membrane (PDMS-b-PMMA 공중합체 막의 제조 및 투과특성)

  • Kang, Tae-Beom;Cho, A-Ra;Lee, Hyun-Kyung
    • Membrane Journal
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    • v.18 no.3
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    • pp.219-225
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    • 2008
  • In this research, polydimethylsiloxane-polymethylmethacrylate (PDMS-PMMA) block copolymer was synthesized from polydimethylsiloxane (PDMS) and methylmethacrylate (MMA) monomer using atom transfer radical polymerization (ATRP). The synthesis characterization of the PDMS-b-PMMA copolymer membrane was carried out by a FT-IR, $^1H$-NMR, GPC and DSC. The permeabilities of nitrogen and hydrogen gases were observed being $1.2{\sim}l.5$ barrer and $6.2{\sim}10.5$ barrer, respectively. Simultaneously, selectivities of hydrogen against nitrogen were $5.3{\sim}6.9$. The permeability and selectivity of PDMS-b-PMMA copolymer membrane were showed lower than the PDMS membrane, but higher than the PMMA membrane.