• Title/Summary/Keyword: Multi-component reactions

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Dependence of an Interfacial Diels-Alder Reaction Kinetics on the Density of the Immobilized Dienophile: An Example of Phase-Separation

  • Min, Kyoung-Mi;Jung, Deok-Ho;Chae, Su-In;Kwon, Young-Eun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1679-1684
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    • 2011
  • Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

A Numerical Study on the Effectiveness Factor of Ni Catalyst Pellets for Steam-Methane Reforming (수증기-메탄개질용 Ni 촉매의 유용도에 관한 수치적 연구)

  • Choi, Chong-Gun;Nam, Jin-Hyun;Shin, Dong-Hoon;Jung, Tae-Yong;Kim, Young-Gyu
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.11a
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    • pp.63-66
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    • 2007
  • Reformers which produce hydrogen from natural gas are essential for the operation of residential PEM fuel cells. For this purpose, steam-methane reforming reactions with Ni catalysts is primarily utilized. Commercial Ni catalysts are generally made to have porous pellet shapes in which Ni catalyst particles are uniformly dispersed over Alumina support structures. This study numerically investigates the reduction of catalyst effectiveness due to the mass transport resistances posed by porous structures of spherical catalyst pellets. The multi-component diffusion through porous media and the accurate kinetics of reforming reaction is fully considered in the numerical model. The preliminary results on the variation of the effectiveness factor according to different operation conditions are presented, which is planned to be used to develop correlations in future studies.

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Silica Gel-Supported Polyphosphoric Acid (PPA-SiO2) Catalyzed One-Pot Multi-Component Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and -thiones: An Efficient Method for the Biginelli Reaction

  • Zeinali-Dastmalbaf, Mohsen;Davoodnia, Abolghasem;Heravi, Majid M.;Tavakoli-Hoseini, Niloofar;Khojastehnezhad, Amir;Zamani, Hassan Ali
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.656-658
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    • 2011
  • A green and efficient method for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones and -thiones through one-pot three-component reaction of ethyl acetoacetate, an aryl aldehyde, and urea or thiourea in acetonitrile using silica gel-supported polyphosphoric acid (PPA-$SiO_2$) as catalyst is described. Compared to the classical Biginelli reaction conditions, the present methodology offers several advantages such as high yields, relatively short reaction times, mild reaction condition and a recyclable catalyst with a very easy work up.

Scolecite Catalyzed Facile and Efficient Synthesis of Polyhydroquinoline Derivatives through Hantzsch Multi-component Condensation

  • Gadekar, Lakshman S.;Katkar, Santosh S.;Mane, Shivshankar R.;Arbad, Balasaheb R.;Lande, Machhindra K.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2532-2534
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    • 2009
  • A facile and efficient synthetic route has been developed for the polyhydroquinoline via four component reactions of aldehydes, dimedone, ethyl acetoacetate and ammonium acetate in the presence of catalytic amount of scolecite in ethanol at 70 ${^{\circ}C}$ through Hantzsch reaction. This method gives remarkable advantages such as simple work-up procedure, environmentally friendly, inexpensive, non-toxic and recyclable catalyst, shorter reaction time along with excellent yields.

Numerical study of effect of membrane properties on long-cycle performance of vanadium redox flow batteries

  • Wei, Zi;Siddique, N.A.;Liu, Dong;Sakri, Shambhavi;Liu, Fuqiang
    • Advances in Energy Research
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    • v.4 no.4
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    • pp.285-297
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    • 2016
  • Fundamental understanding of vanadium ion transport and the detrimental effects of cross-contamination on vanadium redox flow battery (VRFB) performance is critical for developing low-cost, robust, and highly selective proton-conducting membranes for VRFBs. The objective of this work is to examine the effect of conductivity and diffusivity, two key membrane parameters, on long-cycle performance of a VRFB at different operating conditions using a transient 2D multi-component model. This single-channel model combines the transport of vanadium ions, chemical reactions between permeated ions, and electrochemical reactions. It has been discovered that membrane selecting criterion for long cycles depends critically on current density and operating voltage range of the cell. The conducted simulation work is also designed to study the synergistic effects of the membrane properties on dynamics of VRFBs as well as to provide general guidelines for future membrane material development.

Product Phase Control During Interdiffusion Reactions (상호 확산 반응 중의 생성상 제어)

  • Park, Joon-Sik;Kim, Ji-Hoon;Perepezko, John R.
    • Journal of Korea Foundry Society
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    • v.26 no.1
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    • pp.27-33
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    • 2006
  • Phase evolutions involving nucleation stages together with diffusional growth have been examined in order to provide a guideline for determining rate limiting stages during phase evolutions. In multiphase materials systems in coatings, composites or multilayered structures, diffusion treatments often result in the development of metastable/intermediate phases at the reaction interfaces. The development of metastable phases during solid state interdiffusion demonstrates that the nucleation reaction can be one controlling factor. Also, the concentration gradient and the relative magnitudes of the component diffusivities provide a basis for a phase selection and the application of a kinetic bias strategy in the phase selection. For multicomponent alloy systems, the identification of the operative diffusion pathway is central to control phase formation. Experimental access to the nucleation and growth stage is discussed in thin film multi layers and bulk samples.

Genesis of Clay Minerals in the Vicinity of Gwangpo Bay, Southern Coast of Korea (광포만 집수유역내에 분포하는 점토광물의 성인에 관한 연구)

  • PARK Maeng-Eon;SONG Yong-Sun;KIM Hee-Joon;KIM Dae-Choul;PAIK In-Sung;CHUNG Sang-Yong;SONG Shi-Tae
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.21 no.4
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    • pp.259-268
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    • 1988
  • Clay deposits in the vicinity of the Gwangpo Bay, southern coast of Korea, occur restrictively in anorthositic masses. Laumontite and meta-halloysite are the predominant clay minerals with iron oxides at the uppermost surface. Chlorite and halloysite occur in deeper zone. Beneath the main clay horizon, but not above, some anorthositic rocks are pervasively altered to quartz, sericite, chlorite, pyrite and montmorillonite along the hydrothermal channels. The hypotheses of hydrothermal and weathering origins of the clay minerals are tested by multi-component equilibrium calculations of the reactions of modified hydrothermal water and rain water with anorthositic rocks at $100^{\circ}C\;and\;25^{\circ}C$, respectively. The calculated mineralogy from the reaction with rain water resembles natural mineral assemblage except for abundance in laumontite. The result implies that the weathering process is the main machanism of the formation of clay deposits in the area.

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