• 제목/요약/키워드: Thermodynamic mechanism

검색결과 167건 처리시간 0.025초

Mechanism Studies on the CSI Reaction with Allyl Ethers by Varying p-Substituent

  • Jung, Young-Hoon;Kim, Ji-Duck
    • Archives of Pharmacal Research
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    • 제26권9호
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    • pp.667-678
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    • 2003
  • We examined the effect of p-substituents in p-substituted cinnamyl methyl ethers and 1-(p-substituted phenyl)allyl methyl ethers with CSI, and confirmed that the CSI reaction of allyl ethers (p-substituted ethers) is a competitive reaction of $S_Ni{\;}and{\;}S_N1$ mechanism according to the stability of the carbocation. And, the only terminal allylic amine was obtained through the migration reaction in thermodynamic reaction condition.

EFFECT OF OVER-EXPANSION CYCLE IN A SPARK-IGNITION ENGINE USING LATE-CLOSING OF INTAKE VALVE AND ITS THERMODYNAMIC CONSIDERATION OF THE MECHANISM

  • Shiga, S.;Hirooka, Y.;Miyashita, Y.;Yagi, S.;Machacon, H.T.C.;Karasawa, T.;Nakamura, H.
    • International Journal of Automotive Technology
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    • 제2권1호
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    • pp.1-7
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    • 2001
  • This paper presents further investigation into the effect of over-expansion cycle in a spark-ignition engine. On the basis of the results obtained in previous studies, several combinations of late-closing (LC) of intake valve and expansion ratio were tested using a single-cylinder production engine. A large volume of intake capacity was inserted into the intake manifold to simulate multi-cylinder engines. With the large capacity volume, LC can decrease the pumping loss and then increase the mechanical efficiency. Increasing the expansion ratio from 11 to 23.9 with LC application can produce about 13% improvement of thermal efficiency which was suggested to be caused by the increased cycle efficiency. The decrease of compression ratio from 11 to 5.5 gives little effect on the thermal efficiency if the expansion ratio could be kept constant. Thus, the expansion ratio is revealed to be a determining factor for cycle efficiency, while compression ratio is no more important, which suggests the usefulness of controlling the intake charge with intake valve closure timing. These were successfully explained by simple thermodynamic calculation and thus the mechanism could be verified by the estimation.

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NaCl 수용액내의 양성자와 디이소부틸니트로소아민의 치환흡착과 열역학적 특성 (Substitutional Adsorption and Thermodynamic Characteristics of Proton and Di-iso-butylnitrosoamine in NaCl Aqueous Solution)

  • 황금소
    • 한국수산과학회지
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    • 제16권3호
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    • pp.239-245
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    • 1983
  • Electrochemical adsorption always was accompanied with solvent displacement and relative size factor(x) of adsorbate and solvent and hydrogen coverage(${\theta}$) on the lead anodic film electrode formed in phosphoric acid in NaCl solution and the sea water at $15{\sim}35^{\circ}C$ were studied by means of constant current-potential method and potentiodynamic cathodic polarization method. In this experiment, various constants and thermodynamic quantities calculated from the hydrogen coverage were also described to explain the reactivities of di-iso-butylnitrosoamine(DBNA) and proton ($H^+$) according to the changes of interactions between solute and solvent in the bulk phase and interphase. It was investigated that the average values of relative size factor and the coverage of hydrogen atoms studied with the electrode of lead anodic film formed in phosphoric acid solution in 60mM DBNA+0.5M NaCl and in 60mM DBNA+$6\%0$ sea water were about 11.0 and 0.2 respectively. Hydrogen evolution was electrochemical mechanism because of substitutional adsorption of aromatic substance with their delocalization of electrons, but in the case of non-charge transfer adsorption of aliphatic substance(DBNA) interacting relatively little with the electrode, it was combination mechanism.

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Degradation of SOFC Cell/Stack Performance in Relation to Materials Deterioration

  • Yokokawa, Harumi;Horita, Teruhisa;Yamaji, Katsuhiko;Kishimoto, Haruo;Brito, M.E.
    • 한국세라믹학회지
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    • 제49권1호
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    • pp.11-18
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    • 2012
  • The characteristic features of solid oxide fuel cells are reviewed from the viewpoint of the thermodynamic variables to be developed inside cells/stacks particularly in terms of gradients of chemical potential, electrical potential and temperature and corresponding flows of air, fuel, electricity and heat. Examples of abrupt destruction of SOFC systems were collected from failures in controlling their steady flows, while continuous degradation was caused by materials behaviors under gradients of chemical potentials during a long operation. The local equilibrium approximation has been adopted in NEDO project on the durability/reliability of SOFC stacks/systems; this makes it possible to examine the thermodynamic stability/reactivity as well as mass transfer under the thermodynamic variable gradients. Major results of the NEDO project are described with a focus on degradation/deterioration of electrolyte and electrode materials.

HTMAB로 표면처리된 안트라사이트에 의한 비소 및 셀렌 이온의 흡착 특성 (Adsorption Characteristics of As and Se Ions by HTMAB Modified Anthracite)

  • 김정배
    • 한국환경과학회지
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    • 제27권3호
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    • pp.167-177
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    • 2018
  • The removal characteristics of As and Se ions from aqueous solution by hexadecyl trimethyl ammonium bromide (HTMAB) modified anthracite (HTMAB-AT) were investigated under various conditions of contact time, pH and temperature. When the pH is 6, the zeta potential value of anthracite (AT) is -24 mV and on the other hand, the zeta potential value of the HTMAB-AT is +44 mV. It can be seen that the overall increase of about 60 mV. Increasing the (+) potential value indicates that the surface of the adsorbent had a stronger positive charge, so adsorption for the anion metal was increased. The isotherm data was well described by Langmuir and Temkin isotherm model. The maximum adsorption capacity was found to be 7.81 and 6.89 mg/g for As and Se ions from the Langmuir isotherm model at 298 K, respectively. The kinetic data was tested using pseudo first and pseudo second order models. The results indicated that adsorption fitted well with the pseudo second order kinetic model. The mechanism of the adsorption process showed that adsorption was dependent on intra particle diffusion model according to two step diffusion. The thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, and ${\Delta}S^{\circ}$) were also determined using the equilibrium constant value obtained at different temperatures. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process.

DNA-Binding and Thermodynamic Parameters, Structure and Cytotoxicity of Newly Designed Platinum(II) and Palladium(II) Anti-Tumor Complexes

  • Mansouri-Torshizi, Hassan;Saeidifar, Maryam;Khosravi, Fatemeh;Divsalar, Adeleh;Saboury, Ali.Akbar;Ghasemi, Zahra Yekke
    • Bulletin of the Korean Chemical Society
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    • 제32권3호
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    • pp.947-955
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    • 2011
  • The complexes [Pd(bpy)(Hex-dtc)]$NO_3$ and [Pt(bpy)(Hex-dtc)]$NO_3$ (bpy is 2,2'-bipyridine and Hex-dtc is hexyldithiocarbamato ligands) were synthesized and characterized by elemental analysis and spectroscopic studies. The cytotoxicity assay of the complexes has been performed on chronic myelogenous leukemia cell line, K562, at micromolar concentration. Both complexes showed cytotoxic activity far better than that of cisplatin under the same experimental conditions. The binding parameters of the complexes with calf thymus DNA (CT-DNA) was investigated using UV-visible and fluorescence techniques. They show the ability of cooperatively intercalating in CT-DNA. Gel filtration studies demonstrated that platinum complex could cleave the DNA. In the interaction studies between the Pd(II) and Pt(II) complexes with CT-DNA, several binding and thermodynamic parameters have been determined, which may provide deeper insights into the mechanism of action of these types of complexes with nucleic acids.

Thermodynamic Analysis of Intergranular Additives in Sintered Nd-Fe-B Magnet

  • Cui, X.G.;Wang, X.H.;Cui, C.Y.;Yin, G.C.;Xia, C.D.;Cheng, X.N.;Xu, X.J.
    • Journal of Magnetics
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    • 제22권2호
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    • pp.244-249
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    • 2017
  • To get deeper insight into the effect of intergranular additives in sintered Nd-Fe-B magnet and consequently improve the properties better, the interaction between additives (oxide, nitride, and carbide) and Nd-rich phase in the temperature range of 298.15-1400 K was analyzed thermodynamically. It can be found that the oxide additives became less stable than nitrides and carbides. Except for calcium oxide, almost all oxides could react with Nd from Nd-rich phase. To be different from oxide additives, the mechanism of nitrides and carbides was defined with various elements, either reaction with Nd from Nd-rich phase or not. The two different mechanisms would show different effects on the microstructure and hence properties of magnet. The thermodynamic analysis had a better agreement with the experimental information.

차가버섯 용매추출분획의 Acetylcholinesterase 저해활성에 대한 동역학 및 열역학적 해석 (Kinetic and Thermodynamic Analysis of AChE Inhibition of Solvent Extract Fractions from Inonotus obliquus)

  • 김학규;허원;홍억기;이신영
    • 산업식품공학
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    • 제15권4호
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    • pp.289-296
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    • 2011
  • Twenty four fractions by solvent extraction and/or acid precipitation from fruit body and culture broth of Inonotus obliquus were prepared, and their inhibitory effect against acetylcholinesterase (AChE) was investigated. Among these fractions, acid (1 M HCl) precipitates from cell-free culture broth and fruit body exhibited the highest inhibitory effect on AChE in vitro. Acid precipitates inhibited AChE activity in a concentration-dependant manner and $IC_{50}$ values of both acid precipitates were 0.53 mg/mL. The inhibition pattern was general non-competitive inhibition. The energetic parameters were also determined by dual substrate/temperature design. Both acid precipitates increased the values of Ea, ${\Delta}H,/;{\Delta}G$ and ${\Delta}H^{\ast}$ decreasing the value of ${\Delta}S$ for AChE. The results implied that the acid precipitates from I. obliquus increased the thermodynamic barrier, leading to the breakdown of ES complex and the formation of products as inhibitory mechanism.

충격 압축에 의한 제논 가스의 이온화 특성 연구 (A Study of the Ionization Characteristics of Xenon Gas by Shock Compression)

  • 이대성;신재렬;최정열;최윤수;김형원
    • 한국군사과학기술학회지
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    • 제13권3호
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    • pp.493-502
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    • 2010
  • In this paper, the ionization characteristics of noble gases are studied numerically behind strong shock waves. As a first step, the equilibrium ionization mechanism of noble gases is modeled in wide ranges of temperature and pressure. As a next step the equilibrium ionization model is coupled with fluid dynamic equations to analyze the local thermodynamic equilibrium(LTE) ionization process at high temperature and pressure conditions behind the strong imploding shock waves. The ionization characteristics of xenon gas is studied in a wide range of test conditions with thermal radiation effects. Hence, the results give optimal conditions of maximum ionization and radiation behind the imploding shock waves.