• Title/Summary/Keyword: Equilibrium Shift

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Analysis on the Langmuir Adsorption Isotherm of the Over-Potentially Deposited Hydrogen (OPD H) at the Polycrystalline Au|Acidic Aqueous Electrolyte Interface Using the Phase-Shift Method

  • Chun Jang H.;Jeon Sang K.
    • Journal of the Korean Electrochemical Society
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    • v.4 no.3
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    • pp.118-124
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    • 2001
  • The Langmuir adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic $H_2$ evolution reaction (HER) at the $poly-Au|0.5M\;H_2SO_4$ aqueous electrolyte interface has been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}\leq{-\phi}\leq90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1\geq{\theta}\geq0)$ at the interface. The phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, i.e., the phase-shift method, can be used as a new method to estimate the Langmuir adsorption isotherm $(\theta\;vs.\;E)$ of the OPD H for the cathodic HER at the interface. At the poly-$Au|0.5M\;H_2SO_4$ electrolyte interface, the equilibrium constant (K) and standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.3\times10^{-6}\;and\;32.2\;kJ\;mol^{-1}$, respectively.

A Unified Framework for Small Signal Stability Analysis of Power Systems and Its Application to Available Transfer Capability (계통의 종합적 미소신호 안정도 해석 알고리듬과 ATC 산정에의 응용에 관한 연구)

  • Kim, Sang-Ahm;Song, Hwa-Chang;Lee, Byong-Jun;Kwon, Sae-Hyuk
    • The Transactions of the Korean Institute of Electrical Engineers A
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    • v.48 no.10
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    • pp.1222-1230
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    • 1999
  • This paper presents the framework for analysis of small-signal stability. In this framework the equilibrium points of system DAE model are traced using continuation method and instability points are determined on the solution path. Especially Implicit shift QR-modified Arnoldi method is utilized to calculated the rightmost eigenvalues. Small-signal stability is becoming one of the major factors that affect the ATC in the environment of deregulation. Stability limited ATC is easily evaluated in this stability analysis process.

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Solid-state Chracterization of the HIV Protease Inhibitor

  • Kim, Yong-Ae;Kim, Ae-Ri
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1729-1732
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    • 2002
  • The LB71350,(3S, 4R)-Epoxy-(5S)-[[N-(1-methylethoxy)carbonyl]-3-(methylsulfonyl)-L-valinyl]amino]-N-[2-methyl-(1R)-[(phenyl)carbonylpropyl-6-phenylhexanamide, is a novel HIV protease inhibitor. Its equilibrium solubility at room temperature was less than $40{\mu}g/mL.$ It was speculated that the low aqueous solubility might be due to the high crystalline lattice energy resulting from intermolecular hydrogen bonds. The present study was carried out to learn the solid-state characteristics of LB71350 using analytical methods such as NMR, FT-IR and XRD. $^{13}C$ Solid-state NMR, solution NMR, and FT-IR spectra of the various solid forms of LB71350 were used to identify the conformation and structure of the solid forms. The chemical shifts of $^{13}C$ solid-state NMR spectra suggest that the crystalline form might have 3 intermolecular hydrogen bondings between monomers.

Geometrically nonlinear analysis of planar beam and frame structures made of functionally graded material

  • Nguyen, Dinh-Kien;Gan, Buntara S.;Trinh, Thanh-Huong
    • Structural Engineering and Mechanics
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    • v.49 no.6
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    • pp.727-743
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    • 2014
  • Geometrically nonlinear analysis of planar beam and frame structures made of functionally graded material (FGM) by using the finite element method is presented. The material property of the structures is assumed to be graded in the thickness direction by a power law distribution. A nonlinear beam element based on Bernoulli beam theory, taking the shift of the neutral axis position into account, is formulated in the context of the co-rotational formulation. The nonlinear equilibrium equations are solved by using the incremental/iterative procedure in a combination with the arc-length control method. Numerical examples show that the formulated element is capable to give accurate results by using just several elements. The influence of the material inhomogeneity in the geometrically nonlinear behavior of the FGM beam and frame structures is examined and highlighted.

Thermodynamic and Kinetic Study on the Protonation of Free Base Tetraphenylporpyrin Derivatives in Solution

  • 유종완;유병수;정갑상;최호섭;유수창
    • Bulletin of the Korean Chemical Society
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    • v.19 no.4
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    • pp.439-444
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    • 1998
  • The protonation of tetraphenylporphyrin (TPP) in acidic organic solutions was analyzed by acid titrimetric and temperature-dependent absorption measurements. Competition between the protonation of free base TPP $(TPPH_2)$ and the solvation of proton by near solvent molecules determines the equilibrium of the diprotonated TPP $(TPPH_4^{2+})$ formation. The diprotonated TPP exists as an ion pair complex with the acid counterions, which are found to affect the degree of red shift of the Soret band. The rotation of the phenyl rings also plays an important role in the diprotonation, as suggested by the decrease in the degree of diprotonation for the fluorophenyl TPP derivatives whose phenyl ring rotation is significantly hindered relative to normal TPP. The difference of fluorescence lifetime between $TPPH_2 \;({\pi}_{FL}=19.6\;ns)\; and\; TPPH_4^{2+} \;({\pi}_{FL}=2.1 \;ns)$ was used advantageously to measure the rate of protonation in the excited state. The protonation of TPPH2 are found to occur much slower than the diffusion of protons from bulk solution to the porphyrin ring. The monoprotonated TPP is suggested to be the transient species for the diprotonation process.

Interaction between Norfolxacin and Single Stranded DNA

  • 여정아;조태섭;Kim, Seog K.;문형랑;준길자;남원우
    • Bulletin of the Korean Chemical Society
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    • v.19 no.4
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    • pp.449-457
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    • 1998
  • We compared various spectroscopic properties of a norfloxacin-single stranded DNA complex with those of norfloxacin-double stranded DNA complex. Norfloxacin binds to both double-and single stranded DNA, and we observed the following spectroscopic changes for both complexes: hypochromism in the norfloxacin absorption region in the absorption spectrum, the characteristic induced CD spectrum consisting of a weak positive band at 323 nm and a strong positive band at 280-300 nm followed by a negative band in the 260 nm region, a strong decrease in the fluorescence intensity and a red-shift in the fluorescence emission spectrum, and shorter fluorescence decay times. These results indicate that the environments of the bound norfloxacin in both DNAs are similar, although the equilibrium constant of the norfloxacin-single stranded DNA was twice as high as the norfloxacin-double stranded DNA complex. Both complexes were thermodynamically favored with similar negative Δ$G^o$. Negative Δ$H^o$ terms contribute to these spontaneous reactions; Δ$S^o$ term was unfavorable.

Thermodynamic Equilibrium and Efficiency of Ethylene Glycol Steam Reforming for Hydrogen Production (에틸렌글리콜의 수증기 개질반응을 이용한 수소제조에 대한 열역학적 평형 및 효율 분석)

  • Kim, Kyoung-Suk;Park, Chan-Hyun;Jun, Jin-Woo;Cho, Sung-Yul;Lee, Yong-Kul
    • Korean Chemical Engineering Research
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    • v.47 no.2
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    • pp.243-247
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    • 2009
  • This study is purposed to analyze thermodynamic properties on the hydrogen production by ethylene glycol steam reforming. Various reaction conditions of temperatures(300~1,600 K), feed compositions(steam/carbon= 0.5~4.5), and pressures(1~30 atm) were applied to investigate the effects of the reaction conditions on the thermodynamic properties of dimethyl ether steam reforming. An endothermic steam reforming competed with an exothermic water gas shift reaction and an exothermic methanation within the applied reaction condition. Hydrogen production was initiated at the temperature of 400 K and the production rate was promoted at temperatures exceeding 500 K. An increase of steam to carbon ratio(S/C) in feed mixture over 1.0 resulted in the increase of the water gas shift reaction, which lowered the formation of carbon monoxide. The maximum hydrogen yield with minimizing loss of thermodynamic conversion efficiency was achieved at the reaction conditions of a temperature of 900 K and a steam to carbon ratio of 3.0.

An Analysis of the Causes of the Welfare Gain Achieved by Congestion Pricing and Transit Subsidies (혼잡통행료와 대중교통 보조금의 효용개선 원인 분석)

  • Rhee, Hyok-Joo;Yu, Sang-Gyun
    • Journal of Korean Society of Transportation
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    • v.31 no.3
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    • pp.74-85
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    • 2013
  • We analyze the efficiency of congestion pricings and transit subsidies in the spatial micro-economic model based on a general equilibrium environment. In this setting, we decompose the total welfare change into component factors and identify the reason of the change in the efficiency caused by policy instruments; these component factors are divided into indirect factors and direct factors including of origin-destination and mode choices. We set up the model as adding mode choice to the standard format in the fashion of Anas and Kim (1996) and extend the methodology proposed by Yu and Rhee (2011) and Rhee (2012) for deriving theoretical and analytical solution. Most of welfare gain comes from the modal shift from car to bus. The relative efficiency of subsidies in relation to the first-best pricing is lower than it of congestion pricings although the change in bus share by subsidies is similar to it by congestion pricing. Subsidies give rise to more modal shift from a car to a bus for long-distance commuting than it caused by congestion pricings. As the increase of bus share for long-distance commuting leads to the increase of cross-commuters passing through CBD, the welfare gain by subsidies is lower than it by congestion pricings.

Post-buckling responses of elastoplastic FGM beams on nonlinear elastic foundation

  • Trinh, Thanh-Huong;Nguyen, Dinh-Kien;Gan, Buntara S.;Alexandrov, S.
    • Structural Engineering and Mechanics
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    • v.58 no.3
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    • pp.515-532
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    • 2016
  • The elastoplastic response of functionally graded material (FGM) beams resting on a nonlinear elastic foundation to an eccentric axial load is investigated by using the finite element method. The FGM is assumed to be formed from ceramic and metal phases with their volume fraction vary in the thickness direction by a power-law function. A bilinear elastoplastic behavior is assumed for the metallic phase, and the effective elastoplastic properties of the FGM are evaluated by Tamura-Tomota-Ozawa (TTO) model. Based on the classical beam theory, a nonlinear finite beam element taking the shift in the neutral axis position into account is formulated and employed in the investigation. An incremental-iterative procedure in combination with the arc-length control method is employed in computing the equilibrium paths of the beams. The validation of the formulated element is confirmed by comparing the equilibrium paths obtained by using the present element and the one available in the literature. The numerical results show that the elastoplastic post-buckling of the FGM beams is unstable, and the post-buckling strength is higher for the beams associated with a higher ceramic content. Different from homogeneous beams, yielding in the FGM beam occurs in the layer near the ceramic layer before in the layer near metal surface. A parametric study is carried out to highlight the effect of the material distribution, foundation support and eccentric ratio on the elastoplastic response of the beams.

Accuracy and applicable range of a reconstruction technique for hybrid rockets

  • Nagata, Harunori;Nakayama, Hisahiro;Watanabe, Mikio;Wakita, Masashi;Totani, Tsuyoshi
    • Advances in aircraft and spacecraft science
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    • v.1 no.3
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    • pp.273-289
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    • 2014
  • Accuracy of a reconstruction technique assuming a constant characteristic exhaust velocity ($c^*$) efficiency for reducing hybrid rocket firing test data was examined experimentally. To avoid the difficulty arising from a number of complex chemical equilibrium calculations, a simple approximate expression of theoretical $c^*$ as a function of the oxidizer to fuel ratio (${\xi}$) and the chamber pressure was developed. A series of static firing tests with the same test conditions except burning duration revealed that the error in the calculated fuel consumption decreases with increasing firing duration, showing that the error mainly comes from the ignition and shutdown transients. The present reconstruction technique obtains ${\xi}$ by solving an equation between theoretical and experimental $c^*$ values. A difficulty arises when multiple solutions of ${\xi}$ exists. In the PMMA-LOX combination, a ${\xi}$ range of 0.6 to 1.0 corresponds to this case. The definition of $c^*$ efficiency necessary to be used in this reconstruction technique is different from a $c^*$ efficiency obtained by a general method. Because the $c^*$ efficiency obtained by average chamber pressure and ${\xi}$ includes the $c^*$ loss due to the ${\xi}$ shift, it can be below unity even when the combustion gas keeps complete mixing and chemical equilibrium during the entire period of a firing. Therefore, the $c^*$ efficiency obtained in the present reconstruction technique is superior to the $c^*$ efficiency obtained by the general method to evaluate the degree of completion of the mixing and chemical reaction in the combustion chamber.