• Title/Summary/Keyword: Chemical waves

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Nonlinear Dynamics of Homogeneous Azeotropic Distillations

  • Lee, Moonyong;Cornelius Dorn;Manfred Morari
    • 제어로봇시스템학회:학술대회논문집
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    • 1998.10a
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    • pp.461-467
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    • 1998
  • In spite of significant nonlinearities even in the simplest model, some types of steady-state and dynamic behavior common for nonlinear systems have never been associated with distillation columns. In recent years, multiplicity of steady states has been a subject of much research and is now widely accepted. Subsequently, stability of steady states has been explored. Another phenomenon that. although widely observed in chemical reactors, has not been associated with models of distillation columns is the existence of periodic oscillations. In this article we study the steady-state and dynamic behavior of the azeotropic distillation of the ternary homogeneous system methanol-methyl butyrate-toluene. Our simulations reveal nonlinear behavior not reported in earlier studies. Under certain conditions, the open-loop distillation system shows a sustained oscillation associated with branching to periodic solutions. The limit cycles are accompanied by traveling waves inside the column. Significant underdamped oscillations are also observed over a wide range of product rates.

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Determination of Uranium in Monazite Sand by Polarographic Method (Polarograph 에 依한 Monazite 鑛石속의 Uranium 의 定量에 關한 硏究)

  • Kim, Hwang-Am;Son, Byong-Yong
    • Journal of the Korean Chemical Society
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    • v.5 no.1
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    • pp.84-87
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    • 1961
  • A polarographic method for rapid determination of Uranium in the presence of foreign ions was proposed. The method is based on the measurement of polarogram in the sulfuric acid as supporting electrolyte. In this medium Uranyl ions give well defined reduction waves, and half-wave potentials are -0.19V vs. S.C.E. as first wave, and uncertain volt. vs. S.C.E. as second wave in $2.4 N-H_2SO_4.$ The first wave has a linear relationship between the concentration of Uranyl ion and wave height. The author also studied a method for rapid determination of Uranium in Korean monazite sand without eliminating the foreign ions. The Korean monazite sands were analyzed by this method and satisfactory result were obtained.

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The Comparison of the Bead Size Effect on the Two Wave Patterns Induced in One Reaction System

  • Heo, Do Seong;Kim, Min Seok;Jo, Sang Jun
    • Bulletin of the Korean Chemical Society
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    • v.22 no.8
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    • pp.867-871
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    • 2001
  • We have studied the characteristic wave propagation in 1,4-CHD-Bromate-Ferroin reaction system and we have examined the bead size effect on the wave propagation of the system by adopting a half-divided Petri dish which is separated into two parts by the size of cation-exchange resin. It has been done to understand the reaction process inducing the characteristic wave behavior in the system. The characteristic wave behavior of the system is in the spontaneous induction of a revival wave with a long time lag. We have obtained a result that the revival wave is not affected by the size of catalyst-doped beads while the initially induced wave is influenced by the size of beads. It means that the two waves are induced by different reaction processes each other and the revival wave is induced by an uncatalyzed reaction process.

Electrochemical Behaviors of Sparteine-Copper (II) Dihalide

  • Sung-Nak Choi;Jin-Hyo Park;Young-In Kim;Yoon-Bo Shim
    • Bulletin of the Korean Chemical Society
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    • v.12 no.3
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    • pp.276-281
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    • 1991
  • Electrochemical behaviors of optically active sparteine-Cu(II) dihalide complexes were investigated by polarography and cyclic voltammetry (CV). These Cu(II) complexes are rather easier to be reduced to Cu(I) states when comparison is made with other nonplaner copper complexes, We have assigned the CV peaks and polarographic waves related to the redox processes for these complexes. We could also observe the exchange reaction of Cu(II) ion in the complex with mercury metal in the cell having mercury pool. The redox mechanism of these complelxes is as follows; The 1st wave appeared at +0.47 V/+0.65 V corresponds to the reaction of $SpCuX_2+ e{\rightleftarrow}SpCuX_{2^-}$ and the 2nd one at +0.26 V/+0.21 V does the reaction of $SpCuX_{2 ^-} +e{\rightleftarrow}SpCuX_2^{2-}$. The 3rd one at -0.35 V/-0.27 V is dueto the reduction of mercury complex formed via exchange reaction. Where, X is chloride ion.

Shock Tube and Modeling Study of the Ignition of Propane

  • Kim, Gil Yeong;Sin, Gwon Su
    • Bulletin of the Korean Chemical Society
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    • v.22 no.3
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    • pp.303-307
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    • 2001
  • The ignition of propane was investigated behind reflected shock waves in the temperature range of 1350-1800 K and the pressure range of 0.75-1.57 bar. The ignition delay time was measured from the increase of pressure and OH emission in the C3H8-O2-Ar system. The relationship between the ignition delay time and the concentrations of propane and oxygen was determined in the form of mass-action expression with an Arrhenius temperature dependence. The numerical calculations were also performed to elucidate the important steps in the reaction scheme of propane ignition using various reaction mechanisms. The ignition delay times calculated from the mechanism of Sung et al.1 were in good agreement with the observed ones.

Tuning Photophysical and Electrochemical Properties of Heteroleptic Cationic Iridium(III) Complexes Containing Substituted 2-Phenylquinoxaline and Biimidazole

  • Sengottuvelan, Nallathambi;Seo, Hoe-Joo;Kang, Sung-Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2309-2314
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    • 2010
  • Design and syntheses of four red phosphorescent heteroleptic cationic iridium(III) complexes containing two substituted phenylquinoxaline (pqx) or benzo[b]thiophen-2-yl-pyridin (btp) main ligands and one 2,2'-biimidazole (H2biim) ancillary ligand are reported: [$(pqx)_2$Ir(biim)]Cl (1), [$(dmpqx)_2$Ir(biim)]Cl (2), [$(dfpqx)_2$Ir(biim)]Cl (3), [$(btp)_2$Ir(biim)]Cl (4). Complex 1 showed a distorted octahedral geometry around the iridium(III) metal ion with cis metallated carbons and trans nitrogen atoms. The absorption, emission and electrochemical properties were systematically evaluated. The complexes exhibited red phosphorescence in the spectral range of 580 to 620 nm with high quantum efficiencies of 0.58 - 0.78 in both solution and solid-state at room temperature depending on the cyclometalated main ligands. The cyclic voltammetry of the complexes (1-3) showed a metal-centered irreversible oxidation in the range of 1.40 to 1.90 V as well as two quasi reversible reduction waves from -1.15 to -1.45 V attributed to the sequential addition of two electrons to the more electron accepting heterocyclic portion of two distinctive cyclometalated main ligands, whereas complex 4 showed a reversible oxidation potential at 1.24 V and irreversible reduction waves at -1.80 V.

Cathodic Reduction of Dichromate Ion (중크롬산이온의 음극 환원반응)

  • Lee Ju-Seong
    • Journal of the Korean Chemical Society
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    • v.21 no.4
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    • pp.276-283
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    • 1977
  • Reduction of dichromate at a platinum cathode in acid solution was studied by cyclic voltammetry and controlled potential electrolysis. Cathodic polarization curve consisted of three waves in unbuffered solution of potassium dichromate having initial pH ranges 1.5∼4.0, with sodium sulfate as the supporting electrolyte. Relative heights of the first and the second waves were, respectively, a function of chromium (Ⅵ) concentration and activity of hydrogen ion, but that of the third wave was not proportional to both of them. The current of the first two peaks were proportional to the sweep rate of potential (${\nu}$), while that of the last peak vs. ${\nu}^{1/2}$ was linear at the sweep rate of less than 50mV/sec. By the controlled potential electrolysis, the reduction of chromium (Ⅵ) was almost completely suppressed at potentials more negative than the last peak and at initial pH's above ca. 2.3 of unbuffered solution. Therefore, these peaks represented, respectively, $Cr_2O_7^{2-}{\to}Cr^{3+},\;2H^+{\to}H_2$ and the formation of a cathodic film.

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Studies on Determination of Titanium from Ilmenite by Polarographic Method (Polarography 에 依한 Titanium 의 定量에 關한 硏究)

  • Kim, Hwang-Am;Kim, Chan-Kuk
    • Journal of the Korean Chemical Society
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    • v.6 no.1
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    • pp.10-13
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    • 1962
  • Titanium in solution of EDTA (Ethylenediaminetetraacetic acid) yield well-defined, reversible polarographic waves. In this report, a polarographic method for rapid determination of titanium in the Korean ilmenite was proposed, This polarographic method is based on the measurement of polarogram in the supporting electrolyte of EDTA. As the pH is increased the wave become more irreversible the diffusion current are diminished, and the half wave potential become more negative. In spite of the complication arising from numerous titanium species, in 0.2 M of EDTA, pH 6.3, the titanium waves are reproducible and analytically useful. In this medium titanium ion give well-defined reduction wave, and the half wave potential were -0.61V vs S.C.E. at pH 6.3. At the same time, the wave had a linear relationship between the concentration of titanium ion and the wave height. The Korean ilmenites were analyzed by this method and satisfactory results were obtained.

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Electrochemical Reduction Behavior of Bilirubin (Bilirubin의 전기화학적 환원거동)

  • Bae Zun Ung;Lee Heung Lark;Jung Mi Sik;Park Tae Myung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.374-378
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    • 1991
  • The electrochemical reduction behavior of Bilirubin (BR) in phosphate buffer (pH 7.8) solution was studied by DC polarography, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. In DC polarogram, two reduction waves of BR were found. The half wave potentials of two reduction waves were -1.32 and -1.51 volts vs. Ag/AaCl respectively. The current type of 1st reduction wave was diffusion-controlled and the 2$^{nd}$ reduction wave was diffusion current containing a little kinetic current. The electrochemical reduction process of BR at each reduction step was all irreversible. The prewave appeared at lower concentration than 3.4 ${\times}$ 10$^{-4}$M, this prewave was identified as adsorption prewave. And the number of electron transfered in reduction steps, n$_{app}$ was two for the 1st reduction step and one for the 2$^{nd}$ reduction step.

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Synthesis of 1-Benzyl-4-Iodomethyl-2-Azetidinone and Electrochemical Reduction on the Iodo Group (1-Benzyl-4-Iodomethyl-2-Azetidinone의 합성과 Iodo기에 대한 전기화학적 환원반응)

  • Kim Il Kwang;Lee Young Haeng;Lee Chai Ho;Chai Kyu Yun;Kim Yoon Geun
    • Journal of the Korean Chemical Society
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    • v.35 no.1
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    • pp.70-77
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    • 1991
  • 1-Benzyl-4-iodomethyl-2-azetidinone(BIMA) was synthesized and its electrochemical reduction was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The irreversible two electron transfer on reductive dehalogenation of iodo group proceeded to form 1-benzyl-4-methyl-2-azetidinone by EEC electrode reaction mechanism at the first reduction step(-1.35 volts vs. Ag-AgCl). The polarographic reduction waves separated into two reduction steps due to anionic surfactant (sodium lauryl sulfate) effects, while the waves were shifted to the positive potential as the concentration of cationic surfactant (cetyltrimethylammonium bromide) increased. Upon the basis of results on the product analysis and interpretation of polarogram with pH variable, EEC electrochemical reaction mechanism was suggested.

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