• Title/Summary/Keyword: Rate Determining Step

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Polarographic Study of Nitrosophenylhydroxylamine (Polarography에 依한 Nitrosophenylhydroxylamine에 關한 硏究)

  • Jung-Eui Hwang;Chong-Jae Chung;Moo-Young Son
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.303-307
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    • 1969
  • The ammonium salt of Nitrosophenylhydroxylamine "called cupferron", is a well-known analytical reagent, which precipitates a great number of metal ions in acid medium. The electrode reduction velocities of cupferron at droping mercury electrode in various supporting electrolytes were measured by Delahay method. The free energy of activation and transfer coefficient for a given electrode reaction are computed from the corresponding current-voltage curve. The number of electrons involved in the rate determining step of the reduction of cupferron is calculated for solutions of various pH.

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Kinetics and Mechanism of the Oxidation of n-Butylamine with Hydrogen Peroxide in the Presence of V(Ⅳ) ($VO^{2+}$촉매존재하에서 과산화수소에 의한 n-부틸아민의 산화반응속도와 메카니즘)

  • Kim, Chang Su;Ju, Geon Hong
    • Journal of the Korean Chemical Society
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    • v.34 no.3
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    • pp.297-303
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    • 1990
  • $VO^{2+}-catalyzed oxidation of n-butylamine by hydrogen peroxide shows that the reaction is a first order in the concentration of n-butylamine, acid added, and VO^{2+}$ as catalyst, respectively. The reactions involve the initial formation of an imine intermediate, followed by hydrolysis to butyraldehyde and ammonia. It is suggested that the rate-determining step is a process dehydrogenation of n-butylammine.

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Rates and Mechanism of the Oxidation of l-Ascorbic Acid with Cu(Ⅱ)-Polyamine Complexes (구리(Ⅱ)-아민류 착물에 의한 l-ascorbic acid의 산화반응속도와 메카니즘)

  • Kim, Sun-Deuk;Park, Jung-Eun;Jang, Ki-Ho;Shin, Han-Chul;Kim, Chang-Su
    • Journal of the Korean Chemical Society
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    • v.39 no.1
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    • pp.29-34
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    • 1995
  • The rates for the oxidation reaction of l-ascorbic acid by Cu(Ⅱ)-polyamine complexes were measured by Onish's method at the pH 4.6. The oxidation process of l-ascorbic acid is proposed to occur by the inner-sphere mechanism that involves the formation of a Cu(Ⅱ)-ascorbic acid complex and electron transfer at the rate-determining step.

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Influence of Solvents on Rates of Reactions of 2,4-Dinitro Substituted Halobenzenes with Substituted Anilines (I) (2,4-이니트로 할로벤젠과 치환된 아닐린의 반응속도에 대한 용매효과 (제1보))

  • Hai Whang Lee;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.21 no.2
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    • pp.83-88
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    • 1977
  • Kinetic studies on the rates of reactions of 2, 4-dinitrochlorobenzene with p-toluidine, aniline and p-chloroaniline in $CH_3CH-CH_3OH$ binary solvent mixtures have been carried out. The experimental results have been explained in terms of the specific solvation by alcoholic hydrogen. It has been shown that the bond breaking step is rate determining in the solvent system studied and the energy barrier is getting low as the solvent changes from acetonitrile to methanol.

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Kinetics and Mechanism of the Aminolysis of O-Methyl-S-Phenylthiocarbonates in Methanol

  • Song, Ho-Bong;Choi, Moon-Ho;Koo, In-Sun;Oh, Hyuck-Keun;Lee, Ik-choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.1
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    • pp.91-94
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    • 2003
  • Kinetic studies of the reaction of O-methyl-S-phenylthiocarbonates with benzylamines in methanol at 45.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn based on (ⅰ) the large magnitude of ${\rho}_X\;and\;{\rho}_Z$, (ⅱ) the normal kinetic isotope effects $(k_H/k_D\;>\;1.0)$ involving deuterated benzylamine nucleophiles, (ⅲ) the positive sign of ${\rho}_{XZ}$ and the larger magnitude of ${\rho}_{XZ}$ than that for normal $S_N2$ processes, and lastly (ⅳ) adherence to the reactivity-selectivity principle (RSP) in all cases.

A New Anchor Shot Detection System for News Video Indexing

  • Lee, Han-Sung;Im, Young-Hee;Park, Joo-Young;Park, Dai-Hee
    • Journal of the Korean Institute of Intelligent Systems
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    • v.18 no.1
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    • pp.133-138
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    • 2008
  • In this paper, we propose a novel anchor shot detection system, named to MASD (Multi-phase Anchor Shot Detection), which is a core step of the preprocessing process for the news video analysis. The proposed system is composed of four modules and operates sequentially: 1) skin color detection module for reducing the candidate face regions; 2) face detection module for finding the key-frames with a facial data; 3) vector representation module for the key-frame images using a non-negative matrix factorization; 4) one class SVM module for determining the anchor shots using a support vector data description. Besides the qualitative analysis, our experiments validate that the proposed system shows not only the comparable accuracy to the recently developed methods, but also more faster detection rate than those of others.

Kinetics and Mechanism of the Pyridinolysis of Aryl Cyclopropanecarboxylates in Acetonitrile

  • Koh, Han-Joong;Kang, Suk-Jin;Kim, Cheol-Ju;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.7
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    • pp.925-930
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    • 2003
  • Kinetic studies of the reaction of Z-aryl cyclopropanecarboxylates with X-pyridines in acetonitrile at 55.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$. These mechanistic conclusions are drawn base on (i) the large magnitude of ρx and ρz, (ii) the positive sign of ρxz and the larger magnitude of ρxz than normal $S_N2$ processes, (iii) a small positive enthalpy of activation, Δ$H^≠$, and a large negative, Δ$S^≠$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.

Rates and Mechanism of Adsorption of Transition Metal Ions on Polystyrene Resins Supported Triethylenetetramine (트리에틸렌테트라아민을 지지시킨 폴리스틸렌 수지에 대한 전이금속이온의 흡착속도와 메카니즘)

  • Kim Sun-Deuk;Shin Yun-Yeol;Kim Chang-Su
    • Journal of the Korean Chemical Society
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    • v.35 no.1
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    • pp.16-23
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    • 1991
  • Resins of polystyrene supported triethylenetetramine of linear and claw types have been prepared by the reaction of triethylenetetramine with chloromethylated polystyrene. The resin supported triethylenetetramines were principally characterized by infrared spectra. Kinetics of adsorption of transition metals on the resin have been investigated. This paper reports the results of the diffusion coefficients and entropies of activation. The rate determining step is a process of diffussion through the particle.

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Kinetics and Mechanisms of the Oxidation of Carbon Monoxide on Ni-Doped $\alpha-Fe_2O_3$

  • Kim, Keu-Hong;Jun, Jong-Ho;Choi, Jae-Shi
    • Bulletin of the Korean Chemical Society
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    • v.5 no.1
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    • pp.41-44
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    • 1984
  • The oxidation of carbon monoxide has been investigated on Ni-doped ${\alpha}-Fe_2O_3$ catalyst at 300 to $450^{\circ}$. The oxidation rates have been correlated with 1.5-order kinetics; first with respect to CO and 1/2 with respect to $O_2$. Carbon monoxide is adsorbed on lattice oxygen of Ni-doped ${\alpha}-Fe_2O_3$, while oxygen appears to be adsorbed on oxygen vacancy formed by Ni-doping. The conductivities show that adsorption of CO on O-lattice produces conduction electron and adsorption of $O_2$ on O-vacancy withdraws the conduction electron from vacancy. The adsorption process of CO on O-lattice is rate-determining step and dominant defect of Ni-doped ${\alpha}-Fe_2O_3$ is suggested from the agreement between kinetic and conductivity data.

Kinetics of Oxidation of Nitrotoluenes by Acidic Hexacyanoferrate (Ⅲ)

  • Bhattacharjee, A. K.;Mahanti, M. K.
    • Bulletin of the Korean Chemical Society
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    • v.4 no.3
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    • pp.120-123
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    • 1983
  • The reaction of hexacyanoferrate (Ⅲ) with nitrotoluenes in aqueous acetic acid containing perchloric acid(1.0 M) at $50^{\circ}C$ gave the corresponding aldehyde as the major product. The order with respect to each of the reactants ― substrate, oxidant and acid ― was found to be unity. The Hammett plot yielded a ${\sigma}^+$ value of -1.30, and the kinetic isotope effect gave a $k_H/k_D$ value of 6.2. The pathway for the conversion of the nitrotoluenes to the products has been mechanistically visualized as proceeding through the benzylic radical intermediate, formed in the rate determining step of the reaction.