• Title/Summary/Keyword: Chemical Reaction Rates

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Computational Modeling of Cyclic Voltammetry on Multi-electron Electrode Reaction using Diffusion Model (확산모델을 이용한 다중전자 전극반응에 대한 순환전위법의 전산모델링)

  • Cho, Ha-Na;Yoon, Do-Young
    • Journal of the Korean Electrochemical Society
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    • v.15 no.3
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    • pp.165-171
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    • 2012
  • Here is implemented MATLAB program to analyze the characteristic curves of cyclic voltammetry which involves the multi-electron electrode reaction considered as key processes in electrochemical systems. For the electrochemical mass-transfer system, Fick's concentration equation subject to semi-infinite diffusion model for the boundary condition was discretized and solved by the explicit finite difference method. The resulting concentration values were converted into currents at each node by using Butler-Volmer equation. Based on the good agreement between the present numerical solution and the existing experimental results, effects of kinetic constants and CV scan rates on the reaction mechanism in multi-electron transfer processes were investigated effectively.

Reaction Monitoring of Imine Synthesis Using Raman Spectroscopy

  • Lee, Moon-Kwon;Kim, Hye-Sung;Rhee, Hak-June;Choo, Jae-Bum
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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    • pp.205-208
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    • 2003
  • Laser-induced Raman spectroscopy has been utilized to demonstrate its feasibility for studying the kinetics of imine formation in chloroform solvent. The imine formation, by the nucleophilic addition of primary amine to the carbonyl group of ketone, has been monitored at ten minute intervals for eight hours. The intensity of the C=O stretching mode at 1684 $cm^{-1}$ was measured to determine the rate constant of the reaction. In order to correct the sample-to-sample fluctuations in Raman peak area, this peak was normalized to the C-Cl bending peak at 666 $cm^{-1}$. By the peak area change during the course of reaction, the second order rates at three different temperatures have been determined. The substituent effects on the π conjugations of imine product have also been investigated. On the basis of Raman frequency shifts, the delocalization properties of the aromatic system modified by substitution of a hydrogen atom with -Cl and $-CH_3O$ groups could be clearly understood.

Substituent Effects for the Menschutkin-Type Reaction of Substituted 2-Phenylethyl arenesulfonates with Substituted Pyridines (치환 2-Phenylethyl arenesulfonate 류와 치환 피리딘류의 Menschutkin 형 반응에 관한 치환기 효과)

  • Soo-Dong Yoh;Joong Hyup Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.413-418
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    • 1989
  • The rates for the reaction of substituted 2-phenylethyl tosylates with substituted pyridines were measured in acetonitrile and that of 2-PNS with substituted pyridines were investigated in both acetonitrile and methanol. The substitutent effect was accelerated by an electron-donating substituent on both substrate and nucleophile. Results showed that More O'Ferrall and quantum mechanical model of predicting transition state structure suggest the reaction proceeds via an $S_N2$ mechanism, in which bond-breaking is more advanced than bond-formation. Transition state variation predicted with the quantum mechanical model is consistent with the experimental results, whereas the predictions provided by the More O'Ferrall plots is found to be inconsistent in leaving group. In the reaction of 2-PNS, the rate constants in acetonitrile were larger than that in methanol.

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An Experimental Study on the Optimal Conditions of Decomposition/Synthesis of Methanol for Heat Transport from Long Distance (장거리 열수송을 위한 메탄올 분해/합성 반응 최적화 조건의 실험적 연구)

  • Yoon, Seok-Mann;Moon, Seung-Hyun;Lee, Seung-Jae;Choi, Soon-Young
    • Journal of Energy Engineering
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    • v.19 no.3
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    • pp.195-202
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    • 2010
  • A third of primary energy is lost as a waste heat. To improve this inefficient use of energy, systems using chemical reaction have been suggested and studied. In this study, methanol decomposition/synthesis reaction as a chemical reaction was selected for long time heat storage and long distance heat transport system because of safe, cheap and gaseous product. The purpose of this study is to find the optimal conditions in the methanol decomposition and synthesis reactions for long distance heat transport. Several parameters such as reaction temperature, pressure, $H_2$/CO ratio, space velocity, catalyst particle size were tested to find the effects on the reaction rates for the methanol synthesis. And the reaction temperature, space velocity, catalyst particle size were tested to find the effects on the production concentration for the methanol decomposition.

A Study of the Isomerization Reaction Rates of Azobenzene Derivatives (아조벤젠 유도체의 이성질화 반응속도에 관한 연구)

  • Yang, Si Yeong;Kim, Jong Gyu;Heo, Yeong Deok;Choe, Yeong Sang
    • Journal of the Korean Chemical Society
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    • v.38 no.8
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    • pp.552-561
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    • 1994
  • The cis → trans thermal isomerization of azobenzene derivatives has been studied. A sizable solvent effect on the rates for thermal isomerization of push-pull azobenzenes are observed. It is suggested that the isomerization proceeds via a rotational mechanism. For non push-pull azobenzenes, the lack of solvent effects on the rate of isomerization was observed. This suggests that the isomerization proceeds via an inversional mechanism for non push-pull azobenzenes.

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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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Rhodium(I) Complexes of 1,1$^\prime$-Bis(diphenylphosphino)-ferrocene as Efficient Catalysts in Regioselective Hydrogenation of Polynuclear Heteroaromatic Compounds

  • Kim, Tae-Jeong;Lee, Kyu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.10 no.3
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    • pp.279-282
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    • 1989
  • Two rhodium(I) complexes of the types [Rh(BPPF)(NBD)]$ClO_4$ (10) and [Rh(BPPF)$Cl]_2$ (11) (BPPF = 1,1'-bis(diphenylphosphino)-ferrocene) have been prepared and investigated as catalysts for the regioselective hydrogenation of polynuclear heteroaromatic nitrogen and sulfur compounds such as quinoline (1), acridine (2), phenanthridine (3), 7,8-benzoquinoline (4), benzothiophene (5), isoquinoline (6), indole (7), pyridine (8), and thiophene (9). Both complexes 10 and 11, except for the cases of indole (7) and mononuclear heteroaromatics 8-9, are very efficient in the selective reduction under quite mild hydrogenation conditions to give the corresponding saturated nitrogen and sulfur heterocyclic analogues of 1-6 in fast conversion rates and in excellent yields. Relative rate studies revealed that the reduction depends significantly on the steric and electronic effects of the substrates. Of the two complexes 10-11, the dimeric species 11 gives faster reaction rates in all cases studied.

Monoclonal Antibody Refolding and Assembly: Protein Disulfide Isomerase Reaction Kinetics

  • Park, Sun-Ho;Ryu, Dewey D.Y.
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.8 no.2
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    • pp.59-63
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    • 2003
  • The protein disulfide isomerase (PDI) reaction kinetics has been studied to evaluate its effect on the monoclonal antibody (Mab) refolding and assembly which accompanies disulfide bend formation. The MAb in vitro assembly experiments showed that the assembly rate of heavy and light chains can be greatly enhanced in the presence of PDI as compared to the rate of assembly obtained by the air-oxidation. The reassembly patterns of MAb in-termediates were identical for both with and without PDI, suggesting that the PDI does not determine the MAb assembly pathway, but rather facilitates the rate of MAb assembly by promoting PDI catalyzed disulfide bond formation. The effect of growth rate on PDI activities for MAb production has also been examined by using continuous culture system. The specific MAb productivity of hybridoma cells decreased as the growth rate increased. However, PDI activities were nearly constant fur a wide range of growth rates except very high growth rate, indicating that no direct correlation between PDI activity and specific MAb productivity exists.

Monoclonal Antibody Refolding and Assembly: Protein Disulfide Isomerase Reaction Kinetics

  • Park, Sun-Ho;Ryu, Dewey D.Y.
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.1 no.1
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    • pp.13-17
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    • 1996
  • The protein disulfide isomerase(PDI) reaction kinetics has been studied to evaluate its effect on the monoclonal antibody(MAb) refolding and assembly which accompanies disulfide bond formation The MAb in vitro assembly experiments showed that the assembly rate of heavy and light chains can be greatly enhanced in the presence of PDI as compared to the rate of assembly obtained by the air-oxidation. The reassembly patterns of MAb intermediates were identical for both with and without PDI, suggesting that the PDI does not determine the MAb assembly pathway, but rather facilitates the rate of MAb assembly by promoting PDI catalyzed disulfide bond formation. The effect of growth rate on PDI activities for MAb production has also been examined by using continuous culture system. The specific MAb productivity of hybridoma cells decreased as the growth rate increased. However, PDI activities were nearly constant for a wide range of growth rates except very high growth rate, indicating that no direct correlation between PDI activity and specific MAb productivity exists.

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Structure-Reactivity Relationships for the Reaction of Aryl Benzoates with Amines (Aryl Benzoates와 Amine류의 반응에 관한 구조-반응성 관계)

  • Cheong, Duk-Young;Kweon, Jeong-Min;Yoh, Soo-Dong;Park, Byung-Soo
    • Journal of the Korean Chemical Society
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    • v.39 no.7
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    • pp.572-577
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    • 1995
  • The reaction rates of aryl substituted(Z)-benzoates with amines were determined by a spectro-photometric method in acetonitrile at various temperatures. Hammett $\rho$, Bronsted ${\beta}$ values, and activation parameters were evaluated from the kinetic data. Linear free energy relationships, activation parameters, and the interpretation of M-O-F-J diagram suggested that these reactions were probably enforced an $S_AN$ mechanism.

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