• 제목/요약/키워드: Reaction order

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Kinetic Studies on Bromine-Exchange Reactions of Antimony Tribromide with $\alpha$-Phenyl-n-butyl and $\alpha$-Phenyl-i-butyl Bromides in Nitrobenzene$^\dag$

  • Rhyu, Sok-Hwan;Choi, Sang-Up
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.408-414
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    • 1987
  • The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

Decolorization Characteristics of Acid and Basic Dyes Using Modified Zero-valent Iron (개질 영가철을 이용한 산성 및 염기성 염료의 탈색 특성)

  • Choi, Jeong-Hak;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.25 no.12
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    • pp.1717-1726
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    • 2016
  • In this study, the reductive decolorization of three acid and basic dyes using modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium coated iron (Pd/Fe)) at various pH conditions (pH 3~5) was experimentally investigated and the decolorization characteristics were evaluated by analyzing the absorbance spectra and reaction kinetics. In the case of acid dyes such as methyl orange and eriochrome black T, color removal efficiencies increased as initial pH of the dye solution decreased. However, the color removal of methylene blue, a basic dye, was not affected much by the initial pH and more than 70% of color was removed within 10 min. During the decolorization reaction, the absorbance of methyl orange (${\lambda}_{max}=464nm$) and eriochrome black T (${\lambda}_{max}=528nm$) decreased in the visible range but increased in the UV range. The absorbance of methylene blue (${\lambda}_{max}=664nm$) also decreased gradually in the visible range. Pseudo-zero order, pseudo-first order, and pseudo-second order kinetic models were used to analyze the reaction kinetics. The pseudo-second order kinetic model was found to be the best with good correlation. The decolorization reaction rate constants ($k_2$) of methylene blue were relatively higher than those of methyl orange and eriochrome black T. The reaction rate constants of methyl orange and eriochrome black T increased with a decrease in the initial pH.

A Study on the Transesterification Reaction Between Methyl Methacylate and Diethanolamine (메틸메타크릴레이트와 디에탄올아민과의 에스테르 교환반응에 관한 연구)

  • Sohn, Byoung-Chung;Park, Keun-Ho;Jeong, Soon-Wook;Nam, Ki-Dae
    • Journal of the Korean Applied Science and Technology
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    • v.3 no.2
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    • pp.41-47
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    • 1986
  • The transesterification reaction between diethanolamine and methyl-methacrylate was kinetically investigated in the presence of various metal acetate catalysts at $120^{\circ}C$. The quantity of methylmethacrylate reacted in the reaction flask was measured by gas chromatography and liquid chromatography, and the reaction rate was investigated by measuring of the quantity of products and reactnts under various catalysts. The transesterification reaction was carried out in the first order reaction kinetics with respect to the concentration of diethanolamine and methylmethacrylate, respectively. The apparent rate constant was found to obey first-order kinetics with respect to the concentration of catalyst. The linear relationship was shown between apparent rate constant and reciprocal absolute temperature, and by the Arrhenius plot, the activation energy has been calculated as 11.08 Kcal with zinc acetate catalyst, 17.99 Kcal without catalyst. The maximum reaction rate was appeared at the range of 1.4 to 1.6 of electronegativity of metal ions and instability constant of metal acetates.

Synthesis of Highly Pure 1,4-Sorbitan for Preparation of Anti-Fogging Agent (Solbitol로부터 무적제 제조용 고순도 1,4-솔비탄의 합성)

  • Yu, Hwa-Yeal;Moon, Bu-Hyun;Ju, Chang-Sik
    • Journal of Environmental Science International
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    • v.17 no.3
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    • pp.351-357
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    • 2008
  • In order to develope an efficient way for the synthesis of highly pure 1,4-sorbitan solution from sorbitol, some experimental studies were performed. The reaction showed first order reaction with activation energy of 118.3 KJ/mol. Color of the product solutions changed to brown with reaction temperature and reaction time. The equilibrium contents of 1,4-sorbitan increased with decrease in reaction pressure, but the content of major impurity, sorbide, showed maximum about 550 torr vacuum with $H_3PO_4$ catalyst. The reasonable catalyst configuration was 0.26 wt% PTSA and 1 wt% $H_3PO_2$ and optimum reaction temperature and pressure range was $110\sim120^{\circ}C$ and $700\sim720$ torr vacuum, respectively. At optimum reaction conditions, we could obtain white product solutions of highly pure 1,4-sorbitan with sorbide less than 10 wt%. This white product solution is advantageous for preparation of high quality span, anti-fogging agent.

Reaction of Furfural Derivatives. Cannizzaro reaction of Furfural, 5-Bromo-and 5-Methylfurfural (Cyclitol 유도체합성을 위한 Furfural 유도체의 반응에 관한 연구. Furfural, 5-Bromo-및 5-Methylfurfural의 Cannizzaro 반응)

  • Sohn Joo Hwan;Kim, Yong In;Nam Ki Dae
    • Journal of the Korean Chemical Society
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    • v.16 no.5
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    • pp.290-297
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    • 1972
  • We have obtained the results of Cannizzaro reaction of furfural, 5-methylfurfural and 5-bromofurfural by using alcoholic potassium hydroxide solution in 95% (V/V) methanol solvent at $0{\sim}40^{\circ}C$. The results are as follows: 1) Their Cannizzaro reaction is fourth-order reaction, and the reaction of furfural proceeds 3 times as rapid as that of 5-methylfurfural and 10 times as slow as that of 5-bromofurfural. 2) Their activation energies of furfural, 5-methylfurfural and 5-bromofurfural in the reaction are 10.46Kcal/mole, 16.27Kcal/mole, and 9.62Kcal/mole respectively, and the calculated activation parameters, and ${\Delta}S^{\neq}$, increase in the order of 5-bromofurfural, furfural and 5-methyl-furfural.

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Kinetics of the KOH Catalyzed-Methanolysis for Biodiesel Production from Fat of Tra Catfish

  • Huong, Le Thi Thanh;Tan, Phan Minh;Hoa, Tran Thi Viet;Lee, Soo
    • Journal of the Korean Applied Science and Technology
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    • v.25 no.4
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    • pp.418-428
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    • 2008
  • Transesterification of fat of Tra catfish with methanol in the presence of the KOH catalyst yields fatty acid methyl esters (FAME) and glycerol (GL). The effects of the reaction temperature and reaction time on rate constants and kinetic order were investigated. Three regions were observed. In the initial stage, the immiscibility of the Tra fat and methanol limited the reaction rate, hence this region was controlled by the mass transfer. Subsequent to this region, produced FAME like a co-solvent made the reaction mixture homogeneous, therefore the conversion rate increased rapidly so it was controlled by the kinetic parameters of the reaction until the equilibrium was approached in the final slow region. A second-order kinetic mechanism was proposed involving second regions for the forward reaction. The rate determining step for the overall KOH catalyzed-methanolysis of Tra fat was the conversion of triglycerides (TG) to diglycerides (DG). This rate constant was increased from 0.003 to $0.019min^{-1}$ when the reaction temperature was increased from 35 to $60^{\circ}C$. Its calculated activation energy was 14.379 ($kcal.mol^{-1}$).

The Nature of Acid-Catalyzed Acetalization Reaction of 1,2-Propylene Glycol and Acetaldehyde

  • Cheng, Chen;Chen, Hui;Li, Xia;Hu, Jianli;Liang, Baochen
    • Korean Chemical Engineering Research
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    • v.53 no.4
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    • pp.463-467
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    • 2015
  • We investigated catalytic activity of ion-exchange resins in acetalization of 1,2-propylene glycol with acetaldehyde. The impacts of reaction variables, such as temperature, reaction time, catalyst loading and feedstock composition, on the conversion of 1,2-propylene glycol were measured. The life of the catalyst was also studied. Furthermore, the reaction kinetics of 1,2-propylene glycol acetalization was studied. It was found that reaction rate followed the first-order kinetics to acetaldehyde and 1,2-propylene glycol, respectively. Therefore, overall acetalization reaction should follow the second-order reaction kinetics, expressed as. Key words: 1,2-propylene Glycol, 2,4-dimethyl-1,3-dioxolane, Ion-exchange Resin, Polyhydroxy Compounds, Acetalization $r=kC^{nA}_AC^{nB}_B=19.74e^{\frac{-6650}{T}}C^1_AC^1_B$.

A Study on the Ester Interchange Reaction of Dimethyl Naphthalate with Ethylene Glycol (Dimethyl Naphthalate와 Ethylene Glycol의 에스테르 교환반응에 관한 연구)

  • Sho, Soon-Yong;Cheong, Seong-Ihl
    • Polymer(Korea)
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    • v.25 no.1
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    • pp.25-32
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    • 2001
  • The kinetics of ester interchange reaction of dimethyl naphthalate(DMN) with ethylene glycol(EG) has been studied in the range of 180-200 $^{\circ}C$ using zinc and manganese catalysts. The reaction was performed in a semibatch reactor under nonisothermal condition and the degree of reaction was calculated from experimental data of methanol removal rate and reaction temperature. As a reaction model, both the functional group model and the molecular species model were applied and analysed. In case of zinc catalyst, the ratio of reaction rate of methyl hydroxyethyl naphthalate(MHEN) with EG on that of DMN with EG is about 1.4, whereas in case of manganese catalyst the ratio is about 4.3, which implies that the reaction rate is quite dependent on the type of catalyst. In case of zinc catalyst, the reaction order of catalyst concentration on either DMN or MHEN and EG is less than 1, whereas in case of manganese catalyst, the reaction order is larger than 1. The activation energy for zinc and manganese catalyst, irrespective of the type of molecular species, e.g., DMN and MHEN, were found to be 25000 and 28750 cal/mol, respectively. As a result of comparing two reaction model, the molecular species model fits well for the experimental data.

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Reaction Mechanism for Zeolite A Synthesis from Hadong Kaolin (하동 고령토로부터 Zeolite A 합성 반응기구)

  • 권영수;김면섭
    • Journal of the Korean Ceramic Society
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    • v.20 no.3
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    • pp.255-259
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    • 1983
  • Am(rphous aluminosilicate zeolite A and hydroxysodalite were obtained by reaction of Hadong kaolin(halloysite) with IN sodium hydroxide solntion in the temperature range of 60 to 10$0^{\circ}C$ For determination of the mechanism of the reaction Various possible mechanisms were compared with the experimental results. It was observed that the reaction mechamism of zeolite A synthesis from Hadong kaolin was first order consecu-tive reaction as follows : halloysitelongrightarrowamorphous aluminosilicatelongrightarrowzeolite Alongrightarrowhydroxysodalite

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The Effect of External Noise on Dynamic Behaviors of the Schlogl Model with the Second Order Transition for a Photochemical Reaction

  • 김경란;Lee, Dong J.;신국조
    • Bulletin of the Korean Chemical Society
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    • v.16 no.11
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    • pp.1119-1121
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    • 1995
  • The method for the Schlo"gl model with the first order transition is extended to the Scho;gl model with the second order transition for a photochemical reaction. We obtain the explicit results of the time-dependent average and the time correlation function at the unstable steady state of the model in the neighborhood of the Gaussian white noise and then discuss the effect of noise on the dynamic properties.