• Title/Summary/Keyword: Rate-Controlling Reaction

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Kinetic Studies on the Addition of Potassium Cyanide to α,N-Diphenylnitrone

  • 김태린;김영호;변상용
    • Bulletin of the Korean Chemical Society
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    • v.20 no.6
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    • pp.712-714
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    • 1999
  • The rate constants for the nucleophilic addition of potassium cyanide to α,N-diphenylnitrone and its derivatives (p-OCH3, p-CH3, p-Cl, and p-NO2) were determined by ultraviolet spectrophotometer at 25℃, and the rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: At high pH, the cyanide ion to carbon-nitrogen double bond was rate controlling, however, in acidic media, the reaction proceeded by the addition of hydrogen cyanide molecule to carbon-nitrogen double bond after protonation at oxygen of a,N-diphenylnitrone. In the range of neutral pH, these two reactions occured competitively.

Kinetic Studies on the Nucleophilic Addition of Thiophenol Derivatives to 4'-[N- (9-Acridinyl) ]-1'-( N- methanesulfonyl) -3'-methoxyquinonediimide

  • 김태린;정동인;변상용
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.374-379
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    • 1997
  • The rate constants for the nucleophilic addition of thiophenol derivatives (p-OCH3, H, p-CH3, m-CH3, p-Br and p-NO2) to 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide (AMQD) were determined by ultraviolet spectrophotometer in water at 5 ℃, and rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, Bronsted plot, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: Below pH 2.5, the reaction proceeded by the addition of thiophenol molecule to 6'-position of quinonoid after protonation at the acridinyl nitrogen. Above pH 6.2, the addition of sulfide anion to 6'-position of quinonoid was rate controlling. However, in the range of pH 3.0-6.0, these two reactions occured competively.

Study on the Treatability of High-Concetration Wastewater by ABBR (ASBR에 의한 고농도폐수의 혐기성처리 연구)

  • 김종찬;김요용;김세진;정일현
    • Journal of environmental and Sanitary engineering
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    • v.10 no.1
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    • pp.98-105
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    • 1995
  • In the treatment of wastewater or sewage plant sludge with high solid concentration, high rate digestion process in which heating and mixing occur at a time is mainly used, and in the case of wastewater containing solid matter below 1000mg/ℓ the recently developed AF or UASB is developed Recently and commonly utilized. But these processes have weakpoints such as clogging of packing media and need of long period of trial run after microorganism granulation. In this point of view, there are active researches on the ASBR( anaerobic sequence batch reaction ) that is capable of treating of organic matter with reactor that has no packing materials and controlling the inflow time, reaction time sedimentation time and outflow time by time control without loss of microorganisms. The objectives of this study are to evaluate the efficiency of ASBR process according to the reaction time, change of treated water quality and gas output rate in the treatment of wheat plant wastewater.

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Kinetics Studies on the Mechanism of Hydrolysis of S-Phenyl-S-vinyl-N-p-tosylsulfilimine Derivatives

  • Pyun, Sang-Yong;Kim, Tae-Rin;Lee, Chong-Ryoul;Kim, Whan-Gi
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.306-310
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    • 2003
  • Hydrolysis reactions of S-phenyl-S-vinyl-N-p-tosylsulfilimine (VSI) and its derivatives at various pH have been investigated kinetically. The hydrolysis reactions produced phenylvinylsulfoxide and p-toluene sulfonamide as the products. The reactions are first order and Hammett ρ values for pH 1.0, 6.0, and 11.0 are 0.82, 0.45, and 0.57, respectively. This reaction is not catalyzed by general base. The plot of k vs pH shows that there are three different regions of the rate constants $(k_t)$ in the profile.; At pH < 2 and pH > 10, the rate constants are directly proportional to the concentrations of hydronium and hydroxide ion catalyzed reactions, respectively. The rate constant remains nearly the same at 2 < pH < 10. On the bases of these results, the plausible hydrolysis mechanism and a rate equation have been proposed: At pH < 2.0, the reaction proceeds via the addition of water molecule to sulfur after protonation at the nitrogen atom of the sulfilimine, whereas at pH > 10.0, the reaction proceeds by the addition of hydroxide ion to sulfur directly. In the range of pH 2.0-10.0, the addition of water to sulfur of sulfilimine appears to be the rate controlling step.

A Study on the Catalytic Oxidation Reaction of Carbon Monoxide with Nickel Oxide (NiO 촉매에 의한 CO 산화반응에 관한 연구)

  • Jae Shi Choi;Keu Hong Kim
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.241-247
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    • 1969
  • The catalytic reaction between carbon monoxide and oxygen was investigated with the various nickel oxide catalysts at different partial pressures of carbon monoxide and oxygen and at reaction temperatures in the region of 120$^{circ}$to 250$^{circ}C$. The reaction has the highest rate with the nickel oxide catalyst which is sintered at low temperature. A reaction mechanism to explain the data is derived. From the Arrhenius equation, the activation energies in the region of experimental temperatures are found to be from 5.49 to 9.15 kcal/mole. The concentration of excess oxygen in the nickel oxide seems to vary according to the sintering temperatures and periods and is the controlling factor in determining the type of kinetics followed by the catalytic reaction.

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Effect of Cement Particle Size on Properties of Ordinary Portland Cement (보통 포틀랜드 시멘트 물성에 미치는 시멘트 입도의 영향)

  • Byun, Seung-Ho;Kim, Hyeong-Cheol;Kim, Jae-Young;Choi, Hyun-Kuk;Song, Jong-Taek
    • Journal of the Korean Ceramic Society
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    • v.47 no.5
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    • pp.394-400
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    • 2010
  • This study examined the effects of particle size on characteristics of cement by controlling the particle size of commercial cement. Through a size adjustment, the cement has increasing more of particles that are less than $10{\mu}m$ in size so the initial reaction time has been shortened as a result of improvement in the early hydration reaction. Additionally, it showed a great characteristics of strength from the early age and the initial hydration heat has been increased as well. In the upper and middle parts cements, the initial hydration reaction rate contribution is high with the $10{\mu}m$ compared to original cement. So the initial hydration reaction rate is improved and as a result, it also showed relatively high hydration heat as well. Additionally, adiabatic temperature also showed an increase rate in the results.

Global Fitting Functions for Kinetics of Fe-Selective Chlorination in Ilmenite and Successive Chlorination of Beneficiated TiO2 (일메나이트 중 철의 선택적 염화와 선광된 TiO2의 추가 염화반응에 대한 글로벌 피팅함수)

  • Chung, Dong-Kyu;Won, Yong Sun;Kim, Yong-Ha;Jung, Eun-Jin;Song, Duk-Yong
    • Korean Journal of Materials Research
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    • v.29 no.7
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    • pp.412-424
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    • 2019
  • Global fitting functions for Fe-selective chlorination in ilmenite($FeTiO_2$) and successive chlorination of beneficiated $TiO_2$ are proposed and validated based on a comparison with experimental data collected from the literature. The Fe-selective chlorination reaction is expressed by the unreacted shrinking core model, which covers the diffusion-controlling step of chlorinated Fe gas that escapes through porous materials of beneficiated $TiO_2$ formed by Fe-selective chlorination, and the chemical reaction-controlling step of the surface reaction of unreacted solid ilmenite. The fitting function is applied for both chemical controlling steps of the unreacted shrinking core model. The validation shows that our fitting function is quite effective to fit with experimental data by minimum and maximum values of determination coefficients of $R^2$ as low as 0.9698 and 0.9988, respectively, for operating parameters such as temperature, $Cl_2$ pressure, carbon ratio and particle size that change comprehensively. The global fitting functions proposed in this study are expressed simply as exponential functions of chlorination rate(X) vs. time(t), and each of them are validated by a single equation for various reaction conditions. There is therefore a certain practical merit for the optimal process design and performance analysis for field engineers of chlorination reactions of ilmenite and $TiO_2$.

Control of Persulfate Activation Rate and Improvement of Active Species Transfer Rate Using Selenium-modified ZVI (셀레늄으로 개질된 영가철을 이용한 과황산 활성화 속도 조절 및 활성종 전달율 향상에 관한 연구)

  • Hee-won Kwon;Hae-Seong Park;In-seong Hwang;Jeong-Jin Kim;Young-Hun Kim
    • Journal of Environmental Science International
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    • v.32 no.1
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    • pp.57-65
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    • 2023
  • The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

Advancements in Polymer-Filler Derived Ceramics

  • Greil, Peter
    • Journal of the Korean Ceramic Society
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    • v.49 no.4
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    • pp.279-286
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    • 2012
  • Microstructure tailoring of filler loaded preceramic polymer systems offers a high potential for property improvement of Si-based ceramics and composites. Advancements in manufacturing of bulk materials by controlling microstructure evolution during thermal induced polymer-ceramic transforma-tion and polymer-filler reactions will be presented. Rate controlled pyrolysis, multilayer gradient laminate design and surface modification by gas solid reaction are demonstrated to yield ceramic components of high fractional density and superior mechanical properties. Emerging fields of applications are presented.

Product Phase Control During Interdiffusion Reactions (상호 확산 반응 중의 생성상 제어)

  • Park, Joon-Sik;Kim, Ji-Hoon;Perepezko, John R.
    • Journal of Korea Foundry Society
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    • v.26 no.1
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    • pp.27-33
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    • 2006
  • Phase evolutions involving nucleation stages together with diffusional growth have been examined in order to provide a guideline for determining rate limiting stages during phase evolutions. In multiphase materials systems in coatings, composites or multilayered structures, diffusion treatments often result in the development of metastable/intermediate phases at the reaction interfaces. The development of metastable phases during solid state interdiffusion demonstrates that the nucleation reaction can be one controlling factor. Also, the concentration gradient and the relative magnitudes of the component diffusivities provide a basis for a phase selection and the application of a kinetic bias strategy in the phase selection. For multicomponent alloy systems, the identification of the operative diffusion pathway is central to control phase formation. Experimental access to the nucleation and growth stage is discussed in thin film multi layers and bulk samples.