• Title/Summary/Keyword: General order kinetics

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Efficient use of ferrate(VI) for the remediation of wastewater contaminated with metal complexes

  • Sailo, Lalsaimawia;Pachuau, Lalramnghaki;Yang, Jae Kyu;Lee, Seung Mok;Tiwari, Diwakar
    • Environmental Engineering Research
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    • v.20 no.1
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    • pp.89-97
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    • 2015
  • Remediation of wastewater contaminated with metal(II)-complexed species (Cu(II)-NTA (NTA: nitrilotriacetic acid), Cu(II)-EDTA (EDTA: ethylenediamine tetraacetic acid) and Cd(II)-EDTA is attempted using the potential applicability of ferrate(VI). Kinetics of pollutant degradation is obtained with the removal of ferrate(VI) studied at wide range of pH (8.0-10.0) and the concentration of metal(II)-complexed species (0.3 to 15.0 mmol/L) employing a constant dose of ferrate(VI) i.e., 1.0 mmol/L. Pseudo-first-order and pseudo-second-order rate constants were obtained in the reduction of ferrate(VI) which was then employed to obtain the overall rate constants of the pollutant degradation. The mineralization of NTA and EDTA was obtained with the change in TOC (total organic carbon) values collected by the ferrate(VI) treated pollutant samples. Decrease in pH and molar pollutant concentrations was greatly favored the percent mineralization of NTA or EDTA by the ferrate(VI) treatment. The treated pollutant samples were filtered and subjected for AAS (atomic absorption spectrophotometric) analysis to assess the simultaneous removal of copper and cadmium from aqueous solutions at the studied pH as well at the elevated pH 12.0. Results show that an enhanced removal of cadmium or copper was achieved at pH 12.0. Overall, ferrate(VI) possesses multifunctional application in wastewater treatment as it oxidizes the degradable impurities and removes metallic impurities by coagulation process.

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.

Design and Optimization of Solid Dispersed Osmotic Pump Tablets of Aceclofenac, A Better Approach to Treat Arthritis

  • Edavalath, Sudeesh;Rao, B. Prakash
    • Journal of Pharmaceutical Investigation
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    • v.41 no.4
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    • pp.217-225
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    • 2011
  • The aim of this work was to prepare porous osmotic pump tablets for controlled delivery of Aceclofenac. Aceclofenac solid dispersion was prepared to improve the solubility by using the drug - carrier (Mannitol) ratio of 1:1. The osmotic pump tablets were prepared using the solid dispersed product of Aceclofenac. The formulation contains potassium chloride as osmotic agent, cellulose acetate as semipermeable membrane, poly ethylene glycol (PEG 4000) as pore former and sodium lauryl sulphate (SLS) as solubility enhancer. The formulations were designed by the general factors such as osmotic agent and pore former. All formulations were evaluated for various physical parameters and, the in vitro release studies were conducted as per USP. The drug release kinetic studies such as zero order, first order, and Higuchi and Korsmeyer peppas were determined and compared. All the formulations gave more controlled release compared to the marketed tablet studied. Numerical optimization techniques were applied to found out the best formulation by considering the parameter of in vitro drug release kinetics and dissolution profile standards. It was concluded that the porous osmotic pump tablets (F7) composed of Aceclofenac solid dispersion/Potassium chloride/Lactose/Sodium lauryl sulphate/Magnesium Stearate (400/40/95/10/5, mg/tab) and coating composition with Cellulose acetate/ PEG 4000 (60/40 %w/w) is the most satisfactory formulation. The porous osmotic pump tablets provide prolonged, controlled, and gastrointestinal environment-independent drug release.

The Control Rod Speed Design for the Nuclear Reactor Power Control Using Optimal Control Theory (최적제어이론에 의한 원자로 제어봉속도의 설계)

  • Lee, Yoon-Joon
    • Nuclear Engineering and Technology
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    • v.26 no.4
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    • pp.536-547
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    • 1994
  • The state feedback optimal control techniques are used in designing the reactor control system. The mathematical plant model with the temperature feedback effects is established from the one delayed neutron group point kinetics equation and the singly lumped thermal-hydraulic balance equations, and is expressed in terms of state variables. The LQR (Linear Quadratic Regulator) control system is designed, being followed by the LQG (Linear Quadratic Gaussian) design to determine the optimal conditions of rod movement for the desired reactor power responses. And two different servo control schemes, the ordinary feedback system and the order increased regulating system, are proposed for the purpose of input tacking. The general control characteristics such as stability margins and output responses are discussed. Comparing each other, it is found that the order increased regulating system has far better control characteristics than the ordinary feedback system.

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Stabilization of Retinol through Incorporation into Liposomes

  • 이승철;육현균;이동훈;이경은;황용일;Richard D. Ludescher
    • BMB Reports
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    • v.35 no.4
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    • pp.358-363
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    • 2002
  • Chemical and photochemical processes during storage and preparation rapidly degrade retinol, the most active form of vitamin A. therefore, the efficacy of incorporation into liposomes in order to modulate the kinetics of retinol degradation was investigated. Retinol was readily incorporated into multilamellar liposomes that were prepared form soybean phosphatidylcholine; the extent of the incorporation was 98.14±0.93% at pH 9.0 at a ratio of 0.01 : 1 (wt:wt) retinol : phospholipid. It was only marginally lower at higher retinol concentrations. The pH of the hydration buffer had a small effect. The incorporation efficiency ranged from 99.25±0.47% at pH 3 to 97.45±1.13% at pH 11. The time course of the retinol degradation in the aqueous solution in liposomes was compared to that of free retinol and free retinol with α-tocopherol under a variety of conditions of pH(3, 7, and 11), temperature(4, 25, 37, and 50℃), and light exposure(dark, visible, and UV). The retinol that was incorporated into the liposomes degraded significantly slower than the free retinol or retinol with α-tocopherol at pH 7 and 11. At pH 3, where the free retinol degrades rapidly, the degradation kinetics were similar in liposomes and the presence of α-tocopherol. At pH 7.0 and 4℃ in the light, for example, free aqueous retinol was completely degraded within 2 days, while only 20% of the retinol in the liposomes were degraded after 8 days. In general, the protective effect of the liposome incorporation was greater at low temperatures, at neutral and high pH, and in the dark. The results suggest that protection is greater in the solid, gel phase than in the fluid liquid crystalline phase lipids. These results indicate that the incorporation into liposomes can extend the shelf-life of retinol under a variety of conditions of temperature, pH, and ambient light conditions.

Kinetics of Chromium(III) Oxidation by Various Manganess Oxides (망간 산화물에 의한 3가 크롬의 산화)

  • Chung, Jong-Bae;Zasoski, Robert J.;Lim, Sun-Uk
    • Applied Biological Chemistry
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    • v.37 no.5
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    • pp.414-420
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    • 1994
  • Birnessite, pyrolusite and hausmannite were synthesized and tested for the ability to oxidize Cr(III) to Cr(VI). These oxides differed in zero point of charge, surface area, and crystallinity. The kinetic study showed that Cr(III) oxidation on the Mn-oxide surface is a first-order reaction. The reaction rate was various for different oxide at different conditions. Generally the reaction by hausmannite, containing Mn(III), was faster than the others, and oxidation by pyrolusite was much slower. Solution pH and initial Cr(III) concentration had a significant effect on the reaction. Inhibited oxidation at higher pH and initial Cr(III) concentration could be due to the chance of Cr(III) precipitation or complexing on the oxide surface. Oxidations by birnessite and hausmannite were faster at lower pH, but pyrolusite exhibited increased oxidation capacity at higher pH in the range between 3.0 and 5.0. Reactions were also temperature sensitive. Although calculated activation energies for the oxidation reactions at pH 3.0 were higher than the general activation energy for diffusion, there is no experimental evidence to suggest which reaction is the rate limiting step.

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A Study on the Resource Development by Heat Dissolution in Electric Arc Furnace of Clinker generated in the Recycling Process of Electric Arc Furnace Dust (전기로 제강분진의 재활용과정에서 발생된 Clinker의 전기로에서의 가열용해에 의한 자원화에 관한 연구)

  • Jae-hong Yoon;Chi-hyun Yoon;Akio Honjo
    • Journal of the Korean Society for Heat Treatment
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    • v.36 no.1
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    • pp.22-32
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    • 2023
  • In general, when scrap is dissolved in an electric arc furnace, the amount of electric furnace steel dust (EAFD) generated is about 1.5% of the scrap charge amount, and the electric furnace steel dust collected by the bag filter is charged into the Rotary Kiln or Rotary Hearth Furnace (RHF), and the zinc component is recovered as crude zinc oxide, at which time a clinker of Fe-Base is generated. In this research, first, for the efficient resource conversion of electric furnace steel dust, a reduction and roasting experiment was conducted and the reaction kinetics was examined. As a result of the experiment, it was observed that the reduction and roasting reaction was actively conducted in the range of 1100~1150℃, and melting occurred in the range of 1250℃. In the past, this clinker was widely used as a roadbed material for road construction and an Fe-Source for cement production, but in recent years, it has been mainly reclaimed due to strengthening environmental standards. However, landfill treatment is by no means a desirable treatment method due to environmental pollution caused by leachate, expensive landfill costs, and waste of Fe resources. Therefore, in order to more actively recycle the Fe component in the clinker, first of all the clinker was pulverized into an optimal particle size, and anthracite and binder (starch) were added to the magnetic material obtained by specific gravity and magnetic separation for briquet. As a experimental results, it was possible to efficiently separate clinker as Fe component and other slag component by specific gravity and magnetic force. As a results of loading and dissolving the manufactured briquet clinker in an electric arc furnace, it was observed that the unit of power and production yield were clearly improved and the carbon addition effect in molten metal was also somewhat.

Application of Ferrate(VI) on the Decomplexation of Cu(II)-EDTA

  • Tiwari, Diwakar;Yang, Jae-Kyu;Chang, Yoon-Young;Lee, Seung-Mok
    • Environmental Engineering Research
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    • v.13 no.3
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    • pp.131-135
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    • 2008
  • In this study, Fe(VI) was employed as a multi-functional agent to treat the simulated industrial wastewater contaminated with Cu(II)-EDTA through oxidation of EDTA, decomplexation of Cu(II)-EDTA and subsequent removal of free copper through precipitation. The decomplexation of $10^{-4}\;M$ Cu(II)-EDTA species was performed as a function of pH at excess concentration of Fe(VI). It was noted that the acidic conditions favor the decomplexation of Cu(II)-EDTA as the decomplxation was almost 100% up to pH 6.5, while it was only 35% at pH 9.9. The enhanced degradation of Cu(II)-EDTA with decreasing the pH could be explained by the different speciation of Fe(VI). $HFeO_4^-$ and $H_2FeO_4$, which are relatively more reactive than the unprotonated species $FeO_4^{2-}$, are predominant species below neutral pH. It was noted that the decomplexation reaction is extremely fast and within 5 to10 min of contact, 100% of Cu(II)-EDTA was decomplexed at pH 4.0. However, at higher pH (i.e., pH 10.0) the decomplexation process was relatively slow and it was observed that even after 180 min of contact, maximum ca 37% of Cu(II)-EDTA was decomplexed. In order to discuss the kinetics of the decomplexation of Cu(II)-EDTA, the data was slightly fitted better for the second order rate reaction than the first order rate reaction in the excess of Fe(VI) concentration. On the other hand, the removal efficiency of free Cu(II) ions was also obtained at pH 4.0 and 10.0. It was probably removed through adsorption/coagulation with the reduced iron i.e., Fe(III). The removal of total Cu(II) was rapid at pH 4.0 whereas, it was slow at pH 10.0. Although the decomplexation was 100% at lower pH, the removal of free Cu(II) was relatively slow. This result may be explicable due to the reason that at lower pH values the adsorption/coagulation capacity of Fe(III) is greatly retarded. On the other hand, at higher pH values the decomplexation of Cu(II)-EDTA was partial, hence, slower Cu(II) removal was occurred.

A Study on Formation and Thermal Decomposition Kinetics of PU Elastomers by Dynamic DSC and TGA Analysis (Dynamic DSC 및 TGA 열분석을 이용한 PU Elastomer의 중합반응 및 열분해 반응 Kinetics에 관한 연구)

  • Yoon, Soo-Koong;Ahn, Won-Sool
    • Elastomers and Composites
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    • v.42 no.1
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    • pp.47-54
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    • 2007
  • Reaction kinetics of polyurethane elastomers (PU) were studied using dynamic DSC and TGA for three PU samples of general purpose (Sample A), high temperature cross-likable CASE purpose with MOCA (Sample B), and RT cross-likable CASE purpose grade (Sample C). From DSC results, sample with MOCA(Sample B) showed lower shift of peak temperature, while showing broader thermograms than those of general purpose grade (Sample A). On the other hand, RT cross-linkable PU grade (Sample C) showed an interesting double mode reaction patterns, i.e., a lower temperature reaction at about $70\;^{\circ}C$, and a higher temperature reaction in the range of $140{\sim}170\;^{\circ}C$, indicating that it requires 2-step reaction process in order to complete the reaction. Once the cross-linking reaction completed, however, TGA results showed that all the samples would be considered to have similar chemical structures, showing similar decomposition processes. Sample C, especially, had showed decomposition properties of both Sample A and Sample B. Formation activation energies calculated from Kissinger method showed 10.39, 65.85, 36.52(Low $T_p$) and 18.21(High $T_p$) kcal/mol, while decomposition activation energies were 31.94, 30.84, 24.16 kcal/mol, respectively.

Lipid Peroxidation and Its Nutritional Significance (지방질의 과산화와 영양)

  • 최홍식
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.23 no.5
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    • pp.867-878
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    • 1994
  • A general overview of the lipid peroxidation and its nutritional significance are presented ,with emphasis on the reaction mechaisms, peroxidized products, further interaction and nutritional/biological deterioration in a series of oxidative process. Overall mechanism with various factors and elements for initiation , propagation and termination of free radical reaction is reviewed and the primary /secondary products of peroxidized lipids are defined. Since these products are potentially reactive substances that can cause deterioration of proteins /amino acids and vitamins (carotene, tocopherols and ascorbic acid etc), mechanism and actual damages of their deterioration in some foods and biological models are outlined. Especially , chemical changes caused by interaction of peroxidized products (related hydroperoxides, radicals and malonaldehye etc) and protein are emphasized here. And also, the detailed mechanisms on radical scavenging of the these vitamins which are the most prominent natural antioxidants are presented . Additionally , the possible roles of peroxidicaed lipids and their secondary products in the process of aging an carcinogenesis are briefly discussed . However, it is important to not that more detailed and integrated studies on the reaction kinetics, energetics of peroxidation, their decomposed products , biochemical interaction potential damaging/aging / carcinogenic effects, protection from their oxidative spoilage and novel antioxidants in food and heterogeneous biological systems will be essential in order to assessing the implication of lipid peroxidation to human nutrition and health.

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