• Title/Summary/Keyword: Zero order kinetics

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Estimating dehalogenation reactivity of nanoscale zero-valent iron by simple colorimetric assay by way of 4-chlorophenol reduction

  • Mines, Paul D.;Kaarsholm, Kamilla M.S.;Droumpali, Ariadni;Andersen, Henrik R.;Hwang, Yuhoon
    • Environmental Engineering Research
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    • v.25 no.2
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    • pp.197-204
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    • 2020
  • A number of different nanoscale zero-valent iron (nZVI) materials have been prepared and compared depending on the desired properties for the particular application, but different physicochemical properties of this prepared nZVI make it difficult to universally compare and standardize them to the same scale. In this study, we aimed to demonstrate a simple microplate-based colorimetric assay using 4-chlorophenol as an indicator with respect to the remediation of real treatment targets, such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and atrazine. Effect of nickel contents on 4-chlorophenol reduction was successfully investigated by the miniaturized colorimetric assay. In the same manner, the effect of nickel contents on dehalogenation of TCE, TCA, and atrazine was investigated and the pseudo-first-order kinetic constants were compared with the results for 4-chlorophenol. The similar pattern could be observed between 4-chlorophenol reduction obtained by colorimetric assay and TCE, TCA, atrazine reduction obtained by a traditional chromatographic method. The reaction kinetics does not match perfectly, but the degree of reaction can be estimated. Therefore, the colorimetric assay can be a useful and simple screening tool to determine nZVI reactivity toward halogenated organics before it is applied to a particular remediation site.

Evaluation of buccal mucoadhesive [P(AA-co-PEGMM)] copolymer films containing butorphanol tartrate (Butolphanol tartrate 함유 구강점막 점착성 [P(AA-co-PEGMM)] 공중합체 필름의 평가)

  • Kim, Joun-Sik;Han, Kun
    • Journal of Pharmaceutical Investigation
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    • v.32 no.1
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    • pp.1-6
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    • 2002
  • The mucoadhesive characteristics of [P(AA-co-PEGMM)] films by estimating the glass transition temperature $(T_g)$, analyzing surface energy and studying FT-IR was previously reported. In this study, the possibility of buccal mucoadhesive dosage form of [P(AA-co-PEGMM)] films by mucoadhesive force measurements and dissolution tests were also investigated. Mucoadhesiveness of [P(AA-co-PEGMM)] films was compared with cr-PAA and cr-PEGMM films crosslinked with 3% ethyleneglycol dimethacrylate (EGDMA). The buccal mucoadhesive force of [P(AA-co-PEGMM)] films increased with increasing content of PEGMM. [P{AA-co-PEGMM (18 mole%)}] films showed a significantly greater mucoadhesiveness than cr-PAA and cr-PEGMM films. The mucoadhesive force measured in normal saline (pH 5.0) was higher than that measured in phosphate buffer (pH 6.8) because of the pH dependence of hydrogels with carboxyl ions within the PAA. Moreover, the mucoadhesive force of [P{AA-co-PEGMM (18 mole%)}] films was at maximum after 2 hr attachment of buccal mocosa and it was maintained over $1\;N/cm^2$ for up to 10 hr. In dissolution studies, the release of butorphanol tartrate from [P(AA-co-PEGMM)] films increased with increasing PEGMM content, and films prepared with 18 mole% PEGMM gave almost zero order release kinetics.

Reductive Degradation Kinetics and Pathways of Chlorophenolic Organic Pollutants by Nickel-Coated Zero Valent Iron (니켈로 코팅된 영가금속을 이용한 염소계 페놀화합물의 반응경로 및 반응율 평가)

  • Shin, Seung-Chul;Kim, Young-Hun;Ko, Seok-Oh
    • Journal of Korean Society of Environmental Engineers
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    • v.28 no.5
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    • pp.487-493
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    • 2006
  • Reductive dechlorination of chlorophenols by nickel coated iron was investigated to understand the feasibility of using Ni/Fe for the in situ remediation of contaminated groundwater. Zero Valent Iron(ZVI) was amended with Ni(II) ions to form bimetal(Ni/Fe). Dechlorination of five chlorophenol compounds and formation of intermediates were examined using Ni/Fe. Rate constant for each reaction pathway was quantified by the numerical integration of a series of differential rate equation. Experimental results showed that the sequence of hydrodechlorination rate constant was in the order of 2-CP>4-CP>2,4-DCP>2,4,6-TCP>2,6-DCP. The hydrodechlorination pathways for the conversion of each chlorophenol compound involves a full dechlorination to phenol via both concerted and stepwise mechanisms. Reaction pathways and corresponding kinetic rate constants were suggested based on the experiments and numerical simulations.

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 Ternary Polymeric Matrix System for Controlled Drug Delivery of Highly Soluble Drug with High Drug Loading : Diltiazem Hydrochloride (염산 딜티아젬의 방출을 제어하기 위한 삼중 폴리머 매트릭스 시스템)

  • Kim, Hyun-Jo;Fassihi, Reza
    • Journal of Pharmaceutical Investigation
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    • v.31 no.1
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    • pp.19-25
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    • 2001
  • The purpose of this study was to use a ternary polymeric matrix system for high drug loading of a highly soluble drug for controlled release delivery. The controlled drug delivery of diltiazem HCl (solubility > 50% in water at $25^{\circ}C$) with high loading dose (the final loading dose of drug was 34%) from a ternary polymeric matrix (gelatin, pectin, HPMC) was successfully accomplished. This simple monolithic system with 240 mg drug loading provided near zero-order release over a 24 hour-period by which time the system was completely dissolved. The release kinetics of diltiazem HCl tablet with high loading dose from the designed ternary polymeric system was dependent on the ratios of HPMC : pectin binary mixture. The release rate increased as pectin : HPMC ratio were increased. Swelling behavior of the ternary system and the ionic interaction of formulation components with cationic diltiazem molecule appear to control drug diffusion and the release kinetics. Comparable release profiles between commercial product and the designed system were obtained. The binding study between gelatin with diltiazem HCl showed the presence of two binding sites for drug interaction with subsequent controlled diffusion upon swelling. This designed delivery system is easy to manufacture and drug release behavior is highly reproducible and offers advantages over the existing commercial product.

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Comparison of the Kinetic Behaviors of Fe2O3 Spherical Submicron Clusters and Fe2O3 Fine Powder Catalysts for CO Oxidation

  • Yoo, Seung-Gyun;Kim, Jin-Hoon;Kim, Un-Ho;Jung, Jin-Seung;Lee, Sung-Han
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1379-1384
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    • 2014
  • ${\alpha}-Fe_2O_3$ spherical particles having an average diameter of ca. 420 nm and ${\alpha}-Fe_2O_3$ fine particles (< 10 ${\mu}m$ particle size) were prepared to examine as catalysts for CO oxidation. Kinetic studies on the catalytic reactions were performed in a flow reactor using an on-line gas chromatography system operated at 1 atm. The apparent activation energies and the partial orders with respect to CO and $O_2$ were determined from the rates of CO disappearance in the reaction stage showing a constant catalytic activity. In the temperature range of $150-275^{\circ}C$, the apparent activation energies were calculated to be 13.7 kcal/mol on the ${\alpha}-Fe_2O_3$ spherical submicron clusters and 15.0 kcal/mol on the ${\alpha}-Fe_2O_3$ fine powder. The Pco and $Po_2$ dependencies of rate were investigated at various partial pressures of CO and $O_2$ at $250^{\circ}C$. Zero-order kinetics were observed for $O_2$ on both the catalysts, but the reaction order for CO was observed as first-order on the ${\alpha}-Fe_2O_3$ fine powder and 0.75-order on the ${\alpha}-Fe_2O_3$ spherical submicron clusters. The catalytic processes including the inhibition process by $CO_2$ on the ${\alpha}-Fe_2O_3$ spherical submicron powder are discussed according to the kinetic results. The catalysts were characterized using XRD (X-ray powder diffraction), FE-SEM (field emission-scanning electron microscopy), HR-TEM (high resolution-transmission electron microscopy), and $N_2$ sorption measurements.

Sonochemical Oxidation Reactions in 300 kHz Sonoreactor for Various Liquid Height/Volume Conditions (다양한 액상 수위/부피 조건에서의 300kHz 초음파 캐비테이션 산화반응 분석 연구)

  • Lee, Seongeun;Son, Younggyu
    • Journal of Korean Society on Water Environment
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    • v.38 no.5
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    • pp.211-219
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    • 2022
  • In this study, the effect of liquid height/volume on sonochemical oxidation reactions was investigated in 300 kHz sonoreactors. The gas mixture of Ar/O2 (50:50) was applied in two modes including saturation and sparging, and zero-order reaction (KI dosimetry) and first-order reaction (Bisphenol A (BPA) degradation) were used to quantitatively analyze sonochemical oxidation reactions. For the zero-order reaction, the highest sonochemical oxidation activity was obtained for the liquid height of 5𝛌, and the lowest height for both the gas saturation and sparging conditions. In addition, the sparging did not enhance the sonochemical oxidation activity for all height conditions except for 50𝛌, where very low activity was obtained. It was found that in sonochemiluminescence (SCL) images the sonochemical active zone was formed adjacent to the liquid surface for the gas sparging condition due to the formation of the standing wave field while the active zone was formed adjacent to the transducer at the bottom due to the blockage of ultrasound. For the first-order reaction, the highest activity was also obtained at 5𝛌 and the comparison based on the reactant mass was not appropriate because the concentration of the reactant (BPA) decreased significantly as the reaction time elapsed. Consequently, it was revealed that the determination of optimal liquid height (ultrasound irradiation distance) based on the wavelength of the applied ultrasound frequency was very important for the optimal design of sonoreactors in terms of reaction efficiency and reactor size.

Development of Controlled Release Oral Drug Delivery System by Membrane-Coating Method-I - Preparation and pharmaceutical evaluation of controlled release acetaminophen tablets-

  • Shim, Chang-Koo;Kim, Ki-Man;Kim, Young-Il;Kim, Chong-Kook
    • Archives of Pharmacal Research
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    • v.13 no.2
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    • pp.151-160
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    • 1990
  • In order to develop a controlled-release oral drug delivery system (DDS) which sustains the plasma acetaminophen (AAP) concentration for a certain period of time, microporous membrane-coated tablets were prepared and evaluated in vitro. Firstly, highly water-soluble core tablet of AAP were prepared with various formulations by wet granulation and compression technique. Then the core tablets were coated with polyvinychloride (PVC) in which micronized sucrose particles were dispersed. Effect of formula compositions of core tablets and coating suspensions on the pharmaceutical characteristics such as drug release kinetics and membrane stability of the coated tablets was investigated in vitro. AAP was released from the coated tablets as a zero-order rate in a pH-independent manner. This independency of AAP release to pH change from 1.2 to 7.2 is favorable for the controlled oral drug delivery, since it will produce a constant drug release in the stomach and intestine regardless of the pH change in the GI tract. Drug release could be extended upto 10 h according to the coating condition. The release rate could be controlled by changing the formula compositions of the core tablets and coating suspensions, coat weight per each tablet, and especially PVC/sucrose ratio and particle size of the sucrose in the coating suspension. The coated tablets prepared in this study had a fairly good pharmaceutical characteristics in vitro, however, overall evaluation of the coated tablet should await in vivo absorption study in man.

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Kinetics Determination of Quality Changes for the Optimization of Food Dehydration (식품건조공정 최적화에의 적용을 위한 품질 변화 Kinetics 결정)

  • Lee, Dong-Sun;Pyun, Yu-Ryang
    • Korean Journal of Food Science and Technology
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    • v.20 no.2
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    • pp.272-279
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    • 1988
  • Kinetics of ascorbic acid destruction and browning were evaluated by the dynamic test using actual drying data in order to apply in the optimization of food dehydration. Radish was chosen as a test material because it has many typical quality characteristics during drying. Radish was dried in the cabinet dryer with being measured in moisture, food temperature, ascorbic acid and browning. Using moisture and temperature history, proposed kinetic model was integrated and parameters of the model were searched by the iteration scheme to show minimum discrepancy between predicted and experimental data. Ascorbic acid destruction and browning were represented by first and zero order reaction respectively. Arrhenius equation was used to describe temperature dependence. Several mathematical functions of moisture dependence were compared in the model simplicity and residual sum of square. Attained kinetic models were analyzed as functions of temperature and moisture. Rate of ascorbic acid destruction was low at high moisture content, increased with moisture decrease to show a maximum at the moisture of $9{\sim}12g/g$ dry solid, and then decreased up to full dryness. Browning rate increased with moisture decrease to show a sharp maximum at $4{\sim}6g/g$ dry solid and decreased with further moisture decrease.

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Effect of Aeration on Removal of phenolic Compounds in Soil (공기공급이 토양내 페놀화합물 제거에 미치는 영향)

  • 박준석;남궁완;황의영
    • Journal of Korea Soil Environment Society
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    • v.5 no.2
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    • pp.3-12
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    • 2000
  • This study was carried out to evaluate the effect of aeration on removal of phenolic compounds in soils. Phenol, 2,4-dichlorophenol, and pentachlorophenol as phenolic compounds were chosen in this study. Texture of soil used was sandy loam. Temperature and moisture content of the soils in lab-scale reactors were maintained at $25^{\circ}C$ and at 15%, respectively. Phenolic compounds vaporized from reactors were trapped by methylene chloride solution. Phenolic compounds were applied to the soils as individual compound Aeration improved the phenol degradation rate in soil, while it did not in case of 2,4-dichlorophenol and pentachlorophenol. The amount of phenol vaporized by aeration was only 0.3of of that of initial phenol compound added to the soil. First order kinetics described the degradation rates of phenolic compounds better than zero order kinetics.

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