• Title/Summary/Keyword: pseudo-first-order reaction

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Remediation of Perchloroethylene Contaminated Soil by Fenton Oxidation (펜톤 산화법에 의한 PCE 오염 토양의 정화)

  • Lee, Byung-Dae;Kim, Yeoung-Chan
    • Journal of the Korean Applied Science and Technology
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    • v.22 no.2
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    • pp.136-141
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    • 2005
  • This paper presents applicability of Fenton oxidation to perchloroethylene(PCE) contaminated soil. The initial concentration of PCE was 187mg/kg and Fenton oxidation conditions were 1.0M $H_2O_2$ and 0.5M $Fe^{2+}$. More than 97% of PCE decomposition and 98% of dechlorination were obtained within 5 hrs. It was found that the decomposition of PCE by Fenton oxidation was followed pseudo first order and its reaction coefficient was 0.78 $hr^{-1}$. GC-MS and GC-ECD analysis of reaction intermediates confirmed only the presence of trichloroacetic acid(i.e., 1.0% of initial PCE concentration). Under Fenton oxidation conditions, it was proposed that PCE was decomposed not simultaneously but one by one.

Effects of Activated Carbon Particle Sizes on Caffeine Adsorptions (활성탄 입자 크기가 카페인 흡착에 미치는 영향)

  • Kim, Tae-Yang;Do, Si-Hyun;Hong, Seong-Ho
    • Journal of Korean Society of Water and Wastewater
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    • v.29 no.3
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    • pp.407-414
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    • 2015
  • The effect of activated carbon particle diameter (i.e. US sieve No. $8{\times}10$ ($d_p{\approx}2.19mm$), $18{\times}20$ ($d_p{\approx}0.92mm$), $50{\times}60$ ($d_p{\approx}0.27mm$) and $170{\times}200$ ($d_p{\approx}0.081mm$) on caffeine adsorption is investigated. BET surface area was increased with decreasing particle diameter ($d_p$), and caffeine adsorption rates increased with decreasing $d_p$. Moreover, pseudo-second order model is predicted the experimental data more accurately than pseudo-first order model, and the fastest rate constant ($k_2$) was $1.7g\;mg^{-1}min^{-1}$ when $d_p$ was 0.081 mm. Surface diffusion coefficient (Ds) was decreased with decreasing $d_p$ based on the minimum sum of square error (SSE). Practically, certain ranges of Ds are acceptable with high reliability ($R^2$) and it is determined that the effect of $d_p$ on Ds is unclear. The effect of pH on caffeine adsorption indicated the dependency of m/L ratio (mass liquid ratio) and $pH_{pzc}$. The $pH_{pzc}$ (i.e. $7.9{\pm}0.2$) was not affected by $d_p$. The higher caffeine adsorption at pH 4 and pH 7 than at pH 10 is due to $pH_{pzc}$, not $pk_a$ of caffeine.

Separation and Adsorption-Desorption Characteristics of Heavy Rare Earth Elements (Gd, Tb, Dy) using P507 Resin (P507 추출수지를 이용한 중희토류 원소(Gd, Tb, Dy)의 흡탈착 분리특성에 관한 연구)

  • Lee, Sungeun;Kim, Joung Woon;Jeon, Jong Hyuk;Jun, Hong Myeong;Lee, Jin Young;Han, Choon
    • Resources Recycling
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    • v.25 no.4
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    • pp.60-67
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    • 2016
  • This study was conducted to establish the adsorption-desorption mechanism and the optimum condition of chromatographic operation for separations of heavy rare earth elements (Gd, Tb, Dy) using a p507-containing resin. By employing Langmuir and Freundlich isotherm together with pseudo first and second order kinetics, absorption-desorption reaction mechanism was investigated. Langmuir and Freundlich isotherm was applied under assumption that adsorption reaction occurs in form of monolayer, and because the result was identical to the assumption, now we know adsorption of heavy rare earth elements occurs in form of monolayer. Concerning the pseudo first and second order kinetic, the pseudo second order seemed to be more suitable to represent heavy rare earth element adsorption mechanism. By using the extraction chromatography to separate heavy rare earth elements, ${\alpha}^{Tb}_{Gd}=1.24$, and ${\alpha}^{Dy}_{Tb}=1.03$ were confirmed in eluent HCl 0.25 M which indicates almost perfect separations of three elements. Furthermore, as concentrations of eluent became higher, the resolution value decreased and the elution area got shortened.

The Effect of Reaction Temperature and Volume in the Sonolysis of 1,4-Dioxane (1,4-Dioxane의 초음파 처리시 반응 온도와 부칙의 영향)

  • Son, Hyun-Seok;Choi, Seok-Bong;Eakalak, Khan;Zoh, Kyung-Duk
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.10
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    • pp.1114-1122
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    • 2005
  • This research investigates the effects of sonication mode, reaction temperature and volume on sonolysis of 1,4-dioxane in order to increase the degradation efficiency and kinetics. The degradation efficiency in case with pulse mode was about 10 % higher than that in case with continuous mode. The degradation profiles in both cases, which were performed without the control of reaction temperature and in 1000 mL, were composed of three steps. However, 1,4-D was mainly degraded in the initiation step as the first portion and the acceleration step as the second portion. The initial step agreed with zero-order expression well, while the acceleration step could be fitted with pseudo 1st-order expression. The kinetic model in case with $5^{\circ}C$ and 300 mL conformed to pseudo 1st-order, while that in cases with $10^{\circ}C$ to $40^{\circ}C$ agreed with zero-order expression. The degradation efficiency and profile of 1,4-D in the experiment with $20^{\circ}C$ and 300 mL was higher and simpler than that in case with $20^{\circ}C$ and 1000 mL. The reaction temperature and volume influence bubble intensity, which was produced in sonication. The increase of bubble intensity induced to augment the production of OH radical in sonication.

Kinetics on the Reaction of 3,5-Diaryl-1,2,4-dithiazolium Triodide with Hydrazine (삼요오드화 3,5-디아릴-1,2,4-디지아졸륨과 히드라진과의 반응에 관한 반응속도론적 연구)

  • Moon-Hwan Park;Chang-Suk Kim;Soon-Yung Hong
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.448-451
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    • 1985
  • Pseudo first-order rate constants for reactions of seven m- or p- phenyl-ring substituted 3,5-diphenyl 1,2,4-dithiazolium triodides with hydrazine in excess, in pyridine, were determined by a UV spectrophotometry. For these reactions, calculated some activation parameters, identified the reaction products, and investigated the effect of substituent on the reaction rate. These reactions were accelerated by electron-withdrawing substituents and obeyed the Hammett rule. From the observed kinetics, a reaction mechanism was proposed.

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Studies on the Metal-Exchange Reaction of Tetrahedral Cu(II) Complex with Mercuric Ion and Mercury Metal (정사면체 구조를 갖는 Cu(II) 착물과 수은(II) 및 수은(0)과의 금속 교환반응 연구)

  • Young Tae Gong;Sung Nak Choi;Yoon-Bo Shim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.223-229
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    • 1992
  • Mechanistic studies on the metal-exchange reactions of sparteine copper(II) dichloride [$SpCuCl_2$] with Hg(II) ion and Hg(0) metal have been carried out with the aid of Cyclic Voltammetry and UV-visible spectrophotometry. The metal exchange reaction of $SpCuCl_2$ with both Hg(II) ion and Hg(0) metal follows pseudo-first order kinetics. Rate constants and activation parameters of metal exchange reaction have been evaluated and reported. Experimental results indicate that the rate determining step for the exchange reaction is the cleavage of Cu(II)-N bond in the transient binuclear complex of Cu(II) and mercury(II) bound to sparteine ligand.

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Kinetics of CO2 Absorption in Aqueous DETA and DEEA Solutions by Wetted-Wall Column (젖은 벽탑을 이용한 디에틸렌트리아민과 디에틸에탄올아민 수용액의 CO2 흡수속도 측정)

  • You, Jong Kyun;Lee, Jun;Hong, Yeon Ki
    • Korean Chemical Engineering Research
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    • v.60 no.4
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    • pp.582-587
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    • 2022
  • Biphasic solvents are attracting attention as energy-reducing solvents for capturing CO2 from flue gas in combustion process. In this study, considering diethylenetriamine (DETA) and diethylethanolamine (DEEA) mixed solvents, one of the biphasic solvents by blending of two types of amines, the CO2 absorption rates of DETA and DEEA was measured by wetted wall column. The effects of DETA and DEEA concentrations and operating temperature on the overall mass transfer coefficient were investigated. As a result, the overall mass transfer coefficient was proportional to the DETA concentration. However, in the case of the DEEA concentration, the effect was small and when the concentration was exceeded, the overall mass transfer coefficient decreased. The DETA aqueous solution showed little change in the overall mass transfer coefficient with the operating temperature, whereas the DEEA aqueous solution increased the overall mass transfer coefficient with the operating temperature. As a result of obtaining the observed reaction rate constant under the pseudo-first-order reaction assumption, it was found that the observed reaction rate constant in DETA aqueous solution was proportional to the DETA concentration, but DEEA did not fit the pseudo-first-order reaction assumption.

A Study on the Decomposition of Water Soluble Dyes by UV/TiO2 (UV/TiO2에 의한 수용성 염료의 분해에 관한 연구)

  • 정갑섭
    • Journal of Environmental Science International
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    • v.12 no.3
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    • pp.319-324
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    • 2003
  • The characteristics of photocatalytic decomposition of dye waste water by titanium dioxide was studied in a batch reactor under constant strength of ultra-violet ray. The decomposition rate of methyl orange by TiO$_2$ was pseudo-first order, anatase type TiO$_2$ was more effective than rutile type below the dosage of 5g. The decomposition rate was increased with decreasing initial pH, increasing reaction temperature and oxidant concentration. The decomposition rate of water soluble dyes was decreased in order of rhodamine B>eosin Y>methyl orange.

FERRATE(VI) FOR WASTE WATER TREATMENT : OXIDATION OF CYANIDE IN AQUEOUS MEDIUM

  • Tiwari, Diwakar;Kim, Hyoung-Uk;Lee, Seung-Mok;Yang, Jae-Kyu;Kim, Hyun-Ook
    • Environmental Engineering Research
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    • v.11 no.6
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    • pp.318-324
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    • 2006
  • The higher valence state of iron i.e., Fe(VI) was employed for the oxidation of one of an important toxic ion, cyanide in the aqueous medium. Cyanide was oxidized into cyanate, which is 1,000 times less toxic to cyanide and often accepted for its ultimate disposal. It was to be noted that Fe(VI) is a very powerful oxidizing agent and can oxidize most of the cyanide within few minutes i.e., ca 5 mins of contact. The data was obtained by the UV-Visible measurements for the Fe(VI) decomposition. The UV-Visible data was used to evaluate the overall rate constant for second order redox reaction between ferrate(VI) and cyanide. Also the pseudo first order rate constant was calculated as keeping the cyanide concentration in excess.

Metal Ion Catalysis in Nucleophilic Substitution Reaction of 4-Nitrophenyl Picolinate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Hong, Yeon-Ju;Kim, Song-I;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2483-2487
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    • 2010
  • Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.