• Title/Summary/Keyword: reaction kinetics

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A Study for Kinetics and Oxidation Reaction of Alcohols using (C10H8N2H)2Cr2O7 ((C10H8N2H)2Cr2O7를 이용한 알코올들의 산화반응과 반응속도에 관한 연구)

  • Park, Young-Cho;Kim, Soo-Jong
    • The Journal of the Convergence on Culture Technology
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    • v.8 no.6
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    • pp.927-933
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    • 2022
  • We synthesized (C10H8N2H)2Cr2O7, The structure of the product was characterized with FT-IR(infrared) and elemental analysis. The oxidation of benzyl alcohol by (C10H8N2H)2Cr2O7 in organic solvents showed that the reactivity increased with the increase of the dielectric constant. The oxidation of alcohols was examined by (C10H8N2H)2Cr2O7 in DMF, acetone. As a resuit, (C10H8N2H)2Cr2O7 was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones(65%~95%). The selective oxidation of alcohols was also examined by (C10H8N2H)2Cr2O7 in DMF, acetone. (C10H8N2H)2Cr2O7 was selective oxidizing agent(15%~95%) of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary ones. In the presence of DMF solvent with acidic catalyst such as H2SO4. (C10H8N2H)2Cr2O7 oxidized benzyl alcohol(H) and its derivatives. The Hammett reaction constant(ρ) was -0.69(308K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Sorption and Ion Exchange Characteristics of Chabazite: Competition of Cs with Other Cations (차바자이트의 흡착 및 이온 교환 특성: Cs 및 다른 양이온과의 경쟁)

  • Baek, Woohyeon;Ha, Suhyeon;Hong, Sumin;Kim, Seonah;Kim, Yeongkyoo
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.2
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    • pp.59-71
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    • 2016
  • To investigate the sorption characteristics of Cs, which is one of the major isotopes of nuclear waste, on natural zeolite chabazite, XRD, EPMA, EC, pH, and ICP analysis were performed to obtain the informations on chemical composition, cation exchange capacity, sorption kinetics and isotherm of chabazite as well as competitive adsorption with other cations ($Li^+$, $Na^+$, $K^+$, $Rb^+$, $Sr^{2+}$). The chabazite used in this experiment has chemical composition of $Ca_{1.15}Na_{0.99}K_{1.20}Mg_{0.01}Ba_{0.16}Al_{4.79}Si_{7.21}O_{24}$ and its Si/Al ratio and cation exchange capacity (CEC) were 1.50 and 238.1 meq/100 g, respectively. Using the adsorption data at different times and concentrations, pseudo-second order and Freundlich isotherm equation were the most adequate ones for kinetic and isotherm models, indicating that there are multi sorption layers with more than two layers, and the sorption capacity was estimated by the derived constant from those equations. We also observed that equivalent molar fractions of Cs exchanged in chabazite were different depending on the ionic species from competitive ion exchange experiment. The selectivity sequence of Cs in chabazite with other cations in solution was in the order of $Na^+$, $Li^+$, $Sr^{2+}$, $K^+$ and $Rb^+$ which seems to be related to the hydrated diameters of those caions. When the exchange equilibrium relationship of Cs with other cations were plotted by Kielland plot, $Sr^{2+}$ showed the highest selectivity followed by $Na^+$, $Li^+$, $K^+$, $Rb^+$ and Cs showed positive values with all cations. Equilibrium constants from Kielland plot, which can explain thermodynamics and reaction kinetics for ionic exchange condition, suggest that chabazite has a higher preference for Cs in pores when it exists with $Sr^{2+}$ in solution, which is supposed to be due to the different hydration diameters of cations. Our rsults show that the high selectivity of Cs on chabazite can be used for the selective exchange of Cs in the water contaminated by radioactive nuclei.

Chemical Reactions in Surfactant Solutions (Ⅳ) : Micellar Rate Effect on Reactions of Hydroxide and o-Iodosobenzoate Ions with Organic Phosphinates (계면활성제 용액속에서의 화학반응 (제 4 보) : $OH^-$ 및 o-Iodosobenzoate 이온에 의한 유기 포스피네이트의 탈인산화 반응에 미치는 CTAX 미셀의 영향)

  • Hong, Yeong Seok;Kim, Hyeon Muk
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.753-762
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    • 1994
  • Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

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Kinetics and mechanism of chromate reduction by biotite and pyrite (흑운모 및 황철석에 의한 6가 크롬의 환원 반응속도와 반응기작)

  • 전철민;김재곤;문희수
    • Economic and Environmental Geology
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    • v.36 no.1
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    • pp.39-48
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    • 2003
  • The removal of chromate from aqueous solution using finely ground pyrite and biotite was investigated by batch experiments and the kinetics and the mechanism of chromate reduction were discussed. The chromate reduction by pyrite was about hundred times faster than that by biotite and was also faster at pH 3 than at pH 4. When pyrite was used, more than 90% of initial chromate was reduced within four hours at pH 4 and within 40 min. at pH 3. However, more than 400 hours was taken for the reduction of 90% of initial chromate by biotite. The results indicate that the rate of chromate reduction was strongly depending on the amount of Fe(II) in the minerals and on the dissolution rate of Fe(II) from the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH))$_3$$_{ (s)}$, which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than expected values. When biotite was used, amounts of decreased Fe(II) and reduced Cr(Ⅵ) did not show stoichiometric relationship, which implying there was not only chromate reduction by ferrous ions in the acidic solution but also heterogeneous reduction of ferric ions by the structural ferrous iron in biotite. However, the results from a series of the experiments using Pyrite showed that concentrations of the decreased Fe(II) and the reduced Cr(Ⅵ) were close to the stoichiometric ratio of 3:1. It was because the oxidation of pyrite rapidly created ferrous ions even in oxygenated solutions and the chromate reduction by the ferrous ions was significantly faster than ferrous ion oxygenation.

Adsorption of Arsenic on Goethite (침철석(goethite)과 비소의 흡착반응)

  • Kim, Soon-Oh;Lee, Woo-Chun;Jeong, Hyeon-Su;Cho, Hyen-Goo
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.3
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    • pp.177-189
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    • 2009
  • Iron (oxyhydr)oxides commonly form as secondary minerals of high reactivity and large surface area resulting from alteration and weathering of primary minerals, and they are efficient sorbents for inorganic and organic contaminants. Accordingly, they have a great potential in industrial applications and are also of substantial interest in environmental sciences. Goethite (${\alpha}$-FeOOH) is one of the most ubiquitous and stable forms of iron (oxyhydr)oxides in terrestrial soils, sediments, and ore deposits, as well as a common weathering product in rocks of all types. This study focused on adsorption reaction as a main mechanism in scavenging arsenic using goethite. Goethite was synthesized in the laboratory to get high purity, and a variety of mineralogical and physicochemical features of goethite were measured and related to adsorption characteristics of arsenic. To compare differences in adsorption reactions between arsenic species, in addition, a variety of experiments to acquire adsorption isotherm, adsorption edges, and adsorption kinetics were accomplished. The point of zero charge (PZC) of the laboratory-synthesized goethite was measured to be 7.6, which value seems to be relatively higher, compared to those of other iron (oxyhydr)oxides. Its specific surface area appeared to be $29.2\;m^2/g$ and it is relatively smaller than those of other (oxyhydr)oxides. As a result, it was speculated that goethite shows a smaller adsorption capacity. It is likely that the affinity of goethite is much more larger for As(III) (arsenite) than for As(V) (arsenate), because As(III) was observed to be much more adsorbed on goethite than As(V) in equivalent pH conditions. When the adsorption of each arsenic species onto goethite was characterized in various of pH, the adsorption of As(III) was largest in neutral pH range (7.0~9.0) and decreased in both acidic and alkaline pH conditions. In the case of As(V), the adsorption appeared to be highest in the lowest pH condition, and then decreased with an increase of pH. This peculiarity of arsenic adsorption onto goethite might be caused by macroscopic electrostatic interactions due to variation in chemical speciation of arsenic and surface charge of goethite, and also it is significantly affected by change in pH. Parabolic diffusion model was adequate to effectively evaluate arsenic adsorption on goethite, and the regression results show that the kinetic constant of As(V) is larger than that of As(III).

A Study on the Factors Affecting Removal of Chromium(VI) Using $TiO_{2}$ Photocatalyst in a Circular Type Reactor (순환식 반응기에서 $TiO_{2}$ 광촉매를 이용한 Chromium(VI)의 제거에 미치는 영향인자에 대한 연구)

  • Kim, Hyun-Yong;Cho, Il-Hyoung;Lee, So-Jin;Ki, Won-Ju;Lee, Hong-Keun
    • Journal of Environmental Health Sciences
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    • v.25 no.3
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    • pp.64-69
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    • 1999
  • This study was carried out the removal of Cr(VI) which was known to the toxic pollutant in industry using the process of UV and TiO$_2$ photocatalyst in a circular type reactor. In this experiment, the series of photocatalytic process for the removal of Cr(VI) has been selected as a model reaction in a circular type reactor in order to obtain the basic data on the influence of various experimental parameters such as circulation flow rate, pH of solution, initial Cr(VI) light illumination and TiO$_2$ dosage, and salicylic acid concentration. The results of this study were as follows; 1. With both UV light illumination and TiO$_2$ present, Cr(VI) was more effectively eliminated than with either UV or TiO$_2$ alone. 2. As the circulation flow rate of solution increased, the removal efficiency of Cr(VI) was increased. However, over 2.4 l/min of circulation flow rate, the efficiency wa limited. 3. A increase in the photocatalytic removal of Cr(VI) was noticed with decreasing pH. 4. An increase in the photocatalytic removal of Cr(VI) was noticed with decreasing Initial Cr(VI) concentration and first order kinetics was observed from the result at different initial concentration of Cr(VI). 5. Photocatalytic removal efficiency of Cr(VI) increased with increasing TiO$_2$ dosage. However, over 1.0 g/l of TiO$_2$ dosage, the efficiency reached a plateau. 6. As low concentration of saliculic acid were added, there was an increase in the removal efficiency of Cr(VI). However, over 300 mg/l of salicylic acid, the efficiecy was decreased. It eas found that application of photocatalysis to water treatment that contains both Cr(VI) and salicylic acid was possible.

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Degradation Kinetics of Anthocyanin Pigment Solutions from Purple-fleshed Sweet Potato Cultivars (자색고구마 품종별 안토시아닌 색소의 분해에 대한 속도론적 연구)

  • Park, Jeong-Seob;Bae, Jae-O;Chung, Bong-Woo;Jung, Mun-Yhung;Choi, Dong-Seong
    • The Korean Journal of Food And Nutrition
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    • v.24 no.4
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    • pp.559-566
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    • 2011
  • The effects of pH and temperature on degradation of anthocyanin in purple-fleshed sweet potato cultivars(Mokpo No.62, Borami, Jami, Sinjami and Ayamurasaki) were determined at pH ranges of 1 to 5 and temperature ranges of 20 to $80^{\circ}C$. The anthocyanin contents of five sweet potato varieties were 3.9, 3.8, 4.7, 4.1, 4.2 mg/g of dried sweet potato, respectively. Degradations of anthocyanins at different pHs and temperatures followed the first-order reaction. Our results clearly showed that the anthocyanin stability of purple-fleshed sweet potato was dependent on the source of the sweet potato cultivars. Anthocyanin obtained from Borami showed the highest stability. The half-life of antocyanin degradation of purple sweet potato cultivars(Mokpo No.62, Borami, Jami, Sinjami and Ayamurasaki) at pH 3 were 22.2, 28.3, 26.3, 23.4, 22.7 days at $60^{\circ}C$, respectively. A significant decrease in anthocyanin stability was observed at temperatures above $40^{\circ}C$. Activation energies of purple-fleshed sweet potato cultivars at different temperatures were 54.67, 60.93, 71.73, 59.35, 62.28 kJ/mol, respectively.

Adsorption Characteristics and Parameters of Acid Black and Quinoline Yellow by Activated Carbon (활성탄에 의한 Acid Black과 Quinoline Yellow의 흡착특성 및 파라미터)

  • Yi, Kyung Ho;Hwang, Eun Jin;Baek, Woo Seung;Lee, Jong-Jib;Dong, Jong-In
    • Clean Technology
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    • v.26 no.3
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    • pp.186-195
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    • 2020
  • The isothermal adsorption, dynamic, and thermodynamic parameters of Acid black (AB) and Quinoline yellow (QY) adsorption by activated carbon were investigated using the initial concentration, contact time, temperature, and pH of the dyes as adsorption parameters. The adsorption equilibrium data fits the Freundlich isothermal adsorption model, and the calculated Freundlich separation factor values found that activated carbon can effectively remove AB and QY. Comparing the kinetic data showed that the pseudo second order model was within 10% error in the adsorption process. The intraparticle diffusion equation results were divided into two straight lines. Since the slope of the intraparticle diffusion line was smaller than the slope of the boundary layer diffusion line, it was confirmed that intraparticle diffusion was the rate-controlling step. The thermodynamic experiments indicated that the activation energies of AB and QY were 19.87 kJ mol-1 and 14.17 kJ mol-1, which corresponded with the physical adsorption process (5 ~ 40 kJ mol-1). The adsorption reaction was spontaneous because the free energy change in the adsorption of AB and QY by activated carbon was negative from 298 to 318 K. As the temperature increased, the free energy value decreased resulting in higher spontaneity. Adsorption of AB and QY by activated carbon showed the highest adsorption removal rate at pH 3 due to the effect of anions generated by dissociation. The adsorption mechanism was electrostatic attraction.

Adsorption Characteristics Analysis of 2,4-Dichlorophenol in Aqueous Solution with Activated Carbon Prepared from Waste Citrus Peel using Response Surface Modeling Approach (반응표면분석법을 이용한 폐감귤박 활성탄에 의한 수중의 2,4-Dichlorophenol 흡착특성 해석)

  • Lee, Chang-Han;Kam, Sang-Kyu;Lee, Min-Gyu
    • Korean Chemical Engineering Research
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    • v.55 no.5
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    • pp.723-730
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    • 2017
  • The batch experiments by response surface methodology (RSM) have been applied to investigate the influences of operating parameters such as temperature, initial concentration, contact time and adsorbent dosage on 2,4-dichlorophenol (2,4-DCP) adsorption with an activated carbon prepared from waste citrus peel (WCAC). Regression equation formulated for the 2,4-DCP adsorption was represented as a function of response variables. Adequacy of the model was tested by the correlation between experimental and predicted values of the response. A fairly high value of $R^2$ (0.9921) indicated that most of the data variation was explained by the regression model. The significance of independent variables and their interactions were tested by the analysis of variance (ANOVA) and t-test statistics. These results showed that the model used to fit response variables was significant and adequate to represent the relationship between the response and the independent variables. The kinetics and isotherm experiment data can be well described with the pseudo-second order model and the Langmuir isotherm model, respectively. The maximum adsorption capacity of 2,4-DCP on WCAC calculated from the Langmuir isotherm model was 345.49 mg/g. The rate controlling mechanism study revealed that film diffusion and intraparticle diffusion were simultaneously occurring during the adsorption process. The thermodynamic parameters indicated that the adsorption reaction of 2,4-DCP on WCAC was an endothermic and spontaneous process.

Effects of Rice Straw and Gypsum on the Changes of Urease, Nitrate Reductase and Nitrite Reductase Activities in Saline Paddy Soil (간척답토양(干拓沓土壤)에 볏짚 및 석고시용(石膏施用)이 뇨효소(尿酵素), 초산환원효소(硝酸還元酵素) 및 아초산환원효소(亞硝酸還元酵素)의 활성(活性)에 미치는 영향(影響))

  • Lee, Sang Kyu;Kim, Young Sig;Hwang, Seon Woong;Park, Jun Kyu;Chang, Young Sun
    • Korean Journal of Soil Science and Fertilizer
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    • v.18 no.1
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    • pp.105-110
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    • 1985
  • A incubation study was conducted to find out the effects of rice straw and gypsum as soil ameriolite on urease, nitrate and nitrite reductase activities in newly reclaimed saline sandy soil. The results obtained were summarized as follows: 1. Very low urease activities were observed in saline soil if contrast to high productive paddy soil. Urease activities were lower at 5 days than that of 25 and 50 days after incubation. Remarkably high urease activities were obtained by the application of rice straw and gypsum. 2. Comparing with NPK treatment, application of rice straw and gypsum were enhanced the activities of nitrate and nitraite reductase. 3. Positive correlation (r=0.5501 p=0.05) was obtained between urease activities and ammonium nitrogen concentration in soil. 4. Cyclic oxidation and reduction of nitrate and nitrite in soil were obtained in terms of first order microbial kinetics reaction in case of application of rice straw and gypsum, respectively. 5. Positive correlation (r=0.6296 p=0.05) was obtained between the activitie of nitrite reductase and nitrate reductase in soil.

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