• Title/Summary/Keyword: Kinetic Constants

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Kinetic Studies on the Thermal Degradation of Ginsenosides in Ginseng Extract (Ginsenosides의 처리온도(處理溫度) 및 시간(時閭)에 따른 반응속도론적(反應速度論的) 연구(硏究))

  • Choi, Jin-Ho;Kim, Doo-Ha;Sung, Hyun-Soon;Kim, Woo-Jung;Oh, Sung-Ki
    • Korean Journal of Food Science and Technology
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    • v.14 no.3
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    • pp.197-202
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    • 1982
  • Kinetic study for the thermal degradation of ginsenosides in ginseng extract was conducted. The results indicate that the thermal degradation followed first order kinetics and rate constants varied substantially depending on the types of ginsenosides and heat treatment temperatures. Activation energy calculated by Arrhenius plots ranged from 16.80 kcal/mole to 30.10 kcal/mole and $Q_{10}$ values ranged from 2.01 to 3.49. Correlation coefficients between the change of ginsenoside contents by thermal degradation and heat treatment temperature were $0.995{\sim}0.999$. The dependence on temperatures of the decomposition rate constant of total ginsenoside can be expressed as $k=4.574{\times}10^8$ exp(8898.8/T).

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Analysis of the Factors Affecting Anaerobic Thermophilic Digestibility of Food Wastes (음식물쓰레기의 고온 혐기성 소화도에 미치는 요소에 대한 분석)

  • Kim, Do Hee;Hyun, Seung Hoon;Kim, Kyung Woong;Cho, Jaeweon;Kim, In S.
    • Journal of the Korea Organic Resources Recycling Association
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    • v.8 no.2
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    • pp.130-139
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    • 2000
  • Serial basic tests were conducted for the determination of fundamental kinetics and for the actual application of kinetic parameter to food waste digestion with precise measurement of methane production under a thermophilic condition. The effects of food particle size, sodium ion concentration, and volatile solid (VS) loading rate on the anaerobic thermophilic food waste digestion process were investigated. Results of serial test for the determination of fundamental kinetic coefficients showed the value of k (maximum substrate utilization rate coefficient) and KS (half-saturation coefficient) as $0.24hr^{-1}$ and $700mg/{\ell}$, respectively, for non-inhibiting organic loading range. No inhibition effect was shown until $5g/{\ell}$ of sodium ion concentration was applied to a serum bottle reactor. However, the volume of methane gas was decreased gradually when the concentrations of more than $5g/{\ell}$ of sodium ion applied. All sizes of food waste particle showed the same constants (A : 0.45) but the maximum substrate utilization rate constant ($k_{HA}$) was inversely proportional to particle size. As an average particle size increased from 1.02 mm to 2.14 mm, $k_{HA}$ decreased from $0.0033hr^{-1}$ to $0.0015hr^{-1}$. The result reveals that particle size is one of the most important factors in anaerobic food waste digestion. There was no inhibition effect of sodium ion when VS loading rate was $30g/{\ell}$. And maximum injection concentration of VS loading rate was determined about $40g/{\ell}$.

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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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Chemical Reactivity between Ni(II)-Macrocycle Complex Ions ($NiL_m{^{2+}}$) and $CN^-$ (Ni(II)-거대고리 리간드 착이온 ($NiL_m{^{2+}}$) 과 $CN^-$ 이온간의 반응성)

  • Yu-Chul Park;Jong-Chul Byun
    • Journal of the Korean Chemical Society
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    • v.31 no.4
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    • pp.334-343
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    • 1987
  • The Chemical reactions between $NiL_m{^{2+}}\{$Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}$}\and\ CN^-$ ion were studied by the spectrophotometric method. The equilibrium constants (K_1$) for the 1:1 complex ion, $[NiL_m(CN)]^+\;with\;NiL_m{^{2+}}\;and\;CN^-$ ion were determined in the range of 3 to $25^{\circ}C$. The $K_1\;for\;Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;Ni(1[14]4-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;at\;15^{\circ}C$ was 4.7, 5.3, 6.2, 7.5, 9.4, and 9.8, respectively. The values of $K_1$ decreased with increasing temperature. From the temperature effect on equilibrium constant ($K_1$), thermodynamic parameters $({\Delta}H^{\circ},\;{\Delta}S^{\circ},\;{\Delta}G^{\circ})$ for reaction were evaluated and the reaction of $NiL_m{^{2+}}\;and\;CN^-$ ion was exothermic. $NiL_m{^{2+}\;reacts\;with\;CN^-$ ion to give $Ni(CN)_4{^{2-}}$ ion and macrocyclic ligand $(L_m)$. The kinetics of formation of the $Ni(CN)_4{^{2-}}$ ion of varying the $[CN^-],\;[HCN],\;and\;[OH^-]$ have been investigated at 3∼$25^{\circ}C\;and\;0.5M\;NaClO_4$. Maintaining a constant $[CN^-],\;k_{obs}/[CN^-]^2$ increases linearly with increasing [HCN]. In the presence of large quantities of $[OH^-],\;k_{obs}/[CN^-]^2$ also increases linearly with $[OH^-]$. From the temperature effect on kinetic constant (k_{obs})$, parameter of activation $({\Delta}H^{\neq},\;{\Delta}S^{\neq})$ of reaction of $NiL_m{^{2+}}\;with\;CN^-$ ion were determined. For the $Ni(rac-1[14]7-diene)^{2+},\;Ni(meso-1[14]7-diene)^{2+},\;{\alpha}-Ni(rac-[14]-decane)^{2+},\;{\beta}-Ni(rac-[14]-decane)^{2+},\;and\;Ni(meso-[14]-decane)^{2+}\;series\;{\Delta}H^{\neq}$ gradually decrease as the d-d transition energy, $ν(cm^{-1})$ decrease. And the reaction of the five $NiL_m{^{2+}}\;with\;CN^-$ ion take place by way of equal paths.

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Kinetic and Statistical Analysis of Adsorption and Photocatalysis on Sulfamethoxazole Degradation by UV/$TiO_2$/HAP System (UV/$TiO_2$/HAP 시스템에서 Sulfamethoxazole의 흡착과 광촉매반응에 대한 동역학적 및 통계적 해석)

  • Chun, Suk-Young;Chang, Soon-Woong
    • Journal of the Korean GEO-environmental Society
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    • v.13 no.5
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    • pp.5-12
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    • 2012
  • Antibiotics have been considered emerging compounds due to their continuous input and persistence in environment. Due to the limited biodegradability and widespread use of these antibiotics, an incomplete removal is attained in conventional wastewater treatment plants and relative large quantities are released into the environment. In this study, it was determined the adsorption and photocatalysis kinetics of antibiotics (Sulfamethoxazole, SMX) with various catalyst (Titanium dioxide; $TiO_2$, Hydroxyapatite; HAP) conditions under UV/$TiO_2$/HAP system. In addition, the statistical analysis of response surface methods (RSM) was used to determine the effects of operating parameters on UV/$TiO_2$/HAP system. $TiO_2$/HAP adsorbent were found to follow the pseudo second order reaction in the adsorption. In the result of applied intrapaticle diffusion model, the constants of reaction rate were $TiO_2$=$0.064min^{-1}$, HAP=$0.2866min^{-1}$ and $TiO_2$/HAP=$0.3708min^{-1}$, respectively.The result of RSM, term of regression analysis in analysis of variance (ANOVA) showed significantly p-value (p<0.05) and high coefficients for determination values($R^2$=96.2%, $R^2_{Adj}$=89.3%) that allowed satisfactory prediction of second order regression model. And the estimated optimal conditions for Y(Sulfamethoxazole removal efficiency, %) were $x_1$(initial concentration of Sulfamethoxazole)=-0.7828, $x_2$(amount of catalyst)=0.9974 and $x_3$(reation time)=0.5738 by coded parameters, respectively. According to the result of intraparticle diffusion model and photocatalysis experiments, it was shown that the $TiO_2$/HAP was more effective system than conventional AOPs(advanced oxidation processes, UV/$TiO_2$ system).

Preparation of Birnessite (δ-MnO2) from Acid Leaching Solution of Spent Alkaline Manganese Batteries and Removals of 1-naphthol (폐 알칼리망간전지의 산 침출액으로부터 버네사이트(δ-MnO2)의 제조 및 1-naphthol 제거)

  • Eom, Won-Suk;Lee, Han-Saem;Rhee, Dong-Seok;Shin, Hyun-Sang
    • Journal of Korean Society of Environmental Engineers
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    • v.38 no.11
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    • pp.603-610
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    • 2016
  • This work studies the synthesis of birnessite (${\delta}-MnO_2$), a catalyst of oxidative-coupling reactions, from the powder of spent alkaline manganese batteries (SABP, <8 mesh) and evaluate its reactivity for 1-naphthol (1-NP) removals. Manganese oxides using commercial reagents ($MnSO_4$, $MnCl_2$) and the acid birnessite (A-Bir) by McKenzie method were also synthesized, and their crystallinity and reactivity for 1-NP were compared with one another. 96% Mn and 98% Zn were extracted from SABP by acid leaching at the condition of solid/liquid (S/L) ratio 1:10 in $1.0M\;H_2SO_4+10.5%\;H_2O_2$ at $60^{\circ}C$. From the acid leaching solution, 69% (at pH 8) and 94.3% (pH>13) of Mn were separated by hydroxide precipitation. Optimal OH/Mn mixing ratio (mol/mol) for the manganese oxide (MO) synthesis by alkaline (NaOH) hydrothermal techniques was 6.0. Under this condition, the best 1-NP removal efficiency was observed and XRD analysis confirmed that the MOs are corresponding to birnessite. Kinetic constants (k, at pH 6) for the 1-NP removals of the birnessites obtained from Mn recovered at pH 8 (${Mn^{2+}}_{(aq)}$) and pH>13 ($Mn(OH)_{2(s)}$) are 0.112 and $0.106min^{-1}$, respectively, which are similar to that from $MnSO_4$ reagent ($0.117min^{-1}$). The results indicated that the birnessite prepared from the SABP as a raw material could be used as an oxidative-coupling catalyst for removals of trace phenolic compounds in soil and water, and propose the recycle scheme of SAB for the birnessite synthesis.

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.

Formation and Dissociation Kinetics of Zinc(II) Complexes of Tetraaza-Crown-Alkanoic Acids (Zinc(Ⅱ) Tetraaza-Crown-Allkanoic Acids 착물의 형성 및 해리 반응속도론)

  • Choi, Ki Young;Kim, Dong Won;Kim, Chang Suk;Park, Byung Bin;Choi, Suk Nam;Hong, Choon Pyo;Ryu, Hae Il
    • Journal of the Korean Chemical Society
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    • v.44 no.5
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    • pp.403-409
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    • 2000
  • The formation and dissociation rates of $Zn^{2+}$ Complexes with l,4,7,10-tetraaza-13,16-diox-acyclooctadecane-N,N',N",N'"-tetraacetic acid (1), 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetramethylacetic acid (2), and 1,4,7,10-tetraaza-13,16- dioxacyclooctadecane-N,N',N",N'"-tetrapropionic acid(3) have been measured by stopped-flow and conventional spectrophotometry. Observations were made at 25.0$\pm$0.1 $^{\circ}C$ and at an ionic strength of 0.10 M NaClO$_4$. The formation reactions of $Zn^{2+}$ ion with 1 and 2 took place by the rapid formation of an intermediate complex (ZnH$_3L^+$) in which the $Zn^{2+}$ ion is incompletely coor-dinated. This might then lead to be a final product in the rate-determining step.ln the pH range 4.76-5.76, the diprotonated (H2L2-) form is the kinetically active species despite of its low concentration. The stability con-stants (log$K_{(ZnH$_3$3$L^+$)}$) and specific water-assisted rate constants (koH) of intermediate complexes have been deter-mined from the kinetic data. The dissociation reactions of $Zn^{2+}$ complexes of 1,2, and 3 were investigated with $Cu^{2+}$ ions as a scavenger in acetate buffer. All complexes exhibit acid-independent and acid-catalyzed con-tributions. The effect of buffer and $Cu^{2+}$ concentration on the dissociation rate has also been investigated. The ligand effect on t dissociation rate of $Zn^{2+}$ complexes is discussed in terms of the side-pendant armsand the chelate ring sizes of the ligands.

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Removal Characteristics of Sulfonamide Antibiotic Compounds in Biological Activated Carbon Process (생물활성탄 공정에서의 Sulfonamide계 항생물질 제거특성)

  • Son, Hee-Jong;Jung, Jong-Moon;Roh, Jae-Soon;Yu, Pyung-Jong
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.2
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    • pp.96-101
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    • 2009
  • In this study, the effects of three different biological activated carbon (BAC) materials (each coal, coconut and wood based activated carbons), empty bed contact time (EBCT) and water temperature on the removal of sulfonamide 5 species in BAC filters were investigated. Experiments were conducted at three water temperatures (5, 15 and $25^{\circ}C$) and four EBCTs (5, 10, 15 and 20 min). The results indicated that coal based BAC retained more attached bacterial biomass on the surface of the activated carbon than the other BACs, increasing EBCT or increasing water temperature increased the sulfonamide 5 species removal in BAC columns. In the coal-based BAC columns, sulfachloropyridazine (SCP), sulfamethazine (SMT) and sulfathiazole (STZ) removal efficiencies were 30~80% and sulfadimethoxine (SDM), sulfamethoxazole (SMX) removal efficiencies were 18~70% for 5~20 min EBCT at $25^{\circ}C$. The kinetic analysis suggested a first-order reaction model for sulfonamide 5 species removal at various water temperatures (5~$25^{\circ}C$). The pseudo-first-order reaction rate constants and half-lives were also calculated for sulfonamide 5 species removal at 5~$25^{\circ}C$. The reaction rate and half-lives of sulfonamide 5 species ranging from 0.0094~0.0718 $min^{-1}$ and 9.7 to 73.7 min various water temperaturs and EBCTs in this study could be used to assist water utilities in designing and operating BAC filters for sulfonamide antibiotic compounds removal.

Enzymatic Characteristics of Water-Insoluble ${\alpha}-Amylase$ Immobilized on Dithiocarbamate Wool (Dithiocarbamate Wool에 고정(固定)된 불용성(不溶性) ${\alpha}-Amylase$의 특성(特性)에 대하여)

  • Lee, Kyung-Hee;Kim, Jong-Deog;Lee, Kang-Ho
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.14 no.2
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    • pp.164-170
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    • 1985
  • Yellowish modified wool, dithiocarbamate(DTC) wool, was synthesized by partial hydrolysis in 0.2 N-NaOH reacting with carbon disulfide to use as ${\alpha}-amylase$ immobilization matrix. ${\alpha}-amylase$ was immobilized reacting with sulfide group of DTC-wool by covalent binding within 1 hour. 0.5 gram of this preparation, $DTC-wool-{\alpha}-amylase$, contained 150 ug of enzyme protein and its specific activity was about 90% of the native one. General properties of $DTC-wool-{\alpha}-amylase$ were a little different from optimum temperature, optimum pH, heat stability, kinetic constants and activation energy. An apparent Michaelis constant and maximum velocity of $DTC-wool-{\alpha}-amylase$ were 5.56 mg/ml and 0.37 mg/ml. $min^{-1}$ respectively, while activation energy was 16.6 kcal/mole.

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