• Title/Summary/Keyword: rate constants

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Oxidative Degradation of PCE/TCE Using $KMnO_4$ in Aqueous Solutions under Steady Flow Conditions (유동조건에서 $KMnO_4$도입에 따른 수용액중 PCE/TCE의 산화분해)

  • Kim, Heon-Ki;Kim, Tae-Yun
    • Economic and Environmental Geology
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    • v.41 no.6
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    • pp.685-693
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    • 2008
  • The rates of oxidative degradation of perchloroethene (PCE) and trichloroethene (TCE) using $KMnO_4$ solution were evaluated under the flow condition using a bench-scale transport experimental setup. Parameters which are considered to affect the reaction rates tested in this study were the contact time (or retention time), and the concentration of oxidizing agent. A glass column packed with coarse sand was used for simulating the aquifer condition. Contact time between reactants was controlled by changing the flow rate of the solution through the column. The inflow concentrations of PCE and TCE were controlled constant within the range of $0.11{\sim}0.21\;mM$ and $1.3{\sim}1.5\;mM$, respectively. And the contact time was $14{\sim}125$ min for PCE and $15{\sim}36$ min for TCE. The $KMnO_4$ concentration was controlled constant during experiment in the range of $0.6{\sim}2.5\;mM$. It was found that the reduction of PCE and TCE concentrations were inversely proportional to the contact time. The exact reaction order for the PCE and TCE degradation reaction could not be determined under the experimental condition used in this study. However, the estimated reaction rate constants assuming pseudo-1st order reaction agree with those reported based on batch studies. TCE degradation rate was proportional to $KMnO_4$ concentration. This was considered to be the result of using high inflow concentrations of reactant, which might be the case at the vicinity of the source zones in aquifer. The results of this study, performed using a dynamic flow system, are expected to provide useful information for designing and implementing a field scale oxidative removal process for PCE/TCE-contaminated sites.

Effect of Temperature on Development and Life Table Parameters of Tetranychus urticae Koch (Acari: Tetranychide) Reared on Eggplants (가지에서 온도별 점박이응애 발육특성 및 생명표 통계량)

  • Kim, Ju;Lee, Sang-Koo;Kim, Jeong-Man;Kwon, Young-Rip;Kim, Tae-Heung;Kim, Ji-Soo
    • Korean journal of applied entomology
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    • v.47 no.2
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    • pp.163-168
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    • 2008
  • Temperature dependent development of Tetranychus. urticae Koch was studied on the leaf of eggplant at 17, 22, 27, 32 and $37^{\circ}C$. T. urticae showed a minimum mortality at $27^{\circ}C$ and it increased at higher or lower temperatures than $27^{\circ}C$. The hatchability was low at 17 and $37^{\circ}C$. The duration of development decreased with increasing temperatures i.e., 5.3d at $37^{\circ}C$ and 25.8d at $17^{\circ}C$. Linear regression analysis of temperature vs. rate of development yielded the higher $r^2{\geq}0.88$ resulting in a good fit of the estimated line in the range of $17{\sim}37^{\circ}C$. Developmental zero temperature was $12.5^{\circ}C$ for the entire immature stage of female and $12.8^{\circ}C$ for that of male. Thermal constants were 80.5 and 74.7 degree days for those of female and male, respectively. Adult life span and oviposition period decreased with increasing temperatures. The number of eggs laid per female peaked at 141.0 eggs at $27^{\circ}C$, while that was a minimum 78.0 eggs at $37^{\circ}C$. Rate of hatchability, ratio of female, and $R_o$ were increased up to $27^{\circ}C$, and than declined thereafter. Intrinsic rate of natural increase (Rm) increased with rising temperatures and showed a maximum 0.5652 at $37^{\circ}C$. Also, ${\lambda}$ increased with increasing temperature. Doubling time (Dt) and generation time (T) decreased with increasing temperature.

The Measurement of Sensitivity and Comparative Analysis of Simplified Quantitation Methods to Measure Dopamine Transporters Using [I-123]IPT Pharmacokinetic Computer Simulations ([I-123]IPT 약역학 컴퓨터시뮬레이션을 이용한 민감도 측정 및 간편화된 운반체 정량분석 방법들의 비교분석 연구)

  • Son, Hye-Kyung;Nha, Sang-Kyun;Lee, Hee-Kyung;Kim, Hee-Joung
    • The Korean Journal of Nuclear Medicine
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    • v.31 no.1
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    • pp.19-29
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    • 1997
  • Recently, [I-123]IPT SPECT has been used for early diagnosis of Parkinson's patients(PP) by imaging dopamine transporters. The dynamic time activity curves in basal ganglia(BG) and occipital cortex(OCC) without blood samples were obtained for 2 hours. These data were then used to measure dopamine transporters by operationally defined ratio methods of (BG-OCC)/OCC at 2 hrs, binding potential $R_v=k_3/k_4$ using graphic method or $R_A$= (ABBG-ABOCC)/ABOCC for 2 hrs, where ABBG represents accumulated binding activity in basal ganglia(${\int}^{120min}_0$ BG(t)dt) and ABOCC represents accumulated binding activity in occipital cortex(${\int}^{120min}_0$ OCC(t)dt). The purpose of this study was to examine the IPT pharmacokinetics and investigate the usefulness of simplified methods of (BG-OCC)/OCC, $R_A$, and $R_v$ which are often assumed that these values reflect the true values of $k_3/k_4$. The rate constants $K_1,\;k_2\;k_3$ and $k_4$ to be used for simulations were derived using [I-123]IPT SPECT and aterialized blood data with a standard three compartmental model. The sensitivities and time activity curves in BG and OCC were computed by changing $K_l$ and $k_3$(only BG) for every 5min over 2 hours. The values (BG-OCC)/OCC, $R_A$, and $R_v$ were then computed from the time activity curves and the linear regression analysis was used to measure the accuracies of these methods. The late constants $K_l,\;k_2\;k_3\;k_4$ at BG and OCC were $1.26{\pm}5.41%,\;0.044{\pm}19.58%,\;0.031{\pm}24.36%,\;0.008{\pm}22.78%$ and $1.36{\pm}4.76%,\;0.170{\pm}6.89%,\;0.007{\pm}23.89%,\;0.007{\pm}45.09%$, respectively. The Sensitivities for ((${\Delta}S/S$)/(${\Delta}k_3/k_3$)) and ((${\Delta}S/S$)/(${\Delta}K_l/K_l$)) at 30min and 120min were measured as (0.19, 0.50) and (0.61, 0,23), respectively. The correlation coefficients and slopes of ((BG-OCC)/OCC, $R_A$, and $R_v$) with $k_3/k_4$ were (0.98, 1.00, 0.99) and (1.76, 0.47, 1.25), respectively. These simulation results indicate that a late [I-123]IPT SPECT image may represent the distribution of the dopamine transporters. Good correlations were shown between (3G-OCC)/OCC, $R_A$ or $R_v$ and true $k_3/k_4$, although the slopes between them were not unity. Pharmacokinetic computer simulations may be a very useful technique in studying dopamine transporter systems.

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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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Application of Principle in Metal-Ligand Complexation to Remove Heavy Metals;Time Effects (금속(金屬)-Ligand 착염형성(錯鹽形成)에 의한 중금속(重金屬) 제거(除去) 방법(方法)에 관한 연구(硏究);시간(時間)의 영향(影響))

  • Yang, Jae-E;Shin, Yong-Keon;Kim, Jeong-Je
    • Korean Journal of Environmental Agriculture
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    • v.12 no.1
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    • pp.51-57
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    • 1993
  • Objective of this research was to assess the influence of reaction time on the heavy metal-organic ligand complexation by employing kinetic models. Aqueous solutions of humic (HA) or fulvic acid (FA) were reacted with metal solutions with 1:1 ratio to form complexes. Efficiency of organic ligand on metal removal was determined by separating the precipitates from solution using $0.45\;{\mu}m$ filter paper. Complexation between Cu or Pb and HA or FA followed the first- or multiple first order kinetics, largely depending on metal concentration and kind of organic ligand. Amounts of precipitates were increased proportionally with reaction time but reached to quasiequilibrium where rate of precipitate formation was not varied with time. Copper-ligand complexation was, irrespective of ligand, fitted to the single first order kinetics at Cu concentrations lower than $300{\mu}M$, but this was fitted to the multiple first order kinetics at Cu concentrations higher than $300{\mu}M$. As increasing Cu concentrations, the precipitates formed more readily, judging from the increased rate constants (${\kappa}$). In the multiple first order kinetics, ${\kappa}$ was decreased as reaction steps proceeded. Most of Cu-ligand precipitates were formed within 15 min. FA precipitated Cu more rapidly than HA did. ${\kappa}$ for Pb-HA complexation was decreased but that for Pb-FA reaction was increased, as increasing Pb concentration. Most of Pb-organic ligand complexation occurred within 30 min. Afterwards, ${\kappa}$ values were relatively small and not affected much by time. Pb was precipitated by humic acid more readily than Cu when metal concnetrations were $200{\sim}300{\mu}M$. However, when metal concentrations were in the ranges of $400{\sim}500{\mu}M$, a reversed tendency was observed.

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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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Adsorption Removal of Sr by Barium Impregnated 4A Zeolite (BaA) From High Radioactive Seawater Waste (Barium이 함침된 4A 제올라이트 (BaA)에 의한 고방사성해수폐액에서 Sr의 흡착 제거)

  • Lee, Eil-Hee;Lee, Keun-Young;Kim, Kwang-Wook;Kim, Ik-Soo;Chung, Dong-Yong;Moon, Jei-Kwon;Choi, Jong-Won
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.14 no.2
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    • pp.101-112
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    • 2016
  • This study investigated the removal of Sr, which was one of the high radioactive nuclides, by adsorption with Barium (Ba) impregnated 4A zeolite (BaA) from high-radioactive seawater waste (HSW). Adsorption of Sr by BaA (BaA-Sr), in the impregnated Ba concentration of above 20.2wt%, was decreased by increasing the impregnated Ba concentration, and the impregnated Ba concentration was suitable at 20.2wt%. The BaA-Sr adsorption was added to the co-precipitation of Sr with $BaSO_4$ precipitation in the adsorption of Sr by 4A (4A-Sr) within BaA. Thus, it was possible to remove Sr more than 99% at m/V (adsorbent weight/solution volume)=5 g/L for BaA and m/V >20 g/L for 4A, respectively, in the Sr concentration of less than 0.2 mg/L (actual concentration level of Sr in HSW). It shows that BaA-Sr adsorption is better than 4A-Sr adsorption in for the removal capacity of Sr per unit gram of adsorbent, and the reduction of the secondary solid waste generation (spent adsorbent etc.). Also, BaA-Sr adsorption was more excellent removal capacity of Sr in the seawater waste than distilled water. Therefore, it seems to be effective for the direct removal of Sr from HSW. On the other hand, the adsorption of Cs by BaA (BaA-Cs) was mainly performed by 4A within BaA. Accordingly, it seems to be little effect of impregnated Ba into BaA. Meanwhile, BaA-Sr adsorption kinetics could be expressed the pseudo-second order rate equation. By increasing the initial Sr concentrations and the ratios of V/m, the adsorption rate constants ($k_2$) were decreased, but the equilibrium adsorption capacities ($q_e$) were increasing. However, with increasing the temperature of solution, $k_2$ was conversely increased, and $q_e$ was decreased. The activation energy of BaA-Sr adsorption was 38 kJ/mol. Thus, the chemical adsorption seems to be dominant rather than physical adsorption, although it is not a chemisorption with strong bonding form.

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.

An Empirical Model for Forecasting Alternaria Leaf Spot in Apple (사과 점무늬낙엽병(斑點落葉病)예찰을 위한 한 경험적 모델)

  • Kim, Choong-Hoe;Cho, Won-Dae;Kim, Seung-Chul
    • Korean journal of applied entomology
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    • v.25 no.4 s.69
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    • pp.221-228
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    • 1986
  • An empirical model to predict initial disease occurrence and subsequent progress of Alternaria leaf spot was constructed based on the modified degree day temperature and frequency of rainfall in three years field experiments. Climatic factors were analized 10-day bases, beginning April 20 to the end of August, and were used as variables for model construction. Cumulative degree portion (CDP) that is over $10^{\circ}C$ in the daily average temperature was used as a parameter to determine the relationship between temperature and initial disease occurrence. Around one hundred and sixty of CDP was needed to initiate disease incidence. This value was considered as temperature threshhold. After reaching 160 CDP, time of initial occurrence was determined by frequency of rainfall. At least four times of rainfall were necessary to be accumulated for initial occurrence of the disease after passing temperature threshhold. Disease progress after initial incidence generally followed the pattern of frequency of rainfall accumulated in those periods. Apparent infection rate (r) in the general differential equation dx/dt=xr(1-x) for individual epidemics when x is disease proportion and t is time, was a linear function of accumulation rate of rainfall frequency (Rc) and was able to be directly estimated based on the equation r=1.06Rc-0.11($R^2=0.993$). Disease severity (x) after t time could be predicted using exponential equation $[x/(1-x)]=[x_0/(1-x)]e^{(b_0+b_1R_c)t}$ derived from the differential equation, when $x_0$ is initial disease, $b_0\;and\;b_1$ are constants. There was a significant linear relationship between disease progress and cumulative number of air-borne conidia of Alternaria mali. When the cumulative number of air-borne conidia was used as an independent variable to predict disease severity, accuracy of prediction was poor with $R^2=0.3328$.

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Removal of I by Adsorption with AgX (Ag-impregnated X Zeolite) from High-Radioactive Seawater Waste (AgX (Ag-함침 X 제올라이트)에 의한 고방사성해수폐액으로부터 요오드(I)의 흡착 제거)

  • Lee, Eil-Hee;Lee, Keun-Young;Kim, Kwang-Wook;Kim, Hyung-Ju;Kim, Ik-Soo;Chung, Dong-Yong;Moon, Jei-Kwon;Choi, Jong-Won
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.14 no.3
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    • pp.223-234
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    • 2016
  • This study aimed to the adsorption-removal of high- radioactive iodide (I) contained in the initially generated high-radioactive seawater waste (HSW), with the use of AgX (Ag-impregnated X zeolite). Adsorption of I by AgX (hereafter denoted as AgX-I adsorption) was increased by increasing the Ag-impregnated concentration in AgX, and its concentration was suitable at about 30 wt%. Because of AgCl precipitation by chloride ions contained in seawater waste, the leaching yields of Ag from AgX (Ag-impregnated concentration : about 30~35 wt%) was less than those in distilled water (< 1 mg/L). AgX-I adsorption was above 99% in the initial iodide concentration ($C_i$) of 0.01~10 mg/L at m/V (ratio of weight of adsorbent to solution volume)=2.5 g/L. This shows that efficient removal of I is possible. AgX-I adsorption was found to be more effective in distilled water than in seawater waste, and the influence of solution temperature was insignificant. Ag-I adsorption was better described by a Freundlich isotherm rather than a Langmuir isotherm. AgX-I adsorption kinetics can be expressed by a pseudo-second order rate equation. The adsorption rate constants ($k_2$) decreased by increasing $C_i$, and conversely increased by increasing the ratio of m/V and the solution temperature. This time, the activation energy of AgX-I adsorption was about 6.3 kJ/mol. This suggests that AgX-I adsorption is dominated by physical adsorption with weaker bonds. The evaluation of thermodynamic parameters (a negative Gibbs free energy and a positive Enthalpy) indicates that AgX-I adsorption is a spontaneous reaction (forward reaction), and an endothermic reaction indicating that higher temperatures are favored.