• Title/Summary/Keyword: First-order kinetic equation

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Kinetics and Mechanism for Aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3^-$, NO$_2$, NCS$^-$, H$_2$O} in Hg$^{2+}$ Aqueous Solution ($Hg^{2+}$ 수용액 내에서 cis-[Co(en)$_2$YCl]$^{r+}$ (Y = $NH_3$, NO$_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도와 반응메카니즘)

  • Byung-Kak Park;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.476-482
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    • 1988
  • Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

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Evaluation of Removal Characteristics of Taste and Odor Causing Compounds using Meso-Porous Absorbent (메조공극 흡착제를 이용한 상수원수내 맛·냄새 유발물질 제거특성 평가)

  • Kim, Jong-Doo;Park, Chul-Hwi;Yun, Yeo-Bog;Lee, Dae-Sung;Kim, Hyo-Jeon;Kang, Seok-Tae
    • Journal of Korean Society of Environmental Engineers
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    • v.39 no.1
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    • pp.26-33
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    • 2017
  • The objective of this study was to evaluate the characteristic of adsorption by using a meso-porous adsorbent (MPA), and investigate the removal efficiency of geosmin which taste and odor causing compounds in drinking water supplies through batch test. The results for the adsorption isotherm was analyzed by using the Langmuir equation and Freundlich equation, generally being applied. And the study showed that the both Langmuir and Freundlich equation explains the results better. Both of pseudo-first-order model and pseudo-second-order model were respectively applied for evaluation of kinetic sorption property of geosmin onto MPA. The adsorption experiment results using MPA showed that maximum adsorption capacity of MPA was lower 7 times than that of GAC, and adsorption rate of MPA was faster 11 times than that of GAC, on the basis of pseudo-first-order model. Therefore, it was determined that MPA was effectively able to remove geosmin in drinking water supplies in short EBCT condition, but regeneration cycle in MAP process was shorter than that in conventional process.

The Recovery of Silver from Thiourea Leaching Solution by Cementation Technique (침전법을 이용한 Thiourea 용출용액으로부터 Silver 회수)

  • Kim, Bong-Ju;Cho, Kang-Hee;Choi, Nag-Choul;Park, Cheon-Young
    • Economic and Environmental Geology
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    • v.46 no.1
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    • pp.29-37
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    • 2013
  • In order to apply the silver cementation method using Fe powder from pregnant thiourea leaching solution. Parameters such as the amount of Fe powder addition, agitation speed, and temperature were investigated. The silver cementation rate was increased by the increasing of Fe powder addition, agitation speed, and temperature. The highest silver cementation rate was found when the addition of Fe powder was 50 g/L at the agitation speed of 500 rpm. The silver cementation rate increase with increasing temperature according to the Arrhenius equation and obeys $1^{st}$ order kinetics. The activation energy from the kinetics data was found to be between 13.73 KJ/mol and 17.02 KJ/mol. In the XRD analysis, goethite was detected in the precipitate of the thiourea leach solution. This indicates that an oxidation-reduction reaction had occurred in the thiourea solution due to the addition of the Fe powder.

Kinetic Models for the Quality Factors of Banana by Different Dehydration Methods (바나나의 건조방법(乾燥方法)에 따른 품질변화(品質變化) 인자(因子)에 대한 반응속도(反應速度) 모델링)

  • Kim, Su Yeon;Choi, Yong Hee
    • Current Research on Agriculture and Life Sciences
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    • v.7
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    • pp.175-184
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    • 1989
  • Kinetics of ascorbic acid and browning that may use on the optimization of food dehydration were evaluated. Banana was chosen for this as the representative test material. We have described the destruction of ascorbic acid and browning as first and zero order reactions. The temperature dependence between two reactions were conducted with Arrhenius equation. Finally we have operated SPSS computer programs reapeatedly that we found very dose value of the parameter between result of ascorbic acid and browning. The attained Kinetic models were well prepared for the value of result experiments and the models may use on optimization for dehydration progress. Destruction rate of ascorbic acid and browning rate were low at initiation of progress, increased to show maximum at the low moisture on mid-progress and then decreased gradually. Freeze drying showed the most constant quality of product in this case.

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Limitations of the Transition State Variation Model. Part 8. Dual Reaction Channels for Solvolyses of 3,4-Dimethoxybenzenesulfonyl Chloride

  • Koo, In-Sun;Kwon, Eun-Ju;Choi, Ho-June;Yang, Ki-Yull;Park, Jong-Keun;Lee, Jong-Pal;Lee, Ikc-Hoon;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2377-2381
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    • 2007
  • Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.

Residual Patterns of Acaricides, Etoxazole and Flufenoxuron in Apples (살응애제 Etoxazole 및 Flufenoxuron의 사과 중 잔류양상)

  • Hwang, Jeong-In;Kim, Jang-Eok
    • The Korean Journal of Pesticide Science
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    • v.18 no.2
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    • pp.61-68
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    • 2014
  • Dissipation constants and half-lives of acaricides etoxazole and flufenoxuron in apples were calculated to establish their pre-harvest residue limits (PHRLs). The acaricides were sprayed on apples with single and triple doses based on safe use guidelines, and their residual patterns in the apple were interpreted using first order kinetics equation. The residual amounts of acaricides during the experimental period were below their maximum residue limits (MRL) for apple. The dissipation constants of acaricides in the apples were calculated at 0.0788 for etoxazole and 0.0319 for flufenoxuron corresponding to their biological half-lives; 8.8~21.7 days for etoxazole and 21.7~23.1 days for flufenoxuron. The PHRLs of acaricides in the apple showed the residual amounts of etoxazole and flufenoxuron at the harvesting date would be below their MRLs if their residual amounts were less than 0.87 and 0.88 mg/kg, respectively, at 7 days prior to harvesting the apples.

Kinetic Studies on the Oxidation Reaction of Malonic Acid by Ceric Ion (세륨(Ⅳ)에 의한 말론산의 산화반응에 관한 반응속도론적 연구)

  • Kim, Wang Gi
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.705-709
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    • 1994
  • The kinetics of the oxidation reaction of malonic acid by ceric ion in 1 M sulfuric acid solution at $20^{\circ}C$ have been investigated by spectrophotometric method. The reaction rate at a large excess of malonic acid was found to be pseudo-first order. The observed pseudo-first order rate constants, $k_{obs}$, are dependent on the concentration of malonic acid, [MA], of which relationship has been found to be $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$). A mechanism for the reaction has been suggested on the basis of the above rate equation. The rate determining step may be the electron transfer reaction between enolate type malonate anion, which is formed by the acid dissociation reaction of malonic acid, and Ce(IV). The rate depression in the range of high concentration of MA has been explained by the formation of 1 : 2 chelate between Ce(IV) and malonate. According to the mechanism, the pH dependence of the rate, which was studied by Sengupta et al., has also been explained.

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Biodegradation Kinetics of Diesel in a Wind-driven Bioventing System

  • Liu, Min-Hsin;Tsai, Cyuan-Fu;Chen, Bo-Yan
    • Journal of Soil and Groundwater Environment
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    • v.21 no.5
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    • pp.8-15
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    • 2016
  • Bioremediation, which uses microbes to degrade most organic pollutants in soil and groundwater, can be used in solving environmental issues in various polluted sites. In this research, a wind-driven bioventing system is built to degrade about 20,000 mg/kg of high concentration diesel pollutants in soil-pollution mode. The wind-driven bioventing test was proceeded by the bioaugmentation method, and the indigenous microbes used were Bacillus cereus, Achromobacter xylosoxidans, and Pseudomonas putida. The phenomenon of two-stage diesel degradation of different rates was noted in the test. In order to interpret the results of the mode test, three microbes were used to degrade diesel pollutants of same high concentration in separated aerated batch-mixing vessels. The data derived thereof was input into the Haldane equation and calculated by non-linear regression analysis and trial-and-error methods to establish the kinetic parameters of these three microbes in bioventing diesel degradation. The results show that in the derivation of μm (maximum specific growth rate) in biodegradation kinetics parameters, Ks (half-saturation constant) for diesel substance affinity, and Ki (inhibition coefficient) for the adaptability of high concentration diesel degradation. The Ks is the lowest in the trend of the first stage degradation of Bacillus cereus in a high diesel concentration, whereas Ki is the highest, denoting that Bacillus cereus has the best adaptability in a high diesel concentration and is the most efficient in diesel substance affinity. All three microbes have a degradation rate of over 50% with regards to Pristane and Phytane, which are branched alkanes and the most important biological markers.

Kinetic Studies on Hydration of Akibare and Milyang 23 Brown Rice (아끼바레와 밀양 23호 현미의 수화속도)

  • Kim, Kwang-Joong;Pyun, Yu-Ryang;Cho, Eun-Kyung;Lee, Sang-Kyu;Kim, Sung-Kon
    • Korean Journal of Food Science and Technology
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    • v.16 no.3
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    • pp.297-302
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    • 1984
  • Kinetics of water diffusion during soaking of two brown rice varieties, Akibare (traditional rice) and Milyang 23 (high-yielding rice), were studied. Brown rice reached at the equilibrium moisture content after 18 hours. The absorption of liquid water by brown rice grain was directly proportional to the square root of hydration time and could be described by the simplified solution of Fick's diffusion equation. The diffusion coefficient was given by the Arrhenius relation: $D\;=\;2.738{\time}10^{-1}\;exp\;(-9,300/RT)$ for Akibare and $D\;=\;4.302{\time}10^{-1}\;exp\;(-9,500/RT)$ for Milyang 23. Hydration rate calculated from hardness change followed the equation of a first order reaction. Hydration mechanism of brown rice was changed at the gelatinization temperature of rice starch.

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Characteristics of Isotherm, Kinetic and Thermodynamic Parameters for the Adsorption of Acid Red 66 by Activated Carbon (활성탄에 의한 Acid Red 66의 흡착에 대한 등온선, 동력학 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.26 no.1
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    • pp.30-38
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    • 2020
  • The kinetic and thermodynamic parameters of Acid Red 66, adsorbed by granular activated carbon, were investigated on areas of initial concentration, contact time, and temperature. The adsorption equilibrium data were applied to Langmuir, Freundlich, Temkin, Redlich-Peterson, and Temkin isotherms. The agreement was found to be the highest in the Freundlich model. From the determined Freundlich separation factor (1/n = 0.125 ~ 0.232), the adsorption of Acid Red 66 by granular activated carbon could be employed as an effective treatment method. Temkin's constant related to adsorption heat (BT = 2.147 ~ 2.562 J mol-1) showed that this process was physical adsorption. From kinetic experiments, the adsorption process followed the pseudo-second order model with good agreement. The results of the intraparticle diffusion equation showed that the inclination of the second straight line representing the intraparticle diffusion was smaller than that of the first straight line representing the boundary layer diffusion. Therefore, it was confirmed that intraparticle diffusion was the rate-controlling step. From thermodynamic experiments, the activation energy was determined as 35.23 kJ mol-1, indicating that the adsorption of Acid Red 66 was physical adsorption. The negative Gibbs free energy change (ΔG = -0.548 ~ -7.802 kJ mol-1) and the positive enthalpy change (ΔH = +109.112 kJ mol-1) indicated the spontaneous and endothermic nature of the adsorption process, respectively. The isosteric heat of adsorption increased with the increase of surface loading, indicating lateral interactions between the adsorbed dye molecules.