• Title/Summary/Keyword: Kinetic constants

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Changes of Free Sugar and Organic Acid in the Osmotic Dehydration Process of Apples (사과의 삼투건조시 유리당과 유기산의 변화)

  • Youn, Kwang-Sup;Lee, Jun-Ho;Choi, Yong-Hee
    • Korean Journal of Food Science and Technology
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    • v.28 no.6
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    • pp.1095-1103
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    • 1996
  • In order to minimize the deterioration of dried apple quality, changes of free sugar content, organic acid and ascorbic and during osmotic dehydration with sucrose at various temperature, concentration and immersion time were investigated in this study, total sugar increased as the temperature, concentration and immersion time were increased. Sucrose showed the largest change in content while fructose and glucose showed no and small changes, respectively. Large amounts of malic and fumaric acids, and small amounts of oxalic, citric, maleic and succinic acids were detected. Organic acids were high at low temperature treatment, and became higher with increasing concentration. Loss of ascorbic acid was small at the low temperature and high concentration. Effect of immersion time was negligible. Changes of free sugar, and organic and ascorbic acid followed the first-order and second-order reaction rate equations, respectively. Arrhenius equation was applied to determine the effect of temperature on reaction rate constants with high $r^2$. To predict the changes of quality, a model was established by using the optimum functions of temperature, concentration and immersion time. The model had high $r^2$ value for the quality changes during drying.

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Thermodynamic Analysis of Phenol Adsorption by Powdered Activated Carbon (활성탄에 의한 페놀 흡착의 열역학적 연구)

  • Kim, Hwanik;Lee, Myoung-Eun;Kang, Seoktae;Chung, Jae-Woo
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.3
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    • pp.220-225
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    • 2013
  • The adsorption characteristics of phenol by the powdered activated carbon (PAC) were investigated by series of batch experiments. The pseudo-second-order model described the adsorption kinetics adequately with correlation coefficients over 0.999, indicating chemical adsorption as the rate-limiting step. The kinetic rate constants were from 0.55 to 19.81 mg $mg^{-1}min^{-1}$. The adsorption isotherm followed the Langmuir isotherm, indicating the homogeneous mono-layer adsorption onto the surface of the adsorbent. The values of activation energy, enthalpy and entropy were 17.44 kJ $mol^{-1}$, -8.26 kJ $mol^{-1}$ and -18.94 J $mol^{-1}K^{-1}$, respectively. The Gibbs free energy was in the range of -2.89~-2.14 kJ $mol^{-1}$. The results show that the phenol adsorption is physical, spontaneous and exothermic reaction.

Adsorption Equilibrium, Kinetics and Thermodynamics Studies of Malachite Green Using Zeolite (제올라이트를 이용한 말라카이트 그린의 흡착평형, 동력학 및 열역학 연구)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.18 no.1
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    • pp.76-82
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    • 2012
  • The paper includes utlization of zeolite as potential adsorbent to remove a hazardous malachite green from waste water. The adsorption studies were carried out at 298, 308 and 318 K and effects of temperature, contact time, initial concentration on the adsorption were measured. On the basis of adsorption data Langmuir and Freundlich adsorption isotherm model were also confirmed. The equilibrium process was described well by Freundlich isotherm model, showing a selective adsorption by irregular energy of zeolite surface. From determined isotherm constants, zeolite could be employed as effective treatment for removal of malachite green. From kinetic experiments, the adsorption process followed the pseudo second order model, and the adsorption rate constant ($k_2$) decreased with increasing initial concentration of malachite green. Thermodynamic parameters like activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption. The activation energy calculated from Arrhenius equation indicated that the adsorption of malachite green on the zeolite was physical process. The negative free energy change (${\Delta}G^{\circ}$ =-6.47~-9.07 kJ/mol) and the positive enthalpy change (${\Delta}H^{\circ}$ = +32.414 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption in the temperature range 298~318 K.

A Kinetic Study on Aminolysis of 2-Pyridyl X-Substituted Benzoates: Effect of Changing Leaving Group from 4-Nitrophenolate to 2-Pyridinolate on Reactivity and Mechanism

  • Lee, Jong-Pal;Bae, Ae-Ri;Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3588-3592
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    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

Kinetic Studies on Cooking of Rice of Various Polishing Degrees (도정도별 쌀의 취반에 대한 역학적 연구)

  • Cheigh, Hong-Sik;Kim, Sung-Kon;Pyun, Yu-Ryang;Kwon, Tai-Wan
    • Korean Journal of Food Science and Technology
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    • v.10 no.1
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    • pp.52-56
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    • 1978
  • The mechanism of cooking rice was investigated using a japonica type rice variety, Akibare, of 50%, 70% and 90% polishing degrees. The hardness of rice cooked at various cooking temperatures ($90^{\circ}-120^{\circ}C$) was measured with a Texturometer. The cooking rate followed the equation of a first-order reaction. The reaction rate constants were in the increasing order of 50%, 70% and 90% polished rice. The temperature coefficient of the reaction rate constant at cooking temperatures of ($90^{\circ}-100^{\circ}C$) was about 2 in all rice samples. The activation energies of cooking at temperatures below $100^{\circ}C$ and above $100^{\circ}C$ were about 17,000 and 9,000 cal/mole, respectively. The polishing degrees and water soaking time of rice did not affect the activation energy of cooking; however, the lower polishing degrees and shorter soaking increased the cooking time The experimental results suggested that the cooking process of rice comprises two mechanisms: At temperatures below $100^{\circ}C$ the cooking rate is controlled by the reaction rate of rice constituents with water, and at temperatures above $100^{\circ}C$, it is controlled by the rate of diffusion of water through the cooked portion (or layer) toward the interface of uncooked core in which the reaction is occurring.

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Removal Characteristics of Tetracycline, Oxytetracycline, Trimethoprime and Caffeine in Biological Activated Carbon Process (생물활성탄 공정에서 Tetracycline, Oxytetracycline, Trimethoprime 및 Caffeine 제거특성)

  • Son, Hee-Jong;Hwang, Young-Do;Yoo, Pyung-Jong
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.3
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    • pp.186-192
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    • 2009
  • In this study, The effects of three different activated carbon materials (each coal, coconut and wood based activated carbons), empty bed contact time (EBCT) and water temperature on the removal of pharmaceutical 4 species (oxytetracycline, tetracycline, trimethoprime and caffeine) in BAC filters were investigated. Experiments were conducted at three water temperature (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 BAC, increasing EBCT or increasing water temperature increased the pharmaceutical 4 species removal in BAC columns. In the coal-based BAC columns, removal efficiencies of oxytetracycline and tetracycline were 87~100% and removal efficiencies of trimethoprime and caffeine were 72~99% for EBCT 5~20 min at $25^{\circ}C$. The kinetic analysis suggested a firstorder reaction model for pharmaceutical 4 species removal at various water temperatures (5~$25^{\circ}C$). The pseudo-first-order reaction rate constants and half-lives were also calculated for pharmaceutical 4 species removal at 5~$25^{\circ}C$. The reaction rate and half-lives of pharmaceutical 4 species ranging from 0.0360~0.3954 $min^{-1}$ and 1.75 to 19.25 min various water temperatures and EBCTs, could be used to assist water utilities in designing and operating BAC filters.

Thermal Recovery Behaviors of Neutron Irradiated Mn-Mo-Ni Low Alloy Steel (중성자에 조사된 Mn-Mo-Ni 저합금강의 열처리 회복거동)

  • Jang, Gi-Ok;Ji, Se-Hwan;Sim, Cheol-Mu;Park, Seung-Sik;Kim, Jong-O
    • Korean Journal of Materials Research
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    • v.9 no.3
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    • pp.327-332
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    • 1999
  • The recovery activation energy, the order of reaction and the recovery rate constant were detemined by isochronal and isothermal annealing treatment to investigate the recovery behaviors of neutron irradiated Mn-Mo-Ni low alloy steels$(fluence: 2.3\times10^{19}ncm^{-2}, 553K, E\geq1.0 MeV)$. Vickers microhardness tests were conducted to trace the recovery behavior after heat treatments. The results were analyzed in terms of recovery stages, behavior of responsible defects and recovery kinetics. It was shown that recovery occurred through two annealing stages(stage I : 703-753K, stage n : 813-873K) with re$\infty$very activation energies of 2.5 eV and 2.93 eV for each stage I and n, respectively. From the comparison of unirradiated and irradiated isochronal anneal curves, a radiation anneal hardening(RAH) peak was identified at around 813K. Most of recovery have occurred during about 120 min irrespective of isothermal annealing temperatures of 743K and 833K. Recovery rate constants were determined to be $3.4\times10^{-4}min^{-1} and 7.1\times10^{-4}min^{-1}$ for stage I and II, respectively. The order of reaction was about 2 for both recovery stages. Comparing the obtained data with those of previously reported results on neutron irradiated Mn- Mo- Ni steels, the thermal recovery be­havior of the present material seems to occur by the dissociation of point defect clusters formed during irradiation, and by the recombination process of self-interstitials and vacancies from dissociated vacancy clusters.

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The Methane Reforming by $CO_2$ Using Pelletized Co-Ru-Zr-Si Catalyst (성형 Co-Ru-Zr-Si 촉매를 이용한 이산화탄소에 의한 메탄 리포밍)

  • Nam, Jeong-Kwang;Lee, Ji-Hye;Song, Sang-Hoon;Ahn, Hong-Chan;Chang, Tae-Sun;Suh, Jeong-Kwon;Kim, Seong-Bo
    • Applied Chemistry for Engineering
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    • v.23 no.2
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    • pp.176-182
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    • 2012
  • The methane dry reforming has received the considerable attention in recent years, mainly as an attractive route to produce synthesis gas (CO, $H_2$) from green-house gases ($CH_4$, $CO_2$) for resources. However, this process has not been commercialized due to the high temperature and catalyst deactivation. In this study, Co-Ru-Zr catalysts supported on $SiO_2$ were studied for the characterization of methane dry reforming reaction and the preliminary data for process development were achieved. The crystal structure of catalysts was measured by XRD, the surface area and pore size were analyzed by BET, and the element composition of catalyst were analyzed by EDS. Conversions of methane and carbon dioxide were analyzed by GC. In addition, reaction rate constants were obtained from the reaction kinetic study and the optimum catalyst size that does not affect mass transfer from reactants was also determined. The selected pellet-type catalyst maintained activation for 720 h at $850^{\circ}C$.

1H NMR Kinetic Studies for Degradation of Nitramine Explosives Using PdO Nanoparticle (PdO 나노입자를 이용한 니트라민 폭발물 분해반응에 대한 1H NMR 반응속도연구)

  • Kye, Young-Sik;Kumbier, Mathew;Kim, Dongwook;Harbison, Gerard S.;Langell, Marjorie A.
    • Applied Chemistry for Engineering
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    • v.33 no.3
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    • pp.302-308
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    • 2022
  • The PdO nanoparticle with large surface area was selected to solve the environmental pollution problem at fire range caused by high energy explosives research department explosive (RDX) and high melting explosive (HMX). By simulating water pollution, RDX and HMX nitramine explosives were dissolved in water, followed by the degradation reaction at 313 K by adding PdO. In order to measure the degradation reaction rate of explosives, 1H NMR was used, which can monitor the reaction rate without losing sample during reaction, and observe the progress of the reaction through the spectrum. The results showed that the degradation of RDX and HMX by PdO nanoparticles are pseudo-first order reaction. The degradation of explosives compounds were observed via the chemical shift and peak intensity analysis of NMR peaks. The measured rate constants for these reactions of RDX and HMX were 2.10 × 10-2 and 6.35 × 10-4 h-1, respectively. This study showed that the application of PdO nanoparticles for explosives degradation is a feasible option.

Chemical Reactions in Surfactant Solution (I). Substituent Effects of 2-Alkylbenzimidazolide ions on Dephosphorylation in CTABr Solutions (계면활성제 용액속에서의 화학반응 (제1보). 미셀용액속에서의 탈인산화 반응에 미치는 2-알킬벤즈이미다졸음이온들의 치환기효과)

  • Young-Seuk Hong;Chan-Sik Park;Jung-Bae Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.522-532
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    • 1985
  • The reactions of p-nitrophenyldiphenylphosphate (p-NPDPP) with anions of benzimidazole (BI) and its 2-alkyl derivatives (R-BI) are strongly catalyzed by the micelles of cetyltrimethyl ammonium bromide (CTABr). On the other hand, the first order rate constants $(k'_{R-BI^-})$ and the second order rate constants $(k_{m(R-BI^-)})$ of the reactions mediated by R-$BI^-$in the micellar pseudophase are much smaller than those mediated by $BI^-$. In order to explain the slower rates of the micellar reactions mediated by R-$BI^-$, we compared the concentration-ratios ([R-$BI^-$]/[$BI^-$]) with the first order rate constant-ratios $(k'_{R-BI^-}/k'_{BI^-})$ and the second order constant-ratios $(k_{m(R-BI^-)}/k_{m(BI^-)})$ for the reactions taking place in the micellar pseudophase. The rate constant-ratios were much smaller than the concentration-ratios. For example in a 5 ${\times}10^{-4}$M butyl-BI solution, the two ratios were 0.089 and 0.430 (for the first order) respectively, and in a $10^{-4}$M butyl-BI solution the former was 0.100 (for the second order). This predicts that the reactivities of R-$BI^-$ in the micellar pseudophase are much smaller than that of $BI^-$. Based on the values of several kinetic parameters measured for dephosphorylation of p-NPDPP mediated by R-$BI^-$, a schemetic model is proposed. Due to the hydrophobicity and the steric effect of the alkyl substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long cetyl groups of CTABr. Consequently, the movements of R-$BI^-$ bound to the micelle should be restricted, leading to decreased collison frequencies between the nucleophiles and p-NPDPP. We refer this as an "anchor effect". This effect became more predominent when a larger alky group in R-BI was employed and when a greater concentration of R-BI was used.

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