• Title/Summary/Keyword: General order kinetics

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The Retrieval of Abnormal TL Glow Curves Using Modified Glow Curve Analysis Method

  • Lee, Sang-Yoon;Lee, Kun-Jai;Kim, Jang-Lyul;Chang, Si-Young
    • Nuclear Engineering and Technology
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    • v.29 no.5
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    • pp.385-392
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    • 1997
  • The shape of TL glow curve is a useful indicator for assurance of correct reading of the personal dosimeter. Since the reading procedure of TLD is irreversible, however, an analytic remedy should be considered to procure reliable dosimetric information for the readings with irregular glow con shape. In this study, kinetic trapping parameters of CaSO$_4$ : Dy Teflon personal dosimeter(Teledyne PB-6A) were analyzed by Halperin and Braner's model for general-order kinetics. From these kinetic tapping parameters, we also developed a simple procedure to retrieve the dosimetric information from abnormally distorted glow curves. The computerized glow curve deconvolution(CGCD) fitting of the reference glow curve with kinetic parameters from this study yields relative errors of about 5% from the expected integral. It was also found that the glow curve remedial procedure developed could retrieve the distorted TL glow curves within ewer ranges of 1575. With the glow curve retrieval techniques, doses incurred by gamma radiation can now be successfully re-constructed for the CaSO$_4$ : Dy Teflon dosimeter resulting abnormal glow curves.

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The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Furfurylidene Acetophenone derivatives (Furfurylidene acetophenone유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구)

  • Lee, Ki-Chang;Mok, Gap-Young;Oh, Se-Young;Ryu, Jung-Wok
    • Journal of the Korean Applied Science and Technology
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    • v.14 no.1
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    • pp.27-32
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    • 1997
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

Influence of Temperature and pH on the Stability of Dimethoxy Biphenyl Monocarboxylate${\cdot}$HCl Solutions

  • Choi, Woo-Chang;Kim, Dae-Duk;Shin, Young-Hee;Lee, Chi-Ho
    • Archives of Pharmacal Research
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    • v.24 no.2
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    • pp.159-163
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    • 2001
  • The accelerated stability of dimethoxy biphenyl monocarboxylate.HCl (DDB-S) was investigated in 6 mg/mL water solution in the pH ranging 2-10 and the temperature of $45-85^{\circ}C$. The observed rate of degradation followed first-order kinetics. The energy of activation for DDB-S degradation was calculated to be 14.1 and 16.5 $Kcal/mole$ at pH 5 and in distilled watery respectively. The degradation rate constant ($K_{25^{\circ}C}$) obtained by trending line analysis of Arrhenius plots for DDB-S was $5.3{\times}10^{-6}h^{-1}$. The times to degrade 10% ($t_{10}$) and 50% $t_{500}$) at $K_{25^{\circ}C}$ were 829 and 5,416 days, respectively. DDB-S exhibited the fastest degradation at pH 10 and the slowest rate at pH 5. In addition, at $K_{65^{\circ}C}$, degradation rate constants of DDB-S were 0.066, 0.059, 5.460, 32.171, and $1.4{\times}10^{-6}h^{-1}$ at pH 2, 5, 8, 10 and in distilled water, respectively. These observations indicated that the rate-pH profile of DDB-S showed general acid-base catalysis reaction in the range of pH 2-10.

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Removal of Phenol from Aqueous Solutions by Activated Red Mud: Equilibrium and Kinetics Studies

  • Shirzad-Siboni, Mehdi;Jafari, Seyed-Javad;Farrokhi, Mehrdad;Yang, Jae Kyu
    • Environmental Engineering Research
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    • v.18 no.4
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    • pp.247-252
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    • 2013
  • In this work, removal of phenol from aqueous solutions by activated red mud was investigated. Scanning electron microscopy and energy dispersive X-ray spectroscopy was used to observe the morphology and surface components of activated red mud, respectively. The effects of various parameters on the removal efficiency were studied, such as contact time, pH, initial phenol concentration, and adsorbent dosage. The removal percentage of phenol was initially increased, as the solution pH increased from 3 to 7, and then decreased above neutral pH. The removal percentage of phenol was decreased by increasing the initial phenol concentrations. Adsorption results show that equilibrium data follow the Freundlich isotherm, and kinetic data was well described by a pseudo-second-order kinetic model. Experimental results show that the activated red mud can be used to treat aqueous solutions containing phenol, as a low cost adsorbent with high efficiency.

Investigation of physical characteristics for Al2O3:C dosimeter using LM-OSL

  • Kim, Myung-Jin;Lee, Young-Ju;Kim, Ki-Bum;Hong, Duk-Geun
    • Analytical Science and Technology
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    • v.32 no.4
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    • pp.131-138
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    • 2019
  • This paper reports results on the physical properties of a powder type of $Al_2O_3:C$ commonly used as a luminescence dosimeter using the LM-OSL technique. On the analysis with the general order kinetics model, the LM-OSL signal measured appeared to be composed of three components (fast, medium, slow) showing the largest area in the medium component. The photoionization cross sections of three components were distributed between $10^{-19}{\sim}10^{-21}cm^2$. The values of the thermal assistance energy were evaluated the largest in slow component and the smallest in fast component, which indicates the electrons trapped in defects attributed to slow component should be the most sensitive to thermal vibration among three components. In illumination to blue light, the fast component showed a rapid linear decay and completely disappeared after light exposure time of about 5 s. The medium component decayed with two exponential elements but the slow component did not observed any noticeable change until light exposure time of 40 s. In a dose response study, all components exhibited a linear behaviour up to approximately 10 Gy.

Applications of Third Order Models in Solvolytic Reaction of Aliphatic Substituted Acyl Derivatives in 2,2,2-Trifluoroethanol-Ethanol Systems

  • Ryu, Zoon-Ha;Lim, Gui-Taek;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • v.24 no.9
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    • pp.1293-1302
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    • 2003
  • Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using Cr(VI)-6-Methylquinoline (Cr(VI)-6-Methylquinoline을 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구)

  • Park, Young Cho;Kim, Young Sik
    • Applied Chemistry for Engineering
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    • v.26 no.3
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    • pp.372-376
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    • 2015
  • 6-MQCC (Cr(VI)-6-methylquinoline) complex was synthesized by the reaction of 6-methylquinoline with chromium(VI) trioxide in 6 M HCl. The structure was characterized using IR (Infrared Spectroscopy) and ICP (Inductively Coupled Plasma) analysis. The oxidation of benzyl alcohol using 6-MQCC in various solvents showed that the reactivity increased with the increase of the dielectric constant, in descending order of DMF > acetone > chloroform > cyclohexene. In the presence of DMF solvent with acidic catalyst such as sulfuric acid ($H_2SO_4$), 6-MQCC oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$) were effectively oxidized. Electron-donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308 K). The observed experimental data was used to rationalize the fact that the hydride ion transfer occurred at the rate-determining step.

Preparation of Alkyl Acrylate and Functional Monomer Multi Core-Shell Composite Particles (알킬 아크릴레이트와 관능성 단량체계 다중 Core-Shell 복합입자의 제조)

  • Choi, Sung-Il;Cho, Dae-Hoon;Seul, Soo-Duk
    • Journal of Adhesion and Interface
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    • v.14 no.1
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    • pp.1-12
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    • 2013
  • Multi core-shell composite particles were prepared by the water-born emulsion polymerization of various core monomers such as methyl methacrylate (MMA), ethyl methacrylate (EMA) and shell monomers such as MMA, EMA, 2-hydroxyl ethyl methacrylate (2-HEMA), glycidyl methacrylate (GMA) and methacrylic acid (MAA) in the presence of different concentrations of sodium dodecyl benzene sulfonate (SDBS). The following conclusions are drawn from the conversion, particle size and distribution, average molecular weight, molecular structure, glass transition temperature with DSC, contact angle after plasma treatment, tensile strength and isothermal decomposition kinetics. In the case of the concentration of 0.02 wt% SDBS, the conversion of MMA core-(EMA/GMA) shell composite particles was excellent as 98.5%. In the case of the concentration of 0.03 wt% SDBS, the particle size of EMA core-(MMA/GMA) shell composite particles was high as $0.48{\mu}m$. We confirmed that 3 points of glass transition temperatures appear for multi core-shell composite particles compared to 1~2 points of glass transition temperatures appear for general copolymer particles. Overall, the adhesion strength of shell composite particles was in the order of EMA/MAA > EMA/2-HEMA > EMA/GMA.

Microbial Changes of Salted and Fermented Shrimp by High Hydrostatic Pressure Treatment (초고압처리에 의한 새우젓의 미생물변화)

  • Mok, Chul-Kyoon;Song, Ki-Tae;Lee, Sang-Ki;Park, Jong-Hyun;Woo, Gun-Jo;Lim, Sang-Bin
    • Korean Journal of Food Science and Technology
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    • v.32 no.2
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    • pp.349-355
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    • 2000
  • This study was conducted to enhance the storage stability of fermented shrimp with different salt contents using a high hydrostatic pressure. The effects of the magnitude of pressure and treatment time on the microorganisms of the fermented shrimp were investigated. The highest microbial counts with respect to the salt levels were observed at 18% salt, showing $3.4{\times}10^5\;CFU/g$ for general bacteria, $6.4{\times}10^4\;CFU/g$ for halophilic bacteria, $4.2{\times}10^5\;CFU/g$ for yeast and $3.0{\times}10^4\;CFU/g$ for halophilic yeast. The degree of sterilization increased with the magnitude of pressure and treatment time, and the sterilization could be analyzed by the first order reaction kinetics. The sterilization rate constants $(k_p)$ of the halophilic bacteria was lower than that of general bacteria. The $log(k_p)$ increased linearly with pressure and the slope of the regression line of the halophilic bacteria was greater than that of general bacteria, indicating that the sterilization of the halophilic bacteria was more dependent on the pressure. High hydrostatic pressure treatment was an effective non-thermal sterilization method for the salted and fermented shrimp, and the optimum treatment condition was for 10 min at 6,500 atm.

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Development of the CAP Water Quality Model and Its Application to the Geum River, Korea

  • Seo, Dong-Il;Lee, Eun-Hyoung;Reckhow, Kenneth
    • Environmental Engineering Research
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    • v.16 no.3
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    • pp.121-129
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    • 2011
  • The completely mixed flow and plug flow (CAP) water quality model was developed for streams with discontinuous flows, a condition that often occurs in low base flow streams with in-stream hydraulic structures, especially during dry seasons. To consider the distinct physical properties of each reach effectively, the CAP model stream network can include both plug flow (PF) segments and completely mixed flow (CMF) segments. Many existing water quality models are capable of simulating various constituents and their interactions in surface water bodies. More complicated models do not necessarily produce more accurate results because of problems in data availability and uncertainties. Due to the complicated and even random nature of environmental forcing functions, it is not possible to construct an ideal model for every situation. Therefore, at present, many governmental level water quality standards and decisions are still based on lumped constituents, such as the carbonaceous biochemical oxygen demand (CBOD), the total nitrogen (TN) or the total phosphorus (TP). In these cases, a model dedicated to predicting the target concentration based on available data may provide as equally accurate results as a general purpose model. The CAP model assumes that its water quality constituents are independent of each other and thus can be applied for any constituent in waters that follow first order reaction kinetics. The CAP model was applied to the Geum River in Korea and tested for CBOD, TN, and TP concentrations. A trial and error method was used for parameter calibration using the field data. The results agreed well with QUAL2EU model predictions.