• Title/Summary/Keyword: Kinetic Constant

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INVESTIGATION OF SOOT OXIDATION CHARACTERISTICS IN A SIMULATED DIESEL PARTICULATE FILTER

  • Lee, H.S.;Chun, K.M.
    • International Journal of Automotive Technology
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    • v.7 no.3
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    • pp.261-267
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    • 2006
  • Understanding the mechanism of carbon oxidation is important for the successful modeling of diesel particulate filter regeneration. Carbon oxidation characteristics were investigated by temperature programmed oxidation(TPO) method as well as constant temperature oxidation(CTO) with a flow reactor including porous bed. The activation energy of carbon oxidation was increasing with temperature and had two different constant values in the early and the later stage of the oxidation process respectively in TPO experiment. Kinetic constants were derived and the reaction mechanisms were assumed from the experimental results and a simple reaction scheme was proposed, which approximately predicted the overall oxidation process in TPO as well as CTO.

Methyl Linoleate Oxidation via Electron Transfer in Competition with $^1O_2$ Formation Photosensitized N-Acetyl-L-Tryptophan 3-Methyl Indole

  • Yoon, Min-Joong;Song, Moon-Young;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.291-295
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    • 1985
  • The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

Adsorption Equilibrium, Kinetic and Thermodynamic Param (활성탄을 이용한 Acid Green 27의 흡착평형, 동역학 및 열역학 파라미터의 연구)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.55 no.4
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    • pp.514-519
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    • 2017
  • Adsorption characteristics of acid green 27 dye using activated carbon were investigated as function of adsorbent dose, pH, initial concentration, contact time and temperature. Freundlich isotherm explained adsorption of acid green 27 dye very well and Freundlich separation factors (1/n=0.293~0.387) were found that this process could be employed as effective treatment method. Kinetic studies showed that the kinetic data were well described by the pseudo second-order kinetic model. Pseudo second rate constant ($k_2$) decreased with the increase in initial acid green 27 concentration. Activation energy (10.457 kJ/mol) and enthalpy (79.946 kJ/mol) indicated that adsorption process was physisorption and endothermic. Since Gibbs free energy decreased with increasing temperature, spontaneity of adsorption reaction increased with increasing temperature in the temperature range of 298 K~318 K.

Kinetics of Drying Shiitake Mushroom, Lentinus edodes sanryun No. 1 (표고버섯의 열풍건조속도론(熱風乾燥速度論)에 관한 연구(硏究))

  • Cho, Duk-Bong;Kim, Dong-Pil;Choi, Choon-Soon
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.10 no.1
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    • pp.53-60
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    • 1981
  • Dehydration phenomena has been studied for the shiitake mushroom Lentinus edodes sanryun No.1, through which examine the effect of temperature and air velocity and derivation of its kinetics. Temperature effect for the dehydration rate constant were examined under the constant air velocity (1.5m/sec) with the variation of temperature from $40^{\circ}C$ to $55^{\circ}C$. Water content were reduced exponentially with the course of time and calculated dehydration rate constant values varies with temperature with an Arrhenius-type relationship, which had been expected in the chemical reaction kinetics. Influence of air velocity for the dehydration rate constant under the constant temperature $(45^{\circ}C)$ showed interesting results. For the range 1.0m/sec to 2.0m/sec, dehydration rate constant values are increased with the air velocity, but for the 2.0 to 3.1m/sec, dehydration rate constant values are decreased which were caused by case hardening. One of the selected conditions in the optimal dehydration range, temperature $50^{\circ}C$, air velocity 2m/see, and its measured humidity 38-41%, mathematical model of dehydration curve and dehydration rate equations were developed and the resulting kinetic models were X=6.94 $e^{-0.345t}$ and dx/dt = -2.39 $e^{-0.345t}$

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Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile

  • Hwang, Jae-young;Yang, Ki-yull;Koo, In-Sun;Sung, Dae-Dong;Lee, Ik-choon
    • Bulletin of the Korean Chemical Society
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    • v.27 no.5
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    • pp.733-738
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    • 2006
  • Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

Computational modeling of the atmospheric boundary layer using various two-equation turbulence models

  • Juretic, Franjo;Kozmar, Hrvoje
    • Wind and Structures
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    • v.19 no.6
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    • pp.687-708
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    • 2014
  • The performance of the $k-{\varepsilon}$ and $k-{\omega}$ two-equation turbulence models was investigated in computational simulations of the neutrally stratified atmospheric boundary layer developing above various terrain types. This was achieved by using a proposed methodology that mimics the experimental setup in the boundary layer wind tunnel and accounts for a decrease in turbulence parameters with height, as observed in the atmosphere. An important feature of this approach is pressure regulation along the computational domain that is additionally supported by the nearly constant turbulent kinetic energy to Reynolds shear stress ratio at all heights. In addition to the mean velocity and turbulent kinetic energy commonly simulated in previous relevant studies, this approach focuses on the appropriate prediction of Reynolds shear stress as well. The computational results agree very well with experimental results. In particular, the difference between the calculated and measured mean velocity, turbulent kinetic energy and Reynolds shear stress profiles is less than ${\pm}10%$ in most parts of the computational domain.

Ammonia half-saturation constants of sludge with different community compositions of ammonia-oxidizing bacteria

  • Kayee, Pantip;Rongsayamanont, Chaiwat;Kunapongkiti, Pattaraporn;Limpiyakorn, Tawan
    • Environmental Engineering Research
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    • v.21 no.2
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    • pp.140-144
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    • 2016
  • Owing to the kinetic differences in ammonia oxidation among ammonia-oxidizing microorganisms (AOM), there is no standard set of kinetic values that can be used as a representative set for nitrifying wastewater treatment plant (WWTP) design. As a result, this study clarified a link between the half-saturation constants for ammonia oxidation (Ks) and the dominant ammonia-oxidizing bacterial (AOB) groups in sludge from full-scale WWTPs and laboratory-scale nitrifying reactors. Quantitative polymerase chain reaction analyses revealed that AOB affiliated with the Nitrosomonas oligotropha cluster were the dominant AOM groups in the sludge taken from the low-ammonia-level WWTPs, while AOB associate with the Nitrosomonas europaea cluster comprised the majority of AOM groups in the sludge taken from the high-ammonia-level WWTPs and nitrifying reactors. A respirometric assay demonstrated that the ammonia Ks values for the high-ammonia-level WWTPs and nitrifying reactors were higher than those of the low-ammonia-level plants. Using the Ks values of available AOM cultures as a reference, the Ks values of the analyzed sludge were mainly influenced by the dominant AOB species. These findings implied that.different sets of kinetic values may be required for WWTPs with different dominant AOM species for more accurate WWTP design and operations.

Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3597-3601
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    • 2013
  • The reactions of bis(Y-aryl) chlorothiophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett plots for substituent Y variations in the substrates show biphasic concave upwards with a break point at Y = H. The cross-interaction constants (${\rho}_{XY}$) are positive for both electron-donating and electron-withdrawing Y substituents. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1. The effect of the cross-interaction between Y and Y on the rate changes from negative role with electron-donating Y substituents to positive role with electron-withdrawing Y substituents, resulting in biphasic concave upward free energy correlation with Y. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate involving a predominant frontside attack hydrogen bonded, four-center-type transition state is proposed based on the positive sign of ${\rho}_{XY}$ and primary normal deuterium kinetic isotope effects.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4304-4308
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    • 2011
  • Kinetic studies of the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots for substituent X variations in the nucleophiles are discrete with a break region between 4-Me and H, while the Hammett plots (log $k_2$ vs ${\sigma}_Z$) for substituent Z variations in the leaving groups are linear. The sign of the cross-interaction constant (${\rho}_{XZ}$) is positive for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ (= 2.54) value is observed with the weakly basic nucleophiles compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = 0.17). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a stepwise with a rate-limiting leaving group expulsion from the intermediate involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles.

Kinetics of the KOH Catalyzed-Methanolysis for Biodiesel Production from Fat of Tra Catfish

  • Huong, Le Thi Thanh;Tan, Phan Minh;Hoa, Tran Thi Viet;Lee, Soo
    • Journal of the Korean Applied Science and Technology
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    • v.25 no.4
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    • pp.418-428
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    • 2008
  • Transesterification of fat of Tra catfish with methanol in the presence of the KOH catalyst yields fatty acid methyl esters (FAME) and glycerol (GL). The effects of the reaction temperature and reaction time on rate constants and kinetic order were investigated. Three regions were observed. In the initial stage, the immiscibility of the Tra fat and methanol limited the reaction rate, hence this region was controlled by the mass transfer. Subsequent to this region, produced FAME like a co-solvent made the reaction mixture homogeneous, therefore the conversion rate increased rapidly so it was controlled by the kinetic parameters of the reaction until the equilibrium was approached in the final slow region. A second-order kinetic mechanism was proposed involving second regions for the forward reaction. The rate determining step for the overall KOH catalyzed-methanolysis of Tra fat was the conversion of triglycerides (TG) to diglycerides (DG). This rate constant was increased from 0.003 to $0.019min^{-1}$ when the reaction temperature was increased from 35 to $60^{\circ}C$. Its calculated activation energy was 14.379 ($kcal.mol^{-1}$).