• Bulletin of the Korean Chemical Society
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• 제30권9호
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• pp.1939-1945
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• 2009

Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

• 한국환경과학회지
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• 제17권5호
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• pp.509-516
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• 2008

New functional surfactant, N,N-dimethyl-N-dodecyl-N-(2-methyl benzimidazoyl) ammonium chloride(DDBAC) having benzimidazole(BI) functional group have been synthesized and the critical micellar concentration of DDBAC measured by surface tentiometry and electric conductivity method was $8.9{\times}10^{-4}M$. Micellar effects in DDBAC functional surfactant solution on the hydrolysis of p-nitrophenylacetate(p-NPA), p-nitro-phenylpropionate(p-NPP) and p-nitrophenylvalerate(p-NPV) were observed with change of various pH (Tris-buffer). The pseudo first rate constants of hydrolysis of p-NPA, p-NPP and p-NPV in optimum concentration of DDBAC solution increase to about 160, 280 and 600 times, respectively, as compared with those of aqueous solution at pH 8.00(Tris-buffer). It is considered that benzimidazole functional moiety accelerates the reaction rates of hydrolysis because they act as nucleophile or general base. In optimum concentration of DDBAC solution, the rate constants of hydrolysis of p-NPP and p-NPV increase to about 1.5 and 3.0 times, respectively, as compared with that of p-NPA. It means that the more the carbon numbers of alkyl group of substrates, the larger the binding constants between DDBAC micelle and substrates are. To know the hydrolysis mechanism of p-NPCE(p-NPA, p-NPP and p-NPV), the deuterium kinetic isotope effects were measured in $D_2O$ solutions. Consequently the pseudo first order rate constant ratios in $H_2O$ and $D_2O$ solution, $k_{H_2O}/k_{D_2O}$, were about $2.8{\sim}3.0$ range. It means that the mechanism of hydrolysis were proceeded by nucleophile and general base attack in approximately same value.

• 한국전산유체공학회지
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• 제21권2호
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• pp.12-24
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• 2016

The standard ${\kappa}-{\varepsilon}$ and realizable ${\kappa}-{\varepsilon}$ models are adopted to improve the prediction performance on the recirculating flow. In this paper, the backward facing step flows are used to assess the prediction performance of the recirculation zone. The model constants of turbulence model are obtained by the experimental results and they have a different value according to the flow. In the case of an isotropic flow situation, decaying of turbulent kinetic energy should follow a power law behavior. In accordance with the power law, the coefficients for the dissipation rate of turbulent kinetic energy are not universal. Also, the other coefficients as well as the dissipation coefficient are not constant. As a result, a suitable coefficients can be varied according to each of the flow. The changes of flow over the backward facing step in accordance with model constants of the ${\kappa}-{\varepsilon}$ models show that the reattachment length is dependent on the growth rate(${\lambda}$) and the ${\kappa}-{\varepsilon}$ models can be improved the prediction performance by changing the model constants about the recirculating flow. In addition, it was investigated for the curvature correction effect of the ${\kappa}-{\varepsilon}$ models in the recirculating flow. Overall, the curvature corrected ${\kappa}-{\varepsilon}$ models showed an excellent prediction performance.

• Current Research on Agriculture and Life Sciences
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• 제7권
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• pp.175-184
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• 1989

대표적인 재료로서 바나나를 선정하여 건조방법과 조건에 따른 최적화에 사용할 수 있는 Ascorbic acid 저하속도와 비효소적 갈변속도에 대한 반응속도 예측 모델식을 결정하였다. Ascorbic acid 저하 속도와 비 효소적 갈변속도를 각각 1차반응, 0차반응으로, 두반응의 온도 의존성은 Arrhenius식으로 나타내어 SPSS Computer Program을 이용하여 실제 측정된 Ascorbic acid와 비효소적 갈변의 data에 가장 접근하도록 Parameter를 반복계산하여 찾았다. 얻어진 반응속도식에서의 Parameter값들은 R. SQUARE값이 평균 0.99이상이므로 살험치를 잘 예측하였으며 건조공정의 최적화에 이용될 수 있을 것으로 생각되어진다. Ascorbic acid 저하속도와 비효소적 갈변속도는 건조초기에 낮고 건조가 진행되어 수분함량의 감소와 함께 최대속도를 보이다가 서서히 감소하였다. 이때 동결건조의 경우가 가장 안정된 품질변화를 나타냈음을 알 수 있었다.

• 대한토목학회논문집
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• 제10권4호
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• pp.173-184
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• 1990

본 연구에서는 활성슬러지 하수처리장에 유입된 PAHs의 일종인 anthracene을 대상으로 이의 농도분포, 물리적 혹은 생물학적 변환을 예측하기 위한 수학적 모형을 제안하였다. 이 수학적 모형은 유입 anthracene의 volatilization, biodegradation 및 adsorption/desorption과 같은 반응을 고려한 5개의 연립미분방정식으로 구성되어 있으며, 이들에는 7개의 kinetic rate constants와 18개의 input variables를 포함하고 있다. Steady state simulation의 결과 유입된 anthracene은 1차 침전지에서의 슬러지 배출로 인하여 약 33%가 포기조에서 발생한 volatilization에 의하여 약 61%가 제거되어, 총괄적인 anthracene의 제거율은 약 97%정도이었다. Dynamic simulation의 결과로 본 연구대상 system의 경우에 system이 steady state에 도달하는 시간은 약 160시간 정도로 예측되었다. 이와 아울러 본 연구에서 제안된 수학적 모형의 활용 가능성이 각종 simulation의 결과로 비교적 구체적으로 규명되었다.

• 대한환경공학회지
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• 제27권11호
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• pp.1238-1243
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• 2005

본 연구에서는 해안가에서 자생하는 두 종의 해조류(Laminaria japonica와 Kjellmaniella crassifolia)를 생체흡착제로 사용하여 용액중의 중금속(납) 제거 실험을 통해 생체흡착제의 납의 흡착속도와 흡착평형 특성을 연구하였다. 두 종의 해조류을 사용한 납의 생체흡착은 흡착초기 2시간 이내에 평형에 도달하였다. 흡착속도는 유사 2차 흡착속도식에 의해 거의 정확한 모사가 가능하였으며, 여기에서 산출된 속도상수, $k_{2,ad.}$는 각각 $0.883{\times}10^{-3}$와 $0.628{\times}10^{-3}\;g/mg/min$이었다. 흡착평형은 Langmuir, Redlich-Peterson 및 Koble-Corrigan (Langmuir-Freundlich) 모델식에 의해 잘 모사되었다. 또한, L. japonica와 K. crassifolia의 4가지 중금속에 대한 선택성은 Pb>Cd>Cr>Cu와 Pb>Cu>Cd>Cr순으로 나타났다. 본 실험에 사용된 L. japonica는 pH의 증가에 따라 납의 흡착량도 증가되었다.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.641-644
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• 2005

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

• Korean Chemical Engineering Research
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• 제54권6호
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• pp.734-745
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• 2016

This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

• 한국환경과학회지
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• 제20권2호
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• pp.241-249
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• 2011

In this research, equilibrium of adsorption and kinetics of As(V) removal were investigated. The coal mine drainage sludge(CMDS) was used as adsorbent. To find out the physical and chemical properties of CMDS, XRD (X-ray diffraction), XRF (X-ray fluorescence spectrometer) analysis were carried out. The CMDS was consist of 70% of goethite and 30% of calcite. From the results, an adsorption mechanism of As(V) with CMDS was dominated by iron oxides. Langmuir adsorption isotherm model was fitted well more than Freundlich isotherm adsorption model. Adsorption capacities of CMDS 1 was not different with CMDS 2 on aspect of amounts of arsenic adsorbed. The maximum adsorption amount of two CMDS were respectively 40.816, 39.682 mg/g. However, the kinetic of two CMDS was different. The kinetic was followed pseudo second order model than pseudo first order model. Concentrations of arsenic in all segments of the polymer in CMDS 2 does not have a constant value, but the rate was greater than the value of CMDS 1. Therefore, CMDS 2, which is containing polymer, is more effective for adsorbent to remove As(V).

• Asian-Australasian Journal of Animal Sciences
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• 제13권5호
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• pp.641-644
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• 2000

In vitro true digestibility of cup-plant (Silphium perfoliatum L.) is higher than other alternative forages and comparative to alfalfa (Medicago sativa L.) even at the high neutral detergent fiber (NDF) concentration. This study was conducted to determine whether the digestion kinetic parameters of cup-plant could explain high in vitro true digestibility of cup-plant at the several NDF levels. Cup-plant and alfalfa were both collected in Arlington and Lancaster, Wisconsin to meet the NDF content within 40 to 50% range. The collected samples were incubated with rumen juice to investigate the digestion kinetics at 3, 6, 9, 14, 20, 28, 36, 48, and 72 h. Kinetics was estimated by the model $R=D_0\;e-k(t-L)+U$ where R is residue remaining at time t, and $D_0$ is digestible fraction, k is digestion rate constant, L is discrete lag time, and U is indigestible fraction. Parameters of the model were estimated by the direct nonlinear least squares (DNLS) method. Digestion rate and potential extent of digestion were not statistically different in either forage. However, alfalfa had shorter lag time (p<0.05). The indigestible fraction increased with maturation in alfalfa and in cup-plant (p<0.05). The ratio of indigestible fraction to acid detergent lignin (ADL) was higher in cup-plant than in alfalfa (p<0.05). From the results, alfalfa is probably digested more rapidly than cup-plant, however, cup-plant maintains higher digestibility with maturation due to a relatively slower increase of indigestible fraction in NDF.