• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.191-196
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• 1992

Reaction of N,N-dimethylaniline(N,N-DMA) and iodine in $CHCl_3,\;CH_2Cl_2 : CHCl_3$(1:1), $CH_2Cl_2$(1:1), and CH2Cl2 has been studied kinetically by using conductivity method. Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[N,N-DMA]) are dependent on the N,N-DMA concentration. Second-order rate constants obtained were decreased with increasing N,N-DMA concentration. We analysed these results on the basis of formation of charge transfer complex as a reaction intermediate. From the construction of reaction scheme and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants decreased when the dielectric constant of solvent was increased, and the value is 1.9${\sim}$4.2$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity.${\Delta}H^{\neq}$ is 6.3-12.6kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -234J/mol K.

• Applied Chemistry for Engineering
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• v.10 no.4
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• pp.548-556
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• 1999

The thermal degradation of polyethylene has been studied using a nonisothermal thermogravimetric technique under a nitrogen atmosphere condition at several heating rates from 10 to $50^{\circ}C/min$. To obtain information on the kinetic parameters, the dynamic thermogravimetric analysis curve and its derivative have been analyzed by a variety of analytical methods such as Kissinger, Freeman-Carroll, Flynn-Wall, Coats-Redfern, Chatterjee-Conrad, Friedman, Horowitz-Metzger, Ozawa and Denq methods. The comparative works for the kinetic results obtained from various methods should be performed to determine the kinetic parameters, because three are tremendous differences in the calculated kinetic parameters depending upon the mathematical method taken in the analysis. From this work, it was found that the apparent activation energy of HDPE was larger than those of LDPE and LLDPE.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.307-311
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• 1986

The rates of hydrolysis of the complex, $trans^-[Cr(en)_2F(H_2O)]^{2+}$, have been investigated using spectrophotometric method at various temperatures and pressure. Temperature was 30${\circ}C$ to 50${\circ}C$ and pressure was varied up to 1500bar. The rate constant measured at 30${\circ}C$ is $2.632{\times}10^{-5}sec^{-1}$. The rate constants are decrease with increasing pressure at constants temperature. Activation volume and other activation parameters are calculated from these rate constants. The activation volumes are all positive and lie in the limited range 0.447 ∼ 3.152$cm^3$/mol and the activation entropies are small values. From the results, it was found that this reaction was endothermic and enthalphy controlled reaction in the experimental temperature.

• Tunnel and Underground Space
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• v.13 no.2
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• pp.100-107
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• 2003

Deformation is found by an external force in the rock which has internal stress. So, deformation is increased in time what is stressed under constant load. Rock materials collapse suddenly in a long period when the creep rate increases slightly. So mechanical deformability of the ground is an essential condition for determination of long term safety in structures. The result of analysis in 40%, 50%, 60%, 70% of constant load in creep test, strain velocity constants $\alpha$ and ${\gamma}$ increase with load increasement. Griggs equation is more exact than Li and Xia, Singh equation, and G$_2$of a flow constant by Burger's model decreases with stress increasement, but η$_1$,η$_2$and G$_1$ manifest irregularly in this study.

• Polymer(Korea)
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• v.26 no.4
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• pp.422-430
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• 2002

The kinetics of polycondensation of bishydroxyethyl naphthalate has been studied in the range of 241 -$260^{\circ}C$ using antimony trioxide catalyst. The reaction was performed in a batch reactor and the concentration of reaction mixture was measured with HPLC. The activation energy values of forward and reverse reaction determined from molecular species model were found to be 19.7 and 31.4 kcal/mole, respectively, and the equilibrium constants were in the range of 1.4-2.0, which were larger than that of polycondensation of PET and varied to some degree with temperature. It was confirmed by applying the Flory's distribution function that the reaction rate of the hyroxyethyl group does not depend on the molecular size. By applying functional group model, we observed that there was few difference between the activation energy of the forward reaction and that of reverse reaction, therefore the equilibrium constant has almost constant value of 1.4. The rate constants obtained from functional group model was about 3-4 times larger than that from molecular species model, which showed that both model explains the reaction system well. Although the molecular species model should predict the concentration of as many as ten molecules, it fits for the experimental results well.

• Journal of the Korean Chemical Society
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• v.41 no.8
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• pp.385-391
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• 1997

Diffusion Coefficient$(D_0)$ and electrode reaction rate Constant$(K_0)$ of Co$(dimethyl bipyridine)_3(ClO_4)_2$ were determined by cyclic voltammetry and chronoamperometry. It was also investigated that the effects of solvent, concentration, and scan rate, etc. on the diffusion coefficient and the temperature effect on the rate constant. The peak currents and diffusion coefficients were dcreased as increasing the viscosity of solvent. Diffusion coefficient was $5.54{\times}10^{-6 }cm^2/sec$ and the reaction rate constant was $2.39{\times}10^{-3 }/s$ at 25$^{\circ}C$. The thermodynamic parameters such as ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S$ were calculated from plotting the reaction rate constants versus the solution temperatures. This compound was shown the catalytic effect on the oxygen reduction that the reduction peak current of oxygen was greatly enhanced and the peak potential was shifted to +0.2 volt.

• Journal of Environmental Health Sciences
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• v.27 no.2
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• pp.37-42
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• 2001

Zebrafish(Brachdanio rerio)를 실험어류로 하여 methidathion 과 phosalone의 생물농축계수(bioconcentration factor : BCF)와 배설속도상수 (depuration rate constant) 및 LC$_{50}$를 측정하였다. Methidathion의 24, 48, 72, 96시간 LC$_{50}$는 각각 28.34, 35.98, 24.43, 22.03 mg/$\ell$로 측정되었다. Methidathion 0.22 mg/$\ell$(고농도)와 0.022 mg/$\ell$(저농도)에서 어류 체내에서의 농축정도는 두 농도군에서 각각 12시간 이후에 정류상태에 도달하여 72시간동안 거의 일정하였고, BCF값도 12시간에서 72시간 사이에 고농도와 저농도에서 8.72(n=4)와 11.25(n=4)로 조사되었다. 배설속도상수는 고농도와 저농도에서 6시간 이내에 모두 배설되어 배설속도상수를 구할 수 없었다. Phosalone의 24, 48, 72, 96시간 LC$_{50}$는 각각 3.76, 2.43, 1.86, 1.05 mg/$\ell$로 측정되었다. Zebrafish 체내에서의 농축정도와 BCF값은 고농도(0.01 mg/$\ell$)에서 12시간 이후에 정류상태에 도달하여 72시간동안 거의 일정하였고, BCF값은 12시간에서 72시간 사이에 48.88(n=4)로 측정되었다. 저농도(0.001 mg/$\ell$)에서는 실험 전기간동안 zebrafish 체내에서 phosalone이 검출되지 않아 BCF값을 산출할 수 없었다. Zebrafish 체내에서 phosalone(고농도)의 배설속도상수와 반감기를 구하기 위하여 6,12시간의 배설실험 결과 각각 0.17$hr^{-1}$과 4.01 시간이었다. Methidathion과 phosalone의 BCF값은 phosalone이 methidathion 보다 약 5배 정도 높게 나타났으며, 농약의 배설속도는 phosalone이 methidathion보다 빨랐다.

• Electrical & Electronic Materials
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• v.4 no.4
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• pp.344-353
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• 1991

무정형 SiC 박막을 수평형 CVD반응기로부터 SiH$_{4}$ 및 H$_{2}$를 반응기체로 하여 실리콘 웨이퍼위에 증착시켜 제조하였다. 박막 성장 속도는 상압에서 650.deg.C와 850.deg.C범위에서 측정되었다. 반응기체의 유량은 1000sccm으로 고정하였으며 SiH$_{4}$와 CH$_{4}$의 유량을 변화시켰다. 증착 반응속도식으로 표면 반응이 율속단계인 Eley-Rideal 모델과 SiH$_{4}$와 CH$_{4}$의 종도에 m차로 비례하는 두가지 속도식을 가정하였다. 증착시간에 따른 SiC 박막두께의 측정으로부터 얻은 증착 반응 속도로부터 회귀 분석법에 의하여 두가지 반응속도식의 반응속도 상수를 구하였다. 얻어진 반응속도식에 의해서 계산된 값과 실험치를 비교한 결과 0.15차의 반응속도식이 Eley-Rideal반응기구보다 약산 더 잘 맞음을 알 수 있으나 두 모델 다 약간씩 실험결과와 차이가 나고 있다. 이것은 본 실험의 증착 조건의 율속단계가 확산 단계와 표면 반응 단계의 전이영역 즉 본 실험의 증착조건에서 확산속도와 표면 반응속도가 비슷하기 때문으로 생각된다. 또한 Eley-Rideal 반응기구에서 부터 얻어진 SiH$_{4}$ 및 CH$_{4}$의 흡착평형상수 $K_{s}$ 와 $K_{c}$ 값을 비교하면 1000K이하에서는 $K_{s}$ 가 $K_{c}$ 보다 큰 값을 가지는데 이것은 Gibbs 자유에너지 최소화 방법에서 구한 결과와 일치하였다.

• Proceedings of the Korean Society for Applied Microbiology Conference
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• 1986.12a
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• pp.508-508
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• 1986

이온성 계면활성제 존재하에서 유기용매에 물을 첨가하면 물이 계면활성제에 약해 둘러싸이면서 유기용매에 용해되어 의사 이상계가 형성된다. 이러한 계를 역미셀 또는 W/O microemulsion이라고 하며 계면활성제로 둘러 쌓인 물분자 집하체를 water pool이라고 한다. 그런데, 10여년 전 water pool에 bipolymer를 용해시킬 수 있다는 사실이 밟혀짐에 따라 이러한 체계를 생체막을 단순화시킨 모형막으로서 막을 통해 일어나는 여러 가지 현상의 규명에 이용하거나 물에 불용성인 기질의 효소 촉매반응의 반응계로 이용하는 연구가 꾸준히 이루어져 있다. 본 강연은 역미셀계에 리파제를 용해시켜 유지의 가수분해를 유도함으로써 지방산을 생산하는 방법에 관한 연구이다. 역미셀계에서 리파제의 특성은 에멀전계와 비교했을 때 큰 차이가 없었으며 물과 계면활성제의 몰 비율(R값)은 효소의 초기반응 속도에 커다란 영향을 끼치는 인자로 나타났다. 올리브유 농도가 5%(v/v), AOT농도가 0.1M, 초기 물 농도가 1.0M의 조건에서 유지의 회분식 가수분해 실험을 행한 결과 이 기질은 거의 완전히 가수분해되었으며, 이 반응계에서 R값과 초기 물 농도는 반응의 평형에 커다란 영향을 끼치는 것으로 나타났는데 초기 물 농도가 증가할수록 평형 가수분해율은 증가하였단 이러한 결과를 반응속도론 측면에서 분석한 결과 역미셀계에서 리파제 반응은 에멀전계에서와는 달리 2차 반응을 따르는 것으로 나타났다. 물 농도가 평형 가수 분해율과 속도 변수에 끼치는 영향을 수학적으로 표시하기 위하여 2차 가역적 반응 속도론에 근거하여 가수분해율, 평형상수, 속도상수 둥을 나타내는 식을 유도하였고 이를 바탕으로 여러 가지 실험 조건 하에서 리파제 반응의 반응 시간에 따른 가수분해율을 예측한 결과는 실제 실험 결과와 잘 일치하였다(편차는 5%). 또한 속도상수와 R값과의 관계식 및 유도한 방정식을 이용하여 추정한 초기속도와 평형 가수분해율을 최대화하는 R값은 각각 10.4 와 11.4 였다.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.6 no.2
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• pp.185-193
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• 1996

$2.5^{\circ}\;and\;5^{\circ}$ tilted (100) Si wafer were oxidized in dry oxygen, and the differences in thermal oxidation behavior and oxidation induced stacking faults (OSF) between specimens were investigated. Ellipsometer measurements of the oxide thickness produced by oxidation in dry oxygen from 900 to $1200^{\circ}C$ showed that the oxidation rates of the tilted (100) Si were more rapid than those of the (100) Si and the differences between them decreased as the oxidation temperature increased. The activation energies based on the parabolic rate constant, B for (100) Si, $2.5^{\circ}$ off (100) Si and $5^{\circ}$ off (100) Si were 27.3, 25.9, 27.6 kcal/mol and those on the linear rate constant, B/A were 58.6, 56.6, 57.6 kcal/mol, respectively. Also, considerable decrease in the density of oxidation induced stacking faults for the $5^{\circ}$ off (100) Si was observed through optical microscopy after preferentially etching off the oxide layer, and the angle of stacking faults were changed with tilted angles.