• 한국지반공학회논문집
• /
• 제18권5호
• /
• pp.159-167
• /
• 2002

아연의 주물사에 대한 분배계수는 주물사에 포함된 TOC, 점토 함량, 총 철 함량 등에 따라 변하고 특히 용액 PH에 큰 영향을 받는 것을 관찰하였다. Batch 실험으로부터 얻어진 경험식으로부터분배계수와 제거상수를 예측할 수 있었다. Batch kinetic 실험과 batch sorption 실험으로부터 얻어진 분배계수는 용액 pH가 같을 시 거의 같은 값을 보이고 있다.

• Bulletin of the Korean Chemical Society
• /
• 제13권6호
• /
• pp.632-636
• /
• 1992

Second-order rate constants have been determined spectrophotometrically for nucleophilic substitution reactions of p-nitrophenyl benzoate with various anionic nucleophiles including 6 ${\alpha}$ -effect nucleophiles. The logarithmic second-order rate constants for the aryloxides give a good Bronsted correlation with the respective basicity while the ones for p-chlorothiophenoxide and hydroxide exhibit significantly positive and negative deviations, respectivity, from the Bronsted linear line. The deviations are attributed to a solvation effect rather than a change in the reaction mechanism. The ${\alpha}$-effect nucleophiles except highly basic ones demonstrate significantly higher nucleophilicity (the ${\alpha}$ -effect) than would be predicted from the respective basicity. The effect of solvation and polarizability appears to be important for the ${\alpha}$-effect as well as for the reaction rate.

• Bulletin of the Korean Chemical Society
• /
• 제13권6호
• /
• pp.659-662
• /
• 1992

The pressure-jump relaxation method has been used to determine the rate constants for the formation and dissociation of maganese(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) with some dicarboxylates in aqueous solution at zero ionic strength. The carboxylate ligands used are 3-nitrophthalate, 4-nitrophthalate, and phenylmalonate. The activation parameters have alse been obtained from the temperature dependence of the rate constants. A dissociative interchange mechanism with a chelate ring closure step as rate determining is employed to interpret the kinetic data of manganese(Ⅱ) and cobalt(Ⅱ) complexes. The rates of formation of nickel(Ⅱ) complexes are controlled by both the solvent exchange step and the chelate ring closure step.

• 대한화학회지
• /
• 제65권3호
• /
• pp.185-196
• /
• 2021

For studying the reaction mechanism of the reactions related to NO in the ozone denitration reactions, the harmonic and anharmonic rate constants were calculated by the transition state (TS) theory and Yao and Lin (YL) method. According to above calculations, the reactions of NO with O₃ and NO₃ play an essential role, and the kinetic parameters considering anharmonic effect were fitted. Furthermore, the rate constants were up as temperature increasing, and the tendencies of high temperature were more gradual than the low temperature. The research will provide theoretical basis for the ozone denitration reactions.

• Bulletin of the Korean Chemical Society
• /
• 제6권5호
• /
• pp.259-263
• /
• 1985

Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and $40^{\circ}C$ under various pressures up to 1600 bar. The rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${\Delta}V^{\neq},{\Delta}{\beta}^{\neq},{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${\Delta}V^{\neq}\;and\;{\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation (electrostriction). From the relation between the reaction rate and the dielectric constant of solvent or the number of water molecule participated in the transition state, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

• Applied Biological Chemistry
• /
• 제40권5호
• /
• pp.409-415
• /
• 1997

식품 및 배합사료 첨가제로서 치아민 모노유도체인 치아민 모노로단염이외, 치아민 모노요오드염 치아민 모노브름염 등의 3종류의 용해도를 $40,{\;}50,{\;}60^{\circ}C$에서 구하였고 그 온도에서 4수준(0.5, 1.0, 2.5, 5.0 w/w%)의 물을 첨가한 다음 경시적으로 겉보기 착색속도정수(ka)를 산출하였다. 그리고 산제이외 제제에 대하여는 착색도 가능성을 검토할 목적으로 비교적 조성이 간단한 과립, 정제를 만들어 이것에 3수준(0.5, 1.0, 2.5 w/w%)의 물을 첨가한 후 산제와 동일한 온도에서 경시적으로 착색시험으로부터 ka를 산출하였고, 구배 ka인 직선에 대하여는 회귀분산을 이용하여 직선성의 검정을 행하였다. 실험 범위 내에서는 위험률 5%수준에서 모두 유의한 결과를 얻었다. 과립 및 정제의 착색변화로부터 얻은 ka와 1/T간에 직선적인 관계가 성립하여 Arrhenius식을 만족시켰다.

• 대한화학회지
• /
• 제42권1호
• /
• pp.22-27
• /
• 1998

여러 가지 용매에서 N,N-dimethylaniline에 의한 coumarin 153과 coumarin 481분자의 형광소광효과를 조사하였다. 소광속도상수와 분자의 확산속도상수간의 관계로부터 소광과정이 분자의 확산과 어느정도 상호연관성을 갖고 있음을 알 수 있었다. slip boundary조건 보다stick boundary 조건을 적용하였을 때 분자확산 속도상수와 실험적인 소광속도상수와의 차이가 작게 나타났다. cyclohexane 과 같은 비극성용매에서의 소광속도 상수는 이론적인 확산속도상수 값과 오차범위 내에서 거의 일치하였으나 acetonitrile과 같은 극성용매에서는 소광속도상수는 확산속도상수보다 일관되게 작게 나타났다. 이것은 coumarin 분자의 형광소광이 분자간 확산에 의한 충돌 뿐만 아니라 분자내 전하분리와 같은 과정에 의해서도 진행되는 것으로 해석할 수 있다.

• 전기학회논문지
• /
• 제64권5호
• /
• pp.799-804
• /
• 2015

This study aims at the new analysis of heart beat fluctuations by applying physiological Heart Rate Variability Model with representing the cardiac control system in sympathetic and parasympathetic-coupling oscillator constants, C_s and C_p. To find the effects of coupling constants on the beat-to-beat fluctuations, Integral Pulse Frequency Modulation (IPFM) model is adopted to generate the time series data of ECG R-peaks and represent them by poincaré scattergram plot in the time domain and HRV in the frequency domain, respectively. The actual poincaré plots and HRV spectrum are also analyzed by acquiring the experimental data from the subjects exposed to the emotional-stress invoking environment and the function of the coupling constants are verified in terms of antagonism in sympathetic and parasympathetic activity.

• Bulletin of the Korean Chemical Society
• /
• 제20권1호
• /
• pp.7-15
• /
• 1999

The present paper is a review of the current studies of quantum beats in recombination of spin-correlated radical pairs in solutions as well as of future applications of quantum beats technique for studying these pairs. Examples are given of the use of this method for determining the hfi constants and relaxation times of short-lived radical ions, for finding the rate constants of the reactions of alkane radical cations and for estimating a fraction of singlet-correlated pairs in the pairs in the tracks of ionizing particles. The potentialities of this method, its advantages and limitations are discussed.

• 한국환경보건학회지
• /
• 제27권2호
• /
• pp.108-118
• /
• 2001

This study was performed to investigate the bioconcentration of IBP, methidathion and piperophos. The BCFs(bioconcentration factor), depuration rate constants for three pesticides in zebrafish(Brachydanio rerio) were measured by OECD guideline 305. The concentration of test pesicides were one-hundredth and one-thousandth concentration of 96-hrs L $C_{50}$ in accordance with OECD guideline 305. The results obtained are summarized as follows: The average BCF values of IBP were 5.31(n=4) and 7.30(n=4) at one-hundredth and one-thousandth concentration of 96-hrs L $C_{50}$ . The average BCF values of methidathion were 8.72(n=4) and 11.25(n=4), the average BCF values of piperophos were 34.30(n=4) and 42.60(n=4). Depuration rate constants of IBP were 0.09( $h^{-1}$ ) and 0.08( $h^{-1}$ ), half-life of IBP were 7.70 and 8.66 at each tested concentration. The concentrations of IBP in zebrafish at low and high concentrations rapidly decreased after 12(0.243$\mu\textrm{g}$/g) and 12 hours(0.040$\mu\textrm{g}$/g). Depuration rate constants of methidathion were 0.40( $h^{-1}$ ), half-life of methidathion were 1.73 at one-hunderdth and of 96-hrs L $C_{50}$ , repectively. The concentrations of methidathion in zebrafish at high concentrations rapidly decreased after 6 hours(0.18 $\mu\textrm{g}$/g). Depuration rate constant of low concentration was no measured because methidathion in zebrafish was depurated in 6 hours. Depuration rate constants of piperophos sere 0.15( $h^{-1}$ ) and 0.44( $h^{-1}$ ), half-life of piperophos were 4.62 and 1.58 at each tested concentration. The concentrations of piperophos in zebrafish at los and high concentrations rapidly decreased after 12(0.26$\mu\textrm{g}$/g) and 6 hours(0.015 $\mu\textrm{g}$/g). It was suggested that high BCF of piperophos was due to high Kow(octanol-water partition coefficient). The possibility of bioconcenration was not likely to be high because of its $K_{DEP}$(depuration rate constant) in the evniroment. It was suggested that low BCF of methidathion showed lowest Kow as well as the most rapid $K_{DEP}$. Therefore, the possibility of bioconcentration was not occured in the enviroment. It was suggested that the BCF dtermined for IBP was lower than that of other pesticides due to high Sw(water solubility), show $K_{DEP}$. Therefore, IBP revealed little bioconcentration effect on in aquatic ecosystem.ystem.