• 대한화학회지
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• 제61권1호
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• pp.25-28
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• 2017

Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.383-388
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• 2009

Rates of solvolyses of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ($(PhO)_2$POCl, 2), diphenylphosphinyl chloride ($Ph_2$POCl, 3) and diphenylthiophosphinyl chloride ($Ph_2$PSCl, 4). As with the previously studied of 3~4 solvolyses, an $S_N$ pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ${\Delta}H^{\neq}\;(=11.6{\sim}13.9\;kcal{\cdot}mol^{-1})\;and\;{\Delta}S^{\neq}\; (=\;-32.1\;{\sim}\;-42.7\;cal{\cdot}mol^{-1}{\cdot}K^{-1})$, were determined, and they were in line with values expected for an $S_N$2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in $H_2O/D_2$O) are also well explained by the proposed $S_N$2 mechanism.

• Journal of Ecology and Environment
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• 제30권3호
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• pp.251-255
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• 2007

Self-thinning was measured in Salix communities on Bam Island in Seoul at various age stages. $D^2H$ was used to estimate tree biomass, where D is stem diameter at breast height or 10 cm height for plants with height <1.5 m, and H is height. A log-log plot of density versus $D^2H$ and correlation analysis indicated a significant relationship between density and biomass with equation 'log $D^2H$ = -1.27 log N + 7.06'. This indicates that self-thinning affects biomass in the Salix community with -1.27 as the thinning coefficient. If we assume a thinning exponent -3/2, then the allometric coefficient of the equation, log w = a log $D^2H$ + b, is 1.18. This is much higher than that for any other species studied in Korea. There were statistically significant relationships between age and density and between age and basal area and these relationships suggest guidelines for transplantation of willows and for the assessment of Salix community restoration projects in riverine wetlands based on standard density, basal area, and age. The results of this study may also increase understanding of succession processes in Salix community restoration in riverine wetlands.

• Bulletin of the Korean Chemical Society
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• 제26권8호
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• pp.1241-1245
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• 2005

Solvolyses of trifluoromethanesulfonyl chloride (TFMSC) in water and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45 ${^{\circ}C}$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of TFMSC with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate curves for three aqueous mixtures. The extended Grunwald-Winstein plots for the solvolysis of TFMSC show better correlation. The large negative ${\Delta}S^{\neq}$ and relatively small positive ${\Delta}H^{\neq}$ reveals that the solvolytic reaction proceeds via a typical bimolecular reaction mechanism. The l and m values determined in various solvents are consistent with the proposed mechanism of the general base catalysis $S_AN/S_N2$reaction mechanism for TFMSC solvolyses based on mass law and stoichiometric solvation effect studies.

• 한국응용곤충학회지
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• 제18권3호
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• pp.133-136
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• 1979

벼이삭 선충의 피해를 구명코저 접종시험을 실시하였다. 1. 선충의 기생은 벼의 생육 특히 분얼수에 많은 영향을 주었다. 2. 피해경율은 온도 상승과 더불어 증가하여 출수후에는 약 3배로 늘었다. 3. 생육 및 수량에 영향을 줄 수 있는 피해경율은 $13\%$이상이다. 즉 피해발현 초기에 $5\%$이하일 때는 생육과 수량에 영향이 없었고 $13\%$일때 $19\%,\;21\%$이면 $22\%$의 감수를 초래하였다. 4. 수량구성요소별로는 1000립중 립수 수수의 순으로 영향을 받았다.

• Bulletin of the Korean Chemical Society
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• 제24권11호
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• pp.1590-1598
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• 2003

In this paper we have presented the results for viscosity and self-diffusion constants of model systems for four liquid n-alkanes ($C_{12}, C_{20}, C_{32}, and C_{44}$) in a canonical ensemble at several temperatures using molecular dynamics (MD) simulations. The small chains of these n-alkanes are clearly $<{R_{ee}}^2>/6<{R_g}^2>>1$, which leads to the conclusion that the liquid n-alkanes over the whole temperatures considered are far away from the Rouse regime. Calculated viscosity ${\eta}$ and self-diffusion constants D are comparable with experimental results and the temperature dependence of both ${\eta}$ and D is suitably described by the Arrhenius plot. The behavior of both activation energies, $E_{\eta}$ and $E_D$, with increasing chain length indicates that the activation energies approach asymptotic values as n increases to the higher value, which is experimentally observed. Two calculated monomeric friction constants ${\zeta}$ and ${\zeta}_D$ give a correct qualitative trend: decrease with increasing temperature and increase with increasing chain length n. Comparison of the time auto-correlation functions of the end-to-end vector calculated from the Rouse model for n-dodecane ($C_{12}$) at 273 K and for n-tetratetracontane ($C_{44}$) at 473 K with those extracted directly from our MD simulations confirms that the short chain n-alkanes considered in this study are far away from the Rouse regime.

• 한국환경과학회지
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• 제27권7호
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• pp.499-507
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• 2018

Agricultural meteorological information is an important resource that affects farmers' income, food security, and agricultural conditions. Thus, such data are used in various fields that are responsible for planning, enforcing, and evaluating agricultural policies. The meteorological information obtained from automatic weather observation systems operated by rural development agencies contains missing values owing to temporary mechanical or communication deficiencies. It is known that missing values lead to reduction in the reliability and validity of the model. In this study, the hierarchical Bayesian spatio-temporal model suggests replacements for missing values because the meteorological information includes spatio-temporal correlation. The prior distribution is very important in the Bayesian approach. However, we found a problem where the spatial decay parameter was not converged through the trace plot. A suitable spatial decay parameter, estimated on the bias of root-mean-square error (RMSE), which was determined to be the difference between the predicted and observed values. The latitude, longitude, and altitude were considered as covariates. The estimated spatial decay parameters were 0.041 and 0.039, for the spatio-temporal model with latitude and longitude and for latitude, longitude, and altitude, respectively. The posterior distributions were stable after the spatial decay parameter was fixed. root mean square error (RMSE), mean absolute error (MAE), mean absolute percentage error (MAPE), and bias were calculated for model validation. Finally, the missing values were generated using the independent Gaussian process model.

• Bulletin of the Korean Chemical Society
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• 제17권6호
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• pp.520-524
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• 1996

Solvolyses of phenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for phenyl chloroformate with YCl (based on 2-adamantyl chloride) show marked dispersions into three separate lines for the three aqueous mixtures with a small m value (m< 0.2) and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or carbonyl addition for phenyl chloroformate solvolyses based on mass law and stoichiometric solvation effect studies.

• 한국수자원학회:학술대회논문집
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• 한국수자원학회 2015년도 학술발표회
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• pp.143-143
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• 2015

기존의 빈도해석에서는 자료의 정상성을 가정하며, 이에 따라 적정모형 선정 시에 $x^2$ 검정이나 PPCC(Probability Plot Correlation Coefficient)검정과 같은 적합도 검정방법을 사용한다. 하지만 자료에서 경향성이 나타나거나 평균, 분산, 매개변수 등이 시간에 따라 변하는 등의 비정상성 현상들이 관측됨에 따라 비정상성 빈도해석에 관한 연구들이 활발히 진행되고 있다. 비정상성 빈도해석에서는 시간항과 같은 공변량이 포함된 매개변수를 가지는 비정상성 모형을 적용하게 되는데, 시간에 따라 매개변수가 계속 변하므로 매개변수에 따라 검정통계량이 고정되어 있는 기존의 적합도 검정방법의 적용이 어렵다. 따라서 비정상성 빈도해석의 적정 모형 선정에 적용할 수 있는 방법으로 최우도 함수에 기반한 모형 평가 방법인 AIC와 BIC가 추천되고 있으며 자료길이가 충분하지 않은 경우에는 AIC 대신하여 AICc의 사용이 추천되고 있다. 본 연구에서는 극치사상을 나타내는데 적합한 분포형인 GEV분포형의 위치, 규모 매개변수를 시간항으로 나타낸 다양한 비정상성 GEV모형에 대하여 Monte-Carlo 모의실험을 통해 AICc와 BIC의 적용성을 검토하였으며, 비정상성이 관측되는 실측 자료에 적용해보았다.

• Journal of Advanced Research in Ocean Engineering
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• 제4권4호
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• pp.185-194
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• 2018

In this study, the extreme sloshing pressure was predicted using various statistical models: three-parameter Weibull distribution, generalized Pareto distribution, generalized extreme value distribution, and three-parameter log-logistic distribution. The estimation of sloshing impact pressure is important in design of liquid cargo tank in severe sea state. In order to get the extreme values of local impact pressures, a lot of model tests have been carried out and statistical analysis has been performed. Three-parameter Weibull distribution and generalized Pareto distribution are widely used as the statistical analysis method in sloshing phenomenon, but generalized extreme value distribution and three-parameter log-logistic distribution are added in this study. Additionally, statistical distributions are fitted to peak pressure data using three different parameter estimation methods. The data were obtained from a three-dimensional sloshing model text conducted at Seoul National University. The loading conditions were 20%, 50%, and 95% of tank height, and the analysis was performed based on the measured impact pressure on four significant panels with large sloshing impacts. These fittings were compared by observing probability of exceedance diagrams and probability plot correlation coefficient test for goodness-of-fit.