• Title/Summary/Keyword: volume entropy

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The Positional Effect of Solute Functional Group among Positional Isomers of Phenylpropanol in Hydroxyl Group-Solvent Specific Interactions in Methanol/Water Mixed Solvents Monitored by HPLC

  • Cheong, Won-Jo;Ko, Joung-Ho;Kang, Gyoung-Won
    • Bulletin of the Korean Chemical Society
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    • v.26 no.8
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    • pp.1246-1250
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    • 2005
  • We have evaluated the hydroxyl group-solvent specific interactions by using a Lichrosorb RP18 stationary phase and by measuring the retention data of carefully selected solutes in 50/50, 60/40, 70/30, 80/20, and 90/10(v/v%) methanol/water eluents at 25, 30, 35, 40, 45, and 50 ${^{\circ}C}$. The selected solutes are 3 positional isomers of phenylpropanol, that is, 1-phenyl-1-propanol, 1-phenyl-2-propanol, and 3-phenyl-1-propanol. There exist clear discrepancies in ${\Delta}H^o$ (solute transfer enthalpy from the mobile to the stationary phase) and $T{\Delta}S^o$ (solute transfer entropy) among positional isomers. The difference in ${\Delta}H^o$ and $T{\Delta}S^o$ between secondary alcohols (1-phenyl-1-propanol and 1-phenyl-2-propanol)is negligible compared to the difference between the primary alcohol (1-phenyl-3-propanol) and secondary alcohols. The $T{\Delta}S^o$ values of 3-phenyl-1-propanol are close to those of butylbenzene while the $T{\Delta}S^o$ values of secondary alcohols are close to those of propylbenzene. The difference in ${\Delta}{\Delta}H^o$ (specific solute-mobile phase interaction enthalpy) between the primary alcohol and the secondary alcohol decreases with increase of methanol content in the mobile phase. A unique observation is an extremum for 1-phenyl-3-propanol in the plot of $T{\Delta}{\Delta}S^o$ vs. methanol volume %. The positive sign of $T{\Delta}{\Delta}S^o$ of 3-phenyl-1-propanol implies that the entropy of 3-phenyl-1-propanol is greater than that of the hypothetical alkylbenzene (the same size and shape as phenylpropanol) in the mobile phase.

Theoretical Prediction of the Thermodynamic Properties of Liquid-Crystalline p-Azoxyanisole (액정 p-Azoxyanisole의 열역학적 성질에 대한 이론적인 예측)

  • Youngkyu Do;Mu Shik Jhon;Taikyue Ree
    • Journal of the Korean Chemical Society
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    • v.20 no.2
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    • pp.118-128
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    • 1976
  • The significant structure theory of liquids and the Bragg-Williams approximation of phase transition theory have been applied to the calculation of the thermodynamic properties of p-azoxyanisole which exhibits a liquid crystal phase of the nematic type. The isotropic phase was treated as a normal liquid; and for the nematic phase, in addition to its liquidity, the effect due to the arrangement of molecular-dipoles was considered. The liquidity of the p-azoxyanisole was described by the significant structure theory of liquids, and the Bragg-Williams approximation was used to consider the effect due to the arrangement of molecular-dipoles. The molar volume, vapor pressure, heat capacity at constant pressure, thermal expansion coefficient, compressibility, entropy and enthalpy change at the nematic-isotropic phase transition point, absolute entropy, and absolute Helmholtz free energy were calculated over the temperature range of the nematic and isotropic phases. The calculated results of the thermodynamic properties were compared with the experimental data.

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The Solvolysis of Benzoyl Chloride in Water-Acetone Mixtures Under High Pressure

  • Jee, Jong-Gi;Ree, Taik-Yue
    • Bulletin of the Korean Chemical Society
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    • v.8 no.1
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    • pp.31-39
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    • 1987
  • By using a complete rate constant($k_e$) which treats a solvent (water) as a reactant, and a conventional rate constant($k_c$), which ignores the solvent in describing the rate, the parameters ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were introduced. These quantities represent the volume change, the enthalpy change, and the entropy change accompanying the electrostriction which occurs when solvent molecules condense on the activated complex. The authors measured the rates of the solvolysis of benzoyl chloride in water-acetone mixtures at $15^{\circ}$ to $30^{\circ}C$ and 1 bar to 2500 bars. Applying the authors' theory to the experimental results, the parameters, ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were evaluated, and it was found that they are all negative, indicating that water dipoles condense on the activated complex. They also proposed the following equations: ${\Delta}H^{\neq}_c\;=\;{\Delta}H^{\neq}_e\;+\;{\Delta}H^{\neq}_s\;and\; {\Delta}S^{\neq}_c\;=\;{\Delta}S^{\neq}_e\;+{\Delta}S^{\neq}_s\;,\;where\;{\Delta}H^{\neq}_c\;and\;{\Delta}H^{\neq}_c\;and\;{\Delta}S^{\neq}_s $are the activation enthalpy change and the activation entropy change for the conventional reaction rate, respectively, and ${\Delta}H^{\neq}_e$ and ${\Delta}S^{\neq}_e$ are the corresponding quantities for the complete reaction rate. The authors proposed that for the $SN_1$ type, all the quantities, ${\Delta}V^{\neq}_s,\;{\Delta}S^{\neq}_s\;,{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ are comparatively large, and for the $SN_2$ type, these quantities are smaller than for the $SN_1$ type, and occasionally the case ${\Delta}S^{\neq}_e$ < 0 occurs. Using these criteria, the authors concluded that at high temperature, high pressure and for a high water content solvent, the SN_1$ type mechanism predominates whereas in the reversed case the $SN_2$M type predominates.

Development for rainfall classification based on local flood vulnerability using entropy weight in Seoul metropolitan area (엔트로피 가중치를 활용한 지역별 홍수취약도 기반의 서울지역 강우기준 산정기법)

  • Lee, Seonmi;Choi, Youngje;Lee, Eunkyung;Ji, Jungwon;Yi, Jaeeung
    • Journal of Korea Water Resources Association
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    • v.55 no.4
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    • pp.267-278
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    • 2022
  • Recently Flood damage volume has increased as heavy rain has frequently occurred. Especially urban areas are a vulnerability to flooding damage because of densely concentrated population and property. A local government is preparing to mitigate flood damage through the heavy rain warning issued by Korea Meteorological Administration. This warning classification is identical for a national scale. However, Seoul has 25 administrative districts with different regional characteristics such as climate, topography, disaster prevention state, and flood damage severity. This study considered the regional characteristics of 25 administrative districts to analyze the flood vulnerability using entropy weight and Euclidean distance. The rainfall classification was derived based on probability rainfall and flood damage rainfall that occurred in the past. The result shows the step 2 and step 4 of rainfall classification was not significantly different from the heavy rain classification of the Korea Meteorological Administration. The flood vulnerability is high with high climate exposure and low adaptability to climate change, and the rainfall classification is low in the northern region of Seoul. It is possible to preemptively respond to floods in the northern region of Seoul based on relatively low rainfall classification. In the future, we plan to review the applicability of rainfall forecast data using the rainfall classification of results from this study. These results will contribute to research for preemptive flood response measures.

Adaptability Questions of O-D Table Estimation Models (기종점 통행표 산출모형의 적용성 평가)

  • 오상진;박병호
    • Journal of Korean Society of Transportation
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    • v.17 no.5
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    • pp.99-110
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    • 1999
  • This study deals with the adaptability questions of O-D table estimation models. Its objectives are two-fold; (1) to estimate the characteristics of various O-D table estimation models(i.e. linear regression models. entropy models and statistic models) and (2) to find the model which estimates the O-D table with the best accuracy under the various data conditions. In Pursuing the above, this study gives the particular attentions to the test of the models, using the Sioux Falls network and equilibrium assignment method of MINUTP. The major findings are the followings. Firstly. it finds that the statistic models have the most goodness of fat among all models, if the required data are all Prepared. But it Presents that statistic models are the most sensitive against the underspecification and inconsistency problems of link data. Secondly, It shows that the linear regression models have the worst goodness of fat among all models. But the linear regression models are the most insensitive to the underspecification and inconsistency problems. Thirdly, THE/1 model of entropy model is sensitive against the underspecification and incon-sistency problems, but THE/2 model is insensitive. Finally, other informations like total volume, zonal Production and attraction volumes in 0-D table, help models to gain the better goodness of fit. Especially, in the statistic models. both the zonal production and attraction volume data are helpful to estimate the link volumes. It can be expected that the results dive some implications not only to the selection of optimal model under the various given data, but also to the development or modification of model.

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Modelling of noise-added saturated steam table using the neural networks (신경회로망을 사용한 노이즈가 첨가된 포화증기표의 모델링)

  • Lee, Tae-Hwan;Park, Jin-Hyun
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • 2008.05a
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    • pp.205-208
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    • 2008
  • In numerical analysis numerical values of thermodynamic properties such as temperature, pressure, specific volume, enthalpy and entropy are required. But most of the thermodynamic properties of the steam table are determined by experiment. Therefore they are supposed to have measurement errors. In order to make noised thermodynamic properties corresponding to errors, random numbers are generated, adjusted to appropriate magnitudes and added to original thermodynamic properties. the neural networks and quadratic spline interpolation method are introduced for function approximation of these modified thermodynamic properties in the saturated water based on pressure. It was proved that the neural networks give smaller percentage error compared with quadratic spline interpolation. From this fact it was confirmed that the neural networks trace the original values of thermodynamic properties better than the quadratic interpolation method.

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WAVELET-BASED FOREST AREAS CLASSIFICATION BY USING HIGH RESOLUTION IMAGERY

  • Yoon Bo-Yeol;Kim Choen
    • Proceedings of the KSRS Conference
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    • 2005.10a
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    • pp.698-701
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    • 2005
  • This paper examines that is extracted certain information in forest areas within high resolution imagery based on wavelet transformation. First of all, study areas are selected one more species distributed spots refer to forest type map. Next, study area is cut 256 x 256 pixels size because of image processing problem in large volume data. Prior to wavelet transformation, five texture parameters (contrast, dissimilarity, entropy, homogeneity, Angular Second Moment (ASM≫ calculated by using Gray Level Co-occurrence Matrix (GLCM). Five texture images are set that shifting window size is 3x3, distance .is 1 pixel, and angle is 45 degrees used. Wavelet function is selected Daubechies 4 wavelet basis functions. Result is summarized 3 points; First, Wavelet transformation images derived from contrast, dissimilarity (texture parameters) have on effect on edge elements detection and will have probability used forest road detection. Second, Wavelet fusion images derived from texture parameters and original image can apply to forest area classification because of clustering in Homogeneous forest type structure. Third, for grading evaluation in forest fire damaged area, if data fusion of established classification method, GLCM texture extraction concept and wavelet transformation technique effectively applied forest areas (also other areas), will obtain high accuracy result.

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Influence of Nanodispersed Organoclay on Rheological and Swelling Properties of Ethylene Propylene Diene Terpolymer

  • Acharya Himadri;Srivastava Suneel K.
    • Macromolecular Research
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    • v.14 no.2
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    • pp.132-139
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    • 2006
  • The dispersion of organoclay in ethylene propylene diene terpolymer (EPDM) matrix was correlated with the rheological and swelling properties of nanocomposites. X-ray diffraction pattern (XRD) and transmission electron microscopic (TEM) analysis exhibited the disordered-intercalated structure of EPDM/organoclay nanocomposite. The extent of the disordered phase increased with increasing organoclay content up to a limiting value of 3 wt% after which equilibrium tended towards intercalation. The dispersion effect of organoclay in EPDM matrix was clarified by the physicochemical properties like rheological response and swelling thermodynamics in toluene. The increase in viscoelastic properties of EPDM nanocomposite with increasing organoclay content up to 3 wt%, followed by a subsequent decrease up to 4 wt%, was correlated in terms of the disordered and ordered states of the dispersed nano-clay sheets. Swelling measurements revealed that the change in entropy of the swelling increased with the increase in disorder level but decreased with the increase in intercalation level of organoclay in the disordered-intercalated nanocomposite. The increase in solvent uptake was comparable with the free volume in EPDM matrix upon inclusion of silicate particles, whereas the inhibition in solvent uptake for higher organoclay loading was described by bridging flocculation.

The Effect of Pressure and Temperature on the Durene-Iodine Charge Transfer Complex in n-Hexane (듀렌과 요오드 사이의 전하이동착물에 대한 압력과 온도의 영향)

  • Oh Cheun Kwun;Jeong Rim Kim
    • Journal of the Korean Chemical Society
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    • v.27 no.1
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    • pp.9-17
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    • 1983
  • The effect of pressures and temperatures on the stabilities of the durene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at 25, 40 and $60^{\circ}C$ under $1{\sim}1600$ bars. The equilibrium constant of the complex was increased with pressure and decreased with temperature raising. The absorption coefficient was increased with both pressure and temperature. Changes of volume, enthalpy, free energy and entropy for the formation of complexes were obtained from the equilibrium constants. The red-shift observed at a higher pressure, the blue-shift at a higher temperature, and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions.

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Hippocampus Segmentation and Classification in Alzheimer's Disease and Mild Cognitive Impairment Applied on MR Images

  • Madusanka, Nuwan;Choi, Yu Yong;Choi, Kyu Yeong;Lee, Kun Ho;Choi, Heung-Kook
    • Journal of Korea Multimedia Society
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    • v.20 no.2
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    • pp.205-215
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    • 2017
  • The brain magnetic resonance images (MRI) is an important imaging biomarker in Alzheimer's disease (AD) as the cerebral atrophy has been shown to strongly associate with cognitive symptoms. The decrease of volume estimates in different structures of the medial temporal lobe related to memory correlates with the decline of cognitive functions in neurodegenerative diseases. During the past decades several methods have been developed for quantifying the disease related atrophy of hippocampus from MRI. Special effort has been dedicated to separate AD and mild cognitive impairment (MCI) related modifications from normal aging for the purpose of early detection and prediction. We trained a multi-class support vector machine (SVM) with probabilistic outputs on a sample (n = 58) of 20 normal controls (NC), 19 individuals with MCI, and 19 individuals with AD. The model was then applied to the cross-validation of same data set which no labels were known and the predictions. This study presents data on the association between MRI quantitative parameters of hippocampus and its quantitative structural changes examination use on the classification of the diseases.