• Title/Summary/Keyword: volume entropy

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The Effect of Pressure on the Rate of Solvolysis(Ⅱ). Reactions of Methyl-, Phenyl Chloroformate and 1-Adamantyl Derivatives (가용매분해반응에 대한 압력의 영향(Ⅱ). Methyl-, Phenyl Chloroformate와 1-Adamantyl 유도체에 대한 반응)

  • Kwun, Oh Cheun;Kim, Jeong Rim;Kyong, Jin Burm;Lee, Young Hoon;Kim, Jong Chul
    • Journal of the Korean Chemical Society
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    • v.40 no.5
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    • pp.327-332
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    • 1996
  • The rates of solvolylsis of methyl chloroformate, phenyl chloroformate and 1-adamantyl derivatives in binary solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters were estimated from the rate constants. The activation volume (${\Delta}V_o^{\neq}$) and the activation entropy (${\Delta}S^{\neq}$) are both negative, but the activation enthalpy (${\Delta}H^{\neq}$) is positive. This behavior is discussed in terms of electrostriction of solvation. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies. From these results, it could be estimated that the solvolyses of 1-adamantyl fluoroformate (in aqueous TFE) and 1-adamantyl tosylate have pathway involving unimolecular reaction, while the reaction of methyl chloroformate, phenyl chloroformate and 1-adamantyl fluoroformate (in aqueous alcohol) proceed through a bimolecular reaction.

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Kinetics for the Reaction of Benzyl Benzenesulfonate with Pyridine in Acetone Under High Pressure (Benzyl Benzenesulfonate와 피리딘과의 고압반응에 대한 반응속도론적 연구)

  • Jung-Ui Hwang;Soo-Dong Yoh;Jong-Gi Jee
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.150-154
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    • 1980
  • Kinetic studies of the reaction of benzyl benzenesulfonate with pyridine in acetone were carried out by the electric conductivity method under 1 to 2000 bars and at 20 to $40^{\circ}C$. The rate increases with increasing pressure and temperature. The activation enthalpy $({\Delta}H^{\neq}),\;entropy\;({\Delta}S^{\neq})$ and activation volume $({\Delta}V^{\neq})$ of the reaction are obtained by the above experiment. The isokinetic relationship between $({\Delta}H^{\neq})\;and\;({\Delta}S^{\neq})$ for pressure change in the reaction was shown, and its isokinetic temperature was $342^{\circ}K$. From all of the above results it was found that this reaction precedes on the $S_N2$ reaction mechanism in which the rate of the reaction was determined by $C{\cdots}N$ bond formation at transition state.

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Function Approximation for Refrigerant Using the Neural Networks (신경회로망을 사용한 냉매의 함수근사)

  • Park, Jin-Hyun;Lee, Tae-Hwan
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • v.9 no.2
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    • pp.677-680
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    • 2005
  • In numerical analysis on the thermal performance of the heat exchanger with phase change fluids, the numerical values of thermodynamic properties are needed. But the steam table should be modeled properly as the direct use of thermodynamic properties of the steam table is impossible. In this study the function approximation characteristics of neural networks was used in modeling the saturated vapor region of refrigerant R12. The neural network consists of one input layer with one node, two hidden layers with 10 and 20 nodes each and one output layer with 7 nodes. Input can be both saturation temperature and saturation pressure and two cases were examined. The proposed model gives percentage error of ${\pm}$0.005% for enthalpy and entropy, ${\pm}$0.02% for specific volume and ${\pm}$0.02% for saturation pressure and saturation temperature except several points. From this results neural network could be a powerful method in function approximation of saturated vapor region of R12.

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Measuring Complementarities between Cities in the Korean Southeastern Region : A Network City Approach (영남권 도시들 간의 상보성 측정에 관한 연구: 네트워크 도시 접근)

  • Sohn, Jungyul
    • Journal of the Korean association of regional geographers
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    • v.21 no.1
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    • pp.21-38
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    • 2015
  • This study attempts to estimate the complementarity between 21 cities in the Korean Southeastern Region using data on the network time distance and the volume of flow between the cities. Four types of flows recognized are people, commodities, information and finance. The first two types of flows are thought to be made on the transportation network while the last two are on the communication network. For the purpose of the study, the expected volumes of flows between cities are first estimated using the gravity-based regression and doubly-constrained entropy maximization models. These baseline volumes are then subtracted from the observed volumes of flows (of people and commodities) or the estimated volumes of flows (of information and finance) in order to identify positive differences or complementarities. The result shows that these four types of complementarity flows form distinctive urban networks in terms of spatial pattern and urban hierarchy. This suggests that more customized strategies to different types of complementarity are recommended to properly address the issues related to network infrastructure provision in the pursuit of the network city model in the region.

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Modelling the wide temperature range of steam table using the neural networks (신경회로망을 사용한 넓은 온도 범위의 증기표 모델링)

  • Lee, Tae-Hwan
    • Journal of the Korea Institute of Information and Communication Engineering
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    • v.10 no.11
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    • pp.2008-2013
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    • 2006
  • In numerical analysis on evaluating the thermal performance of the thermal equipment, numerical values of thermodynamic properties such as temperature, pressure, specific volume, enthalpy and entropy are required. But the steam table itself cannot be used without modelling. In this study applicability of neural networks in modelling the wide temperature range of wet saturated vapor region was examined. the multi-layer neural network consists of a input layer with 1 node, two hidden layers with 10 and 20 nodes respectively and a output layer with 6 nodes. Quadratic and cubic spline interpoations methods were also applied for comparison. Neural network model revealed similar percentage error to spline interpolation. From these results, it is confirmed that the neural networks could be powerful method in modelling the wide range of the steam table.

Comparison of the neural networks with spline interpolation in modelling superheated water (물의 과열증기 모델링에 대한 신경회로망과 스플라인 보간법 비교)

  • Lee, Tae-Hwan;Park, Jin-Hyun;Kim, Bong-Hwan
    • Journal of the Korea Institute of Information and Communication Engineering
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    • v.12 no.4
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    • pp.685-690
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    • 2008
  • In numerically evaluating the thermal performance of the heat exchanger, numerical values of thermodynamic properties such as temperature, pressure, specific volume, enthalpy and entropy are required. But the steam table or diagram itself cannot be directly used without modelling. In this study the applicability of neural networks in modelling superheated water vapor was examined. The multi-layer neural networks consist of an input layer with 2 nodes, two hidden layers with 15 and 25 nodes respectively and an output layer with 3 nodes. Quadratic spline interpolation was also applied for comparison. Neural networks model revealed smaller percentage error compared with spline interpolation. From this result, it is confirmed that the neural networks could be a powerful method in modelling the superheated water vapor.

Determination of the Optimal Operating Condition of the Hamworthy Mark I Cycle for LNG-FPSO (LNG-FPSO에의 적용을 위한 Hamworthy Mark I Cycle의 최적 운전 조건 결정)

  • Cha, Ju-Hwan;Lee, Joon-Chae;Roh, Myung-Il;Lee, Kyu-Yeul
    • Journal of the Society of Naval Architects of Korea
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    • v.47 no.5
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    • pp.733-742
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    • 2010
  • In this study, optimization was performed to improve the conventional liquefaction process of offshore plants, such as a LNG-FPSO(Liquefied Natural Gas-Floating, Production, Storage, and Offloading unit) by maximizing the energy efficiency of the process. The major equipments of the liquefaction process are compressors, expanders, and heat exchangers. These are connected by stream which has some thermodynamic properties, such as the temperature, pressure, enthalpy or specific volume, and entropy. For this, a process design problem for the liquefaction process of offshore plants was mathematically formulated as an optimization problem. The minimization of the total energy requirement of the liquefaction process was used as an objective function. Governing equations and other equations derived from thermodynamic laws acted as constraints. To solve this problem, the sequential quadratic programming(SQP) method was used. To evaluate the proposed method in this study, it was applied to the natural gas liquefaction process of the LNG-FPSO. The result showed that the proposed method could present the improved liquefaction process minimizing the total energy requirement as compared to conventional process.

The Pressure Effect of the Association of 2,4,6,N-Tetramethyl Pyridinium Iodide in Ethanol-Water Mixture (에탄올-물 혼합용매내에서 2,4,6,N-Tetramethyl Pyridinium Iodide의 회합에 대한 압력효과)

  • Jung-Ui Hwang;Jong-Gi Jee;Young-Hwa Lee;Uei-Ha Woo
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.79-85
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    • 1984
  • The ionic association constant(K) of 2,4,6, N-tetramethyl pyridinium iodide (TeMPI) in 95 volume percentage ethanol-water mixture were determined by a modified UV and conductance method at $25^{\circ}C$ to $50^{\circ}C$ under 1 to 2,000 bars. The K values increase with increasing pressure and have maximum value at $40^{\circ}C$. The partial molar volume hange (${\Delta}V$) has relatively small negative value and the absolute values of ${\Delta}$ are minimum at $40^{\circ}C$. The ion size parameter(a) of TeMPI have maximum value at $40^{\circ}C$. {\Delta}H^{\circ}$ values are zero, positive and negative at 40^{\circ}C$, $25^{\circ}C$ and $50^{\circ}C$ respectively. Other thermodynamic parameters such as the changes of standard entropy ({\Delta}S^{\circ}$) and free energy {\Delta}G^{\circ}$ were evaluated. From these experimental results, we came to conclusion that TeMPI is stabilized by the elevation of pressure and that of temperature below $40^{\circ}C$ but weakly dimerized at $40^{\circ}C$ because of the intermolecular hydrophobic interaction of eight methyl groups of two molecules. And it thermally decomposed above $50^{\circ}C$.

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A Study for the Effect of Solvent and Temperature on the Retention Behavior of Phenols in Reversed-Phase Liquid Chromatography (역상 액체 크로마토그래피에서 페놀류의 머무름거동에 미치는 용매와 온도의 영향에 관한 연구)

  • Lee Dai Woon;Lee Hoo Keun;Yook Keun Sung;Lee, In Ho;Cho Byung Yun
    • Journal of the Korean Chemical Society
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    • v.37 no.5
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    • pp.503-512
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    • 1993
  • The purpose of this study was to investigate the retention behavior of phenols and to predict their retention in RPLC. The retention data of twenty-five phenols were measured on a $\mu-{Bondapak}\;C_{18}$ and a polymeric $C_{18}$ columns with methanol-water and acetonitrile-water as a mobile phase. From the observation of enthalpy-entropy compensation phenomenon, the following conclusions are drawn with regard to the retention mechanism: 1) the retention mechanism of nitrophenols in different from that of metheyl-and chlorophenols in both mobile phase; 2) in methanol-water mobile phase, the retention mechanism of methyl-and chlorophenols is consistent in the range of methanol-water composition; 3) on the other hand, in the case of acetonitrile-water mobile phase, the retention mechanism depends on the volume fraction of acetonitrile. It means that the retention mechanism can not be explained only by a simple interaction. Based on retention data as compared with two columns, it may be said that the hydrophobic interaction of phenols with polymeric $C_{18}$ column was greater than that with monomeric $C_{18}$ column. The equations for predicting the retention of phenols were derived by using hydrophobic substituent constant $(\pi)$ and the sum of Hammett's constant $(\sigma)$ and Taft's steric constant $(E_s)$.

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Removal of Cs by Adsorption with IE911 (Crystalline Silicotitanate) from High-Radioactive Seawater Waste (IE911 (crystalline silicotitanate) 의한 고방사성해수폐액으로부터 Cs의 흡착 제거)

  • Lee, Eil-Hee;Lee, Keun-Young;Kim, Kwang-Wook;Kim, Ik-Soo;Chung, Dong-Yong;Moon, Jei-Kwon
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.13 no.3
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    • pp.171-180
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    • 2015
  • This study was performed on the removal of Cs, one of the main high- radioactive nuclides contained in the high-radioactive seawater waste (HSW), by adsorption with IE911 (crystalline silicotitanate type). For the effective removal of Cs and the minimization of secondary solid waste generation, adsorption of Cs by IE911 (hereafter denoted as IE911-Cs) was effective to carry out in the m/V (ratio of absorbent weight to solution volume) ratio of 2.5 g/L, and the adsorption time of 1 hour. In these conditions, Cs and Sr were adsorbed about 99% and less than 5%, respectively. IE911-Cs could be also expressed as a Langmuir isotherm and a pseudo-second order rate equation. The adsorption rate constants (k2) were decreased with increasing initial Cs concentrations and particle sizes, and increased with increasing ratios of m/V, solution temperatures and agitation speeds. The activation energy of IE911-Cs was about 79.9 kJ/mol. It was suggested that IE911-Cs was dominated by a chemical adsorption having a strong bonding form. From the negative values of Gibbs free energy and enthalpy, it was indicated that the reaction of IE911-Cs was a forward, exothermic and relatively active at lower temperatures. Additionally, the negative entropy values were seen that the adsorbed Cs was evenly distributed on the IE911.