• Title/Summary/Keyword: volume entropy

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The Effect of Pressures on the Formation of Charge Transfer Complexes of Toluene with Iodine (I) (톨루엔과 요오드 사이의 전하이동착물에 대한 압력의 영향 (I))

  • Kwun Oh Cheun
    • Journal of the Korean Chemical Society
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    • v.19 no.2
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    • pp.73-84
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    • 1975
  • The effect of pressures and temperatures on the stabilities of the toluene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at $25~60{\circ}C$ under 1~1,200 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 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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Calculation and Comparison of Thermodynamic Properties of Hydrogen Using Equations of State for Compressed Hydrogen Storage (상태방정식을 이용한 고압수소 저장을 위한 수소 열역학 물성 계산 및 비교)

  • PARK, BYUNG HEUNG
    • Journal of Hydrogen and New Energy
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    • v.31 no.2
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    • pp.184-193
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    • 2020
  • One of the technical methods to increase the volumetric energy density of hydrogen is to pressurize the gaseous hydrogen and then contain it in a rigid vessel. Especially for automotive systems, the compressed hydrogen storage can be found in cars as well as at refueling stations. During the charging the pressurized hydrogen into a vessel, the temperature increases with the amount of stored hydrogen in the vessel. The temperature of the vessel should be controlled to be less than a limitation for ensure stability of material. Therefore, the accurate estimation of temperature is of significance for safely storing the hydrogen. In this work, three well-known cubic equations of state (EOSs) were adopted to examine the accuracy in regenerating thermodynamic properties of hydrogen within the temperature and pressure ranges for the compressed hydrogen storage. The formulations representing molar volume, internal energy, enthalpy, and entropy were derived for Redlich-Kwong (RK), Soave-Redlioch-Kwong (SRK), and Peng-Robinson (PR) EOSs. The calculated results using the EOSs were compared with literature data given by NIST. It was revealed that the accuracies of RK and SRK EOSs were satisfactorily compatible and better than the results by PR EOS.

A Study of the Ionic Association of the Substituted N-Methyl Pyridinium Iodides (I). N-Methyl Pyridinium Iodide in Ethanol-Water Mixture

  • Jee, Jong-Gi;Kwun, Oh-Cheun
    • Bulletin of the Korean Chemical Society
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    • v.5 no.1
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    • pp.44-49
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    • 1984
  • The ionic association constant (K) of N-methyl pyridinium iodide (NMPI) ion in several ethanol-water mixtures were determined by the combination of UV spectroscopy and conductance measurements using the Shedlovsky function as a correction factor. The measurement of electrical conductance and UV absorption were performed in 95, 90, 80 and 60 volume percentages of ethanol in the solvent mixture at 15, 25, 35 and 45 $({\pm}0.1)^{\circ}C$. The ion size parameter $(r_A+_D-)$ and the dipole moment $({\mu}_A+_D-)$ of NMPI ion were obtained from he linear plots of ln K vs. (1/D) and (D-1)/(2D+1), respectively. These ${\mu}_A+_D-$ values were in good agreement with the values of transition moment calculated from the equation, ${\mu}_{nm}=6.5168{\times}10^{-2}{\times}({\varepsilon}_{max}{\frac{\bar{\nu}_{\frac{1}{2}}}{\bar{\nu}_{max}})^{\frac{1}{2}}$ (Debye) which we have derived. The thermodynamic parameters indicate (1) that the water dipoles have an ordered rearrangement around the dipolar NMPI ions rather than the configuration existing in bulk free waters; and (2) that the equilibrium state between NMPI ion and its component ions are controlled by entropy.

The Study on the Physicochemical Properties of Fluid under High Pressure (1). Effects of Pressure and Temperature on the Pentamethyl Benzene-Iodine Charge Transfer Complex in n-HexaneⅠ

  • Kim, Jeong-Rim;Kwun, Oh-Cheun
    • Bulletin of the Korean Chemical Society
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    • v.6 no.2
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    • pp.74-79
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    • 1985
  • The stabilities of the charge transfer complexes of pentamethyl benzene with iodine in n-hexane have been investigated by UV-spectrophotometric measurements at 25, 40 and 60$^{\circ}C$ up to 1600 bars. The equilibrium constant of the complex formation was increased with pressure while being decreased with temperature raising. Changes of volume, enthalpy, free energy and entropy for the formation of the complexes were obtained from the equilibrium constants. The red-shift at higher pressure, the blue-shift at higher temperature, and the relation between pressure and oscillator strength have been discussed by means of thermodynamic functions. In comparison with the results in the previous studies, the absolute values of ${\Delta}$V at each temperature were increased with the number of methyl groups of polymethyl benzene. However, it can be seen that both ${\Delta}$H and ${\Delta}$S show extreme behaviors in durene near atmospheric pressure but they are negatively increased with the number of methyl groups near 1600 bar. This order of the thermodynamic parameters may be a measure of the relative basicities of polymethyl benzenes toward iodine under each pressure, and these phenomena are explained in terms of a positive inductive effect and a steric hindrance effect of the polymethyl benzene molecule.

The Study on the Physicochemical Properties of Fluid under High Pressure (Ⅱ). The Effect of Pressure and Temperature on the Hexamethyl Benzene-Iodine Charge Transfer Complex in n-Hexane

  • Kwun Oh Cheun;Kim Jeong Rim
    • Bulletin of the Korean Chemical Society
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    • v.6 no.4
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    • pp.186-191
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    • 1985
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of hexamethyl benzene with iodine in n-hexane has been investigated by UV-spectrophotometric measurements. In this experiment the absorption spectra of mixed solutions of hexamethyl benzene and iodine in n-hexane were measured at 25, 40 and $60^{\circ}C$ under 1,200, 600, 1200 and 1600 bar. The equilibrium constant of the complex formation was increased with pressure while being decreased with temperature raising. Changes of volume, enthalpy, free energy and entropy for the formation of the complexes were obtained from the equilibrium constants. The red shift at higher pressure, the blue shift at higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions. In comparison with the results in the previous studies, it can be seen that the pressure dependence of oscillator strength has a extremum behavior in durene as the variation of ${\Delta}H$ or ${\Delta}S$ with the number of methyl groups of polymethyl benzene near atmospheric pressure in the previous study. The shift or deformation of the potential in the ground state and in the excited state of the complexes formed between polymethyl benzene and iodine was considered from the correlation between the differences of the electron transfer energies and the differences of free energies of the complex formation for the pressure variation.

On the Aquation of Dichloro Bis-(Ethylenediamine)-Chromium (III) Cation (Dichloro Bis-(Ethylenediamine)-Chromium (III) 양이온의 수화반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Soung-Oh Bek
    • Journal of the Korean Chemical Society
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    • v.28 no.2
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    • pp.95-101
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    • 1984
  • Aquation reaction kinetics of $[Cr(en)_2Cl_2]^+$complex was carried by the electric conductivity method. Its temperature range was $15^{\circ}C$ to $30^{\circ}C$ and pressure was varied up to 2,000 bars. The reaction rate was increased with increasing temperature, but was reversed to increasing pressure. The activation volume(${\Delta}V^{\neq}$) was increased with increasing temperature and decreased with increasing pressure. At $25^{\circ}C$ and 1 bar it was fairly small positive value, $1.82cm^2/mole$. Activation entropy change(${\Delta}S^{\neq}$) $was calculated as small negative value,-9.019 eu, at $25^{\circ}C$ and 1bar. Referring to the thermodynamic parameters, it was estimated that aquation reaction was proceeded by the interchange-dissociation(Id) mechanism.

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Micromechanical investigation for the probabilistic behavior of unsaturated concrete

  • Chen, Qing;Zhu, Zhiyuan;Liu, Fang;Li, Haoxin;Jiang, Zhengwu
    • Computers and Concrete
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    • v.26 no.2
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    • pp.127-136
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    • 2020
  • There is an inherent randomness for concrete microstructure even with the same manufacturing process. Meanwhile, the concrete material under the aqueous environment is usually not fully saturated by water. This study aimed to develop a stochastic micromechanical framework to investigate the probabilistic behavior of the unsaturated concrete from microscale level. The material is represented as a multiphase composite composed of the water, the pores and the intrinsic concrete (made up by the mortar, the coarse aggregates and their interfaces). The differential scheme based two-level micromechanical homogenization scheme is presented to quantitatively predict the concrete's effective properties. By modeling the volume fractions and properties of the constituents as stochastic, we extend the deterministic framework to stochastic to incorporate the material's inherent randomness. Monte Carlo simulations are adopted to reach the different order moments of the effective properties. A distribution-free method is employed to get the unbiased probability density function based on the maximum entropy principle. Numerical examples including limited experimental validations, comparisons with existing micromechanical models, commonly used probability density functions and the direct Monte Carlo simulations indicate that the proposed models provide an accurate and computationally efficient framework in characterizing the material's effective properties. Finally, the effects of the saturation degrees and the pore shapes on the concrete macroscopic probabilistic behaviors are investigated based on our proposed stochastic micromechanical framework.

An Efficient Search Method of Product Reviews using Opinion Mining Techniques (오피니언 마이닝 기술을 이용한 효율적 상품평 검색 기법)

  • Yune, Hong-June;Kim, Han-Joon;Chang, Jae-Young
    • Journal of KIISE:Computing Practices and Letters
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    • v.16 no.2
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    • pp.222-226
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    • 2010
  • With the continuously increasing volume of e-commerce transactions, it is now popular to buy some products and to evaluate them on the World Wide Web. The product reviews are very useful to customers because they can make better decisions based on the indirect experiences obtainable through these reviews. However, since online shopping malls do not provide ranking results, it is not easy for users to read all the relevant review documents effectively. Product reviews include subjective and emotional opinions. Thus, the review search is different from the general web search in terms of ranking strategy. In this paper, we propose an effective method of ranking the reviews that can reflect user's intention by using opinion mining techniques. The proposed method analyzes product reviews with query words, and sentimental polarity of subjective opinions. Through diverse experiments, we show that our proposed method outperforms conventional ones.

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

  • Lee, Tae-Hwan;Park, Jin-Hyun;Kim, Bong-Hwan
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • 2007.10a
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    • pp.246-249
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    • 2007
  • In numerical analysis for phase change material, 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 used without modelling. In this study applicability of neural networks in modelling superheated vapor region of water was examined by comparing with the quadratic spline. neural network consists of an input layer with 2 nodes, two hidden layers and an output layer with 3 nodes. Quadratic spline interpoation method was also applied for comparison. Neural network model revealed smaller percentage error to quadratic spline interpolation. From these results, it is confirmed that the neural networks could be powerful method in modelling the superheated range of the steam table.

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Comparison of Static Balance Abilities on Respiratory Types in Healthy Adults (호흡 유형에 따른 건강한 성인의 정적균형능력 비교)

  • Yu, Daseul;Lim, Chaegil
    • Journal of The Korean Society of Integrative Medicine
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    • v.8 no.2
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    • pp.63-73
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    • 2020
  • Purpose: To investigate breathing-related changes in the balance ability of healthy adults. Methods: The participants were 36 healthy adults in their 20s and 30s. All participants were trained in three breathing (neutral, thoracic, and abdominal) methods one week before measurements. We used AccuSway to measure each participant's balance ability, using each breathing technique, in two postures (bipedal and unipedal). Results: During the bipedal balance task, abdominal breathing produced significant increases in path length and sway velocity. Abdominal breathing resulted in significant changes in sample entropy at the anteroposterior location compared with neutral breathing (p<.05). In the normalized anteroposterior location, there were significant changes in backward movement during thoracic and abdominal breathing compared with those during neutral breathing (p<.05). During the unipedal balance task, path length and sway velocity increased significantly during voluntary breathing compared with those during neutral breathing (p<.05). There was a significant change in backward movement when abdominal breathing-compared with neutral breathing-was used in the normalized anteroposterior location (p<.05). In the normalized left-right location, there was a significant shift to the right during thoracic breathing compared with that during neutral breathing (p<.05). Conclusion: Compared with neutral breathing, altered voluntary breathing patterns affect balance in healthy adults. Our results indicated that that static balance was more affected by abdominal breathing than by neutral breathing. Future studies should examine variables such as the breathing volume, rhythm, and method.