• Title/Summary/Keyword: entropy change

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Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism

  • Park, Yu-Chul;Cho, Young-Je
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.309-313
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    • 1990
  • The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.

Influence of crystallization treatment on structure, magnetic properties and magnetocaloric effect of Gd71Ni29 melt-spun ribbons

  • Zhong, X.C.;Yu, H.Y.;Liu, Z.W.;Ramanujan, R.V.
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1289-1293
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    • 2018
  • The influence of crystallization treatment on the structure, magnetic properties and magnetocaloric effect of $Gd_{71}Ni_{29}$ melt-spun ribbons has been investigated in detail. Annealing of the melt-spun samples at 610 K for 30 min, a majority phase with a $Fe_3C$-type orthorhombic structure (space group, Pnma) and a minority phase with a CrB-type orthorhombic structure (space group, Cmcm) were obtained in the amorphous matrix. The amorphous melt-spun ribbons undergo a second-order ferromagnetic to paramagnetic phase transition at 122 K. For the annealed samples, two magnetic phase transitions caused by amorphous matrix and $Gd_3Ni$ phases occur at 82 and 100 K, respectively. The maximum magnetic entropy change $(-{\Delta}S_M)^{max}$ is $9.0J/(kg{\cdot}K)$ (5T) at 122 K for the melt-spun ribbons. The values of $(-{\Delta}S_M)^{max}$ in annealed ribbons are 1.0 and $5.7J/(kg{\cdot}K)$, corresponding to the two adjacent magnetic transitions.

Randomized Block Size (RBS) Model for Secure Data Storage in Distributed Server

  • Sinha, Keshav;Paul, Partha;Amritanjali, Amritanjali
    • KSII Transactions on Internet and Information Systems (TIIS)
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    • v.15 no.12
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    • pp.4508-4530
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    • 2021
  • Today distributed data storage service are being widely used. However lack of proper means of security makes the user data vulnerable. In this work, we propose a Randomized Block Size (RBS) model for secure data storage in distributed environments. The model work with multifold block sizes encrypted with the Chinese Remainder Theorem-based RSA (C-RSA) technique for end-to-end security of multimedia data. The proposed RBS model has a key generation phase (KGP) for constructing asymmetric keys, and a rand generation phase (RGP) for applying optimal asymmetric encryption padding (OAEP) to the original message. The experimental results obtained with text and image files show that the post encryption file size is not much affected, and data is efficiently encrypted while storing at the distributed storage server (DSS). The parameters such as ciphertext size, encryption time, and throughput have been considered for performance evaluation, whereas statistical analysis like similarity measurement, correlation coefficient, histogram, and entropy analysis uses to check image pixels deviation. The number of pixels change rate (NPCR) and unified averaged changed intensity (UACI) were used to check the strength of the proposed encryption technique. The proposed model is robust with high resilience against eavesdropping, insider attack, and chosen-plaintext attack.

Drug-Biomacromolecule Interaction (XIII)-Effect of ionic Strength, pH and Temperature on Binding of Cephalothin to Bovine Serum Albumin- (약물과 생체고분자 간의 상호작용(제 13보)-세파로친과 소혈청알부민의 결합에 미치는 이온강도, pH 및 온도의 영향)

  • Kim, Chong-Kook;Lim, Yun-Su;Yang, Ji-Sun;Jeong, Eun-Ju
    • Journal of Pharmaceutical Investigation
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    • v.19 no.3
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    • pp.163-171
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    • 1989
  • To investigate the protein binding characteristics of cephalothin, the effects of ionic strength, pH and temperature on the binding of cephalothin to bovine serum albumin (BSA) were studied by UV difference spectrophotometric method. With increasing ionic strength at constant PH and temperature, association constant decreased, but the number of binding sites sites was about 2 constantly. It may be deduced that the binding process is not only due to electrostatic forces. And the increased association constant at high ionic strength is explained by conformational changes of BSA from complex to subunits. The pH effect on the affinity of interaction indicated that the binding affinity of drug is higher in the neutral region than in the alkaline region. And, at high pH value, the number of binding sites decreased from 2 to 1 because of the conformational changes of BSA in alkaline region. The decrease in binding affinity of BSA to drug with increasing temperature was characteristic of an exothermic reaction. And the negative sign of ${\Delta}G^{\circ}$ meant that the binding process occurs spontaneously under the experimental conditions. In cephalothin-BSA complex formation, since the net enthalpy change value and entropy change value are positive, it is assumed that hydrophobic bindings are predominant in this binding process.

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Thermal stability, magnetic and magnetocaloric properties of Gd55Co35M10 (M = Si, Zr and Nb) melt-spun ribbons

  • Jiao, D.L.;Zhong, X.C.;Zhang, H.;Qiu, W.Q.;Liu, Z.W.;Ramanujan, R.V.
    • Current Applied Physics
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    • v.18 no.12
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    • pp.1523-1527
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    • 2018
  • The thermal stability, magnetic and magnetocaloric properties of $Gd_{55}Co_{35}M_{10}$ (M = Si, Zr and Nb) melts-pun ribbons were studied. The relatively high reduced glass transition temperature ($T_{x1}/T_m$ > 0.60) and low melting point ($T_m$) resulted in excellent glass forming ability (GFA). The Curie temperatures ($T_C$) of melt-spun amorphous ribbons $Gd_{55}Co_{35}M_{10}$ for M = Si, Zr and Nb were 166, 148 and 173 K, respectively. For a magnetic field change of 2 T, the values of maximum magnetic entropy change $(-{\Delta}S_M)^{max}$ for $Gd_{55}Co_{35}Si_{10}$, $Gd_{55}Co_{35}Zr_{10}$ and $Gd_{55}Co_{35}Nb_{10}$ were found to be 2.86, 4.28 and $4.05J\;kg^{-1}K^{-1}$, while the refrigeration capacity (RC) values were 154, 274 and $174J\;kg^{-1}$, respectively. The $RC_{FWHM}$ values of amorphous alloys $Gd_{55}Co_{35}M_{10}$ (M = Si, Zr and Nb) are comparable to or larger than that of $LaFe_{11.6}Si_{1.4}$ crystalline alloy. Large values of $(-{\Delta}S_M)^{max}$ and RC along with good thermal stability make $Gd_{55}Co_{35}M_{10}$ (M = Si, Zr and Nb) amorphous alloys be potential materials for magnetic cooling operating in a wide temperature range from 150 to 175 K, e.g., as part of a gas liquefaction process.

The Electromotive Force and Thermodynamic Properties of the Cell at High Pressure (고압하에서의 전지의 기전력과 열역학적 성질)

  • Jee Jong-Gi;Jung Jong-Jae;Hwang Jung-Ui
    • Journal of the Korean Chemical Society
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    • v.18 no.5
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    • pp.320-328
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    • 1974
  • It is unable to derive the standard emf ($E^{\circ}$) of the cell at high pressure from the conventional method. However, when the concept of the complete equilibrium constant($K{\circ})$) is available to the conventional Nernst equation, it is possible to get the standard emf of the cell at high pressure(complete Nernst equation). Moreover, the other thermodynamic properties, such as the net change of solvation number(k), the compressibility of solvent(${\beta}$), ionization constant(K), the standard free energy change(${\Delta}G^{\circ}$), the standard enthalpy change(${\Delta}H^{\circ}$) and the standard entropy change (${\Delta}S^{\circ}$) of the cell reaction at equilibrium state have been also obtained. In this experiment, the emf of the cell; 12.5 % Cd(Hg)│$CdSO_4(3.105{\times}10^{-3}M),\;Hg_2SO_4│Hg$ have bee measured at temperature from 20 to $35^{\circ}C$ and at pressures from 1 to 2500 atms. The emf of the cell increased with increasing pressure at constant temperature, and did with increasing temperature at constant pressure. The net change of solvation number(k) of the cell reaction was 41.96 at $25^{\circ}C$, and kept constant value with pressure, while, K and ${\Delta}S^{\circ}$ increased with pressure, but whereas ${\Delta}G^{\circ}$ and ${\Delta}H^{\circ}$ decreased. Since the standard emf of the cell at high pressure can be calculated from the complete Nernst equation, the theory of chemical equilibrium could be developed with at high pressure as well as at the atmosphere.

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Topographic and Meteorological Characteristics of Pinus densiflora Dieback Areas in Sogwang-Ri, Uljin (울진 소광리 산림유전자원보호구역 내 금강소나무 고사지역의 지형 환경 특성 분석)

  • Kim, Jaebeom;Kim, Eun-Sook;Lim, Jong-Hwan
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.19 no.1
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    • pp.10-18
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    • 2017
  • Korean Red Pine (Pinus densiflora) has been protected and used as the most ecologically and socio-culturally important tree species in Korea. However, as dieback of Korean red pines has occurred in the protected area of the forest genetic resources. The aims of this study is to identify causes for dieback of pine tree by investigating topographical characteristics of pine tree dieback and its correlation to meteorological factors. We extracted the dead trees from the time series aerial images and analyzed geomorphological characteristics of dead tree concentration area. As a result, 1,956 dead pine trees were extracted in the study region of 2,600 ha. Dieback of pine trees was found mostly in the areas with high altitude, high solar radiation, low topographic wetness index, south and south-west slopes, ridgelines, and high wind exposure compared to other living pine forest area. These areas are classified as high temperature and high drought stress regions due to micro-climatic characteristics affected by topographic factors. As high temperature and drought stress are generally increasing with climate change, we can evaluated that a risk of pine tree dieback is also increasing. Based on these geomorphological characteristics, we developed a pine tree dieback risk map using Maximum Entropy Model (MaxEnt), and it can be useful for establishing Korean red pine protection and management strategies.

Technological Synergy Effect of Business Portfolio : Panel Data Analysis on 50 Largest Chaebols in Korea (사업포트폴리오의 기술시너지효과 :50대 재벌의 패널자료분석)

  • 김태유;박경민
    • Proceedings of the Technology Innovation Conference
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    • 1996.12a
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    • pp.265-295
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    • 1996
  • This paper investigates empirically the relationship between various business portfolio properties (particularly technological properties) and chaebol′s performance using data on the 50 largest chaebols in Korea. In addition to the traditional indexes to measure diversification such as entropy index we calculated inter-industry technological similarity using R&D expenditure data by industry and 1990 Input-output Table in Korea, and obtained chaebol-level technological relatedness and internal transaction proportion from chaebols′business profile, inter-industry technological similarity and 1990 input-output table. We applied factor analysis on 13 business portfolio property indexes and showed that they could be grouped into 3 dimensions, diversification scope, inter-business relatedness and degree of vertical integration. In this paper, using 50 largest chaebols′financial data (1989-1994), we analyzed empirically the effect of business portfolio properties on ROS (Return On Sales) which is conventional index for firm performance and on TFP(Total Factor Productivity) growth which is a pure measure of firm performance. To utilize the advantage of panel data, FEM(Fixed Effect Model) and REM(Random Effect Model) were used. The empirical result shows that the entropy index as a measurement of inter-business relatedness is not significant but technological relatedness index is significant. OLS estimates on pooled data were considerably different from FEM or REM estimates on panel data. By introducing interaction effect among the three variables for business portfolio properties, we obtained three findings. First, only VI (Vertical integration) has a significant positive correlation with ROS. Second, when using TFP growth as an dependent variable, both TR(Technological Relatedness) and f[ are significant and positively related to the deepened variable. Third, the interaction term between TR and VI is significant and negatively affects TFP growth, meaning that TR and VI are substitutes. These results suggest strategic directions on restructuring business portfolio. As VI is increased, chaebols will get more profit. A higher level of either TR or W will increase TFP growth rate. but increase in both TR and VI will have a negative effect on TFP growth. To summarize, certain business portfolio properties such as VI and TR can be considered "resources" themselves since they can affect profit rate and productivity growth. VI and TR have a synergy effect of change in profit rate and productivity growth. VI increases ROS and productivity growth, while TR increases productivity growth representing a technological synergy effect.

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Synthesis and Properties of Polydentate Schiff Base Ligands having $N_nO_2$ (n=3~5) Donor Atoms and their Transition Metal Complexes (여러자리 질소-산소계 시프염기 리간드와 전이금속착물의 합성 및 특성)

  • Kim, Sun-Deuk;Shin, Yun-Yeol;Park, Sung-Woo
    • Analytical Science and Technology
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    • v.11 no.5
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    • pp.366-373
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    • 1998
  • Polydentate Schiff base ligands, BSDT(1,9-bis(2-hydroxyphenyl)-2,5,8-triaza-1,8-nonadiene) having $N_3O_2$ atoms, BSTT(1,12-bis(2-hydroxyphenyl)-2,5,8,11-tetraaza-1,11-dodecadiene) having $N_4O_2$ atoms, BSTP(1,15-bis(2-hydroxyphenyl)-2,5,8,11,14-pentaaza-1,14-pentadodecadiene) having $N_5O_2$ atoms were synthesized. Protonation constants of these polydentate ligands were measured by potentiometry. Stability constants of the complexes between these ligands and the metal ions such as Cu(II), Ni(II) and Zn(II) were measured in DMSO by a polarographic method. It was observed that all metal(II) ions employed in this study formed 1:1 complexes with Schiff base ligands. Stability constants for the complex formation were in the order of Cu(II)>Ni(II)>Zn(II), and for the ligands were in the order of BSTP>BSTT>BSDT. There are due to the increase in the number of donor atoms. Both enthalpy and entropy changes were obtained in negative values. Exothermicity for the complex formation indicated tight binding between the ligands and metal ions. The negative entropy change would be related to the fact that solvent molecules are strongly interacting with the metal complexes.

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Analysis on Isotherm, Kinetic and Thermodynamic Properties for Adsorption of Acid Fuchsin Dye by Activated Carbon (활성탄에 의한 Acid Fuchsin 염료의 흡착에 대한 등온선, 동력학 및 열역학 특성치에 대한 해석)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.58 no.3
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    • pp.458-465
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    • 2020
  • Isotherms, kinetics and thermodynamic properties for adsorption of acid fuchsin (AF) dye by activated carbon were carried out using variables such as dose of adsorbent, pH, initial concentration and contact time and temperature. The effect of pH on adsorption of AF showed a bathtub with high adsorption percentage in acidic (pH 8). Isothermal adsorption data were fitted to the Freundlich, Langmuir, and Dubinin-Radushkevich isotherm models. Freundlich isothem model showed the highest agreement and confirmed that the adsorption mechanism was multilayer adsorption. It was found that adsorption capacity increased with increasing temperature. Freundlich's separation factor showed that this adsorption process was an favorable treatment process. Estimated adsorption energy by Dubinin-Radushkevich isotherm model indicated that the adsorption of AF by activated carbon is a physical adsorption. Adsorption kinetics was found to follow the pseudo-second-order kinetic model. Surface diffusion at adsorption site was evaluated as a rate controlling step by the intraparticle diffusion model. Thermodynamic parameters such as activation energy, Gibbs free energy, enthalpy entropy and isosteric heat of adsorption were investigated. The activation energy and enthalpy change of the adsorption process were 21.19 kJ / mol and 23.05 kJ / mol, respectively. Gibbs free energy was found that the adsorption reaction became more spontaneously with increasing temperature. Positive entropy was indicated that this process was irreversible. The isosteric heat of adsorption was indicated physical adsorption in nature.