• 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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    • 제11권4호
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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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    • 제18권11호
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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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    • 제15권12호
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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.

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

  • 김종국;임연수;양지선;정은주
    • Journal of Pharmaceutical Investigation
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    • 제19권3호
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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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    • 제18권12호
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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.

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

  • 지종기;정종재;황정의
    • 대한화학회지
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    • 제18권5호
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    • pp.320-328
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    • 1974
  • 종래의 방법으로 고압하에서 전지의 표준기전력 $(E^{\circ})$를 산출하는 것은 불가능하다. 그러나 완전평형상수의 개념을 종래의 Nernst 방정식에 적용하므로서 고압하에서 표준기전력을 구할 수 있게 되었다(완전 Nernst방정식). 더욱이 다른 열역학적 성질 이를테면 수화수의 순변화(k), 용매의 압축을(${\beta}$), 전지반응에서 종래의 해리상수(K) 평형상태에서 표준자유에너지변화(${\Delta}G^{\circ}$) 표준엔탈피변화(${\Delta}H^{\circ}$) 및 표준엔트로피변화($S^{\circ}$) 등을 얻었다. 본 실험에서는 전지의 기전력(E)을 $20{\sim}35^{\circ}C$와 1∼2500 atms 범위에서 측정하였다. 일정한 온도에서 전지의 기전력은 압력이 증가함에 따라 증가하였으며, 일정한 압력에서 온도가 증가함에 따라 역시 증가하였다. 전지반응의 수화수의 순변화(k)는 $20^{\circ}C$에서 41.96으로서 압력에 따라 변하지 않고 일정한 값을 유지하였으나 한편 K와 ${\Delta}S^{\circ}C$는 압력에 따라 증가하였으나 ${\Delta}G^{\circ}$${\Delta}H^{\circ}$는 감소하였다. 고압하에서도 완전 Nernst방정식으로부터 표준기전력을 계산할 수 있으므로 상압에서와 마찬가지로 화학평형론을 취급할 수 있게 되었다

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

  • 김재범;김은숙;임종환
    • 한국농림기상학회지
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    • 제19권1호
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    • pp.10-18
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    • 2017
  • 소나무는 우리나라에서 생태적, 사회 문화적으로 가장 중요한 수종으로 보호 이용되어 온 수종이다. 그러나 산림유전자원보호구역 내 금강소나무 고사가 발생하고 있어 명확한 원인 구명 및 대책 마련이 필요하다. 따라서 본 연구에서는 금강소나무의 고사 원인 구명을 위해 시계열 항공영상을 이용하여 금강소나무 고사 발생 전수 조사를 실시하고 고사발생 지역에 대한 지형환경특성을 분석하여, 소나무 고사의 위치적 특성 및 이에 따른 기상 요인과의 연관성을 파악하였다. 그 결과, 2,600ha 연구 대상지 내에서 약 1,956본의 금강소나무 고사목이 추출되었다. 소나무의 고사는 소나무 생육지역에 비해 고도가 높고, 일사량이 많고, 지형습윤지수가 낮은 지역, 남 남서사면, 능선 부위, 풍노출도가 높은 지역에 집중되어 발생한 것으로 나타났다. 이러한 지역은 지형조건에 따라 영향을 받는 미기상 특성에 따라 고온과 건조 스트레스가 상대적으로 높은 지역으로 분류되는 지역이다. 기후변화에 따라 고온 건조 스트레스가 전반적으로 높아지고 있으며 취약지역을 중심으로 스트레스의 임계치를 넘으면서 고사현상이 발생하는 것으로 추정되었다. 이러한 지형환경 특성을 바탕으로 MaxEnt 모형을 이용하여 소나무 고사 발생 위험 지도를 제작하였으며, 이는 향후 소나무 보호 관리 대책 수립에 활용될 수 있다.

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

  • 김태유;박경민
    • 기술경영경제학회:학술대회논문집
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    • 기술경영경제학회 1996년도 제10회 동계학술발표회 논문집
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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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여러자리 질소-산소계 시프염기 리간드와 전이금속착물의 합성 및 특성 (Synthesis and Properties of Polydentate Schiff Base Ligands having $N_nO_2$ (n=3~5) Donor Atoms and their Transition Metal Complexes)

  • 김선덕;신윤열;박성우
    • 분석과학
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    • 제11권5호
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    • pp.366-373
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    • 1998
  • 여러자리 시프염기인 BSDT(1,9-bis(2-hydroxyphenyl)-2,5,8-triaza-1,8-nonadiene), BSTT(1,12-bis(2-hydroxyphenyl)-2,5,8,11-tetraaza-1,11-dodecadiene)와 BSTP(1,15-bis(2-hydroxyphenyl)2,5,8,11,14-pentaaza-1,14-pentadodecadiene)를 합성하여 전위차적정법으로 산해리 상수값을 구하고, DMSO 용매에서 이들 리간드들과 구리(II), 니켈(II), 및 아연(II)등의 전이금속과의 안정도 상수값을 폴라로그래피를 이용하여 구하였다. 이때 금속과 리간드는 1:1착물을 형성하였고, 안정도 상수값은 금속으로서는 Cu(II)>Ni(II)>Zn(II) 순서로, 리간드로서는 BSTP>BSTT>BSDT 순서로 나타남으로서 주개 원자수의 증가에 의존한다는 사실을 알았다. 엔탈피와 엔트로피는 모두 음의 값을 나타내었는데 흡열반응으로서 금속이온과 리간드가 매우 강하게 결합하고 있음을 알 수 있고 극성을 가지는 금속착물이 생성되어 용매인 DMSO와 아주 강한 상호작용을 함으로써 큰 음의 엔트로피 값을 가진 것으로 생각된다.

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

  • 이종집
    • Korean Chemical Engineering Research
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    • 제58권3호
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    • pp.458-465
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    • 2020
  • 활성탄에 의한 acid fuchsin (AF) 염료의 흡착에 대한 등온선, 동력학 및 열역학적 특성치를 흡착제의 양, pH, 초기 농도, 접촉시간 및 온도를 변수로 하여 수행하였다. 활성탄을 사용한 AF의 흡착에 대한 pH의 영향은 산성(pH 8)에서 흡착백분율이 높은 욕조 현상을 나타냈다. 등온흡착 데이터는 Freundlich, Langmuir, Dubinin-Radushkevich 등온흡착식에 맞춰 보았다. Freundlich 식이 가장 높은 일치도를 나타냈으며, 흡착메카니즘이 다분자층 흡착임을 알았다. 흡착용량은 온도증가와 함께 증가하였다. Freundlich의 분리계수는 이 흡착공정이 적합한 처리공정임을 나타냈다. Dubinin-Radushkevich 등온흡착식에 의해 평가된 흡착 에너지는 활성탄에 의한 AF의 흡착이 물리 흡착임을 확인시켰다. 흡착동력학은 유사이차반응속도식에 잘 맞았다. 입자내 확산 모델에 의해 흡착점에서의 표면 확산이 율속단계로 평가되었다. 흡착공정의 활성화 에너지와 엔탈피 변화는 각각 21.19 kJ/mol, 23.05 kJ/mol 이었다. Gibbs 자유 에너지 변화는 흡착반응이 온도가 높아질수록 자발성이 더 진다는 것을 알려주었다. 양의 엔트로피는 이공정이 비가역적이라는 것을 나타냈다. 등량 흡착열은 본질덕으로 물리흡착임을 나타냈다.