• 제목/요약/키워드: Enthalpy and Entropy

검색결과 251건 처리시간 0.02초

熱力學函數間의 直線關係 (第3報) Solvolysis反應에의 應用 (Linear Relationships between Thermodynamic Parameters (Part III) Application to Solvolysis Reaction)

  • 이익춘
    • 대한화학회지
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    • 제7권4호
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    • pp.264-270
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    • 1963
  • 前報에서 誘導한 置換基效果 一般關係式은 溶媒組成에 따르는 常數, Y를 potential energy 項에 代置함으로서 solvolysis 反應에 適用할 수가 있다. 新方程式, $\Delta{\Delta}H^\neq=a'Y+b\Delta{\Delta}S^\neq$, 의 適用性은 文獻에 報告된 35個反應에 對한 直線關係를 調査해 봄으로서 檢討하였다. 結果로 平均 相關係數 0.977을 얻었고, 따라서 이 方程式이 solvolysis反應에 一般的으로 適用됨을 밝혔고, 또 Grunwald-Winstein의 式이 지니는 몇몇 難點을 解決할 수가 있음을 알 수 있었다. enthalypy-entopy 直線效果는 外部 enthalpy와 外部 entropy에 限한 것이며, 嚴格히 말해서 外部 enthalpy entropy 直線效果임을 强調하였다.

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Decreased entropy of unfolding increases the temperature of maximum stability: Thermodynamic stability of a thioredoxin from the hyperthermophilic archaeon Methanococcus jannaschii

  • Lee, Duck-Yeon;Kim, Kyeong-Ae;Kim, Key-Sun
    • 한국자기공명학회논문지
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    • 제8권1호
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    • pp.1-18
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    • 2004
  • A thioredoxin from hyperthermophile, Methanococcus jannashii (MjTRX) was characterized by use of the differential scanning calorimetry to understand the mechanisms of thermodynamic stability. MjTRX has an unfolding transition temperature of 116.5$^{\circ}C$, although the maximum free energy of the unfolding (9.9 Kcal/mol) is similar to that of E. coli thioredoxin (ETRX, 9.0 Kcal/mol). However, the temperature of maximum stability is higher than ETRX by 20$^{\circ}C$, indicating that the unfolding transition temperature increased by shifting the temperature of maximum stability. MjTRX has lower enthalpy and entropy of the unfolding compared to ETRX maintaining a similar free energy of the unfolding. From the structure and the thermodynamic parameters of MjTRX, we showed that the unfolding transition temperature of MjTRX is increased due to the decreased entropy of the unfolding. Decreasing the unfolded state entropy and increasing the folded state entropy can decrease the entropy of the unfolding. In the case of MjTRX, the increased number of proline residues decreased the unfolded state entropy and the increased enthalpy in the folded state increased the folded state entropy.

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물의 T-s 선도 상에서 26 종류의 물성치 작도 및 시스템 해석 프로그램 개발 (Program Development for Drawing of 26 Properties and System Analysis on T-s Diagram of Water or Vapor)

  • 김덕진
    • 대한설비공학회:학술대회논문집
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    • 대한설비공학회 2008년도 동계학술발표대회 논문집
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    • pp.157-164
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    • 2008
  • The temperature-entropy diagram of water or vapor displays graphically the thermophysical properties, so it is very conveniently used in various thermal systems. On general T-s chart of water, there are temperature, pressure, quality, specific volume, specific enthalpy, specific entropy. However, various state and process values besides above properties can be plotted on T-s diagram. In this study, we developed the software drawing twenty six kinds of properties, that is temperature, pressure, quality, specific volume, specific internal energy, specific enthalpy, specific entropy, specific exergy, exergy ratio, density, isobaric specific heat, isochoric specific heat, ratio of specific heat, coefficient of viscosity, kinematic coefficient of viscosity, thermal conductivity, prandtl number, ion product, static dielectric constant, isentropic exponent, velocity of sound, joule-thomson coefficient, pressure coefficient, volumetric coefficient of expansion, isentropic compressibility, and isothermal compressibility. Also, this software can analyze and print the system values of mass flow rate, volume flow rate, internal energy flow rate, enthalpy flow rate, entropy flow rate, exergy flow rate, heat flow rate, power output, power efficiency, and reversible work. Additionally, this software support the functions such as MS-Power Point.

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VS계 반응염료 가수분해반응의 열역학적 해석 (Thermodynamic Analysis on the Hydrolysis Reaction of Vinylsulfonyl Reactive Dyes)

  • 권혁성;전영실;남성우;김인회
    • 한국염색가공학회:학술대회논문집
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    • 한국염색가공학회 2008년도 제38차 학술발표대회
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    • pp.74-76
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    • 2008
  • The hydrolyses of ten VS dyes were examined at 40$^{\circ}C$, 50$^{\circ}C$, and 60$^{\circ}C$ and the kinetic parameters were estimated. The values of free energy, enthalpy and entropy of hydrolysis and reaction with cellulose for VS dyes were calculated. The linear relationship exist between the enthalpy and entropy. The structure and entropy of VS dyes gave a effect on the dimerization for VS reactive dyes. The VS dyes have small value of entropy were formed dimer. It was confirmed that no dimer form for m-substituted VS dyes. There were similarities among various reactions including homo- and mixed dimerization.

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$BiI_3$에 대한 승화압과 승화 표준 엔탈피 (The Sublimation Pressure and Standard Enthalpy of Sublimation of Bismuth Triiodide)

  • 김준학
    • 한국세라믹학회지
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    • 제27권7호
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    • pp.943-951
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    • 1990
  • Steady-state sublimation vapour pressures of anhydrous bismuth triiodide have been measured by the continuous gravimetric Kundsen-effusion method from 430.0 to 558.9 K and equilibrium sublimation pressures were obtained from the steady-state data. Condensation coefficients and their temperature dependence have been derived from the effusiion measurement. Condensation coefficients ranged from 0.159 to 0.048(475 to 500K), the activation enthalpy and entropy for condensation have been obtained as -93.38kTmol-1 and -212.70JK-1mol-1. The standard sublimation enthalpy changes derived by both second(modified sigma function) and third(average enthalpy method) law methods were 138.261$\pm$0.023, 138.74$\pm$0.002kJmol-1 respectively. The standard sublimation entropy change derived by modified sigma function was 191.98$\pm$0.047 JK-1mol-1. The reliable standard sublimation enthalpy change based on a correlation of ΔgcrHom(298.15K) and ΔgcrSom(298.15K), a recommended p(T) equation has been obtained for BiI3(cr) ; 1g(p/Pa)=-C/(T/K)+5.0711g(T/K)-2.838$\times$10-3(T/K)-7.758$\times$103(K/T)2+1.4519 where p is in Pa, T in Kelvin, ΔgcrHom(298.15K) in kJmol-1 and C=(ΔgcrHom(298.15K)-8.7358)/1.9146$\times$10-2.

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R-134a의 열역학적 물성치 계산과 냉동 성능에 관한 연구 (Calculation of the Thermodynamic Properties of R-134a and A Preliminary Study of the Refrigeration Performance)

  • 박영무;이홍원
    • 설비공학논문집
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    • 제3권4호
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    • pp.286-296
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    • 1991
  • The thermodynamic properties of R134a, the prospective R12 alternative, have been computerized using Martin-Hou equation of state and the coefficients given by Willson-Basu. Several experimental results in literatures for PVT data, saturated vapor pressure, saturated liquid density are compared with the calculated results to investigate the accuracy. The average deviation (max. deviation) is 0.13% (0.25%) for saturated liquid density, 0.25% (0.8%) for PVT data. Thermodynamic properties, enthalpy, entropy are compared with the NIST's. The maximum percent difference is 3% for saturated liquid enthalpy, 1.5% for saturated vapor enthalpy, 4% saturated liquid entropy, and 0.7% for saturated vapor entropy. Correction of W-B's coefficients and inclusion of the sixth term of M-H EOS for improvement of accuracy are recommended. R134a and R12 are compared with respect to refrigeration performance. COP's are different from each other within 3%. Refrigeration effect of R134a is superior to that of R12 but refrigeration capacity of R134a is inferior to that of R12 because the volumetric efficiency of the system using R134a is lower than that of the system using R12.

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Papaya Latex에 있는 단백질분해효소(蛋白質分解酪素)들의 열불활성(熱不活性)에 관하여 (Heat Inactivation of Proteolytic Enzymes in Papaya Latex)

  • 노봉수;박관화
    • 한국식품과학회지
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    • 제12권3호
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    • pp.209-215
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    • 1980
  • 파파이야 라텍스를 $(NH_4)_2SO_4$,분획 및 CM-cellulose column을 통과시켜 두개의 획분으로 분리하고 각 획분 별로 pH 7.0, $60{\sim}90^{\circ}C$에서 열 불활성 실험을 행하고 다음과 같은 열역학적인 자료를 얻었다. 1. fraction I 의 z-value는 $25^{\circ}C$이었고 $70^{\circ}C$에서 활성화 엔탈피 (enthalpy of activation) 89.5 kJ/mol, 활성화엔트로피 (entropy of activation) -44.0 kJ/mol K, 활성화 자유에너지(free energy of activation) 104.6 kJ/mol이었다. 2. fraction II 의 z-value는 $23^{\circ}C$이고 $70^{\circ}C$에서 활성화 엔트로피 -22.0 kJ/mol K, 활성화 자유에너지 104.2 kJ/mol이었다. 3. fraction I과 fraction II를 혼합한 경우의 z-value는 $24.6^{\circ}C$, $70^{\circ}C$에서 활성화 엔탈피 90.9 kJ/mol, 활성화 앤트로피 -38.8 J/mol K, 활성화 자유에너지 104.2 kJ/mol이었다. 4. 조 추출액의 z-value는 $23.2^{\circ}C$이고 $70^{\circ}C$에서 활성화 엔트로피 113.8 kJ/mol, 활성화 엔트로피 22.0 kJ/mol K, 활성화자유에너지 106.2 kJ/mol이었다. 이상의 결과에서 fraction I 이 fraction II 보다 열에 안정하다고 볼 수 있었고 파파이야 라텍스에 있는 단백질 분해 효소의 열 안정성은 주로 fraction I 에 기인하는 것 을 알 수 있었다.

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Dehydrogenation of Ethylalcohol Catalyzed by Alcoholdehydrogenase Under High Pressure

  • 지종기;신진영;황정위
    • Bulletin of the Korean Chemical Society
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    • 제10권1호
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    • pp.50-57
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    • 1989
  • A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.

전분의 열확산율 측정 및 물리적 특성에 관한 연구 (Studies on the Measurement of Thermal Diffusivity and Thermophysical Characteristics of Defatted and Nondefatted Starches)

  • 김민용;공재열;김정한;정진웅
    • 한국식품과학회지
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    • 제22권1호
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    • pp.1-6
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    • 1990
  • 곡물류 및 고탄수화물 식품의 저온저장 장치의 설계 및 열역학적 특성 규명의 지표가 되는 열확산율, 엔탈피와 엔트로피의 온도 및 농도의존성과 생각속도의 영향을 측정하여 다음의 결과를 얻었다. 전분을 탈지함으로서 열확산율은 증가하는 효과를 나타내었으나 비열이 큰 지방의 감소로 엔탈피 및 엔트로피는 감소하였다. 동결과정이 진행됨에 따라 엔탈피, 엔트로피 및 자유에너지가 감소함으로서 안정화되었다. 수분함량 $35{\sim}90%$에서의 전분의 엔탈피와 엔트로피 및 자유에너지는 $107{\sim}216 (kcal /moi),\;0.45{\sim}0.94(kcal/mol.\;K),\;15.47{\sim}17.5kcal/mol$로서 수분함량에 따라 선형적으로 증가하는 경향을 나타내었다. 냉각속도 $-2.5{\sim}10.0^{\circ}C/min$에서 엔탈피는 $83{\sim}186kcal/mol$, 엔트로피는 $0.39{\sim}0.78kcal/mol.K$로서 냉각속도가 감소할수록 증가하는 경향을 나타내었다.

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Chloroform-Chloroethanol 용매중에서 Poly(cis-5-methylproline)의 평형 및 열역학적연구 (Equilibrium Studies and Thermodynamics for the Mutarotation of Poly(cis-5-methylproline) in Chloroform-Chloroethanol)

  • 한만정
    • 대한화학회지
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    • 제23권4호
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    • pp.187-197
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    • 1979
  • ChIoroform과 chloroethanol 혼합용매속에서 Poly(cis-5-methylproIine)의 광회전을 측정하였다. 이 혼합용매속에 chloroethanol이 0.5∼10부피%일때 형태 A와 B사이에는 평형상태가 이루어졌다. 광회전을 이용하여 5, 25 및 45$^{circ}$C에서 평형정수를 측정하고 자유엔탈피, 엔탈피 및 엔트로피 변화를 계산하였다. 같은 몰수의 형태 A와 B에서 출발하면 chloroethanol이 3부피% 이상일때는 정방향 변광회전이 일어나고 이하일때는 역방향 회전이 일어났다. 엔탈피와 엔트로피 변화는 정방향 변광회전일때는 양수이고 역방향 변광회전일 때는 음수였다. 반응 추진역은 정방향 회전일때는 엔트로피의 증가이고 역방향 회전일때는 엔탈피의 감소였다. 측정된 열역학적 자료들은 폴리머와 용매사이의 상호작용 즉 용매중의 chloroethanol이 형태 B분자내의 카보닐기와 선택적으로 수소결합을 형성하며, 형태 A와 B의 헝태 에너지 차이에 있다는것을 설명한다

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