• 제목/요약/키워드: Gibbs′ free energy

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Dielectric Relaxation in Ethylene Glycol - Dimethyl Sulfoxide Mixtures as a Function of Composition and Temperature

  • Undre, P.B.;Khirade, P.W.;Rajenimbalkar, V.S.;Helambe, S.N.;Mehrotra, S.C.
    • 대한화학회지
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    • 제56권4호
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    • pp.416-423
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    • 2012
  • Using time domain reflectometry, the complex dielectric spectra between 10 MHz to 20 GHz has been measured in the whole composition range at 10, 20, 30 and $40^{\circ}C$ for the binary mixtures of ethylene glycol and dimethyl sulfoxide. For all the mixtures, only one dielectric loss peak was observed in this frequency range. The relaxation in these mixtures can be described by a single relaxation time using the Debye model. A systematic variation is observed in dielectric constant (${\varepsilon}_0$) and relaxation time (${\tau}$). The excess permittivity (${\varepsilon}^E$), excess inverse relaxation time $(1/{\tau})^E$, Kirkwood correlation factor (g) and thermodynamic parameters viz. enthalpy of activation (${\Delta}H$) and Gibbs free energy of activation (${\Delta}G$) have been determined, to confirm the formation of hydrogen bonded homogeneous and heterogeneous cooperative domains, the dynamics of solute - solute interaction and the hindrance to molecular rotation in the hydrogen bonded glass forming ethylene glycol - dimethyl sulphoxide system.

Impedance Spectroscopy Studies on Corrosion Inhibition Behavior of Synthesized N,N’-bis(2,4-dihydroxyhydroxybenzaldehyde)-1,3-Propandiimine for API-5L-X65 Steel in HCl Solution

  • Danaee, I.;Bahramipanah, N.;Moradi, S.;Nikmanesh, S.
    • Journal of Electrochemical Science and Technology
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    • 제7권2호
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    • pp.153-160
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    • 2016
  • The inhibition ability of N,N-bis(2,4-dihydroxyhydroxybenzaldehyde)-1,3-Propandiimine (DHBP) as a schiff base against the corrosion of API-5L-X65 steel in 1 M HCl solution was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization and scanning electron microscopy. Electrochemical impedance studies indicated that DHBP inhibited corrosion by blocking the active corrosion sites. The inhibition efficiency increased with increasing inhibitor concentrations. EIS data was analysed to equivalent circuit model and showed that the charge transfer resistance of steel increased with increasing inhibitor concentration whilst the double layer capacitance decreased. The adsorption of this compound obeyed the Langmuir adsorption isotherm. Gibbs free energy of adsorption was calculated and indicated that adsorption occurred through physical and spontaneous process. The corrosion inhibition mechanism was studied by potential of zero charge. Polarization studies indicated that DHBP retards both the cathodic and anodic reactions through adsorption on steel surface. Scanning electron microscopy was used to study the steel surface with and without inhibitor.

기전력법을 이용한 용융 Zn-Cd 합금중 Zn의 활동도 측정 (Activity Measurement of Zn in Liquid Zn-Cd Alloy Using EMF Method)

  • 정성엽;정우광;박종진
    • 한국재료학회지
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    • 제12권4호
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    • pp.283-289
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    • 2002
  • The E.M.F of the galvanic cell with fused salt was measured to determine the activities of zinc at 700-820K over the entire composition range of liquid Zn-Cd alloys. The cell used was as follows: (-) W | Zn(pure) $Zn^{2+}(KCI-LiCl)$ | Zn(in Zn-Cd alloy) | W (+) The activities of zinc in the alloys showed positive deviation from Raoult's law over the entire composition range. The activity of cadmium and some thermodynamic functions such as Gibbs free energy, enthalpy, entropy were derived from the results by the thermodynamic relationship. The comparison of the results and the literature data was made. The liquid Zn-Cd alloy is found to be close to the regular solution. The concentration fluctuations in long wavelength limit, $S_{cc}(o)$, in the liquid alloy was calculated from the results.

Geotrichum candidum Lipase의 열불활성(熱不活性)에 관(關)하여 (Thermal Inactivation of Lipase from Geotrichum candidum)

  • 박관화
    • Applied Biological Chemistry
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    • 제20권1호
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    • pp.101-104
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    • 1977
  • Geotrichum candidum이 분비한 lipase를 인산완충용액 중에서 열처리하여 열불활성 곡선을 얻었다. $50^{\circ}C$에서 lipase의 열 불활성 곡선은 고온의 경우와는 달리 일차 반응 속도법칙을 따르지 않았고 고온의 경우에는 일차 반응을 따랐다. $60^{\circ}C$에서의 엔탈피, 엔트로피 및 깁스 자유 에너지의 변화는 각각 120.4 kJ/mol, 73.0 J/mol.K 및 96.9 kJ/mol이었다. 열 불활성 곡선에서 얻은 Geotric hum candidum lipase의 z-value는 $19^{\circ}C$로 pancreas나 우유 중에 존재하는 lipase의 z-value보다 훨씬 큰 값을 나타낸다. 환경인자의 영향으로는 lecithin과 linoleic ac를 첨가하여 열처리 하였는데 실험에 사용한 계면활성제의 농도에서는 별다른 큰 영향을 미치지 않았다.

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몰농도 또는 몰분율로 표시되는 임계 미셀 농도와 열역학적 포텐셜과의 관계 (Critical Micelle Concentration Expressed in Molarity or Mole Fraction and Its Relation to Thermodynamic Potentials)

  • 김홍운;임경희
    • 한국응용과학기술학회지
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    • 제18권4호
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    • pp.325-331
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    • 2001
  • The critical micelle concentration (CMC) at which micelles start to form from a surfactant solution is usually measured in terms of conventional concentration units. However, the thermodynamic potentials are expressed in terms of mole fraction $X_{CMC}$ and $X_{CMC}$ cannot be directly measured experimentally. The Gibbs free energy, ${\Delta}G^{\ast}_{mic}$, in particular is related to $X_{CMC}$ through ${\Delta}G^{\ast}_{mic}$ = $RTlnX_{CMC}$. When it comes to CMC, the molar CMC, $C_{CMC}$, differs only by the proportionality $C^{-1}_{w}$ with $C_{w}$ being the molarity of water. Hence, $C_{CMC}$ is found to be a proper representation of CMC. However, in calculation of ${\Delta}G^{\ast}_{mic}$ and other thermodynamic potentials from the CMC, $X_{CMC}$ or $C_{CMC}/C_{w}$ should be used.

Aqueous phase removal of ofloxacin using adsorbents from Moringa oleifera pod husks

  • Wuana, Raymond A.;Sha'Ato, Rufus;Iorhen, Shiana
    • Advances in environmental research
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    • 제4권1호
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    • pp.49-68
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    • 2015
  • Chemically activated and carbonized adsorbents were prepared from Moringa oleifera pod husks (MOP), characterized and evaluated for their ability to remove a common antibiotic - ofloxacin (OFX) from aqueous solution. The pulverized precursor was steeped in a saturated ammonium chloride solution for a day to give the chemically activated adsorbent (AMOP). A portion of AMOP was pyrolyzed in a muffle furnace at 623 K for 30 min to furnish its carbonized analogue (CMOP). The adsorbents showed favorable physicochemical attributes. The effects of operational parameters such as initial OFX solution pH and concentration, adsorbent dosage, temperature and contact time on OFX removal were investigated. At equilibrium, optimal removal efficiencies of 90.98% and 99.84% were achieved at solution pH 5 for AMOP and CMOP, respectively. The equilibrium adsorption data fitted into both the Langmuir and Freundlich isotherms. Gibbs free energy change (${\Delta}G^o$), enthalpy change (${\Delta}H^o$) and entropy change (${\Delta}S^o$) indicated that the adsorption of OFX was feasible, spontaneous, exothermic and occurred via the physisorption mode. Adsorption kinetics obeyed the Blanchard pseudo-second-order model. The results may find applications in the adsorptive removal of micro-contaminants of pharmaceutical origin from wastewater.

An Isothermal Titration Microcalorimetric Study on the Interaction of Three Water-Soluble Porphyrins with Histone H2B

  • Bordbar, A.K.;Ghaderi, A.R.;Safaei, E.;Tangestaninejad, S.;Eslami, A.;Saboury, A.A.;Moosavi Movahedi, A.A.
    • Bulletin of the Korean Chemical Society
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    • 제24권5호
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    • pp.547-551
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    • 2003
  • In the present work, the interaction of three water soluble porphyrins, tetra(p-trimethyle) ammonium phenyl porphyrin iodide (TAPP) as a cationic porphyrin, tetra sodium meso-tetrakis (p-sulphonato phenyle) porphyrin (TSPP) as an anionic porphyrin and manganese tetrakis (p-sulphonato phenyl) porphinato acetate (MnTSPP) as a metal porphyrin, with histone H₂B have been studied by isothermal titration microcalorimetry at 8 mM phosphate buffer, pH 6.8 and 27 °C. The values of binding constant, entropy, enthalpy and Gibbs free energy changes for binding of the first MnTSPP, and first and second TSPP and TAPP molecules were estimated from microcalorimetric data analysis. The results represent that the process is both entropy and enthalpy driven and histone induces self-aggregation of the porphyrins. The results indicate that both columbic and hydrophobic interactions act as self-aggregation driving forces for the formation of aggregates around histone.

Speckle Removal of SAR Imagery Using a Point-Jacobian Iteration MAP Estimation

  • Lee, Sang-Hoon
    • 대한원격탐사학회지
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    • 제23권1호
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    • pp.33-42
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    • 2007
  • In this paper, an iterative MAP approach using a Bayesian model based on the lognormal distribution for image intensity and a GRF for image texture is proposed for despeckling the SAR images that are corrupted by multiplicative speckle noise. When the image intensity is logarithmically transformed, the speckle noise is approximately Gaussian additive noise, and it tends to a normal probability much faster than the intensity distribution. MRFs have been used to model spatially correlated and signal-dependent phenomena for SAR speckled images. The MRF is incorporated into digital image analysis by viewing pixel types as slates of molecules in a lattice-like physical system defined on a GRF Because of the MRF-SRF equivalence, the assignment of an energy function to the physical system determines its Gibbs measure, which is used to model molecular interactions. The proposed Point-Jacobian Iterative MAP estimation method was first evaluated using simulation data generated by the Monte Carlo method. The methodology was then applied to data acquired by the ESA's ERS satellite on Nonsan area of Korean Peninsula. In the extensive experiments of this study, The proposed method demonstrated the capability to relax speckle noise and estimate noise-free intensity.

Structural Studies on Cyclic Compounds. Substituent Effects on the Reducing Ability of Dihydropyridines

  • Koh Park, Kwang-Hee;Moon, Gyeoung-Un;Kwon, Ki-Sung
    • Bulletin of the Korean Chemical Society
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    • 제8권3호
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    • pp.168-170
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    • 1987
  • The reaction between 1-benzyl-3-carbamoyl-1,4-dihydropyridine (BNAH) 1 and various 1-arylpyridinium salts 2, and the reaction between 1-(4-methylphenyl)-1,4-dihydropyridine 4b and 1-aryl-3-carbamoylpyridinium (1-arylnicotinamide) salts 5 were carried out. The extents of reaction in equilibrium were estimated by nmr integration data. The equilibrium constants for the reactions, K, and the standard Gibbs free energy changes for the reduction of the pyridinium salts to the corresponding 1,4-dihydropyridines ${\Delta}G^{\circ}'$ were evaluated. The Hammett plot of log K for the reaction between 1 and 2, and ${\Delta}G^{\circ}'$ against ${\sigma}_p$ of the substituents in 1-aryl moiety shows linear correlation with the reaction constant ${\rho}$ of 9.4 (for log K vs ${\sigma}_p$) and -54.5 KJ/mole (for ${\Delta}G^{\circ}'$ vs ${\sigma}_p$). It was found that 1-aryl-1,4-dihydropyridines have much higher reducing power than the corresponding 1-aryl-1,4-dihydronicotinamides, and the power is affected greatly by the electron-withdrawing ability of the substituents in aryl group. The reactions were utilized for preparation of 1,4-dihydropyridines bearing highly electron-withdrawing groups such as 4-nitrophenyl and 2,4-dinitrophenyl, which could not be obtained by conventional dithionite reduction of the corresponding pyridinium salts due to the base-labile nature of the salts.

활성탄에 의한 Acid Red 66의 흡착에 대한 등온선, 동력학 및 열역학적 특성 (Characteristics of Isotherm, Kinetic and Thermodynamic Parameters for the Adsorption of Acid Red 66 by Activated Carbon)

  • 이종집
    • 청정기술
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    • 제26권1호
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    • pp.30-38
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    • 2020
  • 입상 활성탄에 대한 Acid Red 66의 흡착 등온선과 동력학적, 열역학적 파라미터에 대해 염료의 초기농도, 접촉시간, 온도를 흡착변수로 하여 조사하였다. 흡착평형자료는 Langmuir, Freundlich, Temkin, Redlich-Peterson 및 Temkin 등온흡착식에 적용하였다. Freundlich 등온흡착식이 가장 잘 맞았으며, 계산된 Freundlich 분리계수 값(1/n = 0.125 ~ 0.232)으로부터 입상 활성탄이 Acid Red 66을 효과적으로 처리할 수 있다는 것을 알 수 있었다. Temkin의 흡착열관련상수(BT = 2.147 ~ 2.562 J mol-1)는 이 공정이 물리흡착임을 나타냈다. 동력학적 실험으로부터 흡착공정은 유사 이차 반응속도식에 잘 맞았다. 입자 내 확산식에 대한 결과는 경계층 확산을 나타내는 첫 번째 직선의 기울기보다 입자내 확산을 나타내는 두 번째 직선의 기울기가 작게 나타나서 입자 내 확산이 율속단계인 것을 확인하였다. 열역학 실험으로부터 활성화 에너지는 35.23 kJ mol-1로 흡착공정이 물리흡착공임을 확인하였다. Gibbs 자유에너지 변화(ΔG = -0.548 ~ -7.802 kJ mol-1)와 엔탈피 변화(ΔH = +109.112 kJ mol-1)은 각각 흡착공정이 자발적 공정 및 흡열과정임을 나타내었다. 등량흡착열은 흡착된 염료분자들의 측면상호작용을 나타내는 표면부하량이 증가함에 따라 증가하였다.