• Title/Summary/Keyword: 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.
    • Journal of the Korean Chemical Society
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    • v.56 no.4
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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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    • v.7 no.2
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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.

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

  • Jeong, Seong-Yeop;Jeong, U-Gwang;Park, Jong-Jin
    • Korean Journal of Materials Research
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    • v.12 no.4
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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.

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

  • Park, K.H.
    • Applied Biological Chemistry
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    • v.20 no.1
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    • pp.101-104
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    • 1977
  • Lipase from Geotrichum candidum was heat inactivated in 0.1M phosphate buffer solution. The thermal inactivation followed first order kinetics for the range of temperatures $50^{\circ}-80^{\circ}C$ except at $50^{\circ}C$. The changes in enthalpy, entropy and Gibbs free energy at $60^{\circ}C$ were 120.4 kJ/mol, 73.0 J/mol K and 96.9 kJ/mol respectively a value of $19^{\circ}C$(Geotrichum candidum lipase) is greater than that of lipases from milk and pancreas. The effect of detergents, lecithin and linoleic acid or the thermal inactivation of lipase was found to be negligible.

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

  • Kim, Hong-Un;Lim, kyung-Hee
    • Journal of the Korean Applied Science and Technology
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    • v.18 no.4
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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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    • v.4 no.1
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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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    • v.24 no.5
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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
    • Korean Journal of Remote Sensing
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    • v.23 no.1
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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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    • v.8 no.3
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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.

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

  • Lee, Jong-Jib
    • Clean Technology
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    • v.26 no.1
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    • pp.30-38
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    • 2020
  • The kinetic and thermodynamic parameters of Acid Red 66, adsorbed by granular activated carbon, were investigated on areas of initial concentration, contact time, and temperature. The adsorption equilibrium data were applied to Langmuir, Freundlich, Temkin, Redlich-Peterson, and Temkin isotherms. The agreement was found to be the highest in the Freundlich model. From the determined Freundlich separation factor (1/n = 0.125 ~ 0.232), the adsorption of Acid Red 66 by granular activated carbon could be employed as an effective treatment method. Temkin's constant related to adsorption heat (BT = 2.147 ~ 2.562 J mol-1) showed that this process was physical adsorption. From kinetic experiments, the adsorption process followed the pseudo-second order model with good agreement. The results of the intraparticle diffusion equation showed that the inclination of the second straight line representing the intraparticle diffusion was smaller than that of the first straight line representing the boundary layer diffusion. Therefore, it was confirmed that intraparticle diffusion was the rate-controlling step. From thermodynamic experiments, the activation energy was determined as 35.23 kJ mol-1, indicating that the adsorption of Acid Red 66 was physical adsorption. The negative Gibbs free energy change (ΔG = -0.548 ~ -7.802 kJ mol-1) and the positive enthalpy change (ΔH = +109.112 kJ mol-1) indicated the spontaneous and endothermic nature of the adsorption process, respectively. The isosteric heat of adsorption increased with the increase of surface loading, indicating lateral interactions between the adsorbed dye molecules.