• Title/Summary/Keyword: 열역학적 분석

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Measurements and Modeling of the Activity Coefficients and Solubilities of L-alanine in Aqueous Electrolyte Solutions (전해질 수용액에서 L-Alanine의 활동도계수와 용해도의 측정 및 모델링)

  • Lee, Bong-Seop;Kim, Ki-Chang
    • Korean Chemical Engineering Research
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    • v.48 no.4
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    • pp.519-533
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    • 2010
  • Activity oefficients and solubilities of L-Alanine in aqueous solutions containing each of four electrolytes(NaCl, KCl, $NaNO_3$ and $KNO_3$) were measured at 298.15 K. The measurements of activity coefficients were carried out in the electrochemical cell coupled with two ion-selective electrodes(cation and anion), and the solubilities were measured by the gravimetric analysis of saturated solutions in equilibrium with the solid phase of L-alanine. To model the activity coefficients and solubilities of amino acid in the amino acid/electrolyte aqueous solutions, thermodynamic relations of the residual Helmholtz free energy in the amino acid/electrolyte aqueous solutions were developed based on the perturbed-chain statistical associating fluid theory(PC-SAFT) combined with the primitive mean spherical approximation(primitive-MSA). In the present model, it is assumed that the zwitterions of L-alanine are associated with each other and cross-associated with water molecules, and also cross-associated with the cation and anion dissociated from an electrolyte(inorganic salt). The activity coefficients and solubilities of L-Alanine calculated from the theoretical model proposed in this work are found to be well agreeable with experimental data.

Characteristic of Oxidation Reaction of Lanthanide Chlorides in Oxygen-Eutectic Salt Bubble Column (산소-공융염 기포탑에서 희토류염화물의 산화반응 특성)

  • Cho, Yung-Zun;Yang, Hee-Chul;Lee, Han-Soo;Kim, In-Tae
    • Korean Chemical Engineering Research
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    • v.47 no.4
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    • pp.465-469
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    • 2009
  • Characteristics of oxidation reaction of four lanthanide chlorides(Ce, Nd, Pr and $EuCl_3$) in a oxygen-eutectic(LiCl-KCl) salt bubble column was investigated. From the results obtained from the thermochemical calculations by HSC chemistry software, the most stable lanthanide compounds in the oxygen-used rare earth chlorides system were oxychlorides(EuOCl, NdOCl, PrOCl) and oxides($CeO_2$, $PrO_2$), which coincide well with results of the Gibbs free energy of the reaction. In this study, similar to the thermochemical results, regardless of the sparging time and molten salt temperature, oxychlorides for Eu, Nd and Pr and oxides for Ce and Pr were formed as a precipitant by a reaction with oxygen. The structure of the rare earth precipitates was divided into two shapes : small cubic(oxide) and large tetragonal (oxychloride) structures. The conversion efficiencies of the lanthanide elements to their molten salt-insoluble precipitates(or compound) were increased with the sparging time and temperature, and Ce showed the best reactivity. In the conditions of $650^{\circ}C$ of the molten salt temperature and 420 min of the sparging time, the conversion efficiencies were over 99% for all the investigated lanthanide chlorides.

Mixed Micellizations of TTAB with Other Surfactants (DTAB, CTAB, Tween-20, Tween-40, and Tween-80) (TTAB와 다른 계면활성제(DTAB, CTAB, Tween-20, Tween-40 및 Tween-80)와의 혼합미셀화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.56 no.5
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    • pp.556-562
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    • 2012
  • The critical micelle concentration (CMC) and the counter-ion binding constant (B) for the mixed micellizations of TTAB (tetradecyltrimethylammonium bromide) with other surfactants (DTAB, CTAB, Tween-20, Tween-40, and Tween-80) in aqueous solution of 4-chlorobenzoic acid (0.5 mM) at $25^{\circ}C$ were determined as a function of ${\alpha}_1$ (the overall mole fraction of TTAB) by using the spectrophotometric method and the conductivity method. Various thermodynamic parameters ($X_i$, ${\gamma}_i$, $C_i$, $a_i^M$, ${\beta}$, and ${\Delta}H_{mix}$) were calculated for each mixed surfactant system and compared with the other mixed surfactant systems by means of the equations derived from the nonideal mixed micellar model. The results show that TTAB/DTAB mixed system has a great positive deviation from the ideal mixed micellar model and the other mixed systems have great negative deviations from the ideal mixed model.

The Study on Magnetic Properties of Transition Metal Doped Semiconductor (전이금속이 치환된 반도체 물질의 자기적 특성 연구)

  • Kim, Jae-Uk;Cha, Byung-Kwan;Ji, Myoung-Jin;Kwon, Tae-Phil;Park, Byoung-Cheon;Kyoung, Dong-Hyoun;Jin, Hoon-Yeol;Kim, Seung-Hoi;Kim, Jong-Gyu
    • Journal of the Korean Chemical Society
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    • v.54 no.6
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    • pp.766-770
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    • 2010
  • This is the study of magnetic properties of transition metal doped diluted magnetic semiconductors(DMSs). The wurtzite structure samples were synthesized by the sol-gel method. The thermodynamic characteristics and magnetic properties of $Zn_{1-x}Co_xO$ single phase was investigated for different doping concentration (x = 0%, 1%, 2%, 3%, 4%, 5%, 10%, 15%). The property of diluted magnetic semiconductors has been comfirmed by X-ray diffraction (XRD), Scanning Electronic Microscope (SEM) and Vibrating sample magnetometer (VSM). The magnetic properties of pure $Zn_{1-x}Co_xO$ is found to be dominated by the ferromagnetic interaction between doped transition metal ions, where by the ferromagnetic coupling strength is simply increased with the concentration(>5%) of the doped transition metal.

Study on the Solubilization of 4-Chlorobenzoic Acid by Aqueous Solutions of Various Cationic, Nonionic, and Mixed Surfactant Systems (양이온성, 비이온성 및 혼합성 계면활성제에 의한 4-클로로벤조산의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Applied Science and Technology
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    • v.31 no.2
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    • pp.244-254
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    • 2014
  • The interactions of 4-chlorobenzoic acid with the micellar system of various cationic, nonionic, and mixed surfactant systems were studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of 4-chlorobenzoic acid into those micellar systems have been measured at various temperatures and various thermodynamic parameters for the solubilization of 4-chlorobenzoic acid have been calculated and analyzed from those changes. The results show that the values of ${\Delta}G^o_s$ are all negative within the measured temperature range and that the values of ${\Delta}H^o_s$ and ${\Delta}S^o_s$ are all positive. The effects of alkyl-group's length of surfactant molecules on the solubilization of 4-chlorobenzoic acid have been also measured. The values of $K_s$ were dependent simultaneously on the alkyl-group's length and the kind of head-group in surfactant molecules. From these changes we can postulate the solubilization site and the degree of interaction of 4-chlorobenzoic acid with the micellar systems.

Chemical Equilibrium between Metalloporphyrins (MTPP and M(o-Cl)TPP) and Basic Ligands(L). (M = $Zn^{2+],\;Cu^{2+},\;Ni^{2+}$: TPP = tetraphenylporphyrin, (o-Cl)TPP = tetrakis (ortho-chlorophenyl)porphyrin: L = imidazole, pyridine, 1-methylimidazole, 2,6-lutidine) (Methalloporphyrin(MTPP 및 M(o-Cl)TPP)과 염기성리간드(L)간의 화학평형. (M = $Zn^{2+},\;Cu^{2+},\;Ni^{2+}$:TPP = tetraphenylporphyrin, (o-Cl)TPP = tetrakis (ortho-chlorophenyl)porphyrin: L = imidazole, pyridine,1-methylimidazole, 2,6-lutidine))

  • Yu Chul Park;Seong Su Kim;Hun Gil Na
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.512-519
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    • 1991
  • The axial ligations of nitrogenous bases (pyridine, imidazole, 1-methylimidazole and 2,6-lutidine) to Zn(II)-, Cu(II)-, and Ni(II)-tetrakis(o-chlorophenyl)porphyrin(o-ClTPP), and -tetraphenylporphyrin (TPP) were investigated in organic solvents $(CH_2Cl_2,\;C_6H_6,\;CH_3NO_2,\;(CH_3)_2CO,\;CHCl_3,\;DMF\;and\;DMSO)$ and at 0.01M of ionic strength. The equilibrium constants for the ligation reactions of methalloporphyrins were determined using spectrophotometric method at 15∼35${\circ}C$. In case of M(II)-TPP the equilibrium constants K were considerably larger than those of M(II)-(o-Cl)TPP, depending on steric effect of the porphyrin. The linear relationships between logK of the axial ligation and $pK_a$ of nitrogenous base were shown in M(II)-TPP, but not in M(II)-(o-Cl)TPP. The stabilities of MTPP(L) were controlled by the reation enthalpy and entropy, while those of M(o-Cl)TPP almost by the reaction entropy. The coordinating power of solvent to the methalloporphyrin were also studied in $CHCl_3,\;(CH_3)_2CO$, DMF and DMSO. From those results the solvent effects on the equilibrium constants were discussed.

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A Thermodynamical Study on the Phase Formation and Sequence by Ion Beam Mixing in Al/Pd System (이온선 혼합에 의한 Al/Pd계의 상형성 및 전이에 관한 열역학적 연구)

  • Choi, Jeong-Dong;Hong, Jin-Seok;Kwak, Joon-Seop;Chi, Eung-Joon;Park, Sang-Wook;Baik, Hong-Koo;Chae, Keun-Hwa;Jung, Sung-Mun;Whang, Chung-Nam
    • Journal of the Korean Vacuum Society
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    • v.2 no.2
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    • pp.209-219
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    • 1993
  • Evaporated Al/Pd thin films were irradiated with various doses to produce intermetallic compounds. In order to study the first phase formation and phase sequence, RBS and TEM studies have been used. It was found that the initial phase formed by irradiation of $5{\times}10^{15}Ar^+/cm^2$ was $Al_3Pd_2$, while $1.5{\times}10^{16}Ar^+/cm^2$ gave the subsequent phase of AlPd. This phenomenon was analysed using effective heat of formation (${\Delta}$H') model. The experimental results agree with that predicted by effective heat of formation model. This model has been extended to predict the first phase formation and phase sequence by ion beam mixing in metal/Si systems as well as metal-metal systems.

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Analysis of Key Parameters for Designing the Spent Nuclear Fuel Disposal Container in Korea (사용후핵연료 처분용기 설계를 위한 주요인자 분석)

  • Choi, Jong-Won;Cho, Dong-Keun;Choi, Hui-Ju
    • Journal of Radiation Protection and Research
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    • v.31 no.1
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    • pp.37-46
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    • 2006
  • For the first step to develop a reference disposal container of spent fuel to be used in a deep geological repository, this paper examined safe dimensions of the disposal container on the points of nuclear criticality and radiation safety and mechanical structural safety and provided basic information for dimensioning the container and configuration of the container components, and establishing the favorable and safe disposal conditions. When the safety factor for stress due to the external loads (hydrostatic and swelling pressure) is taken as 2.0, the safe diameter of the filler material to provide enough container strength under the assumed external loads is found to be 112cm with 13cm spacing between inner baskets in PWR container. Also the thickness of the thinner section between the fuel basket and the surface of the cast insert is determined to be 150 mm. Regarding these dimensions of the container, the PWR fuel container is sketched to accommodate 4 square assemblies or 297 CANDU fuel 297 bundles (33 circle tubes x 9 stacks). However the top and bottom parts need to be checked again through the detail radiation shielding analysis with respects to the emplacement position and handling processes of the disposal container.

Partial Oxidation of Methane for Hydrogen Production over Co and Ni Catalysts (수소생산을 위한 메탄 부분산화용 코발트와 니켈촉매의 반응특성 연구)

  • Lee, Sang-Sik;Hong, Ju-Hwan;Ha, Ho-Jung;Kim, Byung-Kwan;Han, Jong-Dae
    • Korean Chemical Engineering Research
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    • v.48 no.6
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    • pp.776-783
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    • 2010
  • Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. The activities of these catalysts for the partial oxidation of methane was investigated at 1 atm and $CH_4/O_2=2.0$ in the temperature range of $450{\sim}650^{\circ}C$. The reaction activity of $Ni/Al_2O_3$ and $Co/Al_2O_3$ catalysts with different loading was investigated. And the beneficial effects of Ni addition to $Co/Al_2O_3$ and the promotional effects of Ce and La addition to $Ni/Al_2O_3$ and $Co/Al_2O_3$ were investigated. These catalysts were characterized by XRD and SEM/EDX. Comparing catalyst loadings, 10 wt% Co and 10 wt% Ni were found to be optimal at the experimental conditions. The 10 wt% $Ni/Al_2O_3$ and 10 wt% $Co/Al_2O_3$ catalysts in partial oxidation of methane showed $CH_4$ conversions and CO selectivity close to the thermodynamic equilibrium levels, but showed lower $H_2$ selectivity than equilibrium level. The addition of Ni to $Co/Al_2O_3$ exhibited higher $H_2$ selectivity but beneficial effect was not observed in the $CH_4$ conversion. Addition of Ce to $Co/Al_2O_3$ and addition of La to $Ni/Al_2O_3$ a improved the $CH_4$ conversion level and $H_2$ selectivity.

Preparation of Nano Sized Indium Tin Oxide (ITO) Powder with Average Particle Size Below 30 nm from Waste ITO Target by Spray Pyrolysis Process (폐 ITO 타겟으로부터 분무열분해 공정에 의한 평균입도 30 nm 이하의 인듐-주석 산화물 분체 제조)

  • Kim, Donghee;Yu, Jaekeun
    • Resources Recycling
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    • v.27 no.2
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    • pp.24-31
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    • 2018
  • In this study, waste ITO target is dissolved into hydrochloric acid to generate a complex indium-tin chloride solution. Nano sized ITO powder with an average particle size below 30 nm are generated from these raw material solutions by spray pyrolysis process. Also, in this study, thermodynamic equations for the formation of indium-tin oxide (ITO) are established. As the reaction temperature increased from $800^{\circ}C$ to $900^{\circ}C$, the proportion and size of the spherical droplet shape in which nano sized particles aggregated gradually decreased, and the surface structure gradually became densified. When the reaction temperature was $800^{\circ}C$, the average particle size of the generated powder was about 20 nm, and no significant sintering was observed. At a reaction temperature of $900^{\circ}C$, the split of the droplet was more severe than at $800^{\circ}C$, and the rate of maintenance of the initial atomized droplet shape decreased sharply. The average particle size of the powder formed was about 25 nm. The ITO particles were composed of single solid crystals, regardless of reaction temperature. XRD analysis showed that only the ITO phase was formed. Remarkably, the specific surface area decreased by about 30% as the reaction temperature increased from $800^{\circ}C$ to $900^{\circ}C$.