• Title/Summary/Keyword: Thermodynamic Equilibrium

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Open-Loop Responses of Droplet Vaporization to Linear Normal Acoustic Modes

  • Kim, S.Y.;W.S. Yoon
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2004.03a
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    • pp.155-164
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    • 2004
  • In order for studying pressure-coupled dynamic responses of droplet vaporization, open-loop experiment of an isolated droplet vaporization exposed to pressure perturbations in stagnant gaseous environment is numerically conducted, Governing equations are solved for flow parameters at gas and liquid phases separately and thermodynamic parameters at the interfacial boundary are matched for problem closure. For high-pressure effects, vapor-liquid interfacial thermodynamics is rigorously treated. A series of parametric calculations in terms of mean pressure level and wave frequencies are carried out employing a n-pentane droplet in stagnant gaseous nitrogen. Results show that wave instability in view of pressure-coupled vaporization response seems more susceptible at higher pressures and higher wave frequencies. Mass evaporation rate responding to pressure waves is amplified with increase in pressure due to substantial reduction in latent heat of vaporization. Augmentation of perturbation frequency also enhances amplification due to the reduction of phase differences between pressure perturbation and surface temperature fluctuation.

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Influence of Temperature on the Treatment Efficiency of Chlorinated Organic Substances in Groundwater by Permeable Reactive Barrier (염소계 유기화합물로 오염된 지하수의 반응성 투과 벽체 처리 효율에 대한 온도의 영향)

  • Kim, Sun-Hye;Kim, Eun-Zi;Kim, Dong-Su
    • Journal of Korean Society on Water Environment
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    • v.30 no.2
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    • pp.175-183
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    • 2014
  • The influence of temperature on the treatment efficiency of chlorinated organic substances contained in groundwater by permeable reactive barrier which is composed of $Fe^{\circ}$ has been investigated by constructing the Pourbaix diagrams for Fe-$H_2O$ system at different temperatures based on thermodynamic estimation. In aerobic condition, the equilibrium potentials for $Fe^{\circ}/Fe^{2+}$ and $Fe^{2+}/Fe^{3+}$ were observed to increase, therefore, the dechlorination reaction for organic pollutants by $Fe^{\circ}$ was considered to decline with temperature due to the diminished oxidation of reactive barrier. The result for the variations of the ionization fraction of $Fe^{2+}$ and $Fe^{3+}$ ion in the pH range of 0 ~ 2.5 obtained by employing Visual MINTEQ program showed that the ionization fraction of $Fe^{2+}$ increased with pH, however, that of $Fe^{3+}$ decreased symmetrically and the extent of the variation of ionization fraction for both ions was raised as temperature rises. The equilibrium pH for $Fe^{3+}/Fe(OH)_3$ was examined to decrease with temperature so that the treatment efficiency of chlorinated organic substance was expected to decrease with temperature due to the enhanced formation of passivating film in aerobic condition. The change of the reactivity of a specific chemical species with temperature was defined quantitatively based on the area of its stable region in Pourbaix diagram and depending on this the reactivity of $Fe^{3+}$ was shown to decrease with temperature, however, that of $Fe(OH)_3$ was decreased monotonously as temperature is raised for $Fe^{3+}/Fe(OH)_3$ equilibrium system. In anaerobic condition, the equilibrium potential for $Fe^{\circ}/Fe^{2+}$ was observed to rise and the equilibrium pH for $Fe^{2+}/Fe(OH)_2$ were examined to decrease as temperature increases, therefore, similar to that for aerobic condition the efficiency of the dechlorination reaction for organic substances was considered to be diminished when temperature rises because of the reduced oxidation of $Fe^{\circ}$ and increased formation of $Fe(OH)_2$ passivating film.

Studies on the Adsorption and Desorption Characteristics of Cu Ion Using Manganese Nodule as Adsorbent (Mn단괴를 흡착제로 한 Cu이온의 흡착 및 탈착 특성)

  • Kim, Jin-Wha;Kim, Dong-Su
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.3
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    • pp.547-556
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    • 2000
  • A study have been conducted for the adsorption and desorption characteristics of Cu ion using manganese nodule as adsorbent. For 100 ppm Cu ion solution, the adsorbed amount of Cu ion was more than 90 % at equilibrium state. Adsorption was equilibrated in 42 hours the adsorption reaction was shown to be first order reaction. For the desorption reaction of Cu ion in the region of solution pH 3.5~9.5, the desorption was completed in the acidic region, but it has been decreased as the pH was raised. Also, the desorption rate was higher in the acidic region compared with alkaline region. The desorbed amount was decreased as the reaction temperature increased, therefore, the desorption reaction was thought to be exothermic. Also, several thermodynamic properties were calculated based on experimental results and compared with theoretically driven values. To see the effect of complexing agent on the desorption of Cu ion, EDTA was introduced and the des orbed amount increased in the presence of EDTA.

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A Study on the Removal Characteristics of Phenol Using Waste CDQ Dust as Adsorbent (폐CDQ 분진을 흡착제로 한 페놀제거특성에 관한 연구)

  • Kim, Jin-Wha;Lee, Jung-Min;Kim, Dong-Su
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.7
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    • pp.1213-1223
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    • 2000
  • The adsorption characteristics of phenol has been studied by using CDQ (Cokes Drying Quenching) dust as an adsorbent. The adsorption capacity of CDQ dust was shown to be 42% about removal for 300 ppm phenol solution at the equilibrium adsorption time of 60 min. Removal percentage of phenol increased as the initial phenol concentration was raised in the experimental conditions and the adsorption behavior was explained well by Freundlich adsorption isotherm. Kinetic study showed that the adsorption followed 1st, 1.5th, and 2nd-order rate equation in the sequence as the adsorption time passed. Since the adsorption amount of phenol was increased as the adsorption temperature was raised, the adsorption was thought to be endothermic, and several thermodynamic parameters have been calculated based upon experimental data. Adsorbed amount of phenol on CDQ dust changed little according to the variation in the solution pH except for the slight decrease under the strong alkaline condition.

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Review on the Determination of Frumkin, Langmuir, and Temkin Adsorption Isotherms at Electrode/Solution Interfaces Using the Phase-Shift Method and Correlation Constants

  • Chun, Jinyoung;Chun, Jang H.
    • Korean Chemical Engineering Research
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    • v.54 no.6
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    • pp.734-745
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    • 2016
  • This review article described the electrochemical Frumkin, Langmuir, and Temkin adsorption isotherms of over-potentially deposited hydrogen (OPD H) and deuterium (OPD D) for the cathodic $H_2$ and $D_2$ evolution reactions (HER, DER) at Pt, Ir, Pt-Ir alloy, Pd, Au, and Re/normal ($H_2O$) and heavy water ($D_2O$) solution interfaces. The Frumkin, Langmuir, and Temkin adsorption isotherms of intermediates (OPD H, OPD D, etc.) for sequential reactions (HER, DER, etc.) at electrode/solution interfaces are determined using the phase-shift method and correlation constants, which have been suggested and developed by Chun et al. The basic procedure of the phase-shift method, the Frumkin, Langmuir, and Temkin adsorption isotherms of OPD H and OPD D and related electrode kinetic and thermodynamic parameters, i.e., the fractional surface coverage ($0{\leq}{\theta}{\leq}1$) vs. potential (E) behavior (${\theta}$ vs. E), equilibrium constant (K), interaction parameter (g), standard Gibbs energy (${\Delta}G_{\theta}{^{\circ}}$) of adsorption, and rate (r) of change of ${\Delta}G_{\theta}{^{\circ}}$ with ${\theta}$ ($0{\leq}{\theta}{\leq}1$), at the interfaces are briefly interpreted and summarized. The phase-shift method and correlation constants are useful and effective techniques to determine the Frumkin, Langmuir, and Temkin adsorption isotherms and related electrode kinetic and thermodynamic parameters (${\theta}$ vs. E, K, g, ${\Delta}G_{\theta}{^{\circ}}$, r) at electrode/solution interfaces.

Adsorption Equilibrium, Kinetic and Thermodynamic Param (활성탄을 이용한 Acid Green 27의 흡착평형, 동역학 및 열역학 파라미터의 연구)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.55 no.4
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    • pp.514-519
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    • 2017
  • Adsorption characteristics of acid green 27 dye using activated carbon were investigated as function of adsorbent dose, pH, initial concentration, contact time and temperature. Freundlich isotherm explained adsorption of acid green 27 dye very well and Freundlich separation factors (1/n=0.293~0.387) were found that this process could be employed as effective treatment method. Kinetic studies showed that the kinetic data were well described by the pseudo second-order kinetic model. Pseudo second rate constant ($k_2$) decreased with the increase in initial acid green 27 concentration. Activation energy (10.457 kJ/mol) and enthalpy (79.946 kJ/mol) indicated that adsorption process was physisorption and endothermic. Since Gibbs free energy decreased with increasing temperature, spontaneity of adsorption reaction increased with increasing temperature in the temperature range of 298 K~318 K.

Modeling and Measurements of the Activity Coefficients and Solubilities of Amino Acids in the L-valine/electrolyte and L-proline/electrolyte Aqueous Solutions (L-Valine/전해질 및 L-Proline/전해질 수용액에서 아미노산의 활동도계수와 용해도의 측정 및 모델링)

  • Lee, Bong-Seop;Kim, Ki-Chang
    • Korean Chemical Engineering Research
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    • v.50 no.1
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    • pp.93-105
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    • 2012
  • Activity coefficients and solubilities of L-Valine and L-Proline in aqueous solutions containing each of four electrolytes such as 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 amino acid. The measured activity coefficients of electrolytes and amino acids were correlated with the theoretical thermodynamic model presented in the previous work [Korean Chem. Eng. Res. 48(4), 519(2010)]. It was found that the activity coefficients of amino acids and electrolytes described based on the our previous model were well agreeable with experimental data. Also the experimental solubility data of L-Valine and L-Proline were successfully correlated with the thermodynamic relation mentioned in the previous work.

The Physicochemical Properties on the Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구-사염화탄소 용액내에서 헥사메틸벤젠과 여러 전자받게들간의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Kwun Oh Cheun;Kim Myong Ja;Kim Se Kyung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.335-342
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    • 1991
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of 1,3,5-trinitrobenzene, tetrachloro-p-benzoquinone and tetracyanoethylene with hexamethylbenzene in carbon tetrachloride has been investigated by spectrophotometric measurements. The equilibrium constants for the formation of the complexes were obtained at various temperature and pressure, and thermodynamic parameters for the formation of the charge transfer complexes are calculated from these values. The relative stabilities of charge transfer complexes with hexamethylbenzene increase in the order; 1,3,5-trinitrobenzene < tetrachloro-p-benzoquinone < tetracyanoethylene. This may be regarded as an order of relative acidity of these compounds in complexation with hexamethylbenzene and is explained in terms of the negative inductive effect of the ${\pi}$ acceptors. The red-shift at higher pressure, the blue-shift at higher temperature and the relation between pressure and oscillator strength are discussed on the basis of thermodynamic functions.

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The Near Infrared Spectroscopic Studies on the Hydrogen Bonding Ability of Thiopropionamide (티오프로피온 아미드의 수소 결합 능력에 대한 근 적외선 분광학 연구)

  • Ju, Sul-A;Park, Jeunghee;Yoon, Chang-Ju;Choi, Young-Sang
    • Journal of the Korean Chemical Society
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    • v.39 no.11
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    • pp.837-841
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    • 1995
  • Thermodynamic parameters for the hydrogen bonding between thiopropionamide(TPA) and proton donors such as triethylphosphine oxide(TEPO), triphenylphosphine oxide(TPPO), trimethylphosphate(TMP), and tributyl phosphate(TBP) in dilute carbon tetrachloride solution have been measured by near-IR spectroscopy. The νa + amide Ⅱ combination band of TPA has been resolved into two Lorentzian-Gaussian product components which have been identified with monomeric TPA and 1 : 1 hydrogen bonded complex. The equilibrium constants and thermodynamic parameters for the formation of 1 : 1 hydrogen bonded complex have been obtained by the analysis of concentration and temperature dependent spectra. The standard enthalpies for the 1 : 1 hydrogen bonded complex formation of TPA with TEPO, TPPO, TMP, and TBP in CCl4 have been found to be - 21.4, - 16.8, - 12.8, and - 12.9 kJ/mol, respectively. The results are explained by the inductive and steric effects of substituents.

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Isothermal Vapor-Liquid Equilibria at 333.15K and Thermodynamic Excess Properties for the Binary System of Methanol+Dimethyl Carbonate (Methanol+Dimethyl Carbonate 혼합계의 333.15 K 등온 기-액 평형과 열역학 과잉 물성)

  • Han, Kyu-Jin;Park, So-Jin
    • Korean Chemical Engineering Research
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    • v.43 no.3
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    • pp.387-392
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    • 2005
  • Recently, dimethyl carbonate (DMC) is considered as an alternative of MTBE (methyl tert-butyl ether), additive for non-leaded gasoline with their fast biodegradation rate and low toxicity. DMC is usually synthesized so far by oxidative carbonylation of methanol, and recently developed synthetic process is also started with methanol. Since the phase equilibria of the system, consisted of DMC and methanol or other reaction products on different temperature and pressure is necessary for the optimum separation process design and operation. However the reported phase equilibria and physical properties for DMC mixtures in the Dortmund Data Bank (DDB; thermodynamic property data bank) are quite rare. Besides, infinitely dilute properties are not found. In this work, isothermal vapor-liquid equilibria at 333.15 K for methanol+DMC binary system and mixing properties, excess molar volume and viscosity deviation at 298.15 K are directly measured and correlated. Additionally, infinitely dilute activity coefficient of methanol in the DMC solvent at three different temperatures are measured and compared with predicted values using modified UNIFAC (Dortmund).