• Title/Summary/Keyword: thermodynamic model

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Adsorption Equilibrium, Kinetics and Thermodynamics Studies of Malachite Green Using Zeolite (제올라이트를 이용한 말라카이트 그린의 흡착평형, 동력학 및 열역학 연구)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.18 no.1
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    • pp.76-82
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    • 2012
  • The paper includes utlization of zeolite as potential adsorbent to remove a hazardous malachite green from waste water. The adsorption studies were carried out at 298, 308 and 318 K and effects of temperature, contact time, initial concentration on the adsorption were measured. On the basis of adsorption data Langmuir and Freundlich adsorption isotherm model were also confirmed. The equilibrium process was described well by Freundlich isotherm model, showing a selective adsorption by irregular energy of zeolite surface. From determined isotherm constants, zeolite could be employed as effective treatment for removal of malachite green. From kinetic experiments, the adsorption process followed the pseudo second order model, and the adsorption rate constant ($k_2$) decreased with increasing initial concentration of malachite green. Thermodynamic parameters like activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption. The activation energy calculated from Arrhenius equation indicated that the adsorption of malachite green on the zeolite was physical process. The negative free energy change (${\Delta}G^{\circ}$ =-6.47~-9.07 kJ/mol) and the positive enthalpy change (${\Delta}H^{\circ}$ = +32.414 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption in the temperature range 298~318 K.

Comparative Study on the Estimation of CO2 absorption Equilibrium in Methanol using PC-SAFT equation of state and Two-model approach. (메탄올의 이산화탄소 흡수평형 추산에 대한 PC-SAFT모델식과 Two-model approach 모델식의 비교연구)

  • Noh, Jaehyun;Park, Hoey Kyung;Kim, Dongsun;Cho, Jungho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.18 no.10
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    • pp.136-152
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    • 2017
  • The thermodynamic models, PC-SAFT (Perturbed-Chain Statistical Associated Fluid Theory) state equation and the Two-model approach liquid activity coefficient model NRTL (Non Random Two Liquid) + Henry + Peng-Robinson, for modeling the Rectisol process using methanol aqueous solution as the $CO_2$ removal solvent were compared. In addition, to determine the new binary interaction parameters of the PC-SAFT state equations and the Henry's constant of the two-model approach, absorption equilibrium experiments between carbon dioxide and methanol at 273.25K and 262.35K were carried out and regression analysis was performed. The accuracy of the newly determined parameters was verified through the regression results of the experimental data. These model equations and validated parameters were used to model the carbon dioxide removal process. In the case of using the two-model approach, the methanol solvent flow rate required to remove 99.00% of $CO_2$ was estimated to be approximately 43.72% higher, the cooling water consumption in the distillation tower was 39.22% higher, and the steam consumption was 43.09% higher than that using PC-SAFT EOS. In conclusion, the Rectisol process operating under high pressure was designed to be larger than that using the PC-SAFT state equation when modeled using the liquid activity coefficient model equation with Henry's relation. For this reason, if the quantity of low-solubility gas components dissolved in a liquid at a constant temperature is proportional to the partial pressure of the gas phase, the carbon dioxide with high solubility in methanol does not predict the absorption characteristics between methanol and carbon dioxide.

A Study of Fluoride Adsorption in Aqueous Solution Using Iron Sludge based Adsorbent at Mine Drainage Treatment Facility (광산배수 정화시설 철 슬러지 기반 흡착제를 활용한 수용액상 불소 흡착에 관한 연구)

  • Lee, Joon Hak;Kim, Sun Joon
    • Economic and Environmental Geology
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    • v.54 no.6
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    • pp.709-716
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    • 2021
  • In this study, an adsorbent prepared by natural drying of iron hydroxide-based sludge collected from settling basin at a mine drainage treatment facility located in Gangneung, Gangwon-do was used to remove fluoride in an artificial fluoride solution and mine drainage, and the adsorption characteristics of the adsorbent were investigated. As a result of analyzing the chemical composition, mineralogical properties, and specific surface area of the adsorbent used in the experiment, iron oxide (Fe2O3) occupies 79.2 wt.% as the main constituent, and a peak related to calcite (CaCO3) in the crystal structure analysis was analyzed. It was also identified that an irregular surface and a specific surface area of 216.78 m2·g-1. In the indoor batch-type experiment, the effect of changes in reaction time, pH, initial fluoride concentration and temperature on the change in adsorption amount was analyzed. The adsorption of fluoride showed an adsorption amount of 3.85 mg·g-1 16 hours after the start of the reaction, and the increase rate of the adsorption amount gradually decreased. Also, as the pH increased, the amount of fluoride adsorption decreased, and in particular, the amount of fluoride adsorption decreased rapidly around pH 5.5, the point of zero charge at which the surface charge of the adsorbent changes. Meanwhile, the results of the isotherm adsorption experiment were applied to the Langmuir and Freundlich isotherm adsorption models to infer the fluoride adsorption mechanism of the used adsorbent. To understand the thermodynamic properties of the adsorbent using the Van't Hoff equation, thermodynamic constants 𝚫H° and 𝚫G° were calculated using the adsorption amount information obtained by increasing the temperature from 25℃ to 65℃ to determine the adsorption characteristics of the adsorbent. Finally, the adsorbent was applied to the mine drainage having a fluoride concentration of about 12.8 mg·L-1, and the fluoride removal rate was about 50%.

Surface Complexation Modeling of Cadmium Sorption onto Synthetic Goethite and Quartz (표면착물 모델을 이용한 합성 침철광과 석영의 카드뮴 흡착 모사)

  • Ok, Yong-Sik;Jung, Jin-ho;Lee, Ok-Min;Lim, Soo-kil;Kim, Jeong-Gyu
    • Korean Journal of Soil Science and Fertilizer
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    • v.36 no.4
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    • pp.210-217
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    • 2003
  • An alternative method to the empirical approach such as Langmuir and Freundlich model, surface complexation model using thermodynamic database is used to simulate adsorption behavior of cadmium for oxide minerals. Sorption of cadmium onto amorphous silica ($SiO_2$) and synthetic goethite (${\alpha}$-FeOOH) at various conditions of pH, initial cadmium loading, oxide concentration, and ionic strength, were investigated. For both oxide minerals, increasing cadmium concentration resulted in right shifting of the sorption curve of cadmium as the function of pH. The $pH_{50}$, where 50% of cadmium sorbed, of goethite (pH 5.25) was much smaller than that of the silica (pH 7.83). The sorption of cadmium onto both minerals were not affected by the background ion strength from $10^{-1}$ to $10^{-2}$ M of $KNO_3$. It indicated that the binding affinity of goethite surface for cadmium is much stronger than that of silica. The strong affinity of oxide mineral for cadmium can be explained by the existence of coordination or covalent bond between cadmium and surface of it.

Application of Suggested Equations to determine the Elastic Constants of A Transversely Isotropic Rock from Single Specimen (평면이방성 암석의 단일시험편에서 탄성상수 결정에 제안된 수식들의 적용연구)

  • Park, Chul-Whan;Park, Chan;Jung, Yong-Bok;Park, Eui-Seob
    • Tunnel and Underground Space
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    • v.20 no.3
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    • pp.153-168
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    • 2010
  • A fifth equation is required to determine the five independent elastic constants of a transversely isotropic rock from compression test of a single specimen. As an approximation proposed by Saint-Venant has been used for long time, it may cause an erroneous result in some cases, especially for specimen with low angle of anisotropy. Three equations were suggested replacing this traditional equation and proved to be applicable by the model analysis in the previous studies. As Saint-Venant's approximation is turned out the same as the first one of them, it has the characteristics that the apparent Young's modulus is monotonously increasing according to the anisotropic angle. The methodology to analyze the elastic constants from four independent strain measurements by uniaxial compressive test of a single standard specimen is concisely described, and the necessity and compatibility of new suggested equations are discussed. Saint-Venant's approximation can determine the elastic constants close to true values and other equations may be unnecessary in specimens with medium to large angle. Nevertheless, they may become applicable because they can produce the almost same amount. For the specimens of small angle of anisotropy, Saint-Venant's approximation may result in out of general ranges or thermodynamic constraints, but other suggested equations can produce the almost true value. Thus they can be applied before other alternative equation is known. The guide map constructed by model study may decide the most compatible one of the three equations.

Non-Local Plasticity Constitutive Relation for Particulate Composite Material Using Combined Back-Stress Model and Shear Band Formation (비국부 이론을 이용한 입자 강화 복합재 이중후방응력 소성 구성방정식 모델 및 전단밴드 분석)

  • Yun, Su-Jin;Kim, Shin Hoe;Park, Jae-Beom;Jung, Gyoo Dong
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.38 no.10
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    • pp.1057-1068
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    • 2014
  • This paper proposes elastic-plastic constitutive relations for a composite material with two phases-inclusion and matrix phases-using a homogenization scheme. A thermodynamic framework is employed to develop non-local plasticity constitutive relations, which are specifically represented in terms of the second-order gradient terms of the internal state variables. A combined two back-stress evolution equation is also established and the degradation of the state and internal variables is expressed by continuum damage mechanics in terms of the damage factor. Then, deformation localization is analyzed; the analysis results show that the proposed model yields a wide range of shear band formation behaviors depending on the evolution of the specific internal state variables. The analysis results also show good agreement with the results of simplified Rice instability analyses.

Nitrate and Phosphate Adsorption Properties by Aminated Vinylbenzyl Chloride Grafted Polypropylene Fiber (아민형 PP-g-VBC의 NO3-N과 PO4-P 흡착특성)

  • Lee, Yong-Jae;Song, Jee-June;Na, Choon-Ki
    • Journal of Korean Society of Environmental Engineers
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    • v.38 no.10
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    • pp.543-550
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    • 2016
  • Amine-type PP-g-VBC-EDA adsorbent, which possesses anionic exchangeable function, was prepared through photoinduced graft polymerization of vinylbenzyl chloride (VBC) onto polypropylene non-woven fabric and subsequent amination reaction using ethylenediamine (EDA). Adsorption characteristics of anionic nutrients on the PP-g-VBC-EDA adsorbent have been studied by batch adsorption experiments. The equilibrium data well fitted the Langmuir isotherm model, and the maximum monolayer sorption capacity was found to be 59.9 mg/g for $NO_3-N$ and 111.4 mg/g for $PO_4-P$. The adsorption energies were higher than 8 kJ/mol indicating anion-exchange process as the primary adsorption mechanism. The pseudo-second order kinetic model described well the kinetic data and resulted in the activation energy of 9.8-36.7 kJ/mol suggesting that the overall rates of $NO_3-N$ and $PO_4-P$ adsorption are controlled by the chemical process. Thermodynamic parameters such as ${\Delta}G^o$, ${\Delta}H^o$ and ${\Delta}S^o$ indicated that the adsorption nature of PP-g-VBC-EDA for anionic nutrients is spontaneous and exothermic. The PP-g-VBC-EDA could be regenerated by washing with 0.1 N HCl.

Estimation of Denitrification in the Ganghwa Tidal Flat by a Pore Water Model (공극수 모델로 추정한 강화도 갯벌의 탈질산화 작용)

  • Na, Tae-Hee;Lee, Tong-Sup
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.10 no.1
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    • pp.56-68
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    • 2005
  • We measured nitrate and other nutrients in sediment pore waters retrieved from three sites at the southern upper-tidal flats of the Ganghwa Island. Denitrification rate is estimated by applying a simple 1-D model to the nitrate profiles. Results from Jangwha and Dongmak sites are $7.8{\sim}9.4{\times}10^{-7}{\mu}mol{\cdot}cm^{-2}{\cdot}sec^{-1}$, and $1.4{\sim}3.6{\times}10^{-7}{\mu}mol{\cdot}cm^{-2}{\cdot}sec^{-1}$, respectively. Rates are comparable to those reported around the world in an order of magnitude. Denitrification was lower in summer. The rates were about 1.5 times higher at site where the surface sediments consist of relatively coarser particles. This implies that particle size would control the reactant supply to the subsurface sediment. One may claim the denitrification as an evidence of the biogeochemical purification function of tidal flat. However, the purification seems not a general attribute of a tidal flat when whole system is scrutinized by a thermodynamic criterion. Currently the term 'tidal flat' is used when describing the diverse coastal wetlands such as salt marshes, sandy tidal flats and muddy tidal flats, which exhibit quite different ecological functions. Thus it is worthy of mentioning that the classification of coastal wetlands on the basis of sedimentological characteristics and biogeochemical functions should facilitate our understanding.

LES Investigation on The Cryogenic Nitrogen Injection of Swirl Injector Under Supercritical Envionment (초임계 환경에서 와류형 분사기의 극저온 질소 분사 LES 연구)

  • Kang, JeongSeok;Heo, JunYoung;Sung, Hong-Gye;Yoon, YoungBin
    • Journal of the Korean Society for Aeronautical & Space Sciences
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    • v.44 no.4
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    • pp.343-351
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    • 2016
  • Cryogenic spray characteristics of a nitrogen swirl injector operating in supercritical environment have been numerically investigated. By comparing the equation of states(EOS) used for supercritical condition, SRK EOS was applied to predict the nitrogen thermodynamic property under supercritical environment. A Chung's method was implemented for the calculation of viscosity and conductivity and Takahashi's correlation based on Fuller's Theorem was implemented for the calculation of diffusion coefficient. By injecting the nitrogen with 5 bar differential pressure into 50 bar chamber filled with nitrogen, numerical simulation has been conducted. The dynamic Smagorinsky sub-grid scale (SGS) model has been compared with the algebraic Smagorinsky SGS model using FFT frequency analysis. The instability at the liquid film and gas core inside injector and the propagation of pressure oscillation into the injector has been investigated. The spreading angle of swirl injector obtained by numerical calculation has been validated with experimental result.

Adsorption Characteristics of Coconut Shell-based Granular Activated Carbon on a Basic Dye Basic Blue 3 (염기성 염료 Basic Blue 3에 대한 야자계 입상활성탄의 흡착 특성)

  • Park, Ha Neul;Choi, Han Ah;Won, Sung Wook
    • Korean Chemical Engineering Research
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    • v.56 no.1
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    • pp.96-102
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    • 2018
  • In this study, adsorption characteristics of coconut shell-based granular activated carbon (CS-GAC) on Basic Blue 3 (BB3) were evaluated. As the dosage of CS-GAC increased, the removal efficiency of BB3 tended to increase and the initial dye concentration of 50 mg/L was completely removed at 0.2 g dosage. Adsorption equilibrium achieved within 270 and 420 min at the initial concentrations of 25 and 50 mg/L, respectively, and the experimental data were represented by the pseudo-second-order model. The maximum uptakes ($q_{max}$) predicted by the Langmuir model were 34.45, 46.63 and 53.10 mg/g at 298, 308 and 318 K, respectively. The $q_{max}$ value increased as the temperature increased. Also, the Gibbs free energy (${\Delta}G$) was changed to -7.37, -8.19 and -10.40 kJ/mol with increasing temperature. The enthalpy change (${\Delta}H$) and the entropy change (${\Delta}S$) were 34.47 kJ/mol and 0.15 J/mol K, respectively. Therefore adsorption of BB3 by CS-GAC was spontaneous and endothermic.