• Title/Summary/Keyword: Thermodynamics and kinetics

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Removal Characteristics of Sr(II) by Solid-Phase Extractant Prepared by Immobilizing Di-(2-ethylhexyl)phosphoric acid (D2EHPA) and Tri-butyl-phosphate (TBP) in Polysulfone (Polysulfone에 Di-(2-ethylhexyl)phosphoric acid(D2EHPA)와 tri-butyl-phosphate(TBP)를 고정화하여 제조한 고체상 추출제에 의한 Sr(II)의 제거특성)

  • Kam, Sang-Kyu;Jeon, Jin-Woo;Lee, Min-Gyu
    • Journal of Environmental Science International
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    • v.24 no.3
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    • pp.267-274
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    • 2015
  • The feasibility of PS-D2EHPA/TBP beads prepared by immobilizing two extractants D2EHPA and TBP in polysulfone to remove Sr(II) from aqueous solution was investigated in batch system. Batch experiments were carried out to study equilibrium isotherms, kinetics, and thermodynamics. Equilibrium data were fitted using Langmuir, Freundlich, Redlich-Peterson, and Dubinin-Radushkevich equation models at temperatures of 298 K, 313 K, and 328 K. The removal capacity of Sr(II) by PS-D2EHPA/TBP beads obtained from Langmuir model was 2.41 mg/g at 298 K. The experimental data were well represented by pseudo-second-order model. The removal process of Sr(II) by PS-D2EHPA/TBP beads prepared in this study was found to be feasible, endothermic, and spontaneous.

Enhancement effect of phosphate and silicate on water defluoridation by calcined gypsum

  • Al-Rawajfeh, Aiman Eid;Alrawashdeh, Albara I.;Aldawdeyah, Asma;Hassan, Shorouq;Qarqouda, Ruba
    • Advances in environmental research
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    • v.2 no.1
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    • pp.35-49
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    • 2013
  • Research work on removal of fluoride from water, referred to as water defluoridation, has resulted into the development of a number of technologies over the years but they suffer from either cost or efficiency drawbacks. In this work, enhancement effects of phosphate and silicate on defluoridation of water by low-cost Plaster of Paris (calcined gypsum) were studied. To our knowledge, the influence of silicate on defluoridation was not reported. It was claimed, that the presence of some ions in the treated water samples, was decreasing the fluoride removal since these ions compete the fluoride ions on occupying the available adsorption sites, however, phosphate and silicate ions, from its sodium slats, have enhanced the fluoride % removal, hence, precipitation of calcium-fluoro compounds of these ions can be suggested. Percentage removal of $F^-$ by neat Plaster is 48%, the electrical conductance (EC) curve shows the typical curve of Plaster setting which begins at 20 min and finished at 30 min. The addition of phosphate and silicate ions enhances the removal of fluoride to high extent > 90%. Thermodynamics parameters showed spontaneous fluoride removal by neat Plaster and Plaster-silicate system. The percentage removal with time showed second-order reaction kinetics.

An Evaluation of Thermal Stability of Raw Materials in the Vinyl Acetate Polymerization Process (비닐아세테이트 중합공정에서 원료물질의 열적 안정성 평가)

  • Lee, Keun-Won;Han, In-Soo;Lee, Jung-Suk
    • Journal of the Korean Society of Safety
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    • v.25 no.3
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    • pp.61-65
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    • 2010
  • Most of the chemical reactions performed in the chemical industry are exothermic, meaning that thermal energy is released during the reaction. It is also important to understand the thermal hazards such as thermal stabilities and runaway reactions, which are governed by thermodynamics and reaction kinetics of the mixed materials. The paper was described the evaluation of thermal behavior caused by an exothermic batch process in manufacture of the vinyl acetate resin. The aim of the study was to evaluate the thermal stabilities of raw materials with operating conditions such as a reaction inhibitor, heating rate, reaction atmosphere and the mount of methanol charged in the vinyl acetate polymerization process. The experiments were performed in the differential scanning calorimeter(DSC), C 80 calorimeter, and thermal screening unit($TS^u$). It was suggested that we should provide the thermal characteristics for raw materials to present safe precautions with operating conditions in the vinyl acetate polymerization process.

Thermodynamic and experimental analyses of the oxidation behavior of UO2 pellets in damaged fuel rods of pressurized water reactors

  • Jung, Tae-Sik;Na, Yeon-Soo;Joo, Min-Jae;Lim, Kwang-Young;Kim, Yoon-Ho;Lee, Seung-Jae
    • Nuclear Engineering and Technology
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    • v.52 no.12
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    • pp.2880-2886
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    • 2020
  • A small leak occurring on the surface of a fuel rod due to damage exposes UO2 to a steam atmosphere. During this time, fission gas trapped inside the fuel rod leaks out, and the gas leakage can be increased due to UO2 oxidation. Numerous studies have focused on the steam oxidation and its thermodynamic calculation in UO2. However, the thermodynamic calculation of the UO2 oxidation in a pressurized water reactor (PWR) environment has not been studied extensively. Moreover, the kinetics of the oxidation of UO2 pellet also has not been investigated. Therefore, in this study, the thermodynamics of UO2 oxidation under steam injection due to a damaged fuel rod in a PWR environment is studied. In addition, the diminishing radius of the UO2 pellet with time in the PWR environment was calculated through an experiment simulating the initial time of steam injection at the puncture.

Isotherms, Kinetics and Thermodynamic Parameters Studies of New Fuchsin Dye Adsorption on Granular Activated Carbon (입상 활성탄에 대한 New Fuchsin 염료흡착의 등온선, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.25 no.6
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    • pp.632-638
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    • 2014
  • Batch adsorption studies including equilibrium, kinetics and thermodynamic parameters for the adsorption of new fuchsin dye using granular activated carbon were investigated with varying the operating variables such as initial concentration, contact time and temperature. Equilibrium adsorption data were fitted into Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherms. Adsorption equilibrium was mostly well described by Langmuir Isotherm. From the estimated separation factor of Langmuir ($R_L$ = 0.023), and Freundlich (1/n = 0.198), this process could be employed as an effective treatment for the adsorption of new fuchsin dye. Also based on the adsorption energy (E = 0.002 kJ/mol) from Dubinin-Radushkevich isotherm and the adsorption heat constant (B = 1.920 J/mol) from Temkin isotherm, this adsorption is physical adsorption. From kinetic experiments, the adsorption reaction processes were confirmed following the pseudo second order model with good correlation. The intraparticle diffusion was a rate controlling step. Thermodynamic parameters including changes of free energy, enthalpy, and entropy were also calculated to predict the nature of adsorption. The change of enthalpy (92.49 kJ/mol) and activation energy (11.79 kJ/mol) indicated the endothermic nature of adsorption processes. The change of entropy (313.7 J/mol K) showed an increasing disorder in the adsorption process. The change of free energy found that the spontaneity of process increased with increasing the adsorption temperature.

A comparative study on defluoridation capabilities of biosorbents: Isotherm, kinetics, thermodynamics, cost estimation and regeneration study

  • Yihunu, Endashaw Workie;Yu, Haiyan;Junhe, Wen;Kai, Zhang;Teffera, Zebene Lakew;Weldegebrial, Brhane;Limin, Ma
    • Environmental Engineering Research
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    • v.25 no.3
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    • pp.384-392
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    • 2020
  • The presence of high fluoride concentration (> 1.5 mg/L) in water causes serious health problems such as fluorosis, infertility, brain damage, etc., which are endemic to many places in the world. This study has investigated the fluoride removal capacity of the novel activated biochar (BTS) and hydrochar (HTS) using Teff (Eragrostis tef) straw as a precursor. Activated biochar with mesoporous structures and large specific surface area of 627.7 ㎡/g were prepared via pyrolysis process. Low-cost carbonaceous hydrochar were also synthesized by an acid assisted hydrothermal carbonization process. Results obtained from both adsorbents show that the best local maximum fluoride removal was achieved at pH 2, contact time 120 min and agitation speed 200 rpm. The thermodynamic studies proved that the adsorption process was spontaneous and exothermic in nature. Both adsorbents equilibrium data fitted to Langmuir isotherm. However, Freundlich isotherm fitted best for BTS. The maximum fluoride loading capacity of BTS and HTS was found to be 212 and 88.7 mg/g, respectively. The variation could primarily be attributed to a relatively larger Surface area for BTS. Hence, to treat fluoride contaminated water, BTS can be promising as an effective adsorbent.

A study on the interfacial reactions between electroless Ni-P UBM and 95.5Sn-4.0Ag-0.5Cu solder bump (무전해 Ni-P UBM과 95.5Sn-4.0Ag-0.5Cu 솔더와의 계면반응 및 신뢰성에 대한 연구)

  • ;;Sabine Nieland;Adreas Ostmann;Herbert Reich
    • Proceedings of the International Microelectronics And Packaging Society Conference
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    • 2002.05a
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    • pp.85-91
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    • 2002
  • Even though electroless Hi and Sn-Ag-Cu solder are widely used materials in electronic packaging applications, interfacial reactions of the ternary Ni-Cu~Sn system have not been known well because of their complexity. Because the growth of intermetallics at the interface affects reliability of solder joint, the intermetallics in Ni-Cu-Sn system should be identified, and their growth should be investigated. Therefore, in present study, interfacial reactions between electroless Ni UB7f and 95.5Sn-4.0Ag-0.5Cu alloy were investigated focusing on morphology of the IMCs, thermodynamics, and growth kinetics. The IMCs that appear during a reflow and an aging are different each other. In early stage of a reflow, ternary IMC whose composition is Ni$_{22}$Cu$_{29}$Sn$_{49}$ forms firstly. Due to the lack of Cu diffusion, Ni$_{34}$Cu$_{6}$Sn$_{60}$ phase begins growing in a further reflow. Finally, the Ni$_{22}$Cu$_{29}$Sn$_{49}$ IMC grows abnormally and spalls into the molten solder. The transition of the IMCs from Ni$_{22}$Cu$_{29}$Sn$_{49}$ to Ni$_{34}$Cu$_{6}$Sn$_{60}$ was observed at a specific temperature. From the measurement of activation energy of each IMC, growth kinetics was discussed. In contrast to the reflow, three kinds of IMCs (Ni$_{22}$Cu$_{29}$Sn$_{49}$, Ni$_{20}$Cu$_{28}$Au$_{5}$, and Ni$_{34}$Cu$_{6}$Sn$_{60}$) were observed in order during an aging. All of the IMCs were well attached on UBM. Au in the quaternary IMC, which originates from immersion Au plating, prevents abnormal growth and separation of the IMC. Growth of each IMC is very dependent to the aging temperature because of its high activation energy. Besides the IMCs at the interface, plate-like Ag3Sn IMC grows as solder bump size inside solder bump. The abnormally grown Ni$_{22}$Cu$_{29}$Sn$_{49}$ and Ag$_3$Sn IMCs can be origins of brittle failure.failure.

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Comparison of Microstructure and Electrical Conductivity of Ni/YSZ and Cu/YSZ Cathode for High Temperature Electrolysis (고온수전해용 Ni/YSZ와 Cu/YSZ 환원극의 미세구조 및 전기전도도 비교)

  • Kim, Jong-Min;Shin, Seock-Jae;Woo, Sang-Kook;Kang, Kae-Myung;Hong, Hyun-Seon
    • Korean Journal of Materials Research
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    • v.18 no.7
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    • pp.384-388
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    • 2008
  • Hydrogen production via high high-temperature steam electrolysis consumes less electrical energy than compared to conventional low low-temperature water electrolysis, mainly due to the improved thermodynamics and kinetics at elevated temperaturetemperatures. The elementalElemental powders of Cu, Ni, and YSZ are were used to synthesize high high-temperature electrolysis cathodecathodes, of Ni/YSZ and Cu/YSZ composites, by mechanical alloying. The metallic particles of the composites were uniformly covered with finer YSZ particles. Sub-micron sized pores are were homogeneously dispersed in the Ni/YSZ and Cu/YSZ composites. In this study, The cathode materials were synthesized and their Characterizations properties were evaluated in this study: It was found that the better electric conductivity of the Cu/YSZ composite was measured improved compared tothan that of the Ni/YSZ composite. Slight A slight increase in the resistance can be produced for in a Cu/YSZ cathode by oxidation, but it this is compensated offset for by a favorable thermal expansion coefficient. Therefore, Cu/YSZ cermet can be adequately used as a suitable cathode material of in high high-temperature electrolysis.

Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures (압력변화에 따른 퀴놀린 유도체와 p-치환 염화벤조일류의 속도론적 연구)

  • Jong-Wan Lim;Se-Kyong Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.206-212
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    • 2003
  • The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

Prediction of Pathway and Toxicity on Dechlorination of PCDDs by Linear Free Energy Relationship (다이옥신의 환원적 탈염화 분해 경로와 독성 변화예측을 위한 LFER 모델)

  • Kim, Ji-Hun;Chang, Yoon-Seok
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.2
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    • pp.125-131
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    • 2009
  • Reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs) and its toxicity change were predicted by the linear free energy relationship (LFER) model to assess the zero-valent iron (ZVI) and anaerobic dechlorinating bacteria (ADB) as electron donors in PCDDs dechlorination. Reductive dechlorination of PCDDs involves 256 reactions linking 76 congeners with highly variable toxicities, so is challenging to assess the overall effect of this process on the environmental impact of PCDD contamination. The Gibbs free energies of PCDDs in aqueous solution were updated to density functional theory (DFT) calculation level from thermodynamic results of literatures. All of dechlorination kinetics of PCDDs was evaluated from the linear correlation between the experimental dechlorination kinetics of PCDDs and the calculated thermodynamics of PCDDs. As a result, it was predicted that over 100 years would be taken for the complete dechlorination of octachlorinated dibenzo-p-dioxin (OCDD) to non-chlorinated compound (dibenzo-p-dioxin, DD), and the toxic equivalent quantity (TEQ) of PCDDs could increase to 10 times larger from initial TEQ with the dechlorination process. The results imply that the single reductive dechlorination using ZVI or ADB is not suitable for the treatment strategy of PCDDs contaminated soil, sediment and fly ash. This LFER approach is applicable for the prediction of dechlorination process for organohalogen compounds and for the assessment of electron donating system for treatment strategies.