• Title/Summary/Keyword: 화학반응 메카니즘

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Analysis for Adsorption Equilibrium, Kinetic and Thermodynamic Parameters of Aniline Blue Using Activated Carbon (활성탄을 이용한 아닐린 블루의 흡착평형, 동역학 및 열역학 파라미터에 대한 해석)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.57 no.5
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    • pp.679-686
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    • 2019
  • Characteristics of adsorption equilibrium, kinetic and thermodynamic of aniline blue onto activated carbon from aqueous solution were investigated as function of initial concentration, contact time and temperature. Adsorption isotherm of aniline blue was analyzed by Langmuir, Freundlich, Redlich-Peterson, Temkin and Dubinin-Radushkevich models. Langmuir isotherm model fit better with isothermal data than other isotherm models. Estmated Langmuir separation factors ($R_L=0.036{\sim}0.068$) indicated that adsorption process of aniline blue by activated carbon could be an effective treatment method. Adsorption kinetic data were fitted to pseudo first order model, pseudo second order model and intraparticle diffusion models. The kinetic results showed that the adsorption of aniline blue onto activated carbon well followed pseudo second-order model. Adsorption mechanism was evaluated in two steps, film diffusion and intraparticle diffusion, by intraparticle diffusion model. Thermodynamic parameters such as Gibbs free energy, enthalpy and entropy for adsorption process were estimated. Enthalpy change (48.49 kJ/mol) indicated that this adsorption process was physical adsorption and endothermic. Since Gibbs free energy decreased with increasing temperature, the adsorption reaction became more spontaneously with increasing temperature. The isosteric heat of adsorption indicated that there is interaction between the adsorbent and the adsorbate because the energy heterogeneity of the adsorbent surface.

Adsorption Characteristics of Reactive Red 120 by Coal-based Granular Activated Carbon : Isotherm, Kinetic and Thermodynamic Parameters (석탄계 입상활성탄에 의한 Reactive Red 120의 흡착 특성 : 등온선, 동력학 및 열역학 파라미터)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.31 no.2
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    • pp.164-171
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    • 2020
  • Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich's equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (RL = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (RL = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich's equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△Hx = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△Hx < 80 kJ/mol).

The Methane Production from Organic Waste on Single Anaerobic Digester Equipped with MET (Microbial Electrochemical Technology) (미생물 전기화학 기술이 설치된 단일 혐기성소화조에서 유기성폐기물로부터 메탄생성)

  • Park, Jungyu;Tian, Dongjie;Lee, Beom;Jun, Hangbae
    • Journal of Korean Society of Environmental Engineers
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    • v.38 no.4
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    • pp.201-209
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    • 2016
  • Theoretical maximum methane yield of glucose at STP (1 atm, $0^{\circ}C$) is 0.35 L $CH_4/g$ COD. However, most researched actual methane yields of anaerobic digester (AD) on lab scale is lower than theoretical ones. A wide range of them have been reported according to experiments methods and types of organic matters. Recent year, a MET (Microbial electrochemical technology) is a promising technology for producing sustainable bio energies from AD via rapid degradation of high concentration organic wastes, VFAs (Volatile Fatty Acids), toxic materials and non-degradable organic matters with electrochemical reactions. In this study, methane yields of food waste leachate and sewage waste sludge were evaluated by using BMP (Biochemical Methane Potential) and continuous AD tests. As the results, methane production volume from the anaerobic digester equipped with MET (AD + MET) was higher than conventional AD in the ratio of 2 to 3 times. The actual methane yields from all experiments were lower than those of theoretical value of glucose. The methane yield, however, from the AD + MET occurred similar to the theoretical one. Moreover, biogas compositions of AD and AD + MET were similar. Consequently, methane production from anaerobic digester with MET increased from the result of higher organic removal efficiency, while, further researches should be required for investigating methane production mechanisms in the anaerobic digester with MET.

Electrochemical Properties of Molydenum (V) Complexes with Multidentate Ligands Containing Nitrogen or / and Oxygen Donor Atom (질소, 산소 주게원자 리간드를 가진 몰리브덴 (V) 착물의 전기화학적인 성질)

  • Sang Oh OH;Soo Gyun ROH
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.484-495
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    • 1989
  • Reactions of $(Et_4N)_2[MoOCl_5]$ with multidentate ligands containing nitrogen or/and oxygen donor atom (EDTA, DTPA, IDA, CyDTA, OX) produce a series of binuclear molybdate (V) complexes. The prepared Mo (V) complexes has been identified by Elemental Analysis, Infrared Spectra, Proton Magnetic Resonance Spectra, and Electronic Spectra. The electrochemical reduction mechanism has been studied by Cyclic voltammetry, Controlled Potential Coulometry, and Spectrophotometry in pH 3.571-10.375 acetate, borate, phosphate/sodium hydroxide, phosphate, ammonium/ammonia buffers. The cyclic voltammogram of the Mo-EDTA, DTPA, IDA, CyDTA complexes at pH < ca. 6.00 have shown two reduction waves. The first reduction wave shows two electron process and the second reduction wave shows two electron process. The cyclic voltammogram of the Mo-EDTA, DTPA, IDA, CyDTA complexes at pH < ca. 8.00 has shown one reduction wave. This reduction wave show four electron process. The cyclic voltammogram of the Mo-OX complex at pH < ca. 7.2 has shown one reduction wave. This reduction wave show four electron process.

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Kinetic Study of Proton Exchange between Al($H_2O$)$_6^{3+}$ Ion and Bulk Water Molecules (Ⅰ) (Al($H_2O$)$_6^{3+}$ 이온과 물 용매 분자 사이에서의 수소 이온 교환의 반응속도론적 연구 (Ⅰ))

  • Moon-Hwan Cho;Jin-Ho Kim;Chang-Ju Yoon
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.436-442
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    • 1988
  • The $^1H-nmr$ lineshapes of $H_2O$ in the solution containing $Al^{3+}$ ion have been measured as a function of temperature and $H^+$-ion concentration. Above [$H^+$] = 0.06, the lineshape were analyzed by the uncoupled two-site exchange model. From the proton exchange rate between hexaaquaaluminium ion and bulk water as a function of H-ion concentration. These kinetic data could be fitted to a following linear rate law; that is; 1/${\tau}$ = k$_1$/12 + $k_2$[$H^+$]/6. The following proton exchange parameters were obtained; $k_1^{298}$ = 38.5s$^{-1}$ ${\{Delta}H_1^{\neq}$ = $42.9kJ mole^{-1}$ ${\{Delta}S_1^{\neq}$ = -48.6J $mole^{-1}K^{-1}$ $k_2^{298}$ = $172s^{-1}mole^{-1}$ ${\{Delta}H_2^{\neq}$ = 27.8kJ $mole^{-1}$ ${\{Delta}S_2^{\neq}$ = -90.3J $mole^{-1}K^{-1}$ These activation parameters are indicating an associative interchange, Ia, mechanism for the acid-hydrolysis of hexaaquaaluminium ion and the proton exchange between the hydration spheres of $Al^{3+}$ and $H^+$.

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Detonation Characteristics of L. P. G /$O_2$Gas Mixture and the Self-Ignition Condition for the Formation of Detonative Wave (액화석유 가스 (L. P. G) 와 산소 혼합물의 폭발특성 및 점화조건에 관한 연구)

  • Sung Nak Choi;Kyu Sun Shim;Un Sik Kim;Sock Sung Yun;Ung Kim
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.394-402
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    • 1986
  • Detonation reaction in L.P.G./$O_2$ mixture gas has been investigated over the L.P.G. concentration range of 3∼45 volume%. The variation of detonation velocity with mixture ratio is very interesting as it shows and inflection point near at the stoichiometric ratio. This might be ascribed to the fact that the detonation reactions at fuel-rich condition and fuel-lean condition proceed via different mechanisms. The maximum detonation velocity of 2.65km/sec occurs not at stoichiometric ratio(${\phi}$=1) but at fuel-rich condition (${\phi}$=1.57). Assuming that a stable detonation wave must propagates with the constant velocity, The upper and lower limit of detonation were determined and found to be 40.0 and 3.40 L.P.G. volume% respectively. The shock-heating technique was also utilized for the measurement of self-ignition temperature onsetting a stable detonation wave at varous mixture ratios. The self-ignition temperature at stoichiometric ratio is $742{\pm}3{\circ}K$ and the self-ignition temperature increases as the mixture ratio deviates from the stoichiometric condition.

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Characteristics and Parameters for Adsorption of Carbol Fuchsin Dye by Coal-based Activated Carbon: Kinetic and Thermodynamic (석탄계 활성탄에 의한 Carbol Fuchsin의 흡착 특성과 파라미터: 동력학 및 열역학)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.32 no.3
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    • pp.283-289
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    • 2021
  • Adsorption characteristics of carbol fuchsin (CF) dye by coal-based activated carbon (CAC) were investigated using pH, initial concentration, temperature and contact time as adsorption variables. CF dissociates in water to have a cation, NH2+, which is bonded to the negatively charged surface of the activated carbon in the basic region by electrostatic attraction. Under the optimum condition of pH 11, 96.6% of the initial concentration was adsorbed. Isothermal adsorption behavior was analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models. Langmuir's equation was the best fit for the experimental results. Therefore, the adsorption mechanism was expected to be adsorbed as a monolayer on the surface of activated carbon with a uniform energy distribution. From the evaluated Langmuir's dimensionless separation coefficients (RL = 0.503~0.672), it was found that CF can be effectively treated by activated carbon. The adsorption energies determined by Temkin and Dubinin-Radushkevich models were E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. Therefore, the adsorption process was physical (E < 20 J/mol, B < 8 kJ/mol). The experimental result of adsorption kinetics fit better the pseudo second order model. In the adsorption reaction of CF dye to CAC, the negative free energy change increased as the temperature increased. It was found that the spontaneity also increased with increasing temperature. The positive enthalpy change (40.09 kJ/mol) indicated an endothermic reaction.

Preparation of Cr2O3/AP Composites and their Thermal Decomposition Characteristics (Cr2O3/AP 복합체 제조 및 그 열분해 특성)

  • Jung, Jae-Yun;Kim, Jae-Kyeong;Shim, Hong-Min;Kim, Hyoun-Soo;Koo, Kee-Kahb
    • Applied Chemistry for Engineering
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    • v.26 no.2
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    • pp.145-153
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    • 2015
  • $Cr_2O_3/AP$ (ammonium perchlorate) energetic composites were prepared by a method of solvent/anti-solvent. XRD analysis revealed that the crystalline structure of AP in $Cr_2O_3/AP$ composites is the same as that of pure AP. SEM photomicrograph shows that an average size of cuboid $Cr_2O_3/AP$ composites is approximately $2.5{\mu}m$. TGA analysis shows that the addition of submicron $Cr_2O_3$ particles into AP lowers the HTD (high-temperature decomposition) compared to that of neat AP and the activation energy of the $Cr_2O_3/AP$ composites was calculated by the isoconversional Starlink method. Considering changes in the activation energy, the decomposition reaction mechanism of AP was suggested as follows; the decomposition with the formation of nucleation sites renders formation of porous structure in the composites up to conversion of about 0.25 and after further conversion of over 0.3, it seems that decomposition reaction vigorously takes place rather than sublimation of AP.

$Hg^{2+}$-promoted Aquation and Chelation of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = Amines) Complexes ($Hg^{2+}$에 의한 cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = 아민류) 착물의 아쿠아화 및 킬레이트화 반응)

  • Chang Eon Oh;Doo Cheon Yoon;Bok Jo Kim;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.565-578
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    • 1992
  • It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.

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Prediction of Hydrofracture of Rock Salt under Ground at the Waste Isolation Pilot Plant (지하 핵 폐기물 저장 암염의 파괴현상 검증 및 분석)

  • Heo, Gwang-Hee;Lee, Cheo-Keun;Heo, Yol
    • Geotechnical Engineering
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    • v.11 no.3
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    • pp.139-162
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    • 1995
  • The possibility of the development of gas driven hydrofractures at the Waste Isolation Pilot Plant(WIPP) is investigated through analytical and numerical calculations and through laboratory experiments. First, an investigation of the chemical reactions involved shows that a large volume of gas could potentially be generated through the oxidation of iron in the waste. Simple ground water'flow calculations then show that unless regions of high permeability has been created, this gas volume will build up the pressure high enough to cause tensile damage in the horizontal planes of weakness or in the halite itself. The analytical calculations were performed using the concepts of linear elastic fracture mechanics and the numerical calculations were done using the finite element method. Also, laboratory tests were conducted to illustrate possible failure mechanisms. It is possible that after growing horizontal crack in the weaker anhydride layer, the crack could break out of this layer and propagate upward into the halite and toward the ground surface at an inclined argle of around 53$^{\circ}$ above horizontal. To prevent this latter phenomenon the anhydrite must have a fracture toughness less than 0.5590 times than that of the halite. Through the tests, three types of crack(radial vertical cracks, horizontal circular cracks and cone -shaped cracks) were observed.

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