• Title/Summary/Keyword: pseudo second order

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Kinetics Study of the Reaction of Bromine with Phenylhydrazine in Sulfuric Acid Media (페닐히드라진과 브롬의 반응메카니즘에 관한 연구)

  • Park Byoung Bin;Park Il H.;Kong Young Kun;Choi Q. Won
    • Journal of the Korean Chemical Society
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    • v.21 no.4
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    • pp.227-234
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    • 1977
  • The reaction of phenylhydrazine with bromine in sulfuric acid solution has been studied kinetically. The pseudo-second-order rate constant is approximately inversely proportional to hydrogen-ion concentration when the concentration of sulfuric acid is lower than 1M. arom the study of the effect of potassium bromide concentration on the rate constant, it is concluded that both neutral bromine and tribromide ion participate in the reaction, the rate constants in 0.01M $H_2SO_4$ being $5{\times}10^5M^{-1},sec^{-1}\;and\;0. 7{\times}10^5M^{-1},sec^{-1}$, respectively at $20^{\circ}C$. The pseudo-second-order rate constant of 2.4-dinitrophenylhydrazine-bromine reaction is independent of hydrogen ion concentration. From the KBr addition experiment, the rate constants for $Br_2\;and\;Br_3^-$ were obtained as $1.2{\times}10^5M^{-1},sec^{-1}\;and\;2.0{\times}10^4M^{-1},sec^{-1}$, respectively.

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Analysis of Sorption and Desorption Behaviors of Radionuclides (Cobalt and Strontium) in Natural Soil (자연 토양에서의 방사성 핵종(Co, Sr)의 흡/탈착 거동 특성 평가)

  • Cheon Kyeong-Ho;Shin Won Sik;Choi Jeong-Hak;Choi Sang June
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2005.06a
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    • pp.485-495
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    • 2005
  • This study was conducted to investigate sorption and desorption behaviors of radionuclides (Cobalt and Strontium) in natural soil. Sorption kinetics and isotherms were analyzed to predict sorption behaviors of radionuclides in natural soil and the experimental data were fitted to several sorption models. Desorption experiments were also performed with or without CMCD at constant pH and ion strength conditions. The results showed that $Sr^{2+}$ was more strongly sorbed than $Co^{2+}$ in natural soil. Both $Co^{2+}$ and $Sr^{2+}$ followed a pseudo-second order kinetics and Sips model. The desorption-resistance of $Co^{2+}$ and $Sr^{2+}$ was estimated using a natural surfactant Carboxymethyl-${\beta}$-cyclodextrin(CMCD) or non-desorbing fraction. Desorption of radionuclides was partially irreversible and $Sr^{2+}$ was more resistant than $Co^{2+}$ Addition of CMCD facilitated desorption of $Co^{2+}$ and $Sr^{2+}$ from soil.

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Cutting Fluid Effluent Removal by Adsorption on Chitosan and SDS-Modified Chitosan

  • Piyamongkala, Kowit;Mekasut, Lursuang;Pongstabodee, Sangobtip
    • Macromolecular Research
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    • v.16 no.6
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    • pp.492-502
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    • 2008
  • This study examined the adsorption of a synthetic cutting fluid and cutting fluid effluent on chitosan and SDS-modified chitosan, Chitosan and SDS-modified chitosan were prepared in form of beads and fibers. A series of batch experiments were carried out as a function of the initial concentration of cutting fluid, contact time and pH of the fluid. The contact angle study suggested that the SDS-modified chitosan was more hydrophobic than chitosan. The Zeta potential study showed that chitosan, SDS-modified chitosan and synthetic cutting fluid had a point of zero charge (PZC) at pH 7.8, 9 and 3.2, respectively. SDS-modified chitosan has a greater adsorption capacity than chitosan. The experimental results show that adsorption capacity of the cutting fluid on 1.0 g of SDS-modified chitosan at pH 3 and for a contact time of 120 min was approximately 2,500 g/kg. The adsorption capacity of chitosan and SDS-modified chitosan increased with decreasing pH. The Langmuir, Freundlich, and Brunauer Emmett and Teller (BET) adsorption models were used to explain the adsorption isotherm. The Langmuir isotherm fitted well with the experimental data of chitosan while the BET isotherm fitted well with the SDS-modified chitosan data. Pseudo first- and second-order kinetic models and intraparticle diffusion model were used to examine the kinetic data. The experimental data was fitted well to a pseudo second-order kinetic model. The significant uptake of cutting fluid on chitosan and SDS-modified chitosan were demonstrated by FT-IR spectroscopy, SEM and heat of combustion.

Adsorption Kinetic and Thermodynamic Studies of Tricyclazole on Granular Activated Carbon (입상 활성탄에 대한 트리사이크라졸의 흡착동력학 및 열역학적 연구)

  • Lee, Jong-Jib;Cho, Jung-Ho;Kim, H.T.
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.9
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    • pp.623-629
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    • 2011
  • The adsorption characteristics of tricyclazole by granular activated carbon were experimently investigated in the batch adsorption. Kinetic studies of adsorption of tricyclazole were carried out at 298, 308 and 318 K, using aqueous solutions with 250, 500 and 1,000 mg/L initial concentration of tricyclazole. It was established that the adsorption equilibrium of tricyclazole on granular activated carbon was successfully fitted by Freundlich isotherm equation at 298 K. The pseudo first order and pseudo second order models were used to evaluate the kinetic data and the pseudo second order kinetic model was the best with good correlation. Values of the rate constant ($k_2$) have been calculated as 0.1076, 0.0531, and 0.0309 g/mg h at 250, 500 and 1,000 mg/L initial concentration of tricyclazole, respectively. Thermodynamic parameter such as activation energy, standard enthalpy, standard entropy and standard free energy were evaluated. The positive value for enthalpy, -66.43 kJ/mol indicated that adsorption interaction of tricyclazole on activated carbon was an exothermic process. The estimated values for standard free energy were -5.08~-8.10 kJ/mol over activated carbon at 200 mg/L, indicated toward a exothermic process.

Study on Adsorption Kinetic Characteristics of Propineb Pesticide on Activated Carbon (활성탄에 대한 프로피네브 농약의 흡착동력학적 특성 연구)

  • Lee, Jong-Jib;Cho, Jung-Ho;Kim, Heung-Tae
    • Clean Technology
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    • v.17 no.4
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    • pp.346-352
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    • 2011
  • The adsorption characteristics of propineb pesticide onto activated carbon has been investigated for the adsorption in aqueous solution with respect to initial concentration, contact time and temperature in batch experiment. The Langmuir and Freundlich adsorption models were applied to described the equilibrium isotherms and isotherm constants were also determined. The Freundlich model agrees with experimental data well. slope of isotherm line indicate that activated carbon could be employed as effective treatment for removal of propineb. The pseudo first order, pseudo second order kinetic models were use to describe the kinetic data and rate constants were evaluated. The adsorption process followed a pseudo second order model, and the adsorption rate constant($k_2$) decreased with increasing initial concentration of propineb. The activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption. The estimated values for change of free energy were -7.28, -8.27 and -11.66 kJ/mol over activated carbon at 298, 308 and 318 K, respectively. The results indicated toward a spontaneous process. The positive value for change of enthalpy, 54.46 kJ/mol, found that the adsorption of propineb on activated carbon is an endothermic process.

Evaluation of Raw and Calcined Eggshell for Removal of Cd2+ from Aqueous Solution

  • Kim, Youngjung;Yoo, Yerim;Kim, Min Gyeong;Choi, Jong-Ha;Ryoo, Keon Sang
    • Journal of the Korean Chemical Society
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    • v.64 no.5
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    • pp.249-258
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    • 2020
  • The potential use of egg shell and calcined egg shell as adsorbent was evaluated and compared to remove Cd2+ from aqueous solution. The samples were characterized using Thermogravimetry and Differential Thermal Analysis (TG/DTA), Scanning Electron Microscope (SEM), X-ray Diffractometer (XRD), Energy Dispersive X-ray Spectrometer (EDX) and BET Surface Analyzer. The batch-type adsorption experiment was conducted by varying diverse variables such as contact time, pH, initial Cd2+ concentrations and adsorbent dosage. The results showed that, under the initial Cd2+ concentrations ranged from 25 to 200 mg g-1, the removal efficiencies of Cd2+ by egg shell powder (ESP) were decreased steadily from 96.72% to 22.89% with increase in the initial Cd2+ concentration at 2.5 g of dosage and 8 h of contact time. However, on the contrary to this, calcined egg shell powder (CESP) showed removal efficiencies above 99% regardless of initial Cd2+ concentration. The difference in the adsorption behavior of Cd2+ may be explained due to the different pH values of ESP and CESP in solution. Cd2+ seems to be efficiently removed from aqueous solution by using the CESP with a basicity nature of around pH 12. It was also observed that an optimum dosage of ESP and CESP for nearly complete removal of Cd2+ from aqueous solution is approximately 5.0 g and 1.0 g, respectively. Consequently, Cd2+ is more favorably adsorbed on CESP than ESP in the studied conditions. Adsorption data were applied by the pseudo-first-order and pseudo-second-order kinetics models and Freundlich and Langmuir isotherm models, respectively. With regard to adsorption kinetics tests, the pseudo-second-order kinetics was more suitable for ESP and CESP. The adsorption pattern of Cd2+ by ESP was better fitted to Langmuir isotherm model. However, by contrast with ESP, CESP was described by Freundlich isotherm model well.

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.

Sorption Characteristics of Arsenic on Furnace Slag by Adsorption Isotherm and Kinetic Sorption Experiments (등온 및 동적 흡착 실험을 통한 제강 슬래그의 비소 흡착 특성)

  • Oh, Cham-Teut;Rhee, Sung-Su;Igarashi, Toshifumi;Kon, Ho-Jin;Lee, Won-Taek;Park, Jun-Boum
    • Journal of the Korean Geotechnical Society
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    • v.26 no.9
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    • pp.37-45
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    • 2010
  • Sorption characteristics of arsenic on furnace slag were investigated to remove arsenic from groundwater using furnace slag, which is industrial waste generated from steel company. Adsorption isotherm experiments and kinetic sorption experiments were performed and the chemical characteristics of supernatants from these experiments were analyzed. Results showed that all supernatants were alkaline (above pH 9) and the highest ion concentration in the solution was found with calcium (30~50 mg/L). Results of adsorption isotherms were more adequately described by the Freundlich model than Langmuir model. From adsorption isotherms experiments, it was noted that the adsorption amount of As(V) was 87% higher than that of As(III). Results of kinetic sorption experiments were more properly fitted by pseudo second order (PSO) model than pseudo first order model. Equilibrium adsorption amount ($q_e$) and relaxation time ($t_r$) calculated from PSO model increased with initial concentration of arsenic. Equilibrium adsorption amount of As(V) was higher than that of As(III) and relaxation time of As(V) was shorter than that of As(III). Adsorption isotherm results could be predicted by kinetic adsorption results, since equilibrium adsorption amount calculated through PSO model generally agreed with equilibrium adsorption amount measured from adsorption isotherm.

Diethylpyrocarbonate Inactivation of Aspartase from Hafnia Alvei

  • Shim, Jae-Hee;Kim, Hyo-Joon;Yoon, Moon-Young
    • BMB Reports
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    • v.32 no.4
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    • pp.326-330
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    • 1999
  • An aspartase purified from Hafnia alvei was inactivated by diethylpyrocarbonate (DEP) in a pseudo-first-order inactivation. The first-order plot was biphasic. The inactivation process was not saturable and the second order rate constant was $1.3\;M^{-1}s^{-1}$. The inactivated aspartase was reactivated with NH₂OH. The difference absorption spectrum of DEP-inactivated vs native enzyme preparations revealed a marked peak around 242 nm. The pH dependence of the inactivation rate suggests that an amino acid residue having a pK value of 7.2 was involved in the inactivation. L-aspartate, fumarate (substrates), and chloride ion (inhibitor) protected the enzyme against inactivation, indicating that histidine residues for the enzyme activity are located at the active site of this aspartase. Inspection of the presence and absence of $Cl^-$ ion demonstrated that the number of essential histidine residues is less than two. Thus, one or two histidines are in or near the aspartate binding site and participate in an essential step of the catalytic reaction.

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Identification of Volterra Kernels of Nonlinear Van de Vusse Reactor

  • Kashiwagi, Hiroshi;Rong, Li
    • 제어로봇시스템학회:학술대회논문집
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    • 2001.10a
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    • pp.26.3-26
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    • 2001
  • Van de Vusse reactor is known as a highly nonlinear chemical process and has been considered by a number of researchers as a benchmark problem for nonlinear chemical process. Various identification methods for nonlinear system are also verified by applying these methods to Van de Vusse reactor. From the point of view of identification, only the Volterra kernel of second order has been obtained until now. In this paper, the authors show that Volterra kernels of nonlinear Van de Vusse reactor of up to 3rd order are obtained by use of M-sequence correlation method. A pseudo-random M-sequence is applied to Van de Vusse reactor as an input and its output is measured. Taking the cross correlation function between the input and the output, we obtain up to 3rd order Volterra kernels, which is ...

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