• Title/Summary/Keyword: Kinetic Constant

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Irreversible Thermoinactivation Mechanisms of Subtilisin Carlsberg

  • Dong Uk Kim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.600-604
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    • 1989
  • In order to find the rational methods for improving the thermal stability of subtilisin Carlsberg, the mechanisms of irreversible thermoinactivation of the enzyme were studied at $90^{\circ}C.$ At pH 4, the main process was hydrolysis of peptide bond. This process followed first order kinetics, yielding a rate constant of $1.26\;{\times}\;10^{-1}h^{-1}$. Hydrolysis of peptide bond of PMS-subtilisin occurred at various sites, which produced new distinct fragments of molecular weights of 27.2 KD, 25.9 KD, 25.0 KD, 22.3 KD, 19.0 KD, 17.6 KD, 16.5 KD, 15.7 KD, 15.0 KD, 13.7 KD, and 12.7 KD. Most of the new fragments originated from the acidic hydrolysis at the C-side of aspartic acid residues. However 25.0 KD, 15.7 KD, and 13.7 KD which could not be removed in purification steps stemmed from the autolytic cleavage of subtilisin. The minor process at pH 4 was deamidation at asparagine and/or glutamine residues and some extend of aggregation was also observed. However, the aggregation was main process at pH 7 with a first order kinetic constant of $16 h^{-1}.$ At pH 9, the main process seemed to be combination of deamidation and cleavage of peptide bond.

Kinetic analysis of E. coli disinfection using UV-LED (LED 광원 UV에 의한 대장균(E. coli) 소독의 속도론 해석)

  • Kim, Kyeong-Rae;Chang, In-Soung
    • Journal of Korean Society of Water and Wastewater
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    • v.35 no.6
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    • pp.489-496
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    • 2021
  • Water disinfection using UV-LED(Light emitting diode) has many advantages, such as smaller footprint and power consumption as well as relatively longer lifespan than those of conventional mercury-UV lamps. Moreover, UV-LED disinfection is considered an environmentally benign process due to its mercury-free nature. In this study, disinfection using an LED module emitting 275nm UV was carried out. 384 UV-LEDs were put into a cylinder tube with a capacity of 1.7 liters. The UV intensity of the UV-LED module was controlled from 1.7 to 8.4 mW/cm2. The disinfection efficiency for the model microorganism solutions(E. coli ) was monitored. As the UV intensity(I) and contact time(t) varied, inactivation of the microorganisms from 2 to 4-log-removals(i.e., 99 to 99.99% of disinfection efficiency) was achieved. Disinfection using UV-LED was followed to 1st order reaction and the reaction rate constant, k was determined. In addition, the relationship between UV intensity(I) and contact time(t) in order to obtain 99.99% of disinfection efficiency was modeled: I1.2·t= 460, which indicates that the product of UV intensity and contact time requiring 4-log-removals is always constant.

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.

Assessment of the Sorption Characteristics of Cadmium onto Steel-making Slag in Simulated Sea Water Using Batch Experiment (모사해수 조건에서 회분식 실험을 이용한 제강슬래그의 카드뮴 흡착 특성 평가)

  • Kim, Eun-Hyup;Rhee, Sung-Su;Lee, Gwang-Hun;Kim, Yong-Woo;Park, Jun-Boum;Oh, Myoung-Hak
    • Journal of the Korean Geotechnical Society
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    • v.27 no.4
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    • pp.43-50
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    • 2011
  • Steel-making slag was investigated as reactive material for removal of cadmium in coastal area. Batch experiments of the sorption isotherm experiment and kinetic sorption experiment were performed. Result of sorption isotherm was more adequately described by Langmuir model than Freundlich model and theoretical maximum capacity (${\beta}$) of cadmium onto steel-making slag was found. Results of kinetic sorption experiments were evaluated by pseudo second order model to investigate sorption characteristics of cadmium onto steel-making slag. Results showed that the equilibrium sorption amount of cadmium (q$q_e$) increased and the rate constant ($k_2$) and initial sorption rate (h) decreased as the initial cadmium concentration increased. The $q_e$ with simulated sea water was similar to that with deionized water and $k_2$ and h with simulated sea water was lower than those with deionized water. Results of kinetic experiments could be used to predict the result from sorption isotherm, since equilibrium sorption amounts calculated by pseudo second order model generally agreed with those measured from sorption isotherm. The reaction time for the target removal rate could be calculated by the pseudo second order model using kinetic sorption tests results.

Characteristics of Equilibrium, Kinetics and Thermodynamics for Adsorption of Disperse Yellow 3 Dye by Activated Carbon (활성탄에 의한 Disperse Yellow 3 염료의 흡착에 있어서 평형, 동력학 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.27 no.2
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    • pp.182-189
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    • 2021
  • The adsorption of disperse yellow 3 (DY 3) on granular activated carbon (GAC) was investigated for isothermal adsorption and kinetic and thermodynamic parameters by experimenting with initial concentration, contact time, temperature, and pH of the dye as adsorption parameters. In the pH change experiment, the adsorption percent of DY 3 on activated carbon was highest in the acidic region, pH 3 due to electrostatic attraction between the surface of the activated carbon with positive charge and the anion (OH-) of DY 3. The adsorption equilibrium data of DY 3 fit the Langmuir isothermal adsorption equation best, and it was found that activated carbon can effectively remove DY 3 from the calculated separation factor (RL). The heat of adsorption-related constant (B) from the Temkin equation did not exceed 20 J mol-1, indicating that it is a physical adsorption process. The pseudo second order kinetic model fits well within 10.72% of the error percent in the kinetic experiments. The plots for Weber and Morris intraparticle diffusion model were divided into two straight lines. The intraparticle diffusion rate was slow because the slope of the stage 2 (intraparticle diffusion) was smaller than that of stage 1 (boundary layer diffusion). Therefore, it was confirmed that the intraparticle diffusion was rate controlling step. The free energy change of the DY 3 adsorption by activated carbon showed negative values at 298 ~ 318 K. As the temperature increased, the spontaneity increased. The enthalpy change of the adsorption reaction of DY 3 by activated carbon was 0.65 kJ mol-1, which was an endothermic reaction, and the entropy change was 2.14 J mol-1 K-1.

Estimation of the Removal Capacity for Cadmium and Calculation of Minimum Reaction Time of BOF Slag (제강슬래그의 카드뮴 제거능 평가 및 필요반응시간 결정)

  • Lee, Gwang-Hun;Kim, Eun-Hyup;Park, Jun-Boum;Oh, Myoung-Hak
    • Journal of the Korean Geotechnical Society
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    • v.27 no.10
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    • pp.5-12
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    • 2011
  • This study was focused on the reactivity of furnace slag against cadmium to design the vertical drain method with reactive column for improving contaminated sea shore sediment. The kinetic sorption test was performed by changing the initial concentration and pH. Using pseudo-second-order model, the reactivity of furnace slag was quantitatively analyzed. Equilibrium removal amount ($q_e$) of furnace slag increased and rate constant ($k_2$) decreased with the increase of initial cadmium concentration. With the increase of pH, the equilibrium removal amount ($q_e$) and rate constant ($k_2$) increased in the same initial concentration. Required retention time was related to the inverse of the product of the equilibrium removal amount ($q_e$) multiplied by rate constant ($k_2$). The required retention time could be used to design the length of reactive column.

Solvent Extraction of Cu(II) by 2,4-Heptadione in Chloroform (2, 4-Heptadione에 의한 Cu(II)의 용매추출특성)

  • Shin, Jeong-Ho;Jeong, Kap-Seop;Lee, Sang-Hoon;Park, Sang-Wook;Park, Dae-Weon
    • Applied Chemistry for Engineering
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    • v.4 no.4
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    • pp.672-682
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    • 1993
  • 2, 4-Heptadione(abbreviated to 24HTD) was synthesized from methylpropyl ketone and ethyl acetate with sodium amide, and the equilibrium and the kinetic characteristics of copper extraction by 24HTD-chloroform were investigated. Equilibrium constants such as the dissociation constant and the distribution coefficient of 24HTD and the stability constant of the 24HTD-Cu chelate were evaluated from the spectrophotometry, and the overall equilibrium constant of the extraction was also determined. The extracted species of the 24HTD-Cu chelate was found to be $CuR_2$ and the initial rate of the extraction of coupper by 24HTD in chloroform was expressed by $R_0=k[\bar{HR}]([Cu^{2+}]/[H^+])^{0.5}$.

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Degradation Kinetics of Three Veterinary Antibiotics in Composted and Stockpiled Manure

  • Kim, Sung-Chul;Yang, Jae-E.;Ok, Yong-Sik;Jung, Doug-Young;Carlson, Kenneth
    • Korean Journal of Soil Science and Fertilizer
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    • v.45 no.1
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    • pp.43-50
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    • 2012
  • Two typical animal waste management practices, composting and stockpiling, were evaluated for their effect on the degradation of three veterinary antibiotics (VAs), chlortetracycline (CTC), tylosin (TYL), and monensin (MNS). The VAs were applied to horse manure plots subject to composting or stockpiling, and core samples were collected over a period of time. Selected buffer solutions were used to extract the VAs and analysis for concentration was conducted with solid phase extraction (SPE) followed by high performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) technique. The VAs demonstrated rapid dissipation within ten days followed by a gradual decrease in concentration until the end of the experimental period (141 days). All three VAs degraded more rapidly in the composting samples than in the stockpiling samples, particularly between 20 and 60 days of the observation period. Degradation of the three VAs generally followed a first-order kinetic model, and a fitted model with a calculated rate constant was determined for each treatment. TYL in composting showed the fastest degradation, with a calculated rate constant of $0.91day^{-1}$; the slowest degradation was exhibited by MNS in stockpiling, with rate constant of $0.17day^{-1}$. Calculated correlation coefficients ranged from 0.89 to 0.96, indicating a strong correlation between measured concentrations and fitted values in this study. Although concentration of TYL in composting treatment showed below detection limit during the test period, this study suggests that composting can reduce animal waste contaminants prior to field application as fertilizer.

Effects of Chamber Pressure on Dielectric Properties of Sputtered MgTiO3 Films for Multilayer Ceramic Capacitors

  • Park, Sang-Shik
    • Korean Journal of Materials Research
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    • v.20 no.7
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    • pp.374-378
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    • 2010
  • $MgTiO_3$ thin films were prepared by r.f. magnetron sputtering in order to prepare miniaturized NPO type MLCCs. $MgTiO_3$ films showed a polycrystalline structure of ilmenite characterized by the appearance of (110) and (202) peaks. The intensity of the peaks decreased with an increase in the chamber pressure due to the decrease of crystallinity which resulted from the decrease of kinetic energy of the sputtered atoms. The films annealed at $600^{\circ}C$ for 60min. showed a fine grained microstructure without micro-cracks. The grain size and roughness of the $MgTiO_3$ films decreased with the increase of chamber pressure. The average surface roughness was 1.425~0.313 nm for $MgTiO_3$ films prepared at 10~70 mTorr. $MgTiO_3$ films showed a dielectric constant of 17~19.7 and a dissipation factor of 2.1~4.9% at 1MHz. The dielectric constant of the films is similar to that of bulk ceramics. The dielectric constant and the dissipation factor decreased with the increase of the chamber pressure due to the decrease of grain size and crystallinity. The leakage current density was $10^{-5}\sim10^{-7}A/cm^2$ at 200kV/cm and this value decreased with the increase of the chamber pressure. The small grain size and smooth surface microstructure of the films deposited at high chamber pressure resulted in a low leakage current density. $MgTiO_3$ films showed a near zero temperature coefficient and satisfied the specifications for NPO type materials. The dielectric properties of the $MgTiO_3$ thin films prepared by sputtering suggest the feasibility of their application for MLCCs.

Kinetic Studies on the Nucleophilic Substitution Reaction of 4-X-Substituted-2,6-dinitrochlorobenzene with Pyridines in MeOH-MeCN Mixtures

  • Sung, Ryun-Youn;Choi, Ho-june;Lee, Jong-Pal;Park, Jong-Keun;Yang, Ki-Yull;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1579-1582
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    • 2009
  • The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.