• 제목/요약/키워드: kinetic studies

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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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    • 제47권3호
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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.

Micelles in Physical Chemistry Laboratory. Surfactant Catalyzed Oxidation of Glycine by Acidic Permanganate

  • Pare, Brijesh;Kaur, Parwinder;Bhagwat, V.W.;Fogliani, Charles
    • Journal of the Korean Chemical Society
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    • 제48권2호
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    • pp.195-202
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    • 2004
  • Micellar catalysis is an essential part of theoretical and experimental curricular. The sodium dodecylsulfate (SDS) catalyzed reaction between glycine and potassium permanganate in acidic medium is an ideal kinetic experiment for the secondary and undergraduate physical chemistry laboratory, to show the effect of micellar catalysis on rate of the reaction. The reaction is conducted both with and without SDS to observe the rate enhancement in the presence of surfactant. To show surfactant catalysis a plot between k and [SDS] is plotted. As surfactant catalysis is observed even before the critical micelle concentration of SDS, this pre-micellar catalysis can be understood in the light of positive co-operativity. The value of positive cooperative index (n) has been found to be 2.37. Further, dependence of the reaction rate on substrate and oxidant concentrations is also discussed. The reaction follows pseudo-first-order kinetics. The overall reaction is second order, with first-order dependence on both glycine and permanganate concentrations. The theory of surfactant catalysis is also discussed. With the conditions specified in the experiment, total reaction times are in 3~4 hours lab session, thus allowing several data sets to be acquired in a single laboratory period. Preparation of solutions and procedure is also given in detail.

Adsorption Equilibrium, Kinetics and Thermodynamic Parameters Studies of Bismarck Brown R Dye Adsorption on Granular Activated Carbon (입상 활성탄에 대한 비스마르크 브라운 R 염료의 흡착평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • 제24권3호
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    • pp.327-332
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    • 2013
  • Batch experiments were carried out for adsorption equilibrium, kinetics and thermodynamic parameters of the brilliant brown R onto granular activated carbon. The operating variables studied were the initial dye concentration, contact time and temperature. Experimental equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption isotherm by linear regression method. The equilibrium process was well described by Freundlich isotherm model and from the determined separation factor (1/n), granular activated carbon could be employed as an effective treatment for the removal of bismarck brown R. From kinetic experiments, the adsorption processes were found to confirm the pseudo second order model with a good correlation and the adsorption rate constant ($k_2$) increased with increasing adsorption temperature. Thermodynamic parameters like the activation energy, change of Gibbs free energy, enthalpy, and entropy were also calculated to predict the nature of adsorption in the temperature range of 298~318 K. The activation energy was determined as 8.73 kJ/mol for 100 mg/L. It was found that the adsorption of bismarck brown R on the granular activated carbon was physical process. The negative Gibbs free energy change (${\Delta}G$ = -2.59~-4.92 kJ/mol) and the positive enthalpy change (${\Delta}H$ = +26.34 kJ/mol) are indicative of the spontaneous and endothermic nature of the adsorption process.

Studies on the Ethanol Production by Clostridium thermosaccharolyticum (Clostridium thermosaccharolyticum에 의한 에탄올생산에 관한 연구)

  • 조은경;이윤광;변유량;유주현
    • Microbiology and Biotechnology Letters
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    • 제13권4호
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    • pp.397-402
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    • 1985
  • The fermentation of various sugars by C. thermosaccharolyticum was examined under pH controlled, anaerobic condition. The kinetic model for Product formation at various sugars was the combination of growth and non-growth associated mode. In the utilization of a single sugar, glucose was the best carbon source for growth. The specific growth rate of glucose, xylose and cellobiose were 0.363 h$^{-1}$, 0.242 h$^{-1}$ and 0.144 h$^{-1}$ respectively. The production of ethanol from glucose showed a negatively growth associated mode, so the higher growth rate decreased the productivity of ethanol. The maximum concentrations of the produced ethanol were 2.42 g/l, 3.76 g/l, and 3.4 g/l on glucose, xylose, and cellobiose. No glucose was detected during cellobiose fermentation. Sequential utilization of sugars was observed in the mixtures of glucose, xylose and cellobiose. It preferred glucose, followed by xylose and then cellobiose. The presence of other sugars had little or no effect on the rate of another sugar utilization. Cell lysis at the end of fermentation occured more slowly in the mixtures of sugars than a single sugar.

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In vitro Evaluation of Phalaris minor Seeds as Livestock Feed

  • Kaur, J.;Pannu, M.S.;Kaushal, S.;Wadhwa, M.;Bakshi, M.P.S.
    • Asian-Australasian Journal of Animal Sciences
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    • 제19권3호
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    • pp.363-367
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    • 2006
  • The nutritional worth of Phalaris minor seeds was assessed in comparison to conventional cereal grains like maize and wheat. P. minor seeds had higher total ash and cell wall constituents as compared to wheat and maize grains. The CP content of P. minor was comparable to wheat grains but higher than maize grains. The in vitro studies revealed that the net gas production and availability of ME from P. minor was comparable to that of maize but the digestibility of nutrients was significantly (p<0.05) lower than that of conventional cereal grains. The digestion kinetic parameters for DM and CP revealed that P. minor had the highest (p<0.05) soluble fraction (a) followed by wheat and maize. Reverse trend was observed for insoluble but potentially degradable fraction (b). The effective and true DM and CP degradability was significantly (p<0.05) higher in wheat grains followed by that in P. minor and maize grains. The digestibility of OM and NDF was not affected by replacing cereal grains in concentrate mixture with P. minor seeds up to 75 per cent level. But the availability of ME from concentrate mixtures was comparable to control only up to 50% level of replacement. Replacement of cereal grains with P. minor did not affect the rapidly soluble fraction and insoluble but potentially degradable fraction of concentrate mixture containing P. minor up to 75 per cent, but it was depressed significantly at 100% replacement level. The effective and true degradability of DM of concentrate mixtures containing P. minor from 50 to 100 per cent was comparable to that of conventional concentrate mixture (CCM). The wheat based concentrate mixtures showed higher net gas production (208 vs. 201 ml/g DM/24 h), digestibility of nutrients and ME availability (9.64 vs. 9.54 MJ/kg DM) as compared to maize based concentrate mixture. The wheat based concentrate mixture had significantly (p<0.05) higher rumen undegradable fraction and effective degradability. The data conclusively revealed that conventional cereal grains could be replaced with P.minor seeds up to 75 per cent without affecting the availability of nutrients.

Fermentation Kinetics for Production of Carotenoids by ${\beta}$-ionone Resistant Mutant of Xanthophyllomyces dendrorhous (Xanthophyllomyces dendrorhous 변이군주에 의한 Carotenoids 생산 발효의 특성 연구)

  • Park, Ki-Moon;Kim, Young-Jun;Song, Min-Woo;Kang, Seog-Jin;Lee, Jae-Heung
    • KSBB Journal
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    • 제21권4호
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    • pp.286-291
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    • 2006
  • Various ${\beta}$-ionone resistant mutants were isolated from the wild-type red yeast Xanthophyllomyces dendrorhous KCTC 7704. Although the growth of X. dendrorhous KCTC 7704 was strongly inhibited at 0.025 mM ${\beta}$-ionone, one of the ${\beta}$-ionone resistant mutants isolated at 0.1 mM ${\beta}$-ionone by NTG mutagenesis showed rather 70% of relative survival at 0.15 mM ${\beta}$-ionone. Fermentation kinetics study with the mutant was carried out at $20^{\circ}C$ for 4 days in 300-mL baffled flasks. The mutant yielded up to 2.3-fold higher carotenoids content(viz. $1.2{\mu}g$ of total carotenoids per mg of dry cells) compared with the wild-type strain. The production of metabolites such as organic acids could be neglected. Studies on the kinetics with various carbon substrates revealed both an increase in final dry cell mass and a higher total carotenoids content in cell mass with glucose when compared to fructose or sucrose. As a further part of study, the effect of pH on the fermentation kinetics was investigated in glucose-limited chemostat at a dilution rate of $0.04h^{-1}$. When compared to steady-state kinetic parameters obtained at pH 4.0, a significant reduction in cell concentration at pH 3.0 and a lower carotenoids content at pH 5.2 were evident.

Kinetic Studies of Pyrolysis and Char-$CO_2$ Gasification on Low Rank Coals (저급탄의 열분해 및 촤-$CO_2$ 가스화 반응의 속도론적 연구)

  • Kang, Suk-Hwan;Ryu, Jae-Hong;Park, Soo-Nam;Byun, Yong-Soo;Seo, Seok-Jung;Yun, Yong-Seung;Lee, Jin-Wook;Kim, Yong-Jeon;Kim, Joo-Hoe;Park, Sam-Ryong
    • Korean Chemical Engineering Research
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    • 제49권1호
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    • pp.114-119
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    • 2011
  • Thermogravimetric analysis(TGA) was carried out for pyrolysis and char-$CO_2$ gasification of low rank Indonesian ABK coal and China lignite. The pyrolysis rate was successfully described by a two-step model adopting the modified Kissinger method. The shrinking core model, when applied to char-$CO_2$ gasification gave initial activation energy of 189.1 kJ/mol and 260.5 kJ/mol for the ABK coal and China lignite, respectively. Thus, the char-$CO_2$ gasification has been successfully simulated by the shrinking core model. In particular, the activation energy of char-$CO_2$ gasification calculated in this work is similar to the results on the anthracite coal, but considerable difference exists when other models or coal types are used.

Production and Characterization of Raw Starch Hydrolyzing Enzyme from Bacteria (세균에 의한 생전분 분해효소의 생성 및 특성)

  • Park, In-Shik;Nam, In;Kho, Sun-Ok;Kim, Gi-Nahm;Suh, Kyung-Soon
    • Microbiology and Biotechnology Letters
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    • 제18권3호
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    • pp.244-250
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    • 1990
  • A bacterium capable of hydrotyzing raw starch was isolated from soil, which was identified as a strain of Bacillue. The effects of culture conditions and medium compositions on the enzyme production were investigated. Among tested carbon sources, soluble starch and wheat starch were most effective for the production of the enzyme, and the level of concentration for the optimal enzyme production was 0.5%. For nitrogen sources, polypeptone was best for the enzyme production, with the level of 0.5%. The enzyme was maximally produced by cultivating the organism at medium of initial pH 6.5, and temperature of $35^{\circ}C$. The enzyme was partially purified by Sepharose CL-6B gel filtration and DEAESephacel ion-exchange chromatography. The optimal pH and temperature for the enzyme reaction were 6.5 and $70^{\circ}C$, respectively. The enzyme most stable at pH 8.0, and temperature up to $60^{\circ}C$. In kinetic studies, the k, values for corn, wheat, rice and potato starch were 1.7, 1.4,2.5 and 1.090, respectively.

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Studies on Microbial Penicillin Amidase (Part 5) Application of Reinforced Calcium-Alginate Gel Entrappment Method for Immobilization of Penicillin Amidase from Bacillus megaterium (미생물 페니실린 아미다제에 관한 연구 (제 5보) Bacillus megaterium 페니실린 아미다제의 새로운 고정화 방법)

  • Son, Hyeung-Jin;Seong, Baik-Lin;Mheen, Tae-Ick;Han, Moon-Hi
    • Microbiology and Biotechnology Letters
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    • 제9권3호
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    • pp.159-164
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    • 1981
  • Reinforced Calcium-alginate gel entrappment method for enzyme immobilization is described with an example of penicillin amidase from Bacillus megaterium KFCC 10029, a partially constitutive mutant of B. megaterium ATCC 14945. Penicillin amidase recovered from the fermentation broth by adsorption on celite is mixed with alginate and gelatin solution, and cast into a pellet or noodle form by coagulation in calcium salt solution followed by crosslinking with glutaraldehyde. Optimum pH and temperature of the immobilized enzyme preparation were 8.0 and 6$0^{\circ}C$, respectively. Kinetic constants such as Km value and the inhibition constant of 6-APA and phenylacetic acid were 2.6 mM, 7.4 mM and 21.2 mM, respectively. The enzyme leakage from the adsorbent during operation was successfully prevented owing to the increase of physical strength of gel coat. The half lives in a column reactor were 6 and 30 days at the respective temperature of 4$0^{\circ}C$ and 3$0^{\circ}C$, which were the 6-8 fold increased values as compared with those of without entrappment. The results highly recommended the use of reinforced Calcium-alginate gel entrappment method for the enhancement of physical strength and the operational stability of alginate gel entrapped enzyme.

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Development of Three-Dimensional Finite Element Model for Structural Analysis of Airport Concrete Pavements (공항 콘크리트 포장 구조해석을 위한 3차원 유한요소 모형 개발)

  • Park, Hae Won;Shim, Cha Sang;Lim, Jin Seon;Joe, Nam Hyun;Jeong, Jin Hoon
    • International Journal of Highway Engineering
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    • 제19권6호
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    • pp.67-74
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    • 2017
  • PURPOSES : In this study, a three-dimensional nonlinear finite element analysis (FEA) model for airport concrete pavement was developed using the commercial program ABAQUS. Users can select an analysis method and set the range of input parameters to reflect actual conditions such as environmental loading. METHODS : The geometrical shape of the FEA model was chosen by considering the concrete pavement located in the third-stage construction site of Incheon International Airport. Incompatible eight-node elements were used for the FEA model. Laboratory test results for the concrete specimens fabricated at the construction site were used as material properties of the concrete slab. The material properties of the cement-treated base suggested by the Federal Aviation Administration(FAA) manual were used as those of the lean concrete subbase. In addition, preceding studies and pavement evaluation reports of Incheon International Airport were referred for the material properties of asphalt base and subgrade. The kinetic friction coefficient between the concrete slab and asphalt base acquired from a preceding study was used for the friction coefficient between the layers. A nonlinear temperature gradient according to slab depth was used as an input parameter of environmental loading, and a quasistatic method was used to analyze traffic loading. The average load transfer efficiency obtained from an Heavy falling Weight Deflectomete(HWD) test was converted to a spring constant between adjacent slabs to be used as an input parameter. The reliability of the FEA model developed in this study was verified by comparing its analysis results to those of the FEAFAA model. RESULTS : A series of analyses were performed for environmental loading, traffic loading, and combined loading by using both the model developed in this study and the FEAFAA model under the same conditions. The stresses of the concrete slab obtained by both analysis models were almost the same. An HWD test was simulated and analyzed using the FEA model developed in this study. As a result, the actual deflections at the center, mid-edge, and corner of the slab caused by the HWD loading were similar to those obtained by the analysis. CONCLUSIONS : The FEA model developed in this study was judged to be utilized sufficiently in the prediction of behavior of airport concrete pavement.