• Journal of the Korean Chemical Society
• /
• v.40 no.12
• /
• pp.733-740
• /
• 1996

The rate constants for the hydrolysis of 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) were determined by ultraviolet visible spectrophotometer in water at $25^{\circ}C.$ The rate equation which could be applied over wide pH ranges were obtained. On the basis of pH-rate profile, Bronsted plot, hydrolysis product analysis, general base catalysis and substituent effect, the plausible hydrolysis mechanism was proposed: Below pH 3.00, the hydrolysis reaction was proceeded by the attack of water to 4'-position of quinonoid after protonation at nitrogen of acridinyl and between pH 3.00 and 9.00, the addition of water and hydroxide occurred competitively. However, above pH 9.00, the rate constants were dependent upon only the concentration of hydroxide ion.

• Journal of the Korean Chemical Society
• /
• v.17 no.4
• /
• pp.269-274
• /
• 1973

The rate constants of the hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylacrylic acid were determined by Ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of ${\alpha}$-Cyano-${\beta}$-piperonylic acid and especially the catalytic contribution of hydroxide ion which not studied carefully before in acidic media, can be fully explained by the rate equation obtained. The rate equation reveals that; below pH 4.0, the reaction is initiated by the addition of water molecule to ${\alpha}$-Cyano-${\beta}$-piperonyl acrylic acid. At pH $5.0{\sim}7.5$, ${\alpha}$-Cyano-${\beta}$-piperonylacrylic acid compete with ${\alpha}$-Cyano-${\beta}$-piperonyl acrylate ion in adding of water. At pH 8.0, water is the only nucleophile for ${\alpha}$-Cyano-${\beta}$-piperonylacrylate ion, however, above pH 12.0, hydroxide ion is an addendum and the accepter is ${\alpha}$-Cyano-${\beta}$-piperonylacrylate ion.

• Journal of Life Science
• /
• v.21 no.1
• /
• pp.127-133
• /
• 2011

${\beta}$-Galactosidase was immobilized on chitosan bead by covalent bonding using glutaraldehyde. The characteristics of the immobilized enzyme were investigated. Maximum immobilization yield of 75% was obtained on chitosan bead. Optimum pH and temperature for the immobilized enzyme was 7.0 and $50^{\circ}C$, respectively. The immobilized enzyme showed a broader range of pH and temperature compared to a free one. A mathematical model for the operation of the immobilized enzyme in a packed-bed reactor was established and solved numerically. Under different inlet lactose concentrations and feed flow rate conditions, lactose conversion was measured in a packed-bed reactor. The experimental results of continuous operation in a packed-bed reactor were compared to theoretic results using Michaelis-Menten kinetics with competitive product inhibition and external mass transfer resistance. The model predicted the experimental data with errors less than 5%. Process optimization of continuous operation in a packed-bed reactor was also conducted. In a recirculation packed-bed operation, conversion of lactose was 97% in 3 hours. In a continuous packed-bed operation, the effect of flow rate and initial lactose concentration was investigated. Increasing flow rates and initial lactose concentration decreased the conversion of substrate.

• Journal of Korean Society of Environmental Engineers
• /
• v.27 no.11
• /
• pp.1174-1179
• /
• 2005

Up-flow sludge blanket(USB) reactors were used to investigate the effects of N/C(${NO_3}^--N/COD$) ratio on simultaneous denitrification and methanogenesis processes. Without nitrate feeding, 84% of the influent COD was converted into methane. With the increase of N/C ratio, nitrogen gas increased while methane production decreased and stopped finally at the N/C ratio over 0.20. Influent nitrate was completely denitrified into nitrogen gas while nitrate removal efficiency dropped below 40% at N/C ratio of 0.40 because of deficiency in organic carbon. Fraction of COD utilized by denitrification increased at higher N/C ratios. Methanogenesis started to be effected at N/C ratio of 0.05, which could explain the competition for organic carbon between these microorganisms such as denitrifiers and methanogens, rather than inhibitory effect of nitrate and its intermediates. Critical N/C ratio for simultaneous denitrification and methanogenesis was found to be 0.20. Influent COD was removed over 92% by denitrification, methanogenesis and other biochemical reactions including cell growth at these N/C ratios.

• Applied Chemistry for Engineering
• /
• v.18 no.6
• /
• pp.643-649
• /
• 2007

Lipase-catalyzed esterification of structural butanol isomers and n-butyric acid was investigated in supercritical carbon dioxide. The experiments were performed in a high pressure cell for 5 hrs with a stirring rate of 150 rpm at 323.15 K and 130 bar. The Candida Antarctica lipase B (CALB) was used in whole system as a catalyst. The experimental results were analyzed by GC-FID using a INNOWax capillary column. The conversion yield and the tendency of the esterification in supercritical carbon dioxide were compared with estimated results by molecular dynamics simulation. Based on the Ping-Pong Bi-Bi mechanism with competitive inhibition, each step of the reaction was optimized; using this result the transition state was predicted. Conformational preference of isomers was also analyzed using molecular dynamics simulations. This kind of approach will be further extended to the prediction of enzyme-catalyzed reactions using computers.

• Journal of the Korean Chemical Society
• /
• v.40 no.6
• /
• pp.445-452
• /
• 1996

Catalytic hydrogenation of ketones and aldehydes by RuH(NO)$L_3$ ($L_3$: $PPh_3$, PhP($CH_2CH_2PPh_2$)$_2$(etp)) was investigated to examine the reaction mechanism and the competence of hydridonitrosyl complexes as catalysts for organic synthesis. RuH(NO)$L_3$ showed catalytic activity for the hydrogenation and the activities of catalysts were dependent on the steric and electronic factors. The less the steric demands of the substrates become, the more activity the catalysts show. For the electronic effect, the more the partial positive charge on the carbonyl carbon atom in ketones becomes and the more the double bond character of carbonyl group in aldehydes becomes, the more active the catalysts are. These results reflect the difference of reaction mechanisms of two substrates, ketones and aldehydes. Catalytic activities of RuH(NO)(etp) and RuH(NO)($PPh_3$)$_3$ in the presence of extra $PPh_3$ toward hydrogenation showed the existence of a reaction pathway accompanied with the change of the bonding modes of NO ligand. The roles of excess $PPh_3$ change with increase of the mole ratio of $PPh_3$ to catalysts; prevention of ligand dissociation from comlexes → bases → ligands. The activity of RuH(NO)(etp) was lower than that of RuH(NO)($PPh_3$)$_3$ toward the hydrogenation of the same substrates mainly due to the structural difference. These catalysts showed the selectivity toward olefin hydrogenation over carbonyl groups in the competitive reaction.

• Journal of the Mineralogical Society of Korea
• /
• v.29 no.2
• /
• pp.59-71
• /
• 2016

To investigate the sorption characteristics of Cs, which is one of the major isotopes of nuclear waste, on natural zeolite chabazite, XRD, EPMA, EC, pH, and ICP analysis were performed to obtain the informations on chemical composition, cation exchange capacity, sorption kinetics and isotherm of chabazite as well as competitive adsorption with other cations ($Li^+$, $Na^+$, $K^+$, $Rb^+$, $Sr^{2+}$). The chabazite used in this experiment has chemical composition of $Ca_{1.15}Na_{0.99}K_{1.20}Mg_{0.01}Ba_{0.16}Al_{4.79}Si_{7.21}O_{24}$ and its Si/Al ratio and cation exchange capacity (CEC) were 1.50 and 238.1 meq/100 g, respectively. Using the adsorption data at different times and concentrations, pseudo-second order and Freundlich isotherm equation were the most adequate ones for kinetic and isotherm models, indicating that there are multi sorption layers with more than two layers, and the sorption capacity was estimated by the derived constant from those equations. We also observed that equivalent molar fractions of Cs exchanged in chabazite were different depending on the ionic species from competitive ion exchange experiment. The selectivity sequence of Cs in chabazite with other cations in solution was in the order of $Na^+$, $Li^+$, $Sr^{2+}$, $K^+$ and $Rb^+$ which seems to be related to the hydrated diameters of those caions. When the exchange equilibrium relationship of Cs with other cations were plotted by Kielland plot, $Sr^{2+}$ showed the highest selectivity followed by $Na^+$, $Li^+$, $K^+$, $Rb^+$ and Cs showed positive values with all cations. Equilibrium constants from Kielland plot, which can explain thermodynamics and reaction kinetics for ionic exchange condition, suggest that chabazite has a higher preference for Cs in pores when it exists with $Sr^{2+}$ in solution, which is supposed to be due to the different hydration diameters of cations. Our rsults show that the high selectivity of Cs on chabazite can be used for the selective exchange of Cs in the water contaminated by radioactive nuclei.

• Environmental and Resource Economics Review
• /
• v.22 no.4
• /
• pp.613-641
• /
• 2013

This paper uses the error correction model to analyse dynamic gasoline price adjustments of the four refiners. Unlike the existing studies, this model allows a refiner's asymmetric adjustment to changes in the other refiners' prices as well as in its own price and costs. With the estimation results, we can obtain the following findings. First, there are the asymmetric price adjustments to changes in exchange rate and international gasoline price, but showing opposing directions. Second, for most of the refiners, the prices respond immediately to the lagged deviation from the long run equilibrium price, but asymmetrically respond for a few refiners. Third, there are some refiners that adjust their price to the other refiners' price deviation from the long run equilibrium. For some refiners, there are competitive price adjustments to the others' price deviations. These findings imply that a refiner faces inelastic demand, intends to maintain implicitly a relative level of its own price to others, and tends to respond competitively to the others' price deviation from the equilibrium.

• Journal of the Korean GEO-environmental Society
• /
• v.11 no.1
• /
• pp.19-26
• /
• 2010

The batch experiments and response surface methodology (RSM) have been applied to the investigation of the cadmium (Cd) adsorption by coal fly ash (CFA). CFA having maximum Cd removal mass of 8.51 mg/g were calculated from Langmuir model. Cd removal reaction with different initial pH ranged from 4 to 9. When the initial pH was higher, Cd was removed more by adsorption and precipitation. These results suggest that the lower pH cause an increase of $H^+$ ion concentration which competed with Cd ions for exchange sites in CFA. Also, The Cd adsorption was mathematically described as a function of parameters initial Cd concentration ($X_1$), initial pH ($X_2$), and initial CFA mass ($X_3$) being modeled by use of the Box-Behnken methods. Empirical models were developed to describe relationship between the experimental variables and response. Statistical analysis indicates that tree factors ($X_1$, $X_2$, and $X_3$) on the linear term (main effects), and tree factors ($X_1X_2$, $X_1X_3$, and $X_2X_3$) on the non-linear term (Interaction effect; cross-product) had significant effects, respectively. In this case, the value of the adjusted determination coefficient (adjusted $R^2=0.9280$) was closed to 1, showing a high significance of the model. Statistical results showed the order of Cd removal at experimental factors to be initial initial pH > initial Cd concentration > initial CFA mass.

• 한국신재생에너지학회:학술대회논문집
• /
• 2011.11a
• /
• pp.36.1-36.1
• /
• 2011

풍력개발 기술이 발전함에 따라 풍력발전시스템이 점차 대용량화되는 추세이며, 경제성 있는 풍력단지 건설을 위해 점차 대단지화 되어가고 있는 실정이다. 이로 인해 풍력 발전단가(Cost of electricity, COE)도 개선되고 있다. 풍황이 양호한 풍력발전단지의 경우, 풍력발전 COE는 현재 50~60원/kWh 수준으로 타 신재생에너지원에 비해 경쟁력이 높고, 석탄 화력의 COE와 비교해 봐도 동등한 수준 혹은 더욱 경쟁력 있는 수준으로 감소하였다. 풍력발전단지 조성을 위해서는 시스템의 효율과 고효율, 저비용의 풍력발전시스템을 풍황이 좋은 지역에 설치할 때 낮은 COE를 가지는 경제성 있는 발전단지가 가능하다. 동급 용량 풍력발전시스템을 같은 지역에서 설치하여 에너지생산량을 증대시키기 위해서는 블레이드 지름의 증가시켜 유량을 증가시키거나 타워의 높이를 증가시켜 풍속을 증가시키는 방안이 있다. 이 경우 블레이드 길이와 타워 높이 증가에 의한 시스템 비용의 증가가 발생하는데, 에너지생산량 증가에 의한 수익비용과 시스템 비용 증가에 의한 자본비용은 서로 반비례로 영향을 미친다. 이를 위해 최소의 COE의 최대의 순현재가치(Net Present Value, NPV)를 갖는 목적함수로 두고 블레이드의 최적 길이와 타워의 최적 높이를 선정하였다.