• Bulletin of the Korean Chemical Society
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• 제7권6호
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• pp.416-421
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• 1986

The solvent coordination effect on the excited state processes of Mg(II)- and Zn(II)-phthalocyanines has been described. The triplet state of these compounds decays with mixed first and second order kinetics or mainly second order kinetics depending on the solvents used. The first order component of the rate constants decrease along with the series, dimethylsulfoxide (5-coordinated), 1-chloronaphthalene (4-coordinated) and piperidine (6-coordinated), while the second order rate constant is dependent on the diffusion rate constant of the solvents. The excited state quenching by methylviologen or p-benzoquinone is discussed. And ion recombination rate constant is given.

• BMB Reports
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• 제28권1호
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• pp.40-45
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• 1995

Acetolactate synthase purified from Serratia marcescens ATCC 25419 was rapidly inactivated by the thiol specific reagent p-chloromercuribenzoate (PCMB), the tryptophan specific reagent N-bromosuccinimide (NBS), and the arginine modifying reagent phenylglyoxal (PGO). Inactivation by PCMB was prevented by both ${\alpha}$-ketobutyrate and pyruvate, and the second order rate constant for the inactivation was $2480\;M^{-1}{\cdot}min^{-1}$. The reaction order with respect to PCMB was 0.94. The inactivation of the enzyme by NBS was also substantially reduced by both ${\alpha}$-ketobutyrate and pyruvate. The second order rate constant for inactivation by NBS was $15,000\;M^{-1}{\cdot}min^{-1}$, and the reaction order was 2.0. On the other hand, inactivation by PGO was partially prevented by ${\alpha}$-ketobutyrate, but not by pyruvate. The second order rate constant for the inactivation was $1480\;M^{-1}{\cdot}min^{-1}$ and the order of reaction with respect to PGO was 0.75. These results suggest that essential cysteine, tryptophan and arginine are located at or near the substrate binding site.

• 제어로봇시스템학회:학술대회논문집
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• 제어로봇시스템학회 1988년도 한국자동제어학술회의논문집(국제학술편); 한국전력공사연수원, 서울; 21-22 Oct. 1988
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• pp.1018-1021
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• 1988

This study is concerned with modeling an elastomer constitutive relation by utilizing the truncated Volterra series. Actual experimental data from the Instron Tester are obtained for combined input, i.e. constant strain rate followed by a constant strain input. These data are then estimated for step inputs and utilized for the truncated Volterra series models. One second order and one third order truncated Volterra series models have been employed to estimated the force-displacement relation which is one of the prominent properities to characterize the viscoelastic material. The third order Volterra series model has better results, compared with those of the second order Volterra series model.

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2269-2273
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• 2012

Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

• 상하수도학회지
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• 제25권6호
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• pp.971-979
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• 2011

Palm Oil Mill Effluent (POME) is the mixed organic wastewater generated from palm oil industry. In this study, kinetic analysis with treating POME in an anaerobic hybrid reactor (AHR) was performed. Therefore, the AHR was monitored for its performances with respect to the changes of COD concentrations and hydraulic retention time (HRT). Batch tests were performed to find out the substrate removal kinetics by granular sludge from POME. Modified Stover Kincannon, First-order, Monod, Grau second-order kinetic models were used to analyze the performance of reactor. The results from the batch test indicate that the substrate removal kinetics of granular sludge is corresponds to follow Monod's theory. However, Grau second-order model were the most appropriate models for the continuous test in the AHR. The second order kinetic constant, saturation value constant, maximum substrate removal rate, and first-order kinetic constant were 2.60/day, 41.905 g/L-day, 39.683 g/L-day, and 1.25/day respectively. And the most appropriate model was Grau second-order kinetic model comparing the model prediction values and measured COD concentrations of effluent, whereas modified Stover-Kincannon model showed the lowest correlation.

• 대한화학회지
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• 제35권2호
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• pp.111-118
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• 1991

기체 상태의 오존(0.5 torr)과 이산화황간의 반응속도를 연구하였다. 이산화황은 7∼22 torr 의 압력범위에서 90∼155$^{\circ}$C의 온도영역에서 반응시켰다. 오존과 이산화황의 반응속도는 이산화탄소와의 반응보다 빨리 진행되었다. 오존과 이산화황의 반응속도식은 -d(O$_3 )/dt = k _0 (SO _2 )(M)(O _3)+2k _1(SO_2 )(O _3$)였다. 이 속도식의 첫 항은 3분자 반응으로 낮은 온도에서 우세하게 진행되었으며, 속도상수 k$_0 =(9.35{\pm}8.6){\times}10^9e^{-(11.05{\pm}2.04)kcal/RT}(M^{-2}s^{-1}$)이다. 속도식의 두번째 항은 2분자 열분해 반응으로부터 유도된 주된 반응으로 속도상수 k$_1=(1.53{\pm}1.5){\times}10^{11}e^{-22.7 kcal/RT}$이다. 전 반응차수는 주로 2차 반응이며 3차 반응과 복합반응으로 진행되었다.

• BMB Reports
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• 제28권2호
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• pp.124-128
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• 1995

Biodegradative threonine dehydratase purified from Serratia marcescens ATCC 25419 was inactivated by the arginine specific modification reagent, phenylglyoxal (PGO) and the lysine modification reagent, pyridoxal 5'-phosphate (PLP). The inactivation by PGO was protected by L-threonine and L-serine. The second order rate constant for the inactivation of the enzyme by PGO was calculated to be 136 $M^{-1}min^{-1}$. The reaction order with respect to PGO was 0.83. The inactivation of the enzyme by PGO was reversed upon addition of excess hydroxylamine. The inactivation of the enzyme by PLP was protected by L-threonine, L-serine, and a-aminobutyrate. The second order rate constant for the inactivation of the enzyme by PLP was 157 $M^{-1}min^{-1}$ and the order of reaction with respect to PLP was 1.0. The inactivation of the enzyme by PLP was reversed upon addition of excess acetic anhydride. Other chemical modification reagents such as N-ethylmaleimide, 5,5'-dithiobis (2-nitrobenzoate), iodoacetamide, sodium azide, phenylmethyl sulfonylfluoride and diethylpyrocarbonate had no effect on the enzyme activity. These results suggest that essential arginine and lysine residues may be located at or near the active site.

• 한국환경과학회지
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• 제26권7호
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• pp.859-868
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• 2017

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, $Fe^0$) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when $Fe^0$ and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the $Fe^0$ and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the $Fe^0$ and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > $Fe^0$, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

• 대한화학회지
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• 제21권4호
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• pp.227-234
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• 1977

황산산성에서 페닐히드라진과 브롬의 반응을 속도론적으로 검토하였다. 겉보기 2차 반응속도상수는 1M 이하의 황산농도에서는 수소이온 농도에 대략 역비례한다. KBr 첨가의 영향을 검토하여 $Br_2\;및\;Br_3^-$가 반응화학종이고, 이들의 속도상수는 $20^{\circ}C$의 0.01M $H_2SO_4$용액에서 각각 $5{\times}10^5M^{-1},sec^{-1}\;및\;0. 7{\times}10^5M^{-1},sec^{-1}$임을 밝혔다. 2,4-디니트로 페닐히드라진의 브롬과의 반응속도상수는 수소이온 농도에 거의 무관계하며 $Br_2\;및\;Br_3^-$에 대하여 각각 $1.2{\times}10^5M^{-1},sec^{-1}\;및\;2.0{\times}10^4M^{-1},sec^{-1}$이다.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 2005년도 총회 및 춘계학술발표회
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• pp.53-56
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• 2005

A Laboratory study was conducted to evaluate the kinetics of oxidation of trichloroethylene (TCE) in groundwater by potassium permanganate $(KMnO_4)$, Consumption of permanganate by TCE and aquifer materials was also evaluated to obtain an appropriate injection rate of $KMnO_4$. TCE degradation by $KMnO_4$ in the absence of aquifer material showed effective with pseudo-first order rate constant, $k_{obs}=1.8110^{-3}\;s^{-1}\;at\;KMnO_4=500mg/L$. TCE oxidation by $KMnO_4$ was found to be second order reaction and the rate constant, $k=0.65{\pm}0.08\;M^{-1}s^{-1}$, was independent of pH changes. $KMnO_4$ consumption rate by groundwater sampled from field site was not significant, indicating that groundwater containing negligible amount of dissolved organic matter does not have any influence on the $KMnO_4$ degradation. Meanwhile, aquifer materials from field site were actively reacted with permanganate, resulting in the significant consumption of $KMnO_4$. It might be attributed to the existence of metal oxides in aquifer materials, Based on the rate constants obtained from this study, appropriate injection rate of permanganate and TCE removal rate in groundwater could be estimated.