• Bulletin of the Korean Chemical Society
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• v.34 no.5
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• pp.1525-1529
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• 2013

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.211-216
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• 2012

Wet chemical etching of stainless steel foil by aqueous ferric chloride solution was investigated in this study. Effects of various process parameters (e.g. etchant agitation rate, etchant temperature, $Fe^{3+}$ ion concentration, free HCl concentration, specific gravity, etc.) on the etch rate was first studied, and it was found that the etch rate of AK (aluminum-killed) steel, chromium metal and stainless steel (STS430J1L alloy) follows the pseudo-first order reaction equation. When the fatigue ratio of etchant was kept under 16%, sludge was not formed in the solution, and the etched surface showed smooth roughness. The etch rate decreases as Baume of etchant increases, but the effect of free HCl concentration on the etch rate turned out to be minimal. Experimental data were compared with the calculated results from modeled equation, showing very good agreement.

• Ecology and Resilient Infrastructure
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• v.2 no.4
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• pp.330-336
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• 2015

Photocatalytic degradation of bisphenol A (BPA) in aqueous solution was investigated using $TiO_2$ nanoparticles (Degussa P25) in this study. After a 3 hr photocatalytic reaction (${\lambda}=365nm$ and $I=3mW\;cm^{-2}$, $[TiO_2]=2.0g\;L^{-1}$), 98% of BPA ($1.0{\times}10^{-5}M$) was degraded and 89% of the total organic carbon was removed. In addition, BPA degradation by photolytic, hydrolytic and adsorption reactions was found to be 2%, 5% and 13%, respectively. The reaction rate of BPA degradation by photocatalysis decreased with increasing concentration of methanol that is used as a hydroxyl radical scavenger. This indicates that the reaction between BPA and hydroxyl radical was the key mechanism of BPA degradation. The pseudo-first-order reaction rate constant for this reaction was determined to be $7.94{\times}10^{-4}min^{-1}$, and the time for 90% BPA removal was found to be 25 min. In addition, acute toxicity testing using Daphnia magna neonates (< 24 h old) was carried out to evaluate the reduction of BPA toxicity. Acute toxicity (48 hr) to D. magna was decreased from 2.93 TU (toxic unit) to non-toxic after photocatalytic degradation of BPA for 3 hr. This suggests that there was no formation of toxic degradation products from BPA photocatalysis.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.10
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• pp.723-730
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• 2011

In this experiment, persulfate, a strong oxidant for ISCO (In-Situ Chemical Oxidation) was used to degraded RDX in artificial ground water at ambient temperature. Results of RDX degradation by persulfate in a batch reactor showed that the oxidation reaction was pseudo first order with estimated Ea (activation energy) of $1.14{\times}10^2kJ/mol$ and the rate was increased with the increase of reaction temperature. The oxidation of RDX by persulfate increased slightly with the increase of initial solution pH from 4 to 8. The RDX oxidation rate increased 13 times at pH 10 compared with that at pH 4, however, alkaline hydrolysis was found to be the main reaction of RDX degradation rather than oxidation. The study also showed that the oxidation rate of RDX by persulfate was linearly dependent upon the molar ratios of persulfate to RDX from 5 : 1 up to 100 : 1, with a proportion constant of $4{\times}10^{-4}$ ($min^{-1}$/molar ratio) at $70^{\circ}C$. While NOM (Natural Organic Matter) exerted negative effects on the oxidation rate of RDX by persulfate, with a proportion constant of $1.21{\times}10^{-4}$ ($min^{-1}{\cdot}L/mg-NOM$) at $70^{\circ}C$ and persulfate/NOM molar ratio of 10/1. The decrease in RDX oxidation rate was linearly dependent upon the added NOM concentration. However, the estimated activation energy in the presence of 20 mg-NOM/L was within 3.3% error compared to that without NOM, which implies the addition of NOM does not alter intrinsic oxidation reaction.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1951-1956
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• 2011

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

• BMB Reports
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• v.28 no.2
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• pp.112-117
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• 1995

Succinic semialdehyde reductase was inactivated by o-phthalaldehyde. The inactivation followed pseudo-first order kinetics, and the second-order rate constant for the inactivation process was 28 $M^{-1}s^{-1}$ at pH 7.4 and $25^{\circ}C$. The absorption spectrum ($\lambda_{max}$ 337 nm) and fluorescence excitation ($\lambda_{max}$ 340 nm) and fluorescence emission spectra ($\lambda_{max}$ 409 nm) were consistent with the formation of an isoindole derivative in the catalytic site between a cysteine and a lysine residue approximately about 3 $\AA$ apart. The substrate, succinic semialdehyde, did not protect enzymatic activity against inactivation, whereas the coenzyme NADPH protected against o-phthaladehyde induced inactivation of the enzyme. About 1 isoindole group per mol of the enzyme was formed following complete loss of enzymatic activity. These results suggest that the amino acid residues of the enzyme participating in a reaction with o-phthalaldehyde are cysteinyl and lysyl residues at or near the NADPH binding site.

• Journal of Korean Society of Environmental Engineers
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• v.28 no.4
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• pp.397-401
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• 2006

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 material was also evaluated to obtain an appropriate injection rate of $KMnO_4$. TCE degradation by $KMnO_4$ in the absence of aquifer material was effective with a pseudo-first order rate constant, $k_{obs}=5.24{\times}10^{-3}s^{-1}\;at\;KMnO_4=500mg/L$. TCE oxidation by $KMnO_4$ was found to be second order reaction and the rate constant, $k=0.65{\pm}0.08M^{-1}s^{-1}$. Meanwhile, aquifer materials from the 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 the aquifer materials.

• Journal of the Korean GEO-environmental Society
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• v.13 no.9
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• pp.69-74
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• 2012

This study investigated the TNT decomposition by the treatment of alkaline hydrolysis. To obtain this objecitive, spectrum shift characteristics, pH effect, kinetics, and product analysis were examined during the alkaline hydrolysis by means of hydroxide ions. At pH = 12, an aqueous solution of TNT was changed into yellow-brown coloring, in which its absorbances were newly increased in a range of wavelength 400-600 nm. From the kinetic data, pseudo-first-order rate constant in a excess of hydroxide ion, in contrast to TNT concentration, was $0.0022min^{-1}$, which means that the reaction rate between TNT and hydroxide ion can be very slow, and that 1,047 min is necessary to achieve a 90% reduction of the initial TNT. In products analyses, nitrite ions and formic acid were mainly produced by the alkaline hydrolysis, nitrate ions and oxalic acid as minor products were generated.

• Membrane and Water Treatment
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• v.11 no.1
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• pp.69-77
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• 2020

Former studies revealed that sepiolite thermally treated at high temperature have high adsorption capacity for phosphate. However, its micron size (75 ㎛) limits its application to water treatment. In this study, we synthesized sepiolite impregnated polysulfone (PSf) beads to separate it easily from an aqueous solution. PSf beads with different sepiolite ratios were synthesized and their efficiencies were compared. The PSf beads with 30% impregnated sepiolite (30SPL-PSf bead) possessed the optimum sepiolite ratio for phosphate removal. Kinetic, equilibrium, and thermodynamic adsorption experiments were performed using the 30SPL-PSf bead. Equilibrium adsorption was achieved in 24 h, and the pseudo-first-order model was suitable for describing the phosphate adsorption at different reaction times. The Langmuir model was appropriate for describing the phosphate adsorption onto the 30SPL-PSf bead, and the maximum adsorption capacity of the 30SPL-PSf bead obtained from the model was 24.48 mg-PO₄/g. Enthalpy and entropy increased during the phosphate adsorption onto the 30SPL-PSf bead, and Gibb's free energy at 35 ℃ was negative. An increase in the solution pH from 3 to 11 induced a decrease in the phosphate adsorption amount from 27.30 mg-PO₄/g to 21.54 mg-PO₄/g. The competitive anion influenced the phosphate adsorption onto the 30SPL-PSf bead was in the order of NO₃^- > SO₄^2- > HCO_3^-. The phosphate breakthrough from the column packed with the 30SPL-PSf bead began after ~2000 min, reaching the influent concentration after ~8000 min. The adsorption amounts per unit mass of 30SPL-PSf and removal efficiency were 0.775 mg-PO₄/g and 61.6%, respectively. This study demonstrates the adequate performance of 30SPL-PSf beads as a filter for phosphate removal from aqueous solutions.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.10
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• pp.1034-1038
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• 2008

Degradative Solidification/Stabilization(DS/S) is a modification of conventional Solidification/Stabilization(S/S) that incorporates degradative processes for organic contaminant destruction with the low cost of conventional S/S. Inorganic contaminants are immobilized and chlorinated organic contaminants are destroyed by DS/S treatment. In this study, a DS/S using cement/slag/Fe(II) systems as binder was investigated to assess its effectiveness in degrading chloroform(CF) and methylene chloride(MC) contained in hazardous liquid wastes. The initial concentration of CF was 0.26 mM, 1.0 mM, 8.4 mM, 25 mM and 42 mM and Fe(II) was 200 mM. The result showed that degradation of CF in various concentration was in one kind reaction as pseudo-first-order and 95% of 0.26 mM initial concentration of CF was removed in five days. 50 mg/L of heavy metal was added in order to accelerate the rate of degradation of MC and initial concentration of MC was 3.50 mM however, degradation did not occur in system. Thus additional studies needed for degradation of MC and more studies on other reaction pathways products will help elucidate reaction mechanisms and pathways for chlorinated methanes in cement/slag/Fe(II) systems.