• Journal of the Korean Chemical Society
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• v.23 no.2
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• pp.99-103
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• 1979

The reductive amination of three ${\alpha}$,${\beta}$-unsaturated aldehydes, cinnamaldehyde, crotonaldehyde, and acrolein are carried out successfully by tetracarbonylhydridoferrate in the presence of various primary amines. In a typical reaction, a mixture of potassium tetracarbonylhydridoferrate (22 mmole), an amine (22∼44 mole) and ${\alpha}$,${\beta}$-unsaturated aldehyde (22 mmole), in ethanol (30∼50 ml) was stirred for 9∼60 hours at room temperature under carbon monoxide atmosphere. All the products were characterized as secondary amines by mass, infrared, and nmr spectra as well as gas chromatographic data.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.360-362
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• 1989

Catalytic isomerization of unsaturated alcohols to the corresponding carbonyl compounds with$Rh(ClO_4)(CO)(PPh_3)_2\;(1)\;and\;[Rh(CO)(PPh_3)_3]ClO_4$ (2) is faster under hydrogen (where hydrogenation also occurs to give saturated alcohols) than under nitrogen. The isomerization under hydrogen seems to occur through an alkylhydridorhodium(III) complex which also undergoes reductive elimination to give hydrogenation products, saturated alcohols. The isomerization under hydrogen is faster with 2 than with 1, which is understood by acceleration of the last step, enol formation by $PPh_3$ dissociated from 2 and present in the reaction mixture when 2 is used as catalyst. Relative rates of the isomerization observed for different unsaturated alcohols are interpreted by steric effects of substituted groups and numbers of hydrogens to be abstracted by the rhodium of the intermediate, alkylhydridorhodium(III) to undergo the reductive elimination to give enol which is then rapidly converted into a carbonyl compound. It has been observed that the hydrogenation is relatively significant when reactions occur slowly whereas the isomerization is predominant when reactions proceed rapidly.

• Nuclear Engineering and Technology
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• v.54 no.6
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• pp.2329-2333
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• 2022

Base metal corrosion forms a significant issue during the chemical decontamination of the primary coolant loop in nuclear power plants as it is directly related to the economic and safety viability of decommissioning. In this technical note, potentiodynamic evaluations of several base metals (304 stainless steel, SA106 Grade B carbon steel, and alloy 600) were performed to determine their corrosion behavior during the hydrazine (N₂H₄)-based reductive ion decontamination (HyBRID) process. The results suggested that N₂H₄ protected the surface of the base metals in the HyBRID solution, which is primarily composed of H₂SO₄. The corrosion resistance of the carbon steel was further improved through the addition of CuSO₄ to the solution. The corrosion rate of carbon steel in the H₂SO₄-N₂H₄-CuSO₄ solution was lower than that exhibited in an oxalic acid solution, a commonly used reaction medium during commercial decontamination processes. These results indicate the superiority of the HyBRID process with respect to the base metal stability.

• Journal of Korean Society of Environmental Engineers
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• v.28 no.5
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• pp.487-493
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• 2006

Reductive dechlorination of chlorophenols by nickel coated iron was investigated to understand the feasibility of using Ni/Fe for the in situ remediation of contaminated groundwater. Zero Valent Iron(ZVI) was amended with Ni(II) ions to form bimetal(Ni/Fe). Dechlorination of five chlorophenol compounds and formation of intermediates were examined using Ni/Fe. Rate constant for each reaction pathway was quantified by the numerical integration of a series of differential rate equation. Experimental results showed that the sequence of hydrodechlorination rate constant was in the order of 2-CP>4-CP>2,4-DCP>2,4,6-TCP>2,6-DCP. The hydrodechlorination pathways for the conversion of each chlorophenol compound involves a full dechlorination to phenol via both concerted and stepwise mechanisms. Reaction pathways and corresponding kinetic rate constants were suggested based on the experiments and numerical simulations.

• Journal of Soil and Groundwater Environment
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• v.11 no.5
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• pp.35-42
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• 2006

The following results were obtained in the reductive degradation of hexachloroethane (HCA), and surface characteristics by using iron sulfide ($FeS,\;FeS_{2}$) mediators. HCA was degraded to pentachloroethane (PCA), tetrachloroethylene(PCE), trichloroethylene(TCE) and cis-l,2-dichloroethylene (cis-1,2-DCE) by complicated pathways such as hydrogenolysis, dehaloelimination and dehydrohalogenation. FeS had more rapid degradation rates of organic solvent than $FeS_{2}$. In liquidsolid reaction, the reaction rates of organic solvents were investigated to explain surface characteristics of FeS and $FeS_{2}$.. To determine surface characteristics of FeS and $FeS_{2}$, the specific surface area and surface potential of each mineral was determined and the hydrophilic site ($N_{s}$) was calculated. The specific surface area ($107.0470m^{2}/g\;and\;92.6374m^{2}/g$) and the $pH_{ZPC}$ of minerals ($FeS\;PH_{ZPC}=7.42,\;FeS_{2},\;PH_{ZPC}=7.80$) were measured. The results showed that the Ns of FeS and $FeS_{2}$ were $0.053\;site/mm^{2}\;and\;0.205\;site/mm^{2}$, respectively. $FeS_{2}$ had more hydrophilic surface than FeS. In other words, FeS have more hydrophobic surface site than $FeS_{2}$.

• Clean Technology
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• v.15 no.3
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• pp.194-201
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• 2009

Reductive reactivity of zero-valent iron nanoparticles was investigated for removal of nitrate-nitrogen which is considered one of the major water pollutants. To elucidate the difference in reactivity between preparation methods, iron nanoparticles were synthesized respectively from microemulsion and aqueous solution of ferric ions. Iron nanoparticles prepared from microemulsion were deposited on aluminum by electrophoretic method, and their reaction kinetics was compared to that of the same nanoparticles suspended in aqueous batch reaction. With an approximation of pseudo-first-order reaction, rate constants for suspended nanoparticles prepared from microemulsion and dilute aqueous solution were $3.49{\times}10^{-2}min^{-1}$ and $1.40{\times}10^{-2}min^{-1}$, respectively. Iron nanoparticles supported on aluminum showed ca. 30% less reaction rate in comparison with the identical nanoparticles in suspended state. However, supported nanoparticles showed the superior effectiveness in terms of nitrate-nitrogen removal per zero-valent iron input especially when excess amounts of nitrates were present. Iron nanoparticles deposited on aluminum maintained reductive reactivity for more than 3 hours, and produced nitrogen gas as a final reduction product of nitrate-nitrogen.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.136-140
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• 1993

New synthetic method for diethyl N-[4-{[(2,4-diamino-6-yl)methyl]-amino}benzoyl]-L-glutamate(10) which is an intermediate of methotrexate is described. p-Nitrobenzoyl-L-glutamate was obtained via a two-step sequence which involves condensation of p-nitrobenzoyl chloride with diethyl-L-glutamate and Fischer esterification reaction with ethanol. Reductive methylation of diethyl-p-nitrobenzoyl-L-glutamate were carried out by reaction with formic acid and paraformaldehyde in the presence of $PtO_2$ catalyst and yielded diethyl N-(4-methylaminobenzoyl)-L-glutamate(7). It was followed by allylation and iodoazidozation to give the diethyl-p-[N-(2-azido-3-iodopropyl)-N-methyl]aminobenzoyl-L-glutamate(9). The cyclization reaction of compound(9) with 2,4,5,6-tetraaminopyrimidine was carried out by intermolecular nucleophilic substitution to give the desired methotrexate diethylester.

• Journal of the Mineralogical Society of Korea
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• v.22 no.2
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• pp.107-114
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• 2009

In present study, an alternative process for manufacturing ultra marine blue by using kaolin, sulfur, sodium carbonate, silica, and rosin was investigated. From the experiments, it was found in the reductive calcination process that the temperature variation with the bed height of input materials is relatively high due to the inadequate thermal conductivity of them. It was also found that the color of the ultramarine blue manufactured is sensitive for the shape of the input materials and the calcinations conditions, and specially the heating rate is very important to form ultramarine. For manufacturing green ultramarine by using sulfur, sodium carbonate, silicon, and pine resin, an optimum condition was investigated to be the heating rate region below $0.6^{\circ}C/min$, the reaction temperature of $850^{\circ}C$ and the reaction time of 4 hr. At the oxidative calcination process to manufacture ultra marine blue from green ultramarine, the optimum flow rate of air is $500{\sim}550\;{\ell}/kg$ (green ultramarine) and the reaction temperature is $500{\sim}550^{\circ}C$.

• Journal of the Korean Chemical Society
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• v.35 no.3
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• pp.226-232
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• 1991

Adsorption and oxidation of polychlorinated phenols by suspended ${\sigma}-MnO_2$ in aqueous solution have been studied. Of the proposed mechanism, adsorption reaction of chlorophenols onto ${\sigma}-MnO_2$(s) depended upon the pH of the solution and the concentration of chlorophenol. Adsorption isotherms showed a reasonably good fit to the Langmuir isotherm. From the pH dependence of adsorption partition coefficient and the linear relationship between octanol-water partition coefficient and adsorption partiton coefficient of chlorophenol, it is estimated that adsorption is dominated by its hydrophobicity. The rate of electron transfer reaction evaluated from the rate of reductive dissolution of ${\sigma}-MnO_2$(s) depended linearly upon the concentration of chlorophenol and the pH of medium. Observed rate constants ($K_0$) of the meta-substituted chlorophenol were lower than that of the ortho-or para-chlorophenol because of resonance effect of chlorophenoxy radical. It is indicated that this radical is produced in the adsorption process and the electron transfer reaction is rate determining.

• Journal of Environmental Health Sciences
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• v.40 no.2
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• pp.147-156
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• 2014

Objectives: This study was carried out to examine whether the apparent photolysis with or without sensitizers [NaOH and humic acid (HA)] was prompted photodegradation of polychlorinated biphenyl (PCB) in aqueous solution. Methods: PCBs photodegradation occurred using fluorescence black lamps at ${\lambda}_{max}=300nm$. PCB congeners were exposed in 10 ppm HA or 0.05N NaOH solutions, to investigate the decreasing profile of PCB concentration with time. The PCBs were then analyzed by gas chromatography/mass spectrometry (GC-MS). Reductive degradation profile of PCB congeners in the presence of both sensitizers under oxygen-saturated protic conditions was described using the wind-rose diagrams. Results: Use of HA or NaOH decreased PCB concentration with time in the dark and on irradiation, indicating that photolysis underwent through reductive dechlorination through energy transfer and possibly with reactive oxygens. The dechlorination was marked by a chromatographic shift, observed in the GC-MS plots. Therefore it is logical to assume that increasing the dose of sensitizers would increase the photodegradation rates of PCBs. The half-lives of pentachloro-PCB (penta-3) in 0.05N NaOH and 10 ppm HA were estimated at about 47 hours and 39 hours, respectively, under the same experimental conditions of photolysis. It was found that the rate of photolysis of pentachloro-PCB in aqueous solution followed apparent first-order kinetics compared to other congeners. Conclusion: Photochemical degradation (using 328 nm UV light) of penta- and hexa-PCBs in HA or alkaline solution is a viable method for pretreatment method. The results are helpful for the further comprehension of the reaction mechanism for photolytic dechlorination of PCBs in aquatic system.