• Journal of the Korean Chemical Society
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• v.18 no.4
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• pp.223-238
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• 1974

CNDO/2 MO theoretical studies and kinetic studies of halide exchange reactions for alkylchloroformates have been carried out in order to investigate structure-reactivity relationship of alkylchloroformates. From the result of energetics, it was concluded that the most stable configuration of alkylchloroformate is that in which alkyl group and chlorine are trans to each other, and that the hindered rotation about the bond between the carbonyl carbon and alkoxy-oxygen bond is attributed to the ${\pi}-$electron delocalization. It has been found that the large charge separation is due to -M effect of carbonyl and alkoxy oxygens and-I effect of chlorine. The order of rates in solvents studied was $(CH_3)_2 > CO > CH_3CN{\gg}MeOH.$$I^->Br^->Cl^-$ in protic solvent, and of Cl^->Br^- >I^-$ in dipolar aprotic solvents. Alkyl group contribution has the decreasing order of $CH_3-> C_2H-{\gg}i-C_3H_7-.$ The solvent effect has been interpreted on the basis of initial and final state contribution. A transition state model has been suggested, and it has been proposed that the most favorable mechanism is the addition-elimination. From the results of activation parameters and electronic properties, an energy profile has been proposed. Structural factors determining reactivities of alkylchloroformates have been shown to be charge, energy level of ${\alpha}^*LUMO$ to C-Cl bond and ${\alpha}^{\ast} $antibonding strength with respect to C-Cl bond in this MO. Charge and polarizability of nucleophile, and the interaction of these effects with solvent structures are also found to be important.

• Journal of the Korean earth science society
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• v.21 no.6
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• pp.703-718
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• 2000

In order to investigate interannual variation of total ozone and reflectivity over the globe, Nimbus-7/TOMS data were used on the monthly mean and its anomaly for the period of 1979-92. This study also examined MSU channel 4(Ch4; lower-stratosphere) brightness temperature data and two model reanalyses of NCEP and GEOS to compare the ozone variation with atmospheric thermal condition. In addition, the MSU channel 1(Ch1 ; lower-troposphere) brightness temperature was used to compare with the reflectivity. The ozone showed strong annual cycle with downward trend(-6.3${\pm}$0.6 DU/decade) over the globe, and more distinct response to volcanic eruption than El Ni${\tilde{n}$o. The relationship between total ozone and MSU Ch4 observation, and between the ozone and model reanalyses of lower stratosphere temperature showed positive correlation(0.2-0.7) during the period of 1980-92. Reflectivity increased interannually by 0.2${\pm}$0.06%/decade over the globe during the above period and reflected El Ni${\tilde{n}$o(1982-83, 1991-92) well. Its variability in annual cycle was remarkably smaller in tropics than in higher latitudes. This is inferred due to cloud suppression and tropical upwelling regions. Reflectivity correlated negatively(-0.9) to the Ch1 temperature over the globe, but positively(0.2) over tropical ocean. The positive value over the ocean results from the effect of microwave emissivity which increases the Ch1 temperature with enhanced hydrometeor activity. Significant correlations between total ozone and the Ch4 temperature, and between reflectivity and the Ch1 Suggest that the TOMS data may use valuably to better understand the feedback mechanism of climate change.

• Journal of Korean Society for Atmospheric Environment
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• v.22 no.5
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• pp.712-718
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• 2006

In order to investigate the analytical uncertainties associated with sampling and analysis of major greenhouse gaseous pollutants(carbon dioxide and methane), we attempted to quantify their adsorptive loss due to the contact with the container wall(such as Tedlar bag and vial). Using the GC/FID method, some basic experimental parameters(such as reproducibility and method detection limit) have been evaluated as part of the essential QA/QC The reproducibilities of carbon dioxide and methane were estimated as 2.02 and 0.2%, respectively. In addition, method detection limits were measured as 0.61 and 0.06 ng, respectively. A test of sample loss rate has also been made for Tedlar bag and vial by assessing the absolute amount of sample loss on the wall. By transferring the samples contained in Tedlar bag to various sizes of Tedlar bags, we measured differences in the absolute loss quantity due to such transfer. In addition, we also examined such loss mechanism as a function of elapsed time and light penetration rate for vial. As results, carbon dioxide and methane have shown about 2% of sample loss due to such contact. It is also noticed that the amount of loss with vial surface is lower than that of Tedlar bag. Therefore, field collection of greenhouse gases using various container types should be made more cautiously to minimize the possibility of sample loss and bias related to such loss.

• Applied Chemistry for Engineering
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• v.35 no.2
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• pp.134-139
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• 2024

In the steam reforming of methane reactions, the effect of adding noble metals Ru and Pd to a Ni-based catalyst as promoters was analyzed in terms of catalytic activity and hydrogen production. The synthesized catalysts were coated on the surface of a honeycomb-structured metal monolith to perform steam methane reforming reactions. The catalysts were characterized by XRD, TPR, and SEM, and after the reforming reaction, the gas composition was analyzed by GC to measure methane conversion, hydrogen yield, and CO selectivity. The addition of 0.5 wt% Ru improved the reduction properties of the Ni catalyst and exhibited enhanced catalytic activity with a methane conversion of 99.91%. In addition, reaction characteristics were analyzed according to various process conditions. Methane conversion of over 90% and hydrogen yield of more than 3.3 were achieved at a reaction temperature of 800 ℃, a gas hourly space velocity (GHSV) of less than 10000 h^-1, and a ratio of H₂O to CH₄ (S/C) higher than 3.

• Journal of Korea Water Resources Association
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• v.55 no.10
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• pp.785-799
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• 2022

The aim of this study was to characterize the emission pathways and the footprint of greenhouse gases (GHG) in Daecheong Reservoir using the G-res Tool, and to evaluate the GHG emission intensity (EI) compared to other energy sources. In addition, the change in GHG emissions was assessed in response to the total phosphorus (TP) concentration. The GHG flux in post-impoundment was found to be 262 gCO₂eq/m²/yr, of which CO₂ and CH₄ were 45.7% and 54.2%, respectively. Diffusion of CO₂ contributed the most, followed by diffusion, degassing, and bubbling of CH₄. The net GHG flux increased to 510 gCO₂eq/m²/yr because the forest (as CO₂ sink) was lost after dam construction. The EI of Daecheong Reservoir was 86.8 gCO₂eq/kWh, which is 3.7 times higher than the global EI of hydroelectric power, due to its low power density. However, it was remarkable to highlight the value to be 9.5 times less than that of coal, a fossil fuel. We also found that a decrease in TP concentration in the reservoir leads to a decrease in GHG emissions. The results can be used to improve understanding of the GHG emission characteristics and to reduce uncertainty of the national GHG inventory of dam reservoirs.

• Archives of Pharmacal Research
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• v.17 no.6
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• pp.420-423
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• 1994

Various N'-substituted anilino-N-methyl-N'-nitrosoureas(2a-n) were easily prepared from the reaction of substituted phenylhydraines $(3, 4-CH_3, {\;} 3-, {\;} 4-OCH_3, {\;} 3-, {\;} 4-F, {\;} 3, {\;} 4-Cl, {\;} 4-Br, {\;} 2-, {\;} 3-, {\;} 4-NO_2, 4-(NO_2)_2)$ with methyl isocyanate, followed by the nitrosation with 99% HCOOH and dry sodium lnitrite powder. Surprisingly, of these series of analogus, the anilino-nitrocosureas substituted with eletron-withdrawing nitro groups (2k-a) showed significantly low $ED_{30}$ values of $1.4-3.4 {\mu}g/ml.$ In addition, none of these copounds subtituted with electron-donating groups exhibited cytotoxicities.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.657-665
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• 1995

The oxidation of various benzyl ethers and benzyl alkyl ethers to benzoates has been studied in two-phase system of $CH_3CO_2Et$ and aqueous NaOCl (6.6 mol eq.). The oxidant N-oxo-4-methoxy-2,2,6,6-tetramethylpiperidium bromide (N-oxoammonium salt) was prepared in situ and recycled by addition of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (0.03 mol eq., 4-methoxy-TEMPO), co-catalyst KBr (0.03mol eq.) and second oxidant NaOCl. Thus the catalytic amount of 4-methoxy-TEMPO was used. An adjustment of the pH value of below 8.0 was also required for this reaction with 2.5 hr of reaction time at 0∼5$^{\circ}C$. Under these conditions benzyl ethers were oxidized to benzoates. The selectivity of oxidation of benzyl alkyl ethers is dependent on the acidity of hydrogen and steric effect of alkyl group.

• Korean Journal of Materials Research
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• v.16 no.3
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• pp.188-192
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• 2006

The microstructures and mechanical properties of continuously porous $SiC-Si_3N_4$composites fabricated by multi-pass extrusion were investigated at different Si levels added. Si-powder with different weight percentages (0%, 5%, 10%, 15%, 20%) was added to the SiC powder to make the raw mixture powders, with $6wt%Y_2O_3-2wt%Al_2O_3$ as sintering additives, carbon ($10-15{\mu}m$) as a pore-forming agent, ethylene vinyl acetate as a binder and stearic acid ($CH_3(CH_2)_{16}COOH$) as a lubricant. In the continuously porous $SiC-Si_3N_4$ composites, $Si_3N_4$ whiskers like the hairs of nostrils were frequently observed on the wall of the pores. In this study, the morphology of the $Si_3N_4$ whiskers was investigated with the silicon addition content. In the composites containing of 10 wt% Si, a large number of $Si_3N_4$ whiskers was found at the continuous pore regions. In the sample to which 15 wt% Si powder was added, maximum values of about 101 MPa bending strength and 57.5% relative density were obtained.

• Journal of the Korea Organic Resources Recycling Association
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• v.27 no.3
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• pp.81-89
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• 2019

The major problem encountered during the storage of pig slurry (PS) is the release of huge amounts of greenhouse gases (GHGs), which are dominated by methane ($CH_4$). To reduce this, concentrated sulfuric acid has been used as an additive to control the pH of pig slurry to 5.0-6.0. However, other low-risk substitutes have been developed due to some limitations to its use, such as corrosiveness, and hazards to animal and human health. In this study, sugar addition was proposed as an eco-friendly approach for limiting $CH_4$ emission from PS during storage. The pH of PS has been reduced from $7.1{\pm}0.1$ (control) to $5.8{\pm}0.1$, $4.6{\pm}0.1$, $4.4{\pm}0.1$, $4.1{\pm}0.1$, and $4.0{\pm}0.1$, by the addition of 10, 20, 30, 40, and 50 g sugar/L, respectively. Lactate, acetate, and propionate were detected as the dominant organic acids and at sugar concentration above 20 g/L, lactate concentration represented 42-72% (COD basis) of total organic acids. For 40 d of storage, $20.6{\pm}2.3kg\;CO_2\;eq./ton\;PS$ was emitted in the control. Such emission, however, was found to be reduced to $8.7{\pm}0.4$ and $0.4{\pm}0.1kg\;CO_2\;eq./ton\;PS$ at 10 and 20 g/L, respectively. Small amount of $CH_4$ from PS at 10 g/L was emitted until 30 d of storage, while for rest of storage period, it has increased to $8.7{\pm}0.4kg\;CO_2\;eq./ton\;PS$ ( 40% of the control) when methanogens have recovered by increasing pH to 7.0. By the end of storage, VS and COD removal in the control reached 24% and 27%, while their ranges reached 15-4% and 12-17% in the sugar added experiments, respectively. It was found that more than 90% of COD removal was done by aerobic biological process.

• The Korean Journal of Mycology
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• v.24 no.4 s.79
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• pp.293-304
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• 1996

A bacterial strain, KSl, possessing strong antifungal activity was isolated from soil samples of ginseng fields and identified as Bacillus subtilis. In greenhouse test, the culture filtrate of B. subtilis KS1 showed strong protective effect against several fungal diseases of agricultural plants such as cucumber gray mold and wheat leaf rust. In addition, the crude butanol fraction of the culture filtrate exhibited antagonistic effect against several fungi including plant or human pathogens, such as Botrytis maydis, Chytridium lagenarium and Candida albicans. The antifungal compound, SW1, produced by B. subtilis KS1 was purified through consecutive chromatographic separations on a pep-RPC column and a ${\mu}$ Bondapak $C_{18}$ reverse phase column. Temperature and pH showed little effect on the stability of the compound in the ranges $-20-121^{\circ}C$ and pH 4.0-10.0, respectively. The composition and structural characteristics of SW1 were analysed by HPLC and by $^1H-,\;^1H-^1H-COSY$, NOESY, COSY-NOESY and HOHAHA NMR spectroscopy, respectively, which revealed that the compound belongs to iturin A, a typical cyclic antifungal compound produced by B. subtilis. In contrast to the previously reported iturin A compounds which have one or no $-CH_3$ side chain in the hydrophobic hydrocarbon chain of ${\beta}-amino$ acids, SW1 was shown to have a ${\beta}-amino$ acid containing 12-carbon skeleton with two $-CH_3$ side chains.