• Bulletin of the Korean Chemical Society
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• 제23권10호
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• pp.1445-1450
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• 2002

Solvolytic rate constants at 25 $^{\circ}C$ are reported for solvolysis of chlorodithioformate (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, 50%methanol-d/50%D2O, and 2,2,2-trifluroethanol (TFE), and also in TFE-ethanol mixtures. The Grunwald-Winstein plot shows that the three aqueous mixtures exhibit dispersions into separate line. The correlation is improved only slightly by additional parameters NT for solvent nucleophilicity and/or I for aromatic ring parameter. Rate ratios in solvents of the same $Y_cl$ value, having different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance, and the value of 3.35 for $[$k_{40EW}$/$k_97TFE$]_Y$ (EW = ethanol-water), is consistent with an essentially SN1 reaction mechanism. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the SN1 reaction mechanism. log(k/$k_o$) = mY + lN + hI

• 한국재료학회지
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• 제17권10호
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• pp.560-566
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• 2007

AlN plates were fabricated by hot pressing at $1700-1900^{\circ}C$ using yttria and alumina (3 and $10\;{\mu}m$ particle size) powders as additives and characterized: density, thermal conductivity, transverse rupture strength, and grain size measurement by SEM and EDS. Density values of $3.31-3.34\;g/cm^3$ are largely attributed to hot pressing of powder mixtures in carbon mold under $N_2$ atmosphere which caused effective degree of oxygen removal from yttrium-aluminate phase expected to form at $1100^{\circ}C$. The grain size of hot pressed AlN was almost homogeneous, with size approximately from 3.2 to $4.0\;{\mu}m$ after hot pressing. $Al_2O_3$ powder of $3\;{\mu}m$ particle size resulted in better transverse rupture strength and finer grain size compared to $10\;{\mu}m$ $Al_2O_3$ powder. The thermal conductivity of AlN ranged between $83-92.7\;W/m{\cdot}K$ and decreased with $Al_2O_3$ addition. Fine grain size is preferred for better mechanical properties and thermal conductivity.

• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.1963-1967
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• 2010

The rates of solvolysis of 4-morpholinecarbonyl chloride (MPC) have measured at $35.0^{\circ}C$ in water, $D_2O$, $CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol, and 2,2,2-trifluoroethanol. An extended (two-term) Grunwald-Winstein equation correlation gave sensitivities towards changes in solvent nucleophilicity and solvent ionizing power as expected for a dissociative $S_N2$ and/or $S_N1$(ionization) pathway. For nine solvents specific rates were determined at two additional temperatures and higher enthalpies and smaller negative entropies of activation were observed, consistent with the typical dissociative $S_N2$ or $S_N1$(ionization) pathway. The solvent deuterium isotope effect values for the hydrolysis of MPC of $k_{H_2O}/k_{D_2O}$ = 1.27 and for the methanolysis of MPC of $k_{MeOH}/k_{MeOD}$ = 1.22 are typical magnitudes of the $S_N1$ or ionization mechanism.

• 대한화학회지
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• 제24권4호
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• pp.288-294
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• 1980

$CH_3O(CO)Cl,\;CH_3S(CO)Cl\;및\;CH_3S(CS)Cl$/TEX>의 가메탄올 분해반응속도를 메탄올-아세토니트릴 혼합용매하에서 결정하였다. 반응속도는 주로 벌크한 용매성질에 의해서만 아니라 일부 친전자적 특수용매화에 의해서도 영향을 받는다는 것이 실험결과로 알려졌다. 용매의 극성은 반응속도에 영향을 미치는 중요인자는 아니지만, $S_N1$형의 천이상태 안정화에 기여함을 알았다. $CH_3S(CS)Cl$/TEX>의 가메탄올 분해반응은 메탄올에 의한 이탈기의 특수 용매효과 및 큰 유전상수를 가진 용매에 의한 천이상태 안정화가 중요한 $S_N1$형으로 진행됨을 알았다. $CH_3O(CO)Cl$의 가메탄올 분해반응은 위의 경우와는 반대로 $S_N2$형으로 진행됨을 알았다.

• 조명전기설비학회논문지
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• 제29권11호
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• pp.41-46
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• 2015

This study was conducted to discover a substitute of $SF_6$ gas. $SF_6$ gas is widely used across the industries. Thanks to superior electrical properties, in particular, it has been commonly used in electrical industry. However, there have been a lot of studies on its serious effect on global warming. As a substitute of this synthetic gas, a mixture of dry air and $N_2/O_2$ was chosen in this study. In case of $N_2/O_2$, dielectric strength differs depending on the mixing ratio. This study examined dielectric breakdown and flashover after adjusting oxygen percentage in the dry air. This test was conducted in a quasi-uniform electric field depending on pressure, oxygen concentration and gas mixtures. The test results found that dielectric voltage and flashover voltage were the highest at a certain oxygen concentration. It is the results of this photoionization and electron attachment of oxygen.

• 대한화학회지
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• 제30권3호
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• pp.296-300
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• 1986

MeOH-$H_2O$, EtOH-$H_2O$, MeOH-MeCN and MeOH-$(Me)_2$CO 혼합용매계에서 pseudo-saccharinechloride의 가용매분해반응에 대한 유사일차 반응속도상수를 여러 온도에서 구하였다. Kivinen식의 n값과 Grunwald-Winstein식의 m값을 구하고 분광용매화 관계식의 파라메타들을 결정하였다. 이들 용매효과 파라메타와 활성화 파라메타들을 종합하여 볼때 Pseudo saccharinechloride의 가용매 분해반응은 $S_N2$ 반응으로 진행됨을 알았다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 1999년도 추계학술대회 논문집
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• pp.228-231
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• 1999

The preparation and electrical properties of LIPON electrolyte were investigated in order to fabricate all solid state thin film battery. The LIPON thin film was deposited by r.f. sputtering of Li$_3$PO$_4$ target in O$_2$-N$_2$ mixtures. The LIPON deposited at N$_2$+10% O$_2$ ratio had a conductivity at 25 $^{\circ}C$ of 1.8${\times}$10$\^$-6/S/cm. The ion conductivity of the LIPON films decreased as the O$_2$ content of the process gas increased.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.968-973
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• 1998

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.201-204
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• 1986

Reduction of N-arylpyridinium compounds by $NaBH_4$ gave mixtures of the corresponding 1,2-dihydropyridine(major) and 1,4-dihydropyridine(minor), whereas similar reduction by $Na_2S_2O_4$ produced 1,4-dihydropyridines regioselectively. The proportion of 1,4-isomer in the product by $NaBH_4$ reduction appeared to increase with the electron-donating ability of N-aryl groups. When the N-aryl group is p-methylphenyl, p-ethylphenyl or p-methoxyphenyl, the 1,2-dihydropyridines in ethanol-water (4:1) solutions isomerized to the corresponding 1,4-dihydropyridines. N-(p-methylphenyl)-1,2-dihydropyridine and N-(p-ethylphenyl)-1,2-dihydropyridine in solid state also isomerized to the corresponding 1,4-dihydropyridines. The different behaviors of reduction among N-arylpyridiniums and isomerization of the reduction products depending on the substituent in N-aryl group were explained in terms of difference in the electronic effects of the substituents.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2000년도 하계학술대회 논문집
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• pp.5-8
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• 2000

The population density of excited species in dc, rf and laser ablation plume plasmas has been measured using laser absorption spectroscopy. It was shown that, when the plasma was modulated by on and off with, the sensitivity and signal to noise (S/N) ratio became high. For example, the atomic O(3$^{5}$ S$^{o}$ $_2$) Population density, No* in $O_2$/He mixtures was obtained by the highest S/N ratio at a frequency of 2.7kHz. In a 20Torr room air, the lowest No* level to be detectable was shown to be an order of 10$^{7}$ cm$^{-3}$ . The population densities of resonance Ar(1S$_2$) and Xe(1S$_4$) levels were also measured in barrier discharges and laser ablation plasmas.